Intermediate degassing graded fluidized bed hydrogenation modification reaction method for direct coal liquefaction oil

Abstract

The invention relates to an intermediate degassing graded fluidized bed hydrogenation modification reaction method for direct coal liquefaction oil, which can efficiently reduce the aromatic carbon rate of a polycyclic aromatic hydrocarbon reaction product or reduce the dosage of a catalyst, and can improve the adaptability to property fluctuation of liquefied coal. Ammonia, water, methane and light hydrocarbon are removed from the superior reaction product in the intermediate product separation process to obtain intermediate separation liquid, and the intermediate separation liquid enters the subordinate reaction process, so that the method has the advantages that (1) the subordinate reaction process is operated under low ammonia partial pressure and high hydrogen partial pressure, the reaction speed is high, the saturation of limit aromatic hydrocarbon is high, and the coking speed of the catalyst is reduced; (2) the light hydrocarbon product leaves the reaction process in advance to shorten the reaction time; (3) carrying out efficient circular reaction on part of heavy fractionation base oil rich in polycyclic aromatic hydrocarbon obtained from oil generated in the last-stage reaction through a lower-stage reaction process in a low-ammonia gas environment; (4) lower-stage reaction product separated gas enters an upper-stage reaction process in a self-pressure manner for serial use; 5, a reaction temperature increasing operation mode is realized; and (6) the fluctuation amplitude of hydrogen-donor solvent oil performance caused by liquefied coal property fluctuation is reduced.

Description

Technical Field

[0001] The invention relates to an intermediate degassing graded fluidized bed hydrogenation modification reaction method for coal direct liquefaction oil. Background Art

[0002] The coal direct liquefaction reaction process R10 described in the present invention refers to a one-step process for producing oil products based on raw coal. It can be a coal direct liquefaction reaction process with high hydrogen consumption, such as higher than 5.0% by weight (to the coal raw material), such as a coal hydrogenation direct liquefaction reaction process, or it can be a coal direct liquefaction reaction process with low hydrogen consumption, such as lower than 2.5% by weight (to the coal raw material), such as a coal thermal solution reaction process and a coal thermal solution cracking reaction process; the coal direct liquefaction reaction process R10 uses an iron-based coal direct liquefaction catalyst or a non-iron-based coal direct liquefaction catalyst, and its operating pressure can be as high as 17-25MPa or only 1.0-2.5MPa; the reaction process R10, its operating temperature can usually reach 400-465°C.

[0003] In the coal direct liquefaction reaction process R10 of the present invention, no matter how much the chemical hydrogen consumption in the reaction process is, the distillation oil obtained by separating the oil produced by the coal direct liquefaction reaction is called coal direct liquefaction oil, which is a hydrocarbon oil with a high aromatic carbon rate (usually higher than 0.40, generally higher than 0.66, and even higher than 0.8), that is, a high aromatic oil. Due to the wide distribution of carbon numbers of hydrocarbon products in the coal direct liquefaction reaction, according to the selected distillation range of the coal direct liquefaction oil, the coal direct liquefaction oil can be a conventional boiling range below 560°C, that is, containing The 6-ring aromatic hydrocarbons with a conventional boiling point of 500-560°C, the coal direct liquefaction oil can be a conventional boiling range of 50-500°C, that is, it basically does not contain 6-ring aromatic hydrocarbons with a conventional boiling point of 500-560°C; of course, the coal direct liquefaction oil can also contain light residual oil components with a conventional boiling range higher than 560°C, that is, it contains polycyclic aromatic hydrocarbons with more than 7 rings with a conventional boiling point of 560-650°C; the hydrocarbons in the coal direct liquefaction oil with a conventional boiling range higher than 650°C usually belong to the heavy residual oil components, which usually constitute the distillation bottom oil in the unevaporated oil in the distillation process.

[0004] Since coal powder participates in the reaction in the form of oil-coal slurry, the basic conditions for coal direct liquefaction reaction, such as coal powder dispersion, hydrocarbon molecule diffusion, hydrogen molecule dissolution, and catalyst dispersion, can be achieved. Therefore, the coal direct liquefaction reaction process R10 is also called the oil-coal slurry direct liquefaction reaction process R10.

[0005] The coal direct liquefaction reaction process R10 described in the present invention refers to a reaction process in which coal and possible molecular hydrogen are used as raw materials, a specific oil product (usually coal direct liquefaction oil or hydrogenated modified oil of coal direct liquefaction oil) is used as solvent oil, and under certain operating conditions (such as operating temperature, operating pressure, solvent oil / coal weight ratio, hydrogen / solvent oil volume ratio and suitable hydrogenation catalyst), the coal directly undergoes carbon-carbon bond thermal cracking, free radical hydrogenation stabilization, hydrocarbon oil hydrorefining, hydrocarbon oil hydrocracking and other hydrogenation liquefaction reactions.

[0006] The coal direct liquefaction oil described in the present invention refers to the distillate oil obtained by separating the oil generated by the direct liquefaction reaction of coal by hydrogenation. It exists in the effluent of the direct liquefaction reaction of coal by hydrogenation, and is a comprehensive reaction product based on solvent oil, coal consumed in the reaction, and hydrogen transferred by the reaction. It can be a mixed oil of at least any two of the conventional boiling point fraction segment <195°C, the 195°C to 280°C fraction segment, the 280°C to 560°C fraction segment, and the 560°C to 650°C fraction segment. It can be any fraction segment within the range of 195°C to 650°C, and is usually any fraction segment within the range of 195°C to 560°C.

[0007] Depending on the source of the raw coal and the different coal direct liquefaction reaction conditions, the hydrogen content, aromatic carbon rate, organic nitrogen content, organic oxygen content and >350°C fraction yield of coal direct liquefaction oil from different sources are different and fluctuate within a large range. Usually, the hydrogen content is 5.0-11.2wt%, the aromatic carbon rate is 0.23-0.98mol%, the organic nitrogen content is 0.20-1.5wt%, the organic oxygen content is 0.40-6.30wt%, the >350°C fraction yield is 15-65wt%, and the >500°C fraction yield is 5-25wt%.

[0008] The hydrogenation and modification reaction process R20 of coal direct liquefaction oil described in this article refers to the hydrogenation reaction process of converting coal direct liquefaction oil into hydrocarbons with lower aromatic carbon rate and lower impurity content, such as producing hydrogenation and upgrading raw oil, hydrogenation and modification oil with specific impurity content, hydrogenation and modification oil with specific aromatic carbon rate content, hydrogenation and modification oil of specific boiling range distillate oil, etc. The oil generated by the fractionation and hydrogenation modification reaction is obtained to obtain oil products of different boiling range fractions, and then blended to obtain oil products for different purposes, such as hydrogenation and modification solvent oil entering the coal direct liquefaction reaction process R10. The hydrogenation and modification solvent oil has a hydrogenation index PDQI index usually greater than 22 mg / g, generally greater than 24 mg / g. The hydrogenation and modification solvent oil is usually used as coal slurry solvent oil, flushing oil of the plunger rod stuffing box of the plunger-type raw material coal slurry pump, high-pressure instrument flushing oil, pipeline flushing oil and passes through at least a part of the reaction space of the coal hydrogenation and direct liquefaction reaction process R10.

[0009] The hydrogenation and upgrading reaction process R30 of coal direct liquefaction oil described in this article refers to using coal direct liquefaction oil and / or the narrow fraction oil of the coal direct liquefaction oil hydrogenation modification reaction product oil as raw material, at least performing deep hydrogenation refining reaction, and possibly performing selective hydrogenation ring-opening reaction, and even performing subsequent hydrocracking reaction. The quality indicators of the hydrogenated modified product oil produced are determined according to needs, usually the weight content of organic nitrogen is less than 3-10ppm, the weight content of organic sulfur is less than 5-20ppm, and the aromatics content is determined according to needs.

[0010] The aromatic carbon ratio of hydrocarbons refers to the ratio of the number of aromatic carbon atoms to the total number of carbon atoms in the hydrocarbon molecule.

[0011] The hydrogen supply index PDQI of hydrocarbons refers to the number of milligrams of active hydrogen at the β position of the cycloalkyl group in cycloalkyl aromatic hydrocarbons per gram of hydrocarbons.

[0012] For coal direct liquefaction oil or coal direct liquefaction oil hydrogenation modification reaction product oil, which are aromatic-rich mixtures composed of various hydrocarbons with different boiling points, there is a macroscopic correspondence between the hydrogen supply index PDQI of hydrocarbons and their aromatic carbon ratio.

[0013] The gas holdup rate of the logistics in the hydroprocessing reactor refers to the volume ratio of the gas phase in the logistics.

[0014] The liquid holdup of the logistics in the hydroprocessing reactor refers to the volume ratio of the liquid phase in the logistics.

[0015] The feed hydrogen / feed oil volume ratio of the hydroprocessing reactor of the present invention refers to the ratio of the standard state volume flow rate of the hydrogen-rich gas flow to the standard state volume of the feed oil, and the unit is standard cubic meter / cubic meter, i.e. Nm 3 / m 3 .

[0016] The hydrogen / oil volume ratio at a certain point in the hydrogenation reactor of the present invention refers to the ratio of the standard state volume flow rate of the gas phase to the standard state volume of the liquid material, and the unit is standard cubic meter / cubic meter, that is, Nm 3 / m 3 .

[0017] The catalyst liquid time-space number in the hydro-modification reactor of the present invention refers to the ratio of the volume flow rate of the processed fresh crude oil at 0.1 MPaA and 20°C to the volume of the hydrogenation stable catalyst in the static accumulation state, and the unit is h -1 .

[0018] The common coal direct liquefaction reaction process R10 may be the coal hydrogenation direct liquefaction reaction process R10.

[0019] The hydrogenation modification reaction process R20 of coal direct liquefaction oil can be a hydrogenation modification reaction process of hydrogen supply solvent oil for producing high aromatic oil by coal hydrogenation direct liquefaction, also known as solvent oil hydrogenation stabilization reaction process.

[0020] For coal direct liquefaction oil with shallow hydrogenation depth and low chemical hydrogen consumption, the coal direct liquefaction oil has stronger polarity and greater viscosity, so it carries more solid particles and must adopt an ebullating bed hydrogenation modification reaction method. At the same time, its aromatic carbon rate is higher and its heteroatom content is higher. When the hydrogenation modification oil with a low aromatic carbon rate is generated through the hydrogenation modification reaction process R20, the chemical hydrogen consumption is higher and the amount of heteroatom hydrogenation products is higher. Its operation method is completely different from the conventional high-hydrogen consumption coal hydrogenation direct liquefaction to produce high aromatic oil with low hydrogen consumption and low impurity hydride yield hydrogenation modification reaction process R20, which requires a multi-stage or multi-stage hydrogenation modification reaction process R20.

[0021] The following is a combination of the test data of the ebullated bed hydro-modification reaction of coal direct liquefaction to produce a high aromatic oil mixed fraction, to illustrate the general rules of the ebullated bed hydro-modification reaction process of coal direct liquefaction oil mixed fraction.

[0022] Document A01: ① Publication name: "Coal Direct Liquefaction Technology and Engineering", pages 258 to 273 to 282; ② Book code for retrieval: ISBN code: 9-78703-04308-23; ③ Edited by: Wu Xiuzhang, Shu Geping, Li Kejian, Xie Shunmin; ④ Publisher: Science Press; It records the boiling bed hydrogenation stabilization test data of the feed oil of the hydrogenation stabilization unit supporting the coal hydrogenation direct liquefaction project of China Shenhua Group using the boiling bed hydrogenation catalyst FFT-1B. Some of the data have been compiled into Tables 1, 2, 3 and 4.

[0023] Table 1 shows the main properties of the mixed raw materials and their fractions used in the experiment in document A01.

[0024] Table 2 is a summary of the experimental data analysis of FTT1-1B ebullated bed hydrogenation stable catalyst condition 3 in document A01.

[0025] Table 3 is a summary of the experimental data analysis of FTT1-1B ebullated bed hydrogenation stable catalyst condition 4 in document A01.

[0026] Table 4 is an analysis of the differences in experimental data between Condition 4 and Condition 4 for FTT1-1B ebullated bed hydrogenation stable catalyst in Reference A01.

[0027] Table 1 Main properties of the mixed raw materials and their fractions used in the A01 experiment

[0028]

[0029] Table 2 Summary of experimental data analysis of FTT1-1B ebullated bed hydrogenation stable catalyst condition 3 in reference A01

[0030]

[0031]

[0032] Table 3 Summary of experimental data analysis of FTT1-1B ebullated bed hydrogenation stable catalyst condition 4 in reference A01

[0033]

[0034]

[0035] Table 4 Analysis of experimental data differences between condition 4 and condition 4 of FTT1-1B ebullated bed hydrogenation stable catalyst in literature A01

[0036]

[0037] For the mixed raw materials shown in Table 1, the hydrogen supply index PDQI of the oil produced by the ebullated bed hydromodification reaction of the ideal coal direct liquefaction oil is not less than 23.8 (at this time, the hydrogen supply index PDQI of the circulating hydrogen supply solvent is not less than about 23.0), and preferably not less than 25.8 (at this time, the hydrogen supply index PDQI of the circulating hydrogen supply solvent is not less than about 25.0). Usually, the aromatic carbon rate of the 200-350°C fraction of the ebullated bed hydromodification reaction oil is not higher than 25, and the aromatic carbon rate of the >350°C fraction of the ebullated bed hydromodification reaction oil is not higher than 35.

[0038] From the analysis of the total data in Tables 1 to 4, we can see that:

[0039] ① Based on the experimental conditions in Table 2, the hydrogen supply index PDQI of the oil produced by the ebullated bed hydro-modification reaction is only 21.18, which is 2.62 away from 23.8, indicating that the depth of the ebullated bed hydro-modification reaction under the experimental conditions in Table 2 is seriously insufficient;

[0040] ② Based on the experimental conditions in Table 3, the hydrogen supply index PDQI of the oil produced by the ebullated bed hydromodification reaction is only 23.89, which is only 0.09 higher than 23.8, indicating that the depth of the ebullated bed hydromodification reaction under the experimental conditions in Table 3 just meets the minimum requirement. At this time, the amount of ebullated bed hydromodification stabilization catalyst is very large, and two ebullated bed hydromodification reactors need to be set up;

[0041] ③ Based on Table 4, under the condition that the liquid time-space number of the supplementary hydrogenation modification reaction process is the same as the liquid time-space number of the upstream hydrogenation modification reaction process, that is, the volume of the ebullated bed hydrogenation stable catalyst in the supplementary hydrogenation modification reaction process is equal to the volume of the ebullated bed hydrogenation stable catalyst in the upstream hydrogenation modification reaction process, the aromatic carbon rate of the supplementary hydrogenation modification reaction process is reduced by 5.58 mol% and the hydrogen content is increased by 0.37 wt%, which is only 33.1% and 37.76% of the aromatic carbon rate reduction of 16.86 mol% and the hydrogen content increase of 0.98 wt% in the upstream hydrogenation modification reaction process, indicating that the reaction efficiency of the supplementary hydrogenation modification reaction process is far lower. The reaction efficiency of the upstream hydro-modification reaction process; the denitrification rates of the 200-350℃ fraction, the >350℃ fraction, and the whole fraction in the supplementary hydro-modification reaction process are only 3.80%, 10.62%, and 5.32% of the denitrification rates of the 200-350℃ fraction, the >350℃ fraction, and the whole fraction in the upstream hydro-modification reaction process, respectively, indicating that the reaction efficiency of the supplementary hydro-modification reaction process is much lower than that of the upstream hydro-modification reaction process; of course, the supplementary hydro-modification reaction process causes a small amount of high-boiling point components to reduce their boiling points after hydrogenation and enter the low-boiling point component group, but the number is very small and does not affect the above macro judgment;

[0042] An important reason for this result is that a large amount of ammonia is generated in the upstream hydrorefining reaction process and accumulated in the reaction product. Since the ebullated bed hydrorefining reaction process R20 does not allow the use of a large amount of hydrogen to reduce the gas phase concentration of the non-hydrogen gas product components to prevent a substantial reduction in the liquid phase volume ratio of the reaction zone of the ebullated bed hydrorefining reaction process R20 (which will significantly reduce the liquid phase fraction of the reaction zone material and increase the volume of the reaction zone by multiples or even several times), this will inevitably lead to a high degree of deterioration in the gas phase composition of the supplementary ebullated bed hydrorefining reaction process R20, and its ammonia volume concentration can reach 1.5-6.0% by volume, which is tens or even hundreds of times the gas phase ammonia volume concentration of the conventional petroleum-based oil fixed bed hydrorefining reaction process, thereby greatly inhibiting the supplementary ebullated bed hydrorefining reaction process R20 (it controls the catalyst performance of the middle and final stages of the reaction process at the final reaction depth), so the accumulation effect of ammonia in the supplementary ebullated bed hydrorefining reaction process R20 must be weakened;

[0043] ④ Based on the experimental conditions in Table 3, the aromatic carbon rate of the >350°C fraction of the ebullated bed hydromodification reaction product oil is 58.2 mol%, and the hydrogen supply index PDQI is only 12.15, indicating that the >350°C fraction of the ebullated bed hydromodification reaction product oil needs to be further hydromodified to reduce its aromatic carbon rate to about 35-40 mol%, and the hydrogen supply index PDQI is further increased by 7-10. In this way, it is necessary to consider the cyclic hydromodification reaction (extending the reaction time) of the >350°C fraction of the ebullated bed hydromodification reaction product oil, and it is necessary to consider arranging a suitable reaction environment of low ammonia concentration, high hydrogen partial pressure, and high reaction temperature in view of its structural characteristics of many rings, large molecular size, and difficulty in hydrogenation that are not conducive to the hydromodification reaction, so as to improve its reaction efficiency. The reaction conditions are obviously different from the reaction conditions of the upstream hydromodification reaction process, and it is expected to achieve one or more of the following: lower ammonia concentration, higher hydrogen partial pressure, and higher reaction temperature.

[0044] The analysis conclusions of Tables 1 to 4 have suggested that a method for intermediate degassing and graded ebullating bed hydrogenation modification reaction of low-quality coal direct liquefaction oil is needed.

[0045] The method of the present invention also relates to what kind of process is adopted in the accompanying ebullated bed hydrogenation modification reaction process R20 of the coal direct liquefaction oil when the properties of the raw coal fluctuate greatly due to deterioration, resulting in the properties of the oil generated by the coal hydrogenation direct liquefaction reaction, that is, the coal direct liquefaction oil undergoing greatly deterioration fluctuations, so as to reliably, economically and flexibly increase the degree of hydrogenation reduction of the aromatic carbon rate, thereby not reducing or even flexibly increasing the hydrogen supply index PDQI of the ebullated bed hydrogenation modification reaction oil to a certain extent, so as to suppress the greatly deteriorating fluctuations in the properties of the oil generated by the coal hydrogenation direct liquefaction reaction. In a word, how to economically improve the adaptability of the overall coal hydrogenation direct liquefaction conversion process "coal hydrogenation direct liquefaction reaction process R10 + coal direct liquefaction oil boiling bed hydrogenation modification reaction process R20" to the fluctuations in the deterioration of the properties of the raw coal; in other words, the present invention relates to an economical ebullated bed hydrogenation modification reaction method for producing high-aromatic carbon rate coal direct liquefaction oil by greatly reducing the aromatic carbon rate of hydrocarbon oil to produce high-quality ebullated bed hydrogenation modification reaction oil with low aromatic carbon rate.

[0046] The following is an analysis of the fluctuation range of the properties of the coal direct liquefaction oil (boiling bed hydrogenation modification reaction feedstock oil) involved in the coal hydrogenation direct liquefaction project.

[0047] Table 5 is a summary of the properties of the coal direct liquefaction oil (boiling bed hydrogenation modification reaction raw oil) involved in the China Shenhua Group's coal hydrogenation direct liquefaction project. Table 6 is the main properties of the fraction segments of the mixed raw materials corresponding to data group 101 in Table 5. Table 7 is the main properties of the fraction segments of the mixed raw materials corresponding to data group 105 in Table 5.

[0048] As can be seen from Table 5, the properties of the coal direct liquefaction oil (ebullated bed hydrogenation modification reaction raw oil) collected at different times in the coal hydrogenation direct liquefaction project of China Shenhua Group fluctuate in a large range, with a hydrogen content ranging from 9.32 to 10.93 wt% (a difference of 1.61 wt%), an aromatic carbon content of 30 to 56 mol% (a difference of 26 mol%), an organic nitrogen content of 0.2600 to 0.4860 wt% (a difference of 0.2260 wt%), an organic oxygen content of 0.68 to 2.34 wt% (a difference of 1.66 wt%), and a >350 ° C fraction yield of 21.4. ~31.82wt% (a difference of 10.42wt%), and the hydrogen supply index PDQI is 17.13~25.77 (a difference of 8.64). This shows that in order to improve the utilization rate of raw coal in coal mines, the hydrogenation modification reaction method used in the coal hydrogenation direct liquefaction project must have good adaptability to the fluctuation of the properties of coal direct liquefaction oil (boiling bed hydrogenation modification reaction raw oil) in a large range. That is, it can economically and flexibly adjust the depth of hydrogenation modification reaction, otherwise it will limit the utilization rate of raw coal in coal mines and form the so-called sales problem of a large amount of "inferior coal" that does not meet the ideal indicators of coal hydrogenation direct liquefaction projects.

[0049] From the distribution of reaction products, it can be seen that the properties of coal direct liquefaction oil samples in different periods vary greatly: the hydrogen content of the actual processed raw coal direct liquefaction oil of the industrial demonstration unit is only 9.32% by weight, which is a huge decrease of 1.61% by weight compared with the hydrogen content of 10.93% in the coal direct liquefaction oil of the PDU unit. It is obvious that if the hydrogenated stabilized raw oil corresponding to data group C produces the hydrogenated stabilized generated oil with the expected properties corresponding to data group B, then the unit hydrogen consumption of the hydrogenation modification reaction of the hydrogenated stabilized raw oil corresponding to data group C will increase significantly (roughly estimated to increase by 80-100%), that is, the depth of hydrogenation modification reaction will increase significantly. Obviously, the total reaction temperature rise, ammonia yield, water yield, and methane yield will increase significantly. At the same time, the initial optimal hydrogenation modification reaction temperature of the deteriorated hydrogenated stabilized raw oil will be significantly reduced.

[0050] Without considering data set 101, only the fluctuation range of the direct liquefied oil properties of the actual raw coal processed by the ebullated bed hydrostabilization unit of the industrial demonstration project is analyzed, and the conclusions are as follows:

[0051] ① Based on the collected data alone, it can be seen that due to the fluctuations in the properties of R10 raw coal and production operating conditions in the coal hydrogenation direct liquefaction reaction process, the hydrogen supply index PDQI of coal direct liquefaction oil fluctuates between 17.13 and 25.77, with a huge difference of 8.64;

[0052] At the same time, the hydrogen content of coal direct liquefaction oil fluctuates between 9.32 and 10.35wt%, with a huge difference of 1.03wt%. Therefore, the reaction tasks of the ebullient bed hydrogenation modification reaction process R20 required for hydrogenation stability of different coal direct liquefaction oils vary greatly, the catalyst loading varies greatly, the overall reaction heat varies greatly, and the optimal reaction temperature control method must be different;

[0053] ② The aromatic carbon rate of coal direct liquefaction oil fluctuates between 0.44 and 0.568, with a difference of 0.128. Taking the aromatic carbon rate of oil generated by ebullient bed hydrogenation reaction as 0.28 as the benchmark, the reduction range of aromatic carbon rate fluctuates between 0.16 and 0.288, which is a huge difference.

[0054] ③ The aromatic carbon rate of the 200-350℃ fraction of coal direct liquefaction oil fluctuates between 0.3232 and 0.4626, with a huge fluctuation difference of 0.1394. Taking the aromatic carbon rate of the oil generated by the ebullient bed hydromodification reaction of this fraction as 0.25 as the benchmark, the reduction range of the aromatic carbon rate fluctuates between 0.0732 and 0.2126, the latter is 2.90 times the former. Therefore, the hydrogenation depth of R20 in the ebullient bed hydromodification reaction process of this fraction section increases exponentially, and its reaction time needs to be reasonably extended.

[0055] ④ The aromatic carbon rate of the >350℃ fraction of coal direct liquefaction oil fluctuates between 0.7806 and 0.8076, with a small fluctuation; at the same time, the yield of this fraction fluctuates between 0.30 and 0.3182, with a small fluctuation;

[0056] However, compared with the data in data group 101, the aromatic carbon rate of the >350°C fraction of the direct hydrogenated oil fluctuates between 0.539 and 0.8076, with a huge fluctuation difference of 0.2686. Taking the aromatic carbon rate of the oil produced by the ebullient bed hydrogenation reaction of this fraction as 0.40 as the benchmark, the reduction range of the aromatic carbon rate fluctuates between 0.139 and 0.4076, the latter being 2.93 times that of the former; at the same time, the yield of this fraction is between 0.214 and 0.3182. The latter is 1.49 times of the former; therefore, the hydrogenation depth of R20 in the boiling bed hydromodification reaction process of this fraction section increases exponentially, and its reaction time needs to be reasonably extended. Considering that the hydromodification reaction rate of the >350°C fraction section of the coal direct liquefaction oil is significantly lower than the hydromodification reaction rate of the 200-350°C fraction section of the coal direct liquefaction oil, it is necessary to consider the cyclic reaction mode of the hydromodification reaction of the >350°C fraction section of the coal direct liquefaction oil to generate oil.

[0057] Table 5 Summary of properties of coal direct liquefaction oil (ebullated bed hydroprocessing modification reaction feedstock oil) involved in China Shenhua Group's coal hydroprocessing direct liquefaction project

[0058]

[0059] Table 6 Main properties of the fractions of the mixed raw materials corresponding to data set 101 in Table 5

[0060]

[0061] Table 7 Main properties of the fractions of the mixed raw materials corresponding to data set 105 in Table 5

[0062]

[0063]

[0064] Data set 101, from document A01: ① Publication name: "Shenhua Technology" (published in December 2009, Vol. 7, No. 6), pages 59 to 63; ② Article name: Research on the hydrogenation stability of coal direct liquefaction oil products using hydrorefining catalysts; ③ Compiled by: Wu Xiuzhang, Zhu Yufei, Shi Yulin, Shu Geping. The raw oil distillation type in data set 101 comes from document A02: ① Publication name: "Coal Direct Liquefaction Technology and Engineering", pages 260 to 266, pages 280 to 282; ② Retrieval book code: ISBN code: 9-78703-04308-23; ③ Compiled by: Wu Xiuzhang, Shu Geping, Li Kejian, Xie Shunmin; ④ Publisher: Science Press, the raw oil for the ebullient bed hydrogenation modification reaction is

[0065] Data set 102, from document A02: ① Publication name: "Coal Direct Liquefaction Technology and Engineering", pages 258 to 273 to 282; ② Book code for retrieval: ISBN code: 9-78703-04308-23; ③ Compiled by: Wu Xiuzhang, Shu Geping, Li Kejian, Xie Shunmin; ④ Publisher: Science Press, the raw oil for the ebullient bed hydrogenation modification reaction is

[0066] Data set 103, from document A05: ① Publication name: Acta Petrolei Sinica (Petroleum Processing) (published in August 2014, Vol. 30, No. 4), pages 644 to 649; ② Article name: Catalytic hydrogenation of circulating solvent for direct liquefaction of Shenhua coal; ③ Authors: Gao Shansong, Zhang Dexiang, Li Kejian, and Bai Xuemei. The article records that the feed of the hydrogenation stabilization unit of the million-ton Shenhua coal direct liquefaction demonstration unit was used as the hydrogenation raw material, and the effect of reaction temperature on the properties of the circulating solvent for coal direct liquefaction was investigated in a fixed-bed hydrogenation experimental device with a processing capacity of 300mL. Table 1 lists the test results under the conditions of test pressure of 13.7MPa, temperature of 380, hydrogen-oil volume ratio of 800, and liquid time-space number of 1.5h-1. It can be seen that the aromatic carbon rate (fa) reduced by the hydrogenation modification reaction process is very low, and the increased hydrogen supply index PDQI is very small. If the same conditions are repeated on the boiling bed hydrogenation modification reactor of the industrial device, the aromatic carbon rate (fa) reduced by the hydrogenation modification reaction process will be lower, and the increased hydrogen supply index PDQI will be smaller.

[0067] Data set 104, from document A04: ① Publication name: Coal Chemical Industry (published in June 2017, Vol. 45, No. 3), pages 25 to 29; ② Article name: Application and analysis of HRK-658 catalyst in ebullating bed hydrogenation process; ③ Authors: Zhang Chuanjiang and Han Laixi. The article records a set of feeds to the hydrogenation stabilization unit of the million-ton Shenhua coal direct liquefaction demonstration unit.

[0068] Data group 105, from document A03: ① Publication name: "China Coal" (published in May 2020, Volume 46, Issue 5), pages 25 to 29; ② Article name: Research on factors affecting the hydrogen supply of circulating solvents in coal direct liquefaction; ③ Authors: Wang Jianli, Kang Kaitong, Gao Shansong, and Bai Xuemei. The raw oil for the experimental hydrogenation modification reaction adopts the mixed heavy oil of the coal direct liquefaction unit of the million-ton Shenhua coal direct liquefaction demonstration unit.

[0069] Document A01: ① Publication name: "Coal Direct Liquefaction Technology and Engineering", page 241, Table 5-3; ② Book code for retrieval: ISBN code: 9-78703-04308-23; ③ Edited by: Wu Xiuzhang, Shu Geping, Li Kejian, Xie Shunmin; ④ Publisher: Science Press; Records a set of distribution data of various heteroatoms in different fractions of Shenhua coal liquefaction crude oil, see Table 8 of this article.

[0070] Table 8 is a set of distribution data of various heteroatoms in different fractions of Shenhua coal liquefaction crude oil. It can be seen that with the increase of boiling point, the carbon content of the fraction gradually increases and the hydrogen content gradually decreases. In general, the organic nitrogen content is high and the organic oxygen content is high. Among them, the sulfur content is the highest in the fraction <200°C, the nitrogen content is high in the fraction >280°C, the oxygen content is the highest in the fraction 150-220°C, and the nitrogen content of the fraction above 350°C increases rapidly with the increase of boiling point; in the hydrogenation modification reaction process of coal direct liquefaction oil, the hydrogenation and removal of heteroatoms reactions occurring in the coal direct liquefaction oil mainly include hydrogenation desulfurization, denitrification and deoxygenation reactions, and the hydrogenation products are hydrogen sulfide, ammonia and water. In particular, high concentrations of ammonia and water components in the gas phase will strongly inhibit the activity of hydrogenation stable catalysts.

[0071] The data in Table 8 also show that if the fraction above 350°C of coal direct liquefaction oil is processed separately, the heteroatom content of the raw oil is particularly high: the nitrogen content is about 6000 ppm and the oxygen content is about 2.0wt%, and the yield of the hydrogenation and removal of heteroatom reaction products is very high.

[0072] Table 8 Distribution data of various heteroatoms in different fractions of crude oil from Shenhua coal liquefaction

[0073]

[0074] In a broad sense, for the overall coal hydrogenation direct liquefaction conversion process consisting of "coal hydrogenation direct liquefaction reaction process R10 + boiling bed hydrogenation modification reaction process R20 of coal direct liquefaction oil", in the existing process technology, although the raw coal has undergone screening, crushing and washing, coal selection, grinding, drying and other processes to stabilize some properties of the raw coal for the coal hydrogenation direct liquefaction reaction, such as particle size, ash content, water content, and chloride ion content, however, other properties of the raw coal for the coal hydrogenation direct liquefaction reaction that strongly affect the properties of the oil generated by the coal hydrogenation direct liquefaction reaction, such as volatile matter, hydrogen content, organic oxygen content, organic nitrogen content, organic sulfur content and other properties cannot be flexibly and stably controlled. This is because the coal suitable for coal hydrogenation direct liquefaction reaction is a natural solid hydrocarbon material with a very high volatile matter content and / or a very high organic oxygen content and / or a very high organic nitrogen content, and these property indicators fluctuate or even fluctuate greatly. In this way, the coal direct liquefaction oil obtained by the coal hydrogenation direct liquefaction reaction process R10 under certain process flow and certain operating conditions has a polycyclic aromatic hydrocarbon content and an organic oxygen content. , it is inevitable that the organic nitrogen content fluctuates, even fluctuates greatly, and this fluctuation directly affects the aromatic carbon rate or hydrogen supply index, the aromatic carbon rate difference or the hydrogen supply index difference of the coal direct liquefaction oil and its boiling bed hydrogenation modification reaction product oil, that is, it directly affects the hydrogen supply index of the hydrogen supply solvent oil in the circulating reaction material-the coal slurry of the raw material of the coal hydrogenation direct liquefaction reaction, thereby further deteriorating the effect of the coal hydrogenation direct liquefaction reaction (reducing the liquefied oil yield and the liquefied oil hydrogen content). In other words, the deterioration of the coal properties of the coal hydrogenation direct liquefaction reaction raw material on the coal hydrogenation direct liquefaction reaction process R10 is not a single effect but a double effect. Conversely, the boiling bed hydrogenation modification reaction process R20 is not only a production process of the raw material hydrogen supply solvent oil of the coal hydrogenation direct liquefaction reaction process R10, but also must be a process for eliminating all deteriorating fluctuations in the properties of the coal hydrogenation direct liquefaction reaction product oil or at least most of the deteriorating fluctuations. This analysis also suggests that a method for intermediate degassing and graded boiling bed hydrogenation modification reaction of coal direct liquefaction oil is needed.

[0075] The coal direct liquefaction oil described in the present invention usually contains unliquefied coal powder, ash from the coal powder, catalyst particles and other solid particles. When the weight concentration of the solid particles in the coal direct liquefaction oil is high, such as higher than 100 ppm and the diameter of the solid particles contained is larger than the interception particle diameter of the hydrogenation catalyst bed in the downstream fixed bed hydrogenation reaction process, these distillate oils are not suitable for directly entering the downstream fixed bed hydrogenation modification reaction process R20 or the hydrogenation quality improvement reaction process R30, because the excessively high solid particle concentration causes the downstream fixed bed hydrogenation catalyst bed to quickly accumulate solid particles, reduce the flow channel area or block the flow channel, causing the catalyst bed pressure drop to quickly rise to the upper limit value, and ultimately causing the device to be forced to shut down. The continuous operation cycle of the device is too short and is not economical. In order to avoid the above problems, the current hydrogenation reactor system of the hydrogenation modification reaction process R20 of the coal direct liquefaction oil with a high solid content adopts an ebullating bed hydrogenation modification reactor system. Of course, if the solid weight content of the coal direct liquefaction oil KEY separated by the distillation process of the coal hydrogenation direct liquefaction oil is very low, for example, less than 20 ppm, and the diameter of the solid particles contained is lower than the interception particle diameter of the hydrogenation catalyst bed in the downflow fixed bed hydrogenation reaction process, then the coal direct liquefaction oil KEY can use the downflow fixed bed hydrogenation reactor for the hydrogenation modification reaction process R20.

[0076] The ebullated bed hydrogenation stable catalyst R20C used in the ebullated bed hydrogenation modification reaction process R20 of coal direct liquefaction oil can be any suitable carrier-type catalyst, usually an active metal compound component is supported on the carrier, and the active metal is usually in the form of metal sulfide in the ebullated bed hydrogenation modification reaction process R20; in the ebullated bed hydrogenation stable catalyst R20C, the metal elements with hydrogenation activity are mainly elements of group VIB and group VIIB, and the commonly used efficient combinations of hydrogenation catalyst metal components include: two-component combinations of Co-Mo, Ni-Mo, Ni-W, three-component combinations of Ni-Mo-W, Co-Ni-Mo, etc., and different metal components are matched to form different hydrogenation activities; in the ebullated bed hydrogenation stable catalyst, the carrier usually uses alumina or alumina with added silicon oxide, as well as other modified components such as phosphorus, boron, etc., and the ebullated bed hydrogenation stable catalyst R20C is generally It is often acidic and has a capture attraction for hydrocarbons containing donors such as organic oxygen, organic nitrogen, organic sulfur, olefins, and benzene rings; for the ebullated bed hydrogenation stable catalyst R20C, from the perspective of ensuring the hydrogenation saturation of polycyclic aromatic hydrocarbons to ensure the hydrogen supply of the hydrogen-donating solvent oil for direct liquefaction of coal hydrogenation, and taking into account the denitrification and deoxygenation effects, it is generally believed that the Ni-Mo bimetallic component is more suitable; since the carrier of the ebullated bed hydrogenation stable catalyst R20C is usually alumina, alumina composite silica, and the active component belongs to the molybdenum nickel type or tungsten nickel type or tungsten molybdenum nickel type, their hydrogenation active surfaces are all acidic, under the conditions of high ammonia partial pressure and / or high water vapor partial pressure, the shielding effect produced by the active surface of the ammonia and / or water vapor adsorption catalyst will greatly reduce the effective proportion of the active centers of the ebullated bed hydrogenation modification reaction catalyst participating in the reaction, and reduce the hydrogenation modification reaction rate and the ultimate hydrogenation saturation depth.

[0077] Coal direct liquefaction oil containing a large amount of organic nitrogen and / or organic oxygen will inevitably produce a large amount of ammonia and / or water vapor in the ebullated bed hydrogenation modification reaction process R20. The existing ebullated bed hydrogenation modification reaction methods all adopt a high-pressure system single-stage ebullated bed hydrogenation modification reaction process, that is, no high-pressure intermediate reaction product degassing step is set, but all the products of the upstream hydrogenation modification reaction zone are connected in series to the downstream hydrogenation modification reaction zone. As the hydrogenation modification reaction progresses, non-hydrogen gas product components such as water, ammonia, and methane will inevitably accumulate. Since the ebullated bed hydrogenation modification reaction process R20 does not allow the use of a large amount of hydrogen to reduce the gas phase concentration of non-hydrogen gas product components to prevent the substantial reduction in the liquid phase volume ratio of the reaction zone in the ebullated bed hydrogenation modification reaction process R20 (which will significantly reduce the liquid phase volume fraction of the reaction zone material, and double or even several times increase the reaction zone volume) (or a large circulation ratio is required to circulate the liquid phase product to reduce the reaction zone The gas phase volume fraction leads to a too short first reaction cycle of the fresh raw material, that is, it leads to a part of the extremely shallow hydro-modification reaction product oil entering the final hydro-modification reaction product oil), resulting in a highly deteriorated gas phase composition of the final product of the ebullated bed hydro-modification reaction process R20, wherein the water vapor volume concentration can reach 4-15 volume %, the ammonia volume concentration can reach 1.5-6.0 volume %, and the methane gas volume concentration can reach 5-23 volume %, which is dozens or even hundreds of times the gas phase ammonia volume concentration of the conventional petroleum-based oil fixed bed hydro-refining reaction process, and dozens or even thousands of times the gas phase water vapor volume concentration of the conventional oil fixed bed hydro-refining reaction process, thereby greatly inhibiting the catalyst performance of the ebullated bed hydro-modification reaction process R20, especially the middle and final reaction processes that control the final reaction depth. Therefore, the accumulation effect of water vapor, ammonia, and methane gas in the ebullated bed hydro-modification reaction process R20 products must be weakened.

[0078] The operation of the downstream reaction zone of the single-stage ebullating bed hydroprocessing process R20 has the following major disadvantages and results:

[0079] ① In the single-stage ebullated bed hydromodification reaction process R20, the feed of the deteriorating ebullated bed hydromodification reaction needs to achieve a large reduction in the aromatic carbon rate, such as up to 0.20-0.30. At this time, the single-stage ebullated bed hydromodification reactor with liquid reaction product back-mixing has a serious short-circuit flow behavior of "part of the shallow hydromodification reaction oil of the fresh material enters the final hydromodification reaction oil", that is, the uniformity of the reaction depth of the R20 raw oil in the ebullated bed hydromodification reaction process The performance is very poor, that is, the oil discharged from the ebullated bed hydromodification reaction process R20 after only a shallow ebullated bed hydromodification reaction enters the fractionation process of the ebullated bed hydromodification reaction product oil, thereby reducing the hydrogen supply index of the final product oil of the hydromodification reaction to an unacceptable degree. At this time, it is necessary to increase the number of ebullated bed hydromodification reactors to reduce the proportion of the short-circuit flow of the partially reacted raw oil in the overall ebullated bed hydromodification reaction process R20, that is, to improve the uniformity of the reaction depth of the raw oil in the ebullated bed hydromodification reaction process R20;

[0080] ② Single-stage ebullated bed hydromodification reaction process R20, due to the violent liquid phase back-mixing effect in the ebullated bed hydromodification reaction zone, the reaction temperature of the entire ebullated bed hydromodification reaction zone tends to be consistent. For the ebullated bed hydromodification reaction process R20 with high hydrogen consumption of low-quality coal direct liquefaction oil, it is impossible to achieve the upstream ebullated bed hydromodification reaction process R201 using a suitable low reaction temperature to avoid the rapid concentrated reaction of the reactive components in the fresh raw oil, and it is also impossible to achieve the downstream ebullated bed hydromodification reaction process R202 using a suitable high reaction temperature to increase the deep hydromodification reaction rate of the intermediate reaction liquid phase product. At this time, the reasonable process requires increasing the number of ebullated bed hydromodification reactors to achieve differentiated optimization control of the reaction temperature of the upstream reaction process and the reaction temperature of the downstream reaction process;

[0081] ③ In the single-stage ebullated bed hydromodification reaction process R20, the active surface of the ebullated bed hydromodification stable catalyst of the downstream ebullated bed hydromodification reaction process R202 adsorbs a large amount of strongly polar impurity molecules such as ammonia and water, which forms a strong spatial shielding effect on the normal reaction raw oil molecules, greatly reduces the effective active center ratio, greatly reduces the reaction rate, and greatly increases the amount of the ebullated bed hydromodification stable catalyst in the downstream reaction zone. In other words, when the properties of the raw coal direct liquefaction oil of the hydromodification reaction deteriorate, such as the decrease in hydrogen content and the increase in organic nitrogen content, the properties of the oil generated by the hydromodification reaction will be greatly deteriorated, and the hydrogen supply index PDQI of the hydrogen supply solvent oil will be greatly reduced, that is, the single-stage ebullated bed hydromodification reaction method is difficult to flexibly increase the reaction rate to adapt to the fluctuation of the deterioration of the properties of the coal direct liquefaction oil. At this time, a reasonable process requires the removal of strongly polar components such as ammonia and water in the feed of the downstream ebullated bed hydromodification reaction process R202 to optimize the gas phase gas composition of the downstream ebullated bed hydromodification reaction process R202;

[0082] ④ The feed of the deteriorating ebullated bed hydromodification reaction usually contains more polycyclic aromatic hydrocarbons. The reasonable ebullated bed hydromodification reaction process R20 of these polycyclic aromatic hydrocarbons requires high hydrogen partial pressure, low ammonia concentration, and long reaction time. The heavy product oil KHNP of the ebullated bed hydromodification reaction composed of polycyclic aromatic hydrocarbon components separated from the product oil of the ebullated bed hydromodification reaction requires a circulating downstream ebullated bed hydromodification reaction process R202 to reduce the aromatic carbon rate. In order to improve the reaction efficiency of the circulating ebullated bed hydromodification reaction process R20 of the heavy product oil KHNP, the reasonable process requirement is to remove the strong polar components such as ammonia and water in the feed of the downstream ebullated bed hydromodification reaction process R202 to optimize the gas phase gas composition of the downstream ebullated bed hydromodification reaction process R202, so that the downstream ebullated bed hydromodification reaction process R202 becomes a simple process and efficient circulation reaction process of the heavy product oil KHNP;

[0083] ⑤ In the intermediate degassing and separation process of the ebullated bed hydromodification reaction process R20, a hydrogen gas stripping multiple gas-liquid contact deammonification process such as a degassing tower or a deammonification section can be set to fully reduce the ammonia component content in the downstream ebullated bed hydromodification reaction process R202 reaction feed oil (upstream ebullated bed hydromodification reaction product separation liquid and / or downstream ebullated bed hydromodification reaction product circulating liquid), and improve the reaction rate of the downstream ebullated bed hydromodification reaction process R202;

[0084] ⑥ In the single-stage ebullated bed hydrogenation modification process R20, the accumulation effect of non-hydrogen gas product components leads to a significant decrease in the hydrogen partial pressure of the downstream ebullated bed hydrogenation modification process R202, forcing the total operating pressure of the entire high-pressure system to be increased, which will greatly increase the investment in the device; or, in order to increase the hydrogen partial pressure of the downstream ebullated bed hydrogenation modification process R202, a large amount of recycled hydrogen is recycled, which will lead to a significant decrease in the liquid phase volume ratio of the downstream ebullated bed hydrogenation modification process R202, and increase the volume of the reaction zone by multiples or even several times; reasonable process requirements remove non-hydrogen gas components such as ammonia, water, and methane in the feed of the downstream ebullated bed hydrogenation modification process R202 to optimize the gas phase gas composition of the downstream ebullated bed hydrogenation modification process R202 and maintain a reasonable hydrogen-to-oil ratio;

[0085] ⑦ The low molecular weight components in the fresh crude oil that has completed the ebullated bed hydrogenation modification reaction task through the upstream ebullated bed hydrogenation modification reaction process R201 cannot leave the reaction system in time. When passing through the downstream ebullated bed hydrogenation modification reaction process R202, on the one hand, it causes excessive hydrogenation to reduce the hydrogen supply index PDQI, and on the other hand, it increases the volume of the downstream ebullated bed hydrogenation modification reaction process R202 with negative effects.

[0086] In order to improve the single-stage ebullated bed hydrogenation modification reaction process of coal direct liquefaction oil, the basic idea of ​​the present invention is: the intermediate degassing graded ebullated bed hydrogenation modification reaction method of coal direct liquefaction oil can effectively reduce the aromatic carbon rate of polycyclic aromatic hydrocarbon reaction products or reduce the amount of catalyst used, and can improve the adaptability to the fluctuation of liquefied coal properties. The intermediate separation liquid obtained after the upper reaction product is separated from ammonia, water, methane and light hydrocarbons in the intermediate product separation process enters the lower reaction process. The advantages are: ① The lower reaction process is operated under low ammonia partial pressure and high hydrogen partial pressure, and the reaction speed is fast and the limit aromatic ① High hydrocarbon saturation and reduced catalyst coking rate; ② Light hydrocarbon products leave the reaction process in advance to shorten the reaction time; ③ Part of the heavy fractionated bottom oil rich in polycyclic aromatic hydrocarbons obtained from the final reaction product oil is efficiently circulated through the lower reaction process in a low ammonia environment; ④ The separated gas of the lower reaction product enters the upper reaction process by self-pressure and is used in series; ⑤ The reaction temperature increasing operation mode is realized; ⑥ The fluctuation range of the performance of the hydrogen supply solvent oil caused by the fluctuation of the properties of the liquefied coal is reduced, and finally the adaptability of the coal hydrogenation direct liquefaction reaction process R10 to the fluctuation of the deterioration of the properties of the liquefied raw coal is improved.

[0087] Compared with the existing high-pressure system single-stage fluidized bed hydrogenation modification reaction method, the goal of the present invention is to propose an economical method for improving the hydrogen supply index of coal direct liquefaction oil, especially the polycyclic aromatic hydrocarbon components therein. At the same time, it is expected that when the fluctuation of the properties of the raw coal for coal hydrogenation direct liquefaction leads to the fluctuation of the properties of the coal direct liquefaction oil, it will have an effective peak-reducing and suppressing effect on the amplitude of the fluctuation of the properties of the oil generated by the fluidized bed hydrogenation modification reaction, thereby ultimately improving the adaptability of the coal hydrogenation direct liquefaction reaction process R10 to the fluctuation of the properties of the liquefied raw coal.

[0088] The method of the present invention (an intermediate separator is arranged between multi-stage series ebullated bed hydrogenation modification reactors, the intermediate separation liquid is transported without valve, and the intermediate separation gas is separated from the reaction process) is used in combination with the control method for a communicating vessel for a hydrocarbon material upstream expanded bed graded series hydrogenation reaction process proposed by the inventor in Chinese patent ZL202310229274.7 (an intermediate separator is arranged between multi-stage series coal hydrogenation direct liquefaction reactors, the intermediate separation liquid coal slurry is transported without valve, and the intermediate separation gas is separated from the reaction process), thus constituting a complete new "coal hydrogenation direct liquefaction reaction process R10 + coal direct liquefaction oil boiling bed hydrogenation modification reaction process R20" overall coal hydrogenation direct liquefaction conversion method.

[0089] The method of the present invention has not been reported.

[0090] The purpose of the invention is to provide an intermediate degassing graded ebullating bed hydrogenation modification reaction method for direct coal liquefaction oil.

[0091] Chinese Patent ZL201310452935.9 Coal direct liquefaction circulating solvent and its preparation method and application, the preparation method comprises: step S1, hydrogenating a mixture of petroleum refining byproducts and coal direct liquefaction oil to obtain a hydrogenation product; step S2, fractionating the hydrogenation product to obtain light distillate oil, medium distillate oil and heavy distillate oil; step S3, mixing the heavy distillate oil and part of the medium distillate oil to obtain a coal direct liquefaction circulating solvent. In the preparation method of the invention, on the one hand, since the petroleum refining byproducts contain a large amount of aromatics, the hydrogenated product is rich in components such as tetralin, which can significantly improve the hydrogen supply capacity of the circulating solvent and improve the yield of coal direct liquefaction oil; on the other hand, the high value-added diesel fraction less than 350°C in part of the coal direct liquefaction circulating solvent is replaced by petroleum refining byproducts, which improves the diesel yield and significantly improves the economic efficiency of coal hydrogenation direct liquefaction technology; moreover, it can alleviate the existing problem of lightweight circulating solvent. However, the disadvantage of Chinese patent application No. 202110057309.4 is that it cannot effectively reduce the ammonia concentration in the medium in the final reaction space, and thus cannot efficiently increase the limiting depth of the hydrogenation modification reaction, nor can it increase the speed of the hydrogenation modification reaction. It has the disadvantages of large amount of hydrogenation stabilization catalyst and large reactor volume.

[0092] Chinese Patent ZL201310452948.6 Coal direct liquefaction circulating solvent and its preparation method and application, the preparation method comprises: step S1, hydrogenating a mixture of coal tar anthracene oil and coal direct liquefaction oil to obtain a hydrogenation product; step S2, fractionating the hydrogenation product to obtain a light distillate oil, a medium distillate oil and a heavy distillate oil; step S3, mixing the heavy distillate oil and part of the medium distillate oil to obtain a coal direct liquefaction circulating solvent. In the preparation method of the invention, on the one hand, coal tar anthracene oil contains a large amount of aromatic hydrocarbons, and the hydrogenated product is rich in components such as tetralin, which can significantly improve the hydrogen supply capacity of the circulating solvent and improve the yield of coal direct liquefaction oil; on the other hand, coal tar anthracene oil is used to replace part of the high value-added gasoline and diesel fractions less than 350°C in the coal direct liquefaction circulating solvent, thereby improving the diesel yield; moreover, it can alleviate the problem of lightweighting of existing circulating solvents and alleviate the deposition and coking of materials in the reactor of the coal direct liquefaction process. However, the disadvantage of Chinese patent ZL201310452948.6 is that it cannot effectively reduce the ammonia concentration in the medium in the final reaction space, and thus cannot efficiently increase the limit depth of the hydrogenation modification reaction, nor can it increase the speed of the hydrogenation modification reaction. It has the disadvantages of a large amount of hydrogenation stabilization catalyst and a large reactor volume.

[0093] Chinese Patent ZL201410438758.3 discloses a coal direct liquefaction circulating solvent, a processing method thereof and a coal direct liquefaction method using the same, wherein the processing method comprises: step S1, fractionating the coal direct liquefaction oil to obtain heavy oil, i.e. hydrocarbons with a conventional boiling point higher than 200°C; step S2, hydrogenating the heavy oil to obtain the coal direct liquefaction circulating solvent; the processing method of the above-mentioned coal direct liquefaction circulating solvent of the invention first fractionates the coal direct liquefaction oil, selectively cuts the heavy oil fraction therein, and then hydrogenates the heavy oil in a targeted manner, thereby avoiding the "snatching" of hydrogen by light oil and achieving effective hydrogenation of heavy oil, thereby obtaining a coal direct liquefaction circulating solvent with better hydrogen supply performance; the coal direct liquefaction circulating solvent obtained by the processing method of the invention has good hydrogen supply performance for the coal direct liquefaction reaction, high coal conversion efficiency, and can supply the coal direct liquefaction device for long-term stable operation, thereby helping to improve the economic benefits of the enterprise. However, the disadvantages of Chinese Patent ZL201410438758.3 are: first, it cannot effectively reduce the ammonia concentration in the medium in the final reaction space, and thus cannot efficiently increase the limit depth of the hydrogenation modification reaction, nor can it increase the speed of the hydrogenation modification reaction. It has the disadvantages of large amount of hydrogenation stabilization catalyst and large reactor volume; second, it does not achieve the classification and graded hydrogenation stabilization of dicyclic aromatic hydrocarbons and polycyclic aromatic hydrocarbons, and cannot achieve their respective optimal operating pressures, reaction times, etc.

[0094] Chinese Patent 201510300990.5 Coal direct liquefaction circulating hydrogen supply solvent and its preparation method, including the following steps: S1, the coal direct liquefaction oil is subjected to the first catalytic hydrogenation to obtain the first gas phase product and the first liquid phase product; S2, the first liquid phase product is fractionated to obtain light distillate oil, middle distillate oil and heavy distillate oil; S3, part or all of the heavy distillate oil is subjected to the second catalytic hydrogenation to obtain the second liquid phase product; S4, the second liquid phase product is mixed with part or all of the middle distillate oil to form coal direct liquefaction circulating hydrogen supply solvent oil; wherein, the light distillate oil is a distillate oil with a distillation range of less than 200°C, the middle distillate oil is a distillate oil with a distillation range of 200-350°C, and the heavy distillate oil is a distillate oil with a distillation range of more than 350°C. The preparation method can improve the dissolution, dispersion and hydrogen supply effect of the circulating hydrogen supply solvent oil in the coal direct liquefaction reaction process, and further improve the conversion rate of coal and the yield of oil. The disadvantages of this method are that it involves two high-pressure reaction systems, two circulating hydrogen systems, and two product fractionation processes, which requires large investment and high energy consumption.

[0095] Chinese Patent 201610237828.8 Coal direct liquefaction circulating solvent and preparation method thereof, comprising the following steps: S1, fractionating coal direct liquefaction oil under a pressure of 0.02-0.2 MPa to obtain primary low temperature oil, primary medium temperature oil and primary high temperature oil; S2, hydrogenating and fractionating the primary high temperature oil to obtain secondary low temperature oil, secondary medium temperature oil and secondary high temperature oil; S3, proportioning all secondary high temperature oil with a mixed oil of part of primary medium temperature oil and secondary medium temperature oil to obtain coal direct liquefaction circulating solvent, wherein the primary low temperature oil and secondary low temperature oil have a distillation range of <200°C, the primary medium temperature oil and secondary medium temperature oil have a distillation range of 200-320°C, and the primary high temperature oil and secondary high temperature oil have a distillation range of >320°C. The technical scheme of the present invention can improve the coal conversion rate and product oil yield of the coal direct liquefaction process, while reducing the loss of some light oil products and reducing the discharge of residues. This method, on the one hand, recognizes that the hydrogenation stabilization of first-grade high-temperature oil has great room for appreciation in improving the hydrogen supply index, and is the dominant hydrogenation stabilization target raw material oil for obtaining high-quality hydrogen supply solvent oil. On the second hand, it recognizes that the hydrogenation stabilization of first-grade medium-temperature oil has little room for appreciation in improving the hydrogen supply index. In fact, this method abandons the hydrogenation stabilization of first-grade medium-temperature oil to improve the hydrogen supply index. Its essence is that it has not found an economical method to improve the hydrogen supply index of first-grade medium-temperature oil. On the third hand, it cannot effectively reduce the ammonia concentration in the medium in the final reaction space, and thus cannot efficiently increase the limiting depth of the hydrogenation modification reaction, nor can it increase the speed of the hydrogenation modification reaction. It has the disadvantages of large amount of hydrogenation stabilization catalyst and large reactor volume.

[0096] Chinese patent ZL201910194660.0 Coal liquefaction circulating solvent and its preparation method, including the following steps: S1, catalytically hydrogenating coal direct liquefaction oil to obtain hydrogenated oil; S2, fractionating the hydrogenated oil to obtain light distillate oil, middle distillate oil and heavy distillate oil; S3, returning part of the heavy distillate oil and mixing it with the coal direct liquefaction oil for catalytic hydrogenation; S4, mixing another part of the heavy distillate oil with part of the middle distillate oil to form a coal hydrogenation direct liquefaction circulating solvent; wherein, light distillate oil refers to distillate oil with a distillation range of less than 200°C, middle distillate oil refers to distillate oil with a distillation range of 200-350°C, and heavy distillate oil refers to distillate oil with a distillation range of more than 350°C. The preparation method can improve the hydrogen supply capacity of the coal hydrogenation direct liquefaction heavy distillate oil circulating solvent, which is conducive to promoting the liquefaction conversion of coal, and the hydrogenation process route is simple and the operation difficulty is low. Chinese patent ZL201910194660.0 performs a supplementary cyclic hydrogenation modification reaction on a heavy distillate oil which is a hydrogenation stable product with a shallow degree of hydrogenation modification reaction. However, the disadvantage of this method is that the reaction selectivity of the heavy distillate oil in the cyclic reaction process is too low, so the effect of improving the hydrogen supply index of the heavy distillate oil is not ideal. The reasons are:

[0097] ① In the initial reaction zone of a single hydrogenation modification reaction section, since other inferior raw oils, i.e., mixed coal direct liquefaction oil, provide high nitrogen hydrocarbons with stronger electrical conductivity and aromatic hydrocarbons with higher aromaticity, these hydrocarbon oil molecules are preferentially adsorbed on the active surface of the hydrogenation stable catalyst, and the adsorption reaction probability of the heavy distillate oil of the circulation reaction with low organic nitrogen content and low aromaticity is very low, that is, there is a strong competitive adsorption of other inferior hydrocarbons, thereby inhibiting the adsorption and reaction of the heavy distillate oil of the circulation reaction;

[0098] ② In the final reaction zone of a single hydrogenation modification reaction section, high-concentration ammonia molecules with strong electrical conductivity are preferentially adsorbed on the active surface of the hydrogenation stable catalyst, and the adsorption reaction of the heavy distillate oil with low organic nitrogen content and low aromatic content in the circulation reaction is strongly shielded, so the probability of adsorption reaction is much lower, that is, there is a strong competitive adsorption of high-concentration ammonia molecules, thereby inhibiting the adsorption and reaction of the heavy distillate oil in the circulation reaction;

[0099] ③ Compared with the optimal hydroprocessing reaction conditions of heavy distillate oil with low organic nitrogen content and low aromatic content in the circulation reaction, it is impossible to effectively increase the operating pressure, optimize the catalyst composition, or adopt the optimal reaction time, that is, it is forced to adopt deteriorated hydroprocessing reaction conditions, and can only complete the hydroprocessing reaction of part of the heavy distillate oil but not all of the heavy distillate oil. Therefore, it is impossible to effectively increase the limit depth of the hydroprocessing reaction, increase the speed of the hydroprocessing reaction, and solve the shortcomings of large catalyst dosage and large reactor volume.

[0100] The above analysis shows that in order to obtain hydrogen-donating solvent oil with a high hydrogen supply index, a reasonable hydrogenation modification reaction method for direct coal liquefaction oil should follow one or more of the following principles according to the specific situation:

[0101] ① For the raw oil of hydrogenation modification reaction, avoid the mixed processing of 2-ring structure aromatics, 3-ring structure aromatics, 4-ring structure aromatics and even 5-ring structure aromatics as much as possible or reduce the mixing degree as much as possible. The principle is:

[0102] First, classify the hydrostabilization as much as possible to achieve the optimal operating conditions for each. This is suitable for the hydromodification reaction process of coal direct liquefaction oil with a large flow rate, and can also reduce the fractionation energy consumption of the hydrostabilized oil;

[0103] Second, the coal direct liquefied oil, which is the raw material of the hydro-reforming reaction, should be directly sent to the hydro-reforming reaction process as much as possible to reduce the mixing degree of the mixed raw material oil hydro-reforming reaction process;

[0104] ② For the intermediate ammonia product of the ebullated bed hydrogenation modification reaction process R20, the ebullated bed hydrogenation modification reaction process R20 can be discharged in time, and a simple gas-liquid separation process can be used for intermediate ammonia removal operation, or a large amount of hydrogen gas stripping can be used to remove low-boiling point components such as ammonia in the separated liquid, thereby reducing the ammonia concentration in the downstream hydrogenation modification reaction zone and improving the catalyst activity;

[0105] For example, in the ebullient bed hydro-modification reaction process R20 of a mixture of 2-ring and polycyclic aromatic hydrocarbons, how to extend the reaction time of polycyclic aromatic hydrocarbons (such as 3-ring aromatic hydrocarbons) is a method for prolonging the reaction time of polycyclic aromatic hydrocarbons (such as 3-ring aromatic hydrocarbons). The oil generated by the primary hydro-modification reaction, such as the hot high-fraction oil of the primary hydro-modification reaction product, can be depressurized and flash evaporated to separate the low-boiling hydrocarbons in the product, and then the intermediate separation liquid obtained by the depressurized flash evaporated is pressurized and enters the secondary hydro-saturation reaction R22, and a highly selective and efficient reaction is carried out under the conditions of low ammonia and low-boiling hydrocarbons. The separation process of the oil generated by the primary hydro-modification reaction, such as the hot high-fraction oil, does not require heat input from the heating furnace, nor does it require the pressure of the hot high-fraction oil of the primary hydro-modification reaction product to be reduced too much. For example, it is only necessary to reduce the pressure of the hot high-fraction oil of the primary hydro-modification reaction product from 17.0 MPa to 9.0 MPa.

[0106] ③ For the ebullated bed hydrogenation modification reaction process R20 of a mixture of 2-ring and polycyclic aromatic hydrocarbons, how to prolong the reaction time of polycyclic aromatic hydrocarbons (such as 3-ring aromatic hydrocarbons)? In order to avoid excessive hydrogenation saturation reaction of low-ring aromatic hydrocarbons (such as 2-ring aromatic hydrocarbons), the hydrogenation modification reaction products are separated and / or fractionated at a reaction time suitable for the hydrogenation saturation reaction depth of low-ring aromatic hydrocarbons to obtain the expected polycyclic aromatic hydrocarbon fraction oil KRHP, and then the polycyclic aromatic hydrocarbon fraction oil KRH is subjected to a cyclic hydrogenation saturation reaction in the downstream ebullated bed hydrogenation modification reaction process R202 in a low ammonia environment, thereby simplifying the process and improving the reaction efficiency.

[0107] It is obvious that the hydrogenation modification reaction process of coal direct liquefaction oil following the above principles can economically produce hydrogen supply solvent oil with an ideal hydrogen supply index.

[0108] On the basis of the above principles, by optimizing the performance of the catalysts in each reaction stage, rationally allocating hydrogen resources, and appropriately increasing one or more of the operating pressures of the downstream hydrogenation and modification reaction zones, the comprehensive optimization goals of increasing the aromatic hydrogen supply index, simplifying the process, reducing investment, and reducing energy consumption can be achieved. For example, the fresh hydrogen of the entire device passes through the downstream hydrogenation and modification reaction stage to increase its hydrogen partial pressure, and the upstream intermediate separation liquid is pressurized by a pump (for example, without a shaft seal) and then sent to the adjacent downstream hydrogenation and modification reaction zone to form an abnormal operating pressure distribution. The low-ammonia, high-temperature, and high-pressure intermediate separation gas of the downstream hydrogenation and modification reaction stage relies on its own pressure to enter the upstream hydrogenation and modification reaction zone for secondary use. This is also the solution recommended by the present invention. Summary of the invention

[0109] The intermediate degassing graded ebullating bed hydrogenation modification reaction method of coal direct liquefaction oil of the present invention is characterized by:

[0110] The feedstock oil R20F of the ebullated bed hydro-modification reaction process R20 is a hydrocarbon stream containing organic nitrogen and organic oxygen, including dicyclic aromatic hydrocarbons and / or polycyclic aromatic hydrocarbons, and at least a hydrocarbon stream containing distillate oil generated by direct coal liquefaction, with or without carbonaceous solid particles;

[0111] In the ebullated bed hydro-modification reaction process R20, in the presence of hydrogen, liquid hydrocarbons, an ebullated bed hydro-modification catalyst, and in the presence or absence of carbon-containing solid particles, a stream containing hydrocarbon liquid based on the feedstock oil R20F undergoes an ebullated bed hydro-modification reaction to be converted into hydrocarbons with a lower aromatic carbon content to obtain a hydro-modification reaction effluent R20P;

[0112] In the ebullating bed hydro-modification reaction process R20, at least a portion of the organic nitrogen component of the logistics containing hydrocarbon liquid based on the feedstock oil R20F undergoes a hydrogenation hydrogenolysis reaction to produce ammonia, at least a portion of the organic oxygen component of the logistics containing hydrocarbon liquid based on the feedstock oil R20F undergoes a hydrogenation hydrogenolysis reaction to produce water, and at least a portion of the bicyclic aromatic hydrocarbons and / or polycyclic aromatic hydrocarbons of the logistics containing hydrocarbon liquid based on the feedstock oil R20F undergo a hydrogenation saturation reaction to be converted into aromatic hydrocarbons with a lower aromatic carbon rate;

[0113] A hydrocarbon hydro-modification reaction stage, comprising a hydrocarbon hydro-modification reaction process and a gas-liquid separation process of the reaction effluent;

[0114] A hydrocarbon ebullated bed hydro-modification reaction stage, comprising an ebullated bed hydro-modification reaction process and a gas-liquid separation process of the reaction effluent;

[0115] The ebullated bed hydromodification reaction process R20 comprises at least two adjacent ebullated bed hydromodification reaction stages, a hydromodification reactor of other forms using or not using a stream containing hydrocarbon liquid based on the feedstock oil R20F, and a reaction stage of a hydromodification reactor of other forms using or not using a stream containing hydrocarbon liquid based on the feedstock oil R20F, wherein the other forms of hydromodification reactor are selected from one or more of the following:

[0116] ① Micro-expanded bed with process fluid upflow;

[0117] ② Fixed bed with process fluid upflow;

[0118] ③ Fixed bed with downward flow of process fluid;

[0119] ④Suspended bed or slurry bed;

[0120] The ebullated bed hydroprocessing reaction process R20 comprises two or more ebullated bed hydroprocessing reaction stages connected in series for a flow containing hydrocarbon liquid based on the feedstock oil R20F, and is divided into an upstream ebullated bed hydroprocessing reaction stage and a downstream ebullated bed hydroprocessing reaction stage according to the main flow direction of the ebullated bed hydroprocessing reaction process of the feedstock oil R20F, wherein the most downstream ebullated bed hydroprocessing reaction stage is called a final ebullated bed hydroprocessing reaction stage;

[0121] The intermediate product separation process refers to the gas-liquid separation process of the upstream hydro-modification reaction product between two adjacent hydro-modification reaction stages. The intermediate product separation process separates the intermediate product separation gas and the intermediate product separation liquid;

[0122] The average volume concentration of gaseous ammonia in the ebullated bed hydro-modification reaction process refers to the arithmetic mean of the volume concentration of gaseous ammonia at the starting reaction point of the catalyst bed and the volume concentration of gaseous ammonia at the end reaction point of the catalyst bed in the ebullated bed hydro-modification reaction process;

[0123] The average volumetric concentration of ammonia in the gas phase of the ebullated bed hydro-modification reaction process UR2N of any downstream ebullated bed hydro-modification reaction stage is lower than the average volumetric concentration of ammonia in the gas phase of the ebullated bed hydro-modification reaction process UR2M of the adjacent upstream ebullated bed hydro-modification reaction stage;

[0124] The aromatic carbon ratio of all hydrocarbons with a conventional boiling point higher than 220° C. in the reaction effluent of any ebullated bed hydromodification reaction process UR2N is lower than the aromatic carbon ratio of all hydrocarbons with a conventional boiling point higher than 220° C. in the reaction feed of the ebullated bed hydromodification reaction process UR2N;

[0125] In an intermediate product separation process MS of the reaction effluent of any upstream ebullating bed hydro-modification reaction stage, ammonia and water are stripped from the liquid phase separated from the hydro-modification reaction effluent of the stage with or without using a stripping hydrogen stream;

[0126] The ebullated bed hydro-modification reaction process R20 comprises at least a first ebullated bed hydro-modification reaction stage U210 and a second ebullated bed hydro-modification reaction stage U220;

[0127] (1) The first ebullated bed hydro-modification reaction stage U210, comprising the first ebullated bed hydro-modification reaction process UR210 and the first gas-liquid separation process US210;

[0128] A hydrocarbon liquid-containing stream based on the feedstock oil R20F is used as the hydrocarbon-containing feedstock UR210F of the first ebullated bed hydro-modification reaction process UR210;

[0129] In the first ebullated bed hydro-modification reaction process UR210, the hydrocarbon-containing feedstock UR210F is subjected to the first ebullated bed hydro-modification reaction and converted into the first ebullated bed hydro-modification reaction effluent UR210P;

[0130] In the first gas-liquid separation process US210, the gas-liquid mixed phase flow of the first ebullated bed hydro-modification reaction effluent UR210P is separated into a first separated gas containing ammonia and water and a first separated liquid, and part of the ammonia component and part of the water component in the first ebullated bed hydro-modification reaction effluent UR210P enter the first separated gas;

[0131] In the first gas-liquid separation process US210, the liquid phase separated from the gas-liquid mixed phase stream of the first ebullated bed hydro-modification reaction effluent UR210P is stripped with or without the use of the hydrogen-rich gas stream to reduce the ammonia content and water content in the liquid phase after stripping;

[0132] When the first stripping process UB210 is used, the first hydrogen-rich stripping gas contacts the first separation liquid-based stream, i.e., the first stripping liquid, at least once and completes separation, the low-boiling point components in the first stripping liquid enter the gas phase to form the first stripped gas, and the unvaporized first stripping liquid forms the first stripped liquid; the weight content of ammonia in the first stripped liquid is lower than the weight content of ammonia in the first separation liquid; the weight content of ammonia in the first stripped gas is higher than the weight content of ammonia in the first hydrogen-rich stripping gas;

[0133] (2) The second ebullated bed hydroprocessing reaction stage U220, comprising a second ebullated bed hydroprocessing reaction process UR220 and a second gas-liquid separation process US220;

[0134] The hydrocarbon-containing stream based on the first separated liquid is used as the hydrocarbon-containing feedstock UR220F of the second ebullated bed hydro-modification reaction process UR220;

[0135] In the second ebullated bed hydro-modification reaction process UR220, the hydrocarbon-containing feedstock UR220F is subjected to a second ebullated bed hydro-modification reaction and converted into a second ebullated bed hydro-modification reaction effluent UR220P;

[0136] The average volume concentration of ammonia in the gas phase of the second ebullated bed hydro-modification reaction process UR220 is lower than the average volume concentration of ammonia in the gas phase of the first ebullated bed hydro-modification reaction process UR210;

[0137] In the second gas-liquid separation process US220, the gas-liquid mixed phase flow based on the second ebullated bed hydro-modification reaction effluent UR220P is separated into a second separated gas and a second separated liquid, and part of the ammonia component in the second ebullated bed hydro-modification reaction effluent UR220P enters the second separated gas;

[0138] The final ebullated bed hydroprocessing reaction stage U290 includes a final ebullated bed hydroprocessing reaction process UR290 and a final gas-liquid separation process US290;

[0139] A hydrocarbon liquid-containing stream based on the intermediate product separation liquid of the adjacent upstream ebullated bed hydro-modification reaction stage is used as a hydrocarbon-containing feedstock UR290F for the final ebullated bed hydro-modification reaction process UR290;

[0140] In the final ebullated bed hydroprocessing reaction stage U290, the hydrocarbon-containing feedstock UR290F of the final ebullated bed hydroprocessing reaction process UR290 is subjected to the final ebullated bed hydroprocessing reaction and converted into the final ebullated bed hydroprocessing reaction effluent UR290P;

[0141] In the final gas-liquid separation process US290, the gas-liquid mixed phase flow based on the final ebullating bed hydrogenation modification reaction effluent UR290P is separated into the final separation gas and the final separation liquid.

[0142] In the present invention, usually, in the generated oil fractionation process of the ebullated bed hydroprocessing reaction process R20, a heavy fraction KEYL mainly composed of hydrocarbons with a conventional boiling point higher than 320°C is separated from a hydrocarbon flow containing at least a final separation liquid, and a hydrocarbon-containing flow based on part of the heavy fraction KEYL is returned as a circulating reaction material KEYL-R to the ebullated bed hydroprocessing reaction process of any downstream ebullated bed hydroprocessing reaction stage of the ebullated bed hydroprocessing reaction process R20 to carry out a circulating hydrogenation reaction for reducing the aromatic carbon rate.

[0143] In the present invention, usually, in the intermediate product separation process of the reaction effluent of any upstream ebullating bed hydroprocessing reaction stage, the liquid phase separated from the hydroprocessing reaction effluent of this stage is subjected to two or more countercurrent contacts with the liquid phase using a stripping hydrogen flow to strip ammonia and water therein.

[0144] In the present invention, generally, the intermediate product separation process of the reaction effluent of any upstream ebullating bed hydroprocessing reaction stage and the hydrogen stripping process of the liquid phase separated from the hydroprocessing reaction effluent of this stage are completed in the same high-pressure container pressure shell.

[0145] In the present invention, generally, the separated gas obtained in the gas-liquid separation process of the ebullated bed hydro-modification reaction effluent of any ebullated bed hydro-modification reaction stage contains more than 70% of the ammonia component in the ebullated bed hydro-modification reaction effluent of the ebullated bed hydro-modification reaction stage;

[0146] The average volume concentration of gas-phase ammonia in any downstream ebullated bed hydroprocessing reaction process UR2N is lower than 40% of the average volume concentration of gas-phase ammonia at the terminal reaction of the adjacent upstream ebullated bed hydroprocessing reaction process UR2M.

[0147] In the present invention, generally, the separated gas obtained in the gas-liquid separation process of the ebullated bed hydro-modification reaction effluent of any ebullated bed hydro-modification reaction stage contains more than 85% of the ammonia component in the ebullated bed hydro-modification reaction effluent of the ebullated bed hydro-modification reaction stage;

[0148] The average volume concentration of gas-phase ammonia in any downstream ebullated bed hydroprocessing reaction process UR2N is 20% lower than the average volume concentration of gas-phase ammonia at the terminal reaction of the adjacent upstream ebullated bed hydroprocessing reaction process UR2M.

[0149] In the present invention, generally, the source and composition of the raw oil R20F are selected from one or more of the following:

[0150] ① The distillate stream from the fractionation process of coal direct liquefaction to generate oil, mainly composed of hydrocarbons with a conventional boiling point of 200 to 280°C;

[0151] ② The distillate stream from the fractionation process of coal direct liquefaction to generate oil, mainly composed of hydrocarbons with a conventional boiling point of 280 to 370°C;

[0152] ③ The distillate stream from the fractionation process of coal direct liquefaction to generate oil, mainly composed of hydrocarbons with a conventional boiling point of 370 to 470°C;

[0153] ④ The distillate stream from the fractionation process of coal direct liquefaction to generate oil, mainly composed of hydrocarbons with a conventional boiling point of 470 to 525°C;

[0154] ⑤ The distillate stream from the fractionation process of coal direct liquefaction to produce oil, mainly composed of hydrocarbons with a conventional boiling point of 525 to 550°C;

[0155] ⑥ The distillate oil stream from the fractionation process of direct coal liquefaction to produce oil is mainly composed of hydrocarbons with a conventional boiling point of 550 to 650°C.

[0156] In the present invention, the feedstock oil R20F may include one or more of the following, and their overall proportion in the feedstock oil R20F is less than 30% by weight:

[0157] ① The distillate stream from the fractionation process of coal tar, mainly composed of hydrocarbons with a conventional boiling point of 200 to 330°C;

[0158] ② The distillate stream from the fractionation process of coal tar, mainly composed of hydrocarbons with a conventional boiling point of 330 to 400°C;

[0159] ③ The distillate oil stream from the fractionation process of coal tar is mainly composed of hydrocarbons with a conventional boiling point of 400 to 540°C.

[0160] In the present invention, generally, the operating conditions of the ebullated bed hydro-modification reaction zone used in the ebullated bed hydro-modification reaction process R20 are: temperature of 250-440°C, pressure of 8.0-25.0 MPa, hydrogen / feedstock oil volume ratio of 100-400 Nm 3 / m 3 , the weight chemical hydrogen consumption per unit weight of raw oil is 0.4~3.5%.

[0161] In the present invention, generally, the operating conditions of the ebullated bed hydro-modification reaction zone used in the ebullated bed hydro-modification reaction process R20 are: temperature of 300-400°C, pressure of 13.0-20.0 MPa, hydrogen / feedstock oil volume ratio of 200-350 Nm 3 / m 3 , the weight chemical hydrogen consumption per unit weight of crude oil is 1.0~2.5%.

[0162] In the present invention, generally, the solid particle content in the feedstock oil R20F in the ebullated bed hydro-modification reaction is greater than 100 ppm.

[0163] In the present invention, the ebullated bed hydroprocessing reaction process R20 may include two ebullated bed hydroprocessing reaction stages connected in series, and the operation objectives thereof are selected from one or more of the following:

[0164] ① The organic nitrogen hydrodenitrification rate of the first ebullated bed hydromodification reaction stage U210 is 60-95% of the overall denitrification rate of the ebullated bed hydromodification reaction process R20;

[0165] The organic nitrogen hydrodenitrification rate of the second ebullated bed hydromodification reaction stage U220 is 5 to 40% of the overall denitrification rate of the ebullated bed hydromodification reaction process R20;

[0166] ② The aromatic carbon hydroremoval rate of the first ebullated bed hydromodification reaction stage U210 is 60-80% of the overall aromatic carbon hydroremoval rate of the ebullated bed hydromodification reaction process R20;

[0167] The aromatics hydrogenation removal rate of the second ebullated bed hydromodification reaction stage U220 is 20-40% of the overall aromatics hydrogenation removal rate of the ebullated bed hydromodification reaction process R20;

[0168] ③ The reaction temperature rise of the first ebullated bed hydro-modification reaction stage U210 is 40-70% of the overall reaction temperature rise of the ebullated bed hydro-modification reaction process R20;

[0169] The reaction temperature rise of the second ebullated bed hydro-modification reaction stage U220 is 40-60% of the overall reaction temperature rise of the ebullated bed hydro-modification reaction process R20;

[0170] ④ The chemical hydrogen consumption of the first ebullated bed hydroprocessing reaction stage U210 is 40-70% of the overall chemical hydrogen consumption of the ebullated bed hydroprocessing reaction process R20;

[0171] The chemical hydrogen consumption of the second ebullated bed hydro-modification reaction stage U220 is 40-60% of the overall chemical hydrogen consumption of the ebullated bed hydro-modification reaction process R20;

[0172] ⑤ The growth value of the hydrogen supply index of the feedstock R20F produced in the first ebullated bed hydro-modification reaction stage U210 is 40-70% of the growth value of the overall hydrogen supply index of R20 in the ebullated bed hydro-modification reaction process;

[0173] The growth value of the hydrogen supply index generated by the second ebullated bed hydroprocessing reaction stage U220 is 30-60% of the growth value of the overall hydrogen supply index of the ebullated bed hydroprocessing reaction process R20.

[0174] In the present invention, generally, the feedstock oil R20F in the ebullated bed hydro-modification reaction contains carbonaceous solid particles;

[0175] The ebullated bed hydromodification reaction process R20 may include two series-connected hydromodification reaction stages: a first ebullated bed hydromodification reaction stage U210 and a second ebullated bed hydromodification reaction stage U220;

[0176] The second ebullated bed hydro-modification reaction stage U220 can be provided with a liquid product circulation pump to transport the liquid product of the second ebullated bed hydro-modification reaction stage U220, and the working mode is selected from one or more of the following:

[0177] ① delivering the circulating reaction liquid to the second ebullated bed hydro-modification reaction process UR220, and this part of the circulating reaction liquid does not pass through the first ebullated bed hydro-modification reaction process UR210;

[0178] ② Transport circulating reaction liquid to the first ebullated bed hydrogenation modification reaction process UR210.

[0179] In the present invention, generally, the feedstock oil R20F in the ebullated bed hydro-modification reaction contains carbonaceous solid particles;

[0180] The ebullated bed hydromodification reaction process R20 includes two series-connected hydromodification reaction stages: a first ebullated bed hydromodification reaction stage U210 and a second ebullated bed hydromodification reaction stage U220;

[0181] Each ebullated bed hydroprocessing reaction stage can be provided with a liquid reaction product circulation pump, so that part of the liquid product of this reaction stage can be circulated and reacted in the ebullated bed hydroprocessing reaction process of this stage.

[0182] In the present invention, generally, the feedstock oil R20F in the ebullated bed hydro-modification reaction contains carbonaceous solid particles;

[0183] The ebullated bed hydromodification reaction process R20 includes two series-connected hydromodification reaction stages: a first ebullated bed hydromodification reaction stage U210 and a second ebullated bed hydromodification reaction stage U220;

[0184] The first ebullated bed hydro-modification reaction stage U210 can be provided with a first separation liquid delivery pump, and its working mode is selected from one or more of the following:

[0185] ① Transporting circulating reaction liquid to the first ebullated bed hydro-modification reaction process UR210;

[0186] ②Transporting reaction feed liquid to the second ebullated bed hydro-modification reaction process UR220;

[0187] ③ The operating pressure of the second ebullated bed hydrogenation modification reaction stage U220 is higher than the operating pressure of the first ebullated bed hydrogenation modification reaction stage U210, and part or all of the second separated gas enters the first ebullated bed hydrogenation modification reaction process UR210 by relying on its own pressure, and / or, a part of the second separated liquid enters the first ebullated bed hydrogenation modification reaction process UR210 by relying on its own pressure, and a part of the second separated liquid is used as the second separated liquid net product.

[0188] In the present invention, generally, the ebullated bed hydroprocessing reaction process R20 may include three ebullated bed hydroprocessing reaction stages connected in series, and the operation objectives thereof are selected from one or more of the following:

[0189] ① The organic nitrogen hydrodenitrification rate of the first ebullated bed hydromodification reaction stage U210 is 40-70% of the overall denitrification rate of the ebullated bed hydromodification reaction process R20;

[0190] The organic nitrogen hydrodenitrification rate of the second ebullated bed hydromodification reaction stage U220 is 25-40% of the overall denitrification rate of the ebullated bed hydromodification reaction process R20;

[0191] The organic nitrogen hydrodenitrification rate of the third ebullated bed hydromodification reaction stage U230 is 10-20% of the overall denitrification rate of the ebullated bed hydromodification reaction process R20;

[0192] ② The aromatic carbon hydroremoval rate of the first ebullated bed hydromodification reaction stage U210 is 40-70% of the overall aromatic carbon hydroremoval rate of the ebullated bed hydromodification reaction process R20;

[0193] The aromatics hydrogenation removal rate of the second ebullated bed hydromodification reaction stage U220 is 25-40% of the overall aromatics hydrogenation removal rate of the ebullated bed hydromodification reaction process R20;

[0194] The aromatic carbon hydroremoval rate of the third ebullated bed hydromodification reaction stage U230 is 10-20% of the overall aromatic carbon hydroremoval rate of the ebullated bed hydromodification reaction process R20;

[0195] ③ The reaction temperature rise of the first ebullated bed hydro-modification reaction stage U210 is 40-70% of the overall reaction temperature rise of the ebullated bed hydro-modification reaction process R20;

[0196] The reaction temperature rise of the second ebullated bed hydro-modification reaction stage U220 is 25-40% of the overall reaction temperature rise of the ebullated bed hydro-modification reaction process R20;

[0197] The reaction temperature rise of the third ebullated bed hydro-modification reaction stage U230 is 10-20% of the overall reaction temperature rise of the ebullated bed hydro-modification reaction process R20;

[0198] ④ The chemical hydrogen consumption of the first ebullated bed hydroprocessing reaction stage U210 is 40-70% of the overall chemical hydrogen consumption of the ebullated bed hydroprocessing reaction process R20;

[0199] The chemical hydrogen consumption of the second ebullated bed hydro-modification reaction stage U220 is 25-40% of the overall chemical hydrogen consumption of the ebullated bed hydro-modification reaction process R20;

[0200] The chemical hydrogen consumption of the third ebullated bed hydro-modification reaction stage U230 is 10-20% of the overall chemical hydrogen consumption of the ebullated bed hydro-modification reaction process R20;

[0201] ⑤ The growth value of the hydrogen supply index of the feedstock R20F produced in the first ebullated bed hydro-modification reaction stage U210 is 40-70% of the growth value of the overall hydrogen supply index of R20 in the ebullated bed hydro-modification reaction process;

[0202] The growth value of the hydrogen supply index generated by the second ebullated bed hydroprocessing reaction stage U220 is 25-40% of the growth value of the overall hydrogen supply index of the ebullated bed hydroprocessing reaction process R20;

[0203] The increase value of the hydrogen supply index generated by the third ebullated bed hydroprocessing reaction stage U230 is 10-20% of the increase value of the overall hydrogen supply index of the ebullated bed hydroprocessing reaction process R20.

[0204] In the present invention, generally, the feedstock oil R20F contains carbonaceous solid particles;

[0205] In the ebullated bed hydroprocessing reaction process R20, a liquid product circulation pump is provided in any ebullated bed hydroprocessing reaction stage to transport the liquid product of the ebullated bed hydroprocessing reaction stage. The working mode can be selected from one or more of the following:

[0206] ① Transporting circulating reaction liquid to the ebullated bed hydrogenation and modification reaction process at this stage;

[0207] ②Transporting circulating reaction liquid to the existing downstream hydrogenation and modification reaction process

[0208] ③ Transporting circulating reaction liquid to any existing upstream boiling bed hydrogenation modification reaction process.

[0209] In the present invention, generally, the feedstock oil R20F contains carbonaceous solid particles;

[0210] The ebullating bed hydroprocessing reaction process R20 comprises a plurality of hydroprocessing reaction stages connected in series;

[0211] Each ebullated bed hydroprocessing reaction stage can be provided with a liquid reaction product circulation pump, so that part of the liquid product of this reaction stage can be circulated and reacted in the ebullated bed hydroprocessing reaction process of this stage.

[0212] In the present invention, generally, the feedstock oil R20F for the ebullated bed hydro-modification reaction contains carbonaceous solid particles;

[0213] The ebullating bed hydroprocessing reaction process R20 may include three hydroprocessing reaction stages connected in series;

[0214] The first ebullated bed hydro-modification reaction stage U210 is provided with a first separation liquid delivery pump, and its working mode is selected from one or more of the following:

[0215] ① Transporting circulating reaction liquid to the first ebullated bed hydro-modification reaction process UR210;

[0216] ②Transporting reaction feed liquid to the second ebullated bed hydro-modification reaction process UR220;

[0217] ③ The operating pressure of the second ebullated bed hydro-modification reaction stage U220 is higher than the operating pressure of the first ebullated bed hydro-modification reaction stage U210, and the second separated gas partially or completely enters the first ebullated bed hydro-modification reaction process UR210 by its own pressure, and / or a part of the second separated liquid enters the first ebullated bed hydro-modification reaction process UR210 by its own pressure;

[0218] And / or, the second ebullated bed hydro-modification reaction stage U220 is provided with a second separation liquid delivery pump, and its working mode is selected from one or more of the following:

[0219] ① Transporting circulating reaction liquid to the first ebullated bed hydro-modification reaction process UR210;

[0220] ②Transporting the cyclic reaction liquid to the second ebullated bed hydrogenation modification reaction process UR220;

[0221] ③ Transporting reaction feed liquid to the third ebullated bed hydrogenation modification reaction process UR230;

[0222] ④ The operating pressure of the third ebullated bed hydrogenation modification reaction stage U230 is higher than the operating pressure of the second ebullated bed hydrogenation modification reaction stage U220, and the third separated gas partially or completely enters the second ebullated bed hydrogenation modification reaction process UR220 by relying on its own pressure, and / or, a part of the third separated liquid enters the second ebullated bed hydrogenation modification reaction process UR220 by relying on its own pressure, and a part of the third separated liquid is used as the third separated liquid net product.

[0223] In the present invention, generally, the ebullated bed hydroprocessing reaction process R20 comprises two or more hydroprocessing reaction stages connected in series;

[0224] Two or more ebullated bed hydro-modification reaction stages connected in series realize an operation mode of increasing reaction temperature, and the average reaction temperature of the downstream ebullated bed hydro-modification reaction stage is 5 to 30°C higher than the average reaction temperature of the upstream ebullated bed hydro-modification reaction stage;

[0225] The average reaction temperature of the ebullated bed hydroprocessing reaction stage refers to the sum of the product of the arithmetic mean of the process fluid reaction temperature at the starting reaction of the catalyst bed layer and the process fluid reaction temperature at the end reaction of the catalyst bed layer in each reaction zone of the ebullated bed hydroprocessing reaction stage and the volume coefficient of the sub-reaction zone under normal operation;

[0226] The volume coefficient of a sub-reaction zone of the ebullated bed hydroprocessing reaction stage under normal operating conditions refers to the ratio of the volume of the sub-reaction zone to the total volume of all sub-reaction zones of the ebullated bed hydroprocessing reaction stage under normal operating conditions.

[0227] In the present invention, usually, in the generated oil fractionation process of the ebullated bed hydromodification reaction process R20, a heavy fraction KXL is separated from a hydrocarbon flow containing at least the final separation liquid, and part of the heavy fraction KXL is returned as a circulating reaction material KXL-R to any downstream ebullated bed hydromodification reaction stage of the ebullated bed hydromodification reaction process R20 for a cyclic hydrogenation reaction to reduce the aromatic carbon rate. The working mode can be selected from one or more of the following:

[0228] ① In the generated oil fractionation process of the ebullated bed hydromodification reaction process R20, a heavy fraction KXL1 mainly composed of hydrocarbons with a conventional boiling point of 280 to 520° C. is separated from the hydrocarbon flow containing at least the final separation liquid, and part of the heavy fraction KXL1 is returned as a circulating reaction material KXL1-R to any downstream hydromodification reaction process of the ebullated bed hydromodification reaction process R20 for a cyclic hydrogenation reaction to reduce the aromatic carbon rate;

[0229] ② In the generated oil fractionation process of the ebullated bed hydromodification reaction process R20, a heavy fraction KXL2 mainly composed of hydrocarbons with a conventional boiling point of 320 to 520° C. is separated from the hydrocarbon flow containing at least the final separation liquid, and a part of the heavy fraction KXL2 is returned as a circulating reaction material KXL2-R to any downstream hydromodification reaction process of the ebullated bed hydromodification reaction process R20 for a cyclic hydrogenation reaction to reduce the aromatic carbon rate;

[0230] ③ In the generated oil fractionation process of the ebullated bed hydromodification reaction process R20, a heavy fraction KXL3 mainly composed of hydrocarbons with a conventional boiling point of 410-520°C is separated from the hydrocarbon flow at least containing the final separation liquid, and part of the heavy fraction KXL3 is returned as the circulating reaction material KXL3-R to any downstream hydromodification reaction process of the ebullated bed hydromodification reaction process R20 for a circulating hydrogenation reaction to reduce the aromatic carbon rate.

[0231] In the present invention, usually, in the generated oil fractionation process of the ebullated bed hydromodification reaction process R20, a heavy fraction KYL is separated from a hydrocarbon stream containing at least the final separation liquid, and part of the heavy fraction KYL is returned as a circulating reaction material KYL-R to any downstream ebullated bed hydromodification reaction stage of the ebullated bed hydromodification reaction process R20 for a circulating hydrogenation reaction to reduce the aromatic carbon rate. The method for producing the circulating reaction material KYL-R can be selected from one or more of the following:

[0232] ① In the first hot low-pressure separation process based on the logistics of the final separation liquid, the logistics based on the final separation liquid is depressurized and separated into a first hot low-pressure separation gas and a first hot low-pressure separation liquid;

[0233] Part of the first hot low-pressure separation liquid is used as circulating reaction material KYL-R;

[0234] The operating conditions of the first hot low-pressure separation process are: temperature of 320-420°C and pressure of 1.5-4.0 MPa;

[0235] ② In the first hot low-pressure separation process based on the logistics of the final separation liquid, the logistics based on the final separation liquid is depressurized and separated into a first hot low-pressure separation gas and a first hot low-pressure separation liquid;

[0236] In the second hot low-pressure separation process, the first hot low-pressure separation liquid is depressurized and separated into a second hot low-pressure separation gas and a second hot low-pressure separation liquid;

[0237] Part of the second hot low-pressure separation liquid is used as circulating reaction material KYL-R;

[0238] The operating conditions of the first hot low-pressure separation process are: temperature of 320-420°C and pressure of 1.5-4.0 MPa;

[0239] The operating conditions of the second hot low-pressure separation process are: temperature of 320-420°C and pressure of 0.10-0.50 MPa.

[0240] The present invention generally separates the first fractionation tower bottom oil in the first fractionation tower system based on the logistics of the first hot low-pressure separation liquid and / or the second hot low-pressure separation liquid;

[0241] a first fractionation column system, with or without a sidestream distillation column;

[0242] A portion of the bottom oil of the first fractionation tower is used as circulating reaction material KYL-R;

[0243] The operating pressure of the distillation tower is 0.05~0.45MPa.

[0244] In the present invention, generally, in the second fractionation tower system, the second fractionation tower bottom oil is separated based on the logistics of the first fractionation tower bottom oil;

[0245] a second fractionator system, with or without a sidestream distillation column;

[0246] A portion of the bottom oil of the second fractionation tower is used as circulating reaction material KYL-R;

[0247] The second distillation tower is a vacuum distillation tower, and the operating pressure of the second distillation tower is -0.03 to -0.090 MPa.

[0248] In the present invention, usually, in the generated oil fractionation process of the ebullated bed hydromodification reaction process R20, a heavy fraction KEYL mainly composed of hydrocarbons with a conventional boiling point higher than 320° C. is separated from a hydrocarbon stream containing at least a final separation liquid, and a hydrocarbon stream based on part of the heavy fraction KEYL is returned as a circulating reaction material KEYL-R to an ebullated bed hydromodification reaction process of any downstream ebullated bed hydromodification reaction stage of the ebullated bed hydromodification reaction process R20 to carry out a circulating hydrogenation reaction for reducing the aromatic carbon rate;

[0249] The ratio of the weight flow rate of the circulating reaction material KEYL-R to the weight flow rate of the heavy fraction KEYL net product is 0.15 to 7.00;

[0250] The circulating reaction material KEYL-R is returned to the ebullated bed hydrogenation modification reaction process R20 for the cyclic hydrogenation reaction to reduce the aromatic carbon rate, so that the hydrogen supply index of the heavy fraction KEYL net product is increased by 0.5 to 12.0.

[0251] In the present invention, generally, the ratio of the weight flow rate of the circulating reaction material KEYL-R to the weight flow rate of the heavy fraction KEYL net product is 1.00 to 3.0;

[0252] The circulating reaction material KEYL-R is returned to the ebullated bed hydrogenation modification reaction process R20 for the cyclic hydrogenation reaction to reduce the aromatic carbon rate, so that the hydrogen supply index of the heavy fraction KEYL net product is increased by 1.5 to 6.0.

[0253] In the present invention, the ebullated bed hydro-modification reaction process R20 can use two or more parallel ebullated bed hydro-modification reaction series to process narrow fraction oils of different boiling ranges from coal direct liquefaction oil respectively;

[0254] Any ebullated bed hydro-modification reaction series, including two or more ebullated bed hydro-modification reaction stages of its feedstock oil liquid phase connected in series, the intermediate product separation liquid separated in any intermediate product separation process enters the ebullated bed hydro-modification reaction process of the adjacent downstream ebullated bed hydro-modification reaction stage;

[0255] In the gas-liquid separation process of the reaction effluent of any ebullated bed hydro-modification reaction stage, for the liquid phase separated from the ebullated bed hydro-modification reaction effluent of this stage, stripping the ammonia component therein with or without stripping hydrogen;

[0256] The average volumetric concentration of ammonia in the gas phase of any downstream ebullated bed hydroprocessing reaction process is lower than the average volumetric concentration of ammonia in the gas phase of the adjacent upstream ebullated bed hydroprocessing reaction process;

[0257] The aromatic carbon ratio of all hydrocarbons with a normal boiling point higher than 200°C in the reaction effluent of any downstream ebullated-bed hydromodification reaction process is lower than the aromatic carbon ratio of all hydrocarbons with a normal boiling point higher than 200°C in the reaction effluent of the adjacent upstream ebullated-bed hydromodification reaction process.

[0258] The present invention can adopt two parallel series to process the light hydrocarbon stream R20F11A and the medium hydrocarbon stream R20F12A respectively.

[0259] The light hydrocarbon stream R20F11A from coal direct liquefaction oil is mainly composed of hydrocarbons with a conventional boiling point below 280°C;

[0260] The medium hydrocarbon stream R20F12A from the oil generated from direct coal liquefaction is mainly composed of hydrocarbons with a conventional boiling point of 280 to 470°C.

[0261] The present invention can adopt two parallel series to process the light hydrocarbon stream R20F11B and the medium hydrocarbon stream R20F12B of the oil produced by direct coal liquefaction respectively;

[0262] The light hydrocarbon stream R20F11B from the oil produced by direct coal liquefaction is mainly composed of hydrocarbons with a conventional boiling point below 280°C;

[0263] The medium hydrocarbon stream R20F12B from the oil generated from direct coal liquefaction is mainly composed of hydrocarbons with a conventional boiling point of 280 to 520°C.

[0264] The present invention can adopt three parallel series to process light hydrocarbon stream R20F11C from coal direct liquefaction oil, medium hydrocarbon stream R20F12C from coal direct liquefaction oil, and heavy hydrocarbon stream R20F13C from coal direct liquefaction oil respectively;

[0265] The light hydrocarbon stream R20F11C from the oil produced by direct coal liquefaction is mainly composed of hydrocarbons with a conventional boiling point below 280°C;

[0266] The medium hydrocarbon stream R20F12C from the oil produced by direct coal liquefaction is mainly composed of hydrocarbons with a conventional boiling point of 280 to 400°C;

[0267] The heavy hydrocarbon stream R20F13C produced from direct coal liquefaction is mainly composed of hydrocarbons with a conventional boiling point of 400 to 525°C.

[0268] In the present invention, generally, when the ebullated bed hydromodification reaction process R20 processes hydrocarbons mainly composed of conventional boiling points below 320°C, the ebullated bed hydromodification reaction process R20 and the hydromodification reaction process R30 are carried out in series, the reaction effluent of the ebullated bed hydromodification reaction process R20 enters the hydromodification reaction process R30, and / or the hot high-pressure separation gas separated from the reaction effluent of the ebullated bed hydromodification reaction process R20 in its hot high-pressure separation process enters the hydromodification reaction process R30, and / or the hot high-pressure separation liquid separated from the reaction effluent of the ebullated bed hydromodification reaction process R20 in its hot high-pressure separation process, and the hydrocarbon oil mainly composed of hydrocarbons with conventional boiling points below 250°C separated based on the hot high-pressure separation liquid enters the hydromodification reaction process R30.

[0269] In the present invention, generally, the ebullated bed hydroprocessing reaction process R20 comprises two or more ebullated bed hydroprocessing reaction stages connected in series;

[0270] The operating pressure of the ebullated bed hydrogenation modification reaction stage gradually decreases along the process. The operating pressure of the gas-liquid separation process of the reaction product of the upstream ebullated bed hydrogenation modification reaction stage is higher than the operating pressure of the adjacent downstream ebullated bed hydrogenation modification reaction stage. The reaction zone of the downstream ebullated bed hydrogenation modification reaction process and the reaction zone of the upstream ebullated bed hydrogenation modification reaction process are essentially interconnected liquid phase reaction zones of the interconnector type. The liquid level control method of the intermediate gas-liquid separation process adopts the control method of the communicating vessel for the upstream expanded bed staged series hydrogenation reaction process of hydrocarbon materials of Application No. 202310229274.7.

[0271] The present invention, generally, in the final gas-liquid separation process US290, the gas-liquid mixed phase flow of the final ebullating bed hydro-modification reaction effluent is separated into a final separation gas and a final separation liquid;

[0272] In the warm and high pressure separation process, the logistics based on the final separation gas is separated into warm and high pressure gas and warm and high pressure oil. The operating conditions of the warm and high pressure separation process are: temperature of 160-280°C and pressure of 10.0-25.0MPa;

[0273] The degassed oil stream obtained after the high temperature oil fractionation stream is depressurized and degassed enters the fractionation tower of the final stage ebullating bed hydro-modification reaction to generate the oil fractionation process;

[0274] In the hot low-pressure separation process of the final separation liquid, the logistics of the final separation liquid is depressurized and separated into hot low-pressure separation gas and hot low-pressure separation liquid. The operating conditions of the hot low-pressure separation process of the final separation liquid are: temperature of 320-400°C and pressure of 0.40-4.0MPa;

[0275] The hot low-pressure separation liquid is fed into a fractionation tower for the fractionation of the oil produced by the final ebullating bed hydro-modification reaction;

[0276] In the temperature and low pressure separation process, the hot low pressure separation gas is condensed and separated into temperature and low pressure gas and temperature and low pressure oil. The operating conditions of the temperature and low pressure separation process are: temperature 150-300℃, pressure 0.40-4.0MPa;

[0277] The logistics based on low temperature oil separation enters the distillation tower of the final boiling bed hydro-modification reaction to generate oil for the distillation process.

[0278] In the present invention, generally, in the cold high-pressure separation process, the cold high-fraction gas and the cold high-fraction oil are separated after the flow of the warm high-fraction gas is condensed. The operating conditions of the cold high-pressure separation process are: temperature of 20 to 80° C. and pressure of 10.0 to 25.0 MPa;

[0279] In the cold low-pressure separation process, the cold high-fraction oil-based logistics is depressurized and separated into cold low-fraction gas and cold low-fraction oil. The operating conditions of the cold low-pressure separation process are: temperature of 20-80°C and pressure of 0.4-4.0MPa;

[0280] The logistics based on the cold low-fraction oil enters the distillation tower of the final boiling bed hydro-modification reaction to generate the oil in the distillation process.

[0281] In the present invention, generally, in the ebullating bed hydrogenation modification reaction process R20, in the intermediate separation gas cooling high pressure separation process, the intermediate separation gas is separated into the intermediate separation gas cooling high fraction gas and the intermediate separation gas cooling high fraction oil;

[0282] In the cold high-pressure separation process, cold high-fraction gas and cold high-fraction oil are separated after the logistics of the final separation gas is condensed;

[0283] At least a portion of the intermediate separated gas cooled high-fraction gas and / or at least a portion of the intermediate separated gas cooled high-fraction gas and / or the cold high-fraction gas enters the cold high-fraction gas of the ebullated bed hydrogenation modification reaction process R20, and enters the ebullated bed hydrogenation modification reaction process of any ebullated bed hydrogenation modification reaction stage of the ebullated bed hydrogenation modification reaction process R20.

[0284] In the present invention, in the ebullating bed hydrogenation modification reaction process R20, the intermediate separation gas can be separated into intermediate separation gas cooling high-fraction gas and intermediate separation gas cooling high-fraction oil in the intermediate separation gas cooling high-fraction separation process;

[0285] In the cold high-pressure separation process, cold high-fraction gas and cold high-fraction oil are separated after the logistics of the final separation gas is condensed;

[0286] At least a portion of the intermediate separated gas cooled high fraction gas and the final stage cooled high fraction gas enters the ebullated bed hydro-modification reaction process of any ebullated bed hydro-modification reaction stage of the ebullated bed hydro-modification reaction process R20;

[0287] The intermediate separated gas cooled high-fraction gas and / or the final stage cooled high-fraction gas enters the coal hydrogenation direct liquefaction reaction process R10 as exhaust gas and is used as hydrogen raw material.

[0288] In the present invention, in the ebullating bed hydrogenation modification reaction process R20, the intermediate separation gas can be separated into intermediate separation gas cooling high-fraction gas and intermediate separation gas cooling high-fraction oil in the intermediate separation gas cooling high-fraction separation process;

[0289] In the cold high-pressure separation process, cold high-fraction gas and cold high-fraction oil are separated after the logistics of the final separation gas is condensed;

[0290] At least a portion of the intermediate separated gas cooled high fraction gas and the final stage cooled high fraction gas enters the ebullated bed hydro-modification reaction process of any ebullated bed hydro-modification reaction stage of the ebullated bed hydro-modification reaction process R20;

[0291] At least a portion of the intermediate separated gas cooled high-fraction gas and / or at least a portion of the final stage cooled high-fraction gas is used as exhaust gas to enter the membrane separation system of the cooled high-fraction gas of the coal hydrogenation direct liquefaction reaction process R10 and be used as membrane separation feed gas.

[0292] In the present invention, generally, in the ebullated bed hydroprocessing reaction process R20, at least a portion of the new hydrogen enters the ebullated bed hydroprocessing reaction process of the most downstream ebullated bed hydroprocessing reaction stage.

[0293] In the present invention, generally, in the generated oil fractionation process of the ebullated bed hydro-modification reaction process R20, a hydrogen-donating solvent oil DS mainly composed of hydrocarbons having a conventional boiling point between 200 and 550° C. is separated from a hydrocarbon stream containing at least a final separation liquid;

[0294] Coal slurry DS-TM is prepared from hydrogen-donating solvent oil DS and coal powder;

[0295] The material based on coal slurry DS-TM is converted into coal hydrogenation direct liquefaction reaction effluent R10P through coal hydrogenation direct liquefaction reaction process R10;

[0296] Separating the coal hydrogenation direct liquefaction reaction effluent R10P to obtain the coal direct liquefaction product oil distillate R10P-SP;

[0297] The stream based on distillate oil R10P-SP is used as feedstock oil R20F for the ebullated-bed hydro-modification reaction.

[0298] The present invention, generally, in the fractionation process of the product oil in the ebullated bed hydro-modification reaction process R20, a fraction R20P-SP1 mainly composed of hydrocarbons with a conventional boiling point between 200 and 350°C and a heavy fraction R20P-SP2 composed of hydrocarbons with a conventional boiling point higher than 320°C are separated from a hydrocarbon stream containing at least a final separation liquid;

[0299] Part of the material based on fraction R20P-SP1 is used as feedstock for the hydro-upgrading reaction process R30;

[0300] A material based partly on fraction R20P-SP1 and at least partly on heavy fraction R20P-SP2, used alone or in combination as hydrogen supply solvent oil DS;

[0301] Coal slurry DS-TM is prepared from hydrogen-donating solvent oil DS and coal powder;

[0302] The material based on coal slurry DS-TM is converted into coal hydrogenation direct liquefaction reaction effluent R10P through coal hydrogenation direct liquefaction reaction process R10;

[0303] Separating the coal hydrogenation direct liquefaction reaction effluent R10P to obtain the coal direct liquefaction product oil distillate R10P-SP;

[0304] The distillate oil R10P-SP was used as the feed oil R20F for the ebullated bed hydro-modification reaction.

[0305] In the present invention, in the ebullated bed hydrogenation modification reaction process R20, any ebullated bed hydrogenation modification reaction process can be a slurry bed-ebullated bed combined hydrogenation modification reaction mode using a slurry bed hydrogenation catalyst at the same time.

[0306] In the present invention, generally, the feedstock oil R20F of the ebullated bed hydro-modification reaction process R20 has an organic nitrogen content of 0.20 to 1.5 wt % and an organic oxygen content of 0.4 to 9.0 wt %.

[0307] In the present invention, generally, in the produced oil fractionation process of the ebullated bed hydro-modification reaction process R20, a first heavy fraction KEYL1 mainly composed of hydrocarbons with a normal boiling point of 320 to 470° C. and a second heavy fraction KEYL2 mainly composed of hydrocarbons with a normal boiling point of >470° C. are separated from a hydrocarbon stream containing at least a final separation liquid;

[0308] Based on the hydrocarbon-containing flow of part of the second heavy fraction KEYL2 as the circulating reaction material KEYL2-R, the circulating reaction material is returned to any downstream boiling bed hydro-modification reaction stage U2-77 of the boiling bed hydro-modification reaction process R20 to carry out a circulating hydrogenation reaction to reduce the aromatic carbon rate;

[0309] Based on a part of the hydrocarbon-containing flow of the first heavy fraction KEYL1 as a circulating reaction material KEYL1-R, the hydrocarbon-containing flow is returned to any downstream ebullated bed hydro-modification reaction stage U2-88 of the ebullated bed hydro-modification reaction process R20 to carry out a circulating hydrogenation reaction for reducing the aromatic carbon rate;

[0310] The process flow direction of gradually increasing the hydrogenation depth of the feedstock R20F in the ebullated bed hydrogenation modification reaction process R20 is forward flow, and the ebullated bed hydrogenation modification reaction stage U2-88 is located downstream of the ebullated bed hydrogenation modification reaction stage U2-77. DETAILED DESCRIPTION

[0311] Table 9 is a summary of the boiling points, freezing points and densities of typical aromatic components and their comparative hydrides.

[0312] The data listed in Table 9 are from document A01: ① Publication name: "Coal Tar Chemical Engineering", pages 274 to 301; ② Book code for retrieval: ISBN code: 7-5024-2975-1; ③ Editor: Xiao Ruihua; ④ Publisher: Metallurgical Industry Press.

[0313] For coal direct liquefaction oil containing multiple hydrocarbon components with different boiling points, the distillation range of narrow fractions of aromatic hydrocarbons with different ring numbers can be determined based on the data in Table 1, or the maximum number of aromatic rings of hydrocarbon components that may exist in different boiling ranges in the coal direct liquefaction oil can be determined.

[0314] It can be seen from Table 9 that the hydrocarbon components with conventional boiling points below 200°C basically do not contain hydrogen-donating hydrocarbons with a double ring structure.

[0315] As can be seen from Table 9, the conventional boiling point of 350°C is roughly the distillation dividing point between three-ring aromatic hydrocarbons and four-ring aromatic hydrocarbons.

[0316] Table 9 Summary of boiling points, freezing points and densities of typical aromatic components and their comparative hydrides

[0317]

[0318] The hydrogen-donating hydrocarbons described in the present invention refer to partially saturated bicyclic aromatic hydrocarbons and partially saturated polycyclic aromatic hydrocarbons.

[0319] The hydrogen-donating hydrocarbons mentioned in this article refer to hydrocarbon components that have the function of donating hydrogen in the direct oil production process of coal hydrogenation. Hydrogen-donating hydrocarbons include partially saturated dicyclic aromatic hydrocarbons and partially saturated polycyclic aromatic hydrocarbons, which are ideal components of hydrogen-donating solvent oil used in the direct liquefaction process of coal hydrogenation. Among hydrogen-donating hydrocarbons, the hydrogen-donating rate of dicyclic aromatic hydrocarbons is greater than that of tetracyclic aromatic hydrocarbons. The hydrogen-donating rate of dicyclic aromatic hydrocarbons is higher or lower than that of dicyclic aromatic hydrocarbons. Experiments have shown that although polycyclic aromatic hydrocarbons have no hydrogen-donating capacity, they have the ability to transfer hydrogen.

[0320] The hydrogen-donating solvent oil described herein refers to a hydrocarbon oil rich in hydrogen-donating hydrocarbons that has the ability to donate hydrogen in the R10 coal hydrogenation direct liquefaction reaction process.

[0321] The coal hydrogenation direct liquefaction reaction process R10 of the present invention refers to a method for directly liquefying coal by hydrogenation in the presence of solvent oil. There are many different processes according to different solvent oils, catalysts and hydrogenation process conditions, such as the following processes:

[0322] ①Solvent hydrogenation extraction liquefaction method: such as solvent refined coal method I and II (SRC-I and SRC-II), hydrogen supply solvent oil method EDS, Japan New Energy Development Organization liquefaction method (NEDOL), etc., using hydrogen, but the pressure is not too high, solvent oil has a significant effect;

[0323] ② High-pressure catalytic hydrogenation method: such as Germany's new and old liquefaction processes (IG and NewIG) and the United States' hydrogen coal method (H-Coal) belong to this category;

[0324] ③ Co-processing of coal and residual oil: residual oil is used as solvent oil and passes through the reactor together with coal at one time without circulating oil; the residual oil is hydrocracking to convert into light oil at the same time. The United States, Canada, Germany and the Soviet Union have different processes;

[0325] ④ China Shenhua Group's coal direct liquefaction method;

[0326] ⑤ Patent CN100547055C states a hot-melt catalytic method for producing liquid fuel from lignite, which belongs to the process of direct liquefaction of lignite by medium-pressure hydrogenation, including two processes: coal hydrogenation direct liquefaction reaction process R10 and coal direct liquefaction oil hydrogenation stabilization process. In order to improve the conversion rate of coal direct liquefaction and realize the entry of coal raw materials into the coal hydrogenation direct liquefaction reactor, coal is usually made into coal powder before entering the coal hydrogenation direct liquefaction reactor, and is mixed with solvent oil with good hydrogen supply capacity to form oil-coal slurry, which enters the coal hydrogenation direct liquefaction reactor after pressurization and heating.

[0327] In the process of direct liquefaction of coal by hydrogenation, no matter what kind of direct liquefaction process of coal by hydrogenation, the goal is to obtain oil products, the function pursued is "coal to oil", and the chemical change that must exist is "coal hydrogenation". The common characteristics of this type of technology at present are the use of solvent oil and catalyst. The conventional boiling range of solvent oil is generally 195-530°C, and most of them are 195-450°C. Most of the solvent oil is distilled oil or its hydrogenation stabilized oil. Most of the aromatic hydrocarbons contained are aromatic hydrocarbons with 2-4 ring structures, and contain a small amount of 5-ring structure aromatic hydrocarbons. Therefore, no matter what kind of direct liquefaction process of coal by hydrogenation, the effluent oil or coal direct liquefaction oil (usually coal hydrogenation direct liquefaction light oil) or coal direct liquefaction oil stabilized oil produced by it, as long as its composition has the raw material composition characteristics described in the present invention, can be processed using the method of the present invention.

[0328] The coal hydrogenation direct liquefaction reaction process R10, macroscopically speaking, is both a hydrogenation direct liquefaction reaction process of coal carried by coal slurry, a hydrogenation process (or dehydrogenation process) of the hydrogen-donating solvent oil carried by the coal slurry, and a hydrocracking reaction process in which the carbon number of hydrocarbon components (such as hydrocarbons with a conventional boiling point higher than 290°C) in the net produced oil from coal hydrogenation direct liquefaction is reduced.

[0329] The coal direct liquefaction oil refers to the distilled oil obtained by separating the oil generated by the coal hydrogenation direct liquefaction reaction. It exists in the effluent of the coal hydrogenation direct liquefaction reaction. It is a comprehensive reaction product based on the hydrogen supply solvent oil, the coal consumed in the reaction and the hydrogen transferred by the reaction. It is classified according to the number of the most aromatic ring structures, and it includes a conventional boiling point <195°C fraction segment (the most aromatic ring aromatics are monocyclic aromatics), a 195°C~280°C fraction segment (the most aromatic ring aromatics are dicyclic aromatics), and a 280°C~540°C fraction segment (the most aromatic ring aromatics are polycyclic aromatics).

[0330] The conventional boiling point <195°C fraction of coal direct liquefaction oil or its hydrogenation modification reaction product oil is usually not used as a candidate coal slurry solvent oil or hydrogen supply solvent oil for the coal hydrogenation direct liquefaction reaction process R10, because the proportion of R10 modified fraction oil evaporating into the gas phase in the coal hydrogenation direct liquefaction reaction process is too high. The conventional boiling point <195°C fraction of coal direct liquefaction oil basically does not contain aromatic rings with two ring structures such as tetralin, dilin, and naphthalene, and therefore does not have the raw material aromatic ring structure for hydrogenation to stably generate hydrogen supply hydrocarbons.

[0331] The normal boiling point of coal direct liquefaction oil is in the 280℃~540℃ fraction range, and the aromatic hydrocarbons it contains are mainly polycyclic aromatic hydrocarbons.

[0332] The normal boiling point of coal direct liquefaction oil is 280℃~370℃ fraction, containing tricyclic aromatic hydrocarbons.

[0333] The normal boiling point of coal direct liquefaction oil is 370℃~470℃ fraction, containing tetracyclic aromatic hydrocarbons.

[0334] The normal boiling point of coal direct liquefaction oil is 470℃~525℃ fraction, containing pentacyclic aromatic hydrocarbons.

[0335] The normal boiling point of coal direct liquefaction oil is 525℃~550℃ fraction, containing six-ring aromatic hydrocarbons.

[0336] Usually, coal direct liquefaction oil contains a certain amount of aromatic hydrocarbons with more than five rings and gums, which exist in the fractions with conventional boiling points > 470°C. In order to prevent the deterioration of the properties of the R20 feedstock oil in the hydrogenation modification reaction process, their content is generally controlled at a lower value, usually 4 to 9 weight % of the total feedstock oil. The presence of these substances will accelerate the coking rate of the hydrogenation stable catalyst in the R20 hydrogenation modification reaction process.

[0337] After the coal hydrogenation direct liquefaction reaction process R10 operates normally, the hydrogen supply solvent oil is usually the hydrogenated stabilized oil of the coal direct liquefaction oil (usually the distillate oil with the conventional boiling range higher than 200°C) produced by the coal hydrogenation direct liquefaction reaction process R10. The main goal of the coal direct liquefaction oil hydrogenation modification reaction process R20 is to produce the slurry solvent oil for the coal slurry of the coal hydrogenation direct liquefaction reaction raw material. Specifically, it is to increase the content of "components with good hydrogen supply function" in the oil product, such as increasing the content of cycloalkylbenzene and dicycloalkylbenzene components. Based on the fact that the coal direct liquefaction oil contains a large amount of dicyclic aromatic hydrocarbons and a large amount of polycyclic aromatic hydrocarbons, the coal direct liquefaction oil hydrogenation modification reaction process R20 is a "moderate aromatic hydrogenation saturation reaction process" of dicyclic aromatic hydrocarbons and polycyclic aromatic hydrocarbons.

[0338] The ultimate goal of the coal hydrogenation direct liquefaction reaction process R10 is to produce oil products for external supply. Usually, the hydrogenated stable oil produced by the coal direct liquefaction oil hydrogenation modification reaction process R20 is divided into two parts: one part is used as the hydrogen supply solvent oil for the coal hydrogenation direct liquefaction reaction process R10, and the other part is used as the external discharge oil of the coal hydrogenation direct liquefaction oil production process. Usually, at least a part of the coal hydrogenation direct liquefaction light oil produced by the coal hydrogenation direct liquefaction reaction process R10 is used as the external discharge oil A of the coal-to-oil process, and the rest of the coal direct liquefaction oil is used as the raw oil of the coal hydrogenation modification reaction process R20 to produce the hydrogen supply solvent oil and external discharge oil B for the coal hydrogenation direct liquefaction reaction process R10. At this time, there are two external discharge oils, A and B. The final destination of the two external discharge oils A and B is usually to produce high-quality oil products such as diesel fraction and naphtha fraction through the hydrogenation quality improvement reaction process R30.

[0339] The coal direct liquefaction oil mentioned in the present invention refers to the distillate oil obtained by separating the reaction effluent of the coal hydrogenation direct liquefaction reaction process R10, that is, the condensed oil product based on the condensation process of the flash steam of the oil generated by the coal hydrogenation direct liquefaction reaction, which can be a mixture of one, two or more oil products with different properties.

[0340] The document A01 "Coal Direct Liquefaction Technology and Engineering" records a large amount of coal direct liquefaction oil downflow fixed bed hydro-modification reaction test data. Some other documents have also published similar test research data, but these data cannot characterize the effect of the ebullated bed hydro-modification reaction. Using these data to guide the device design will lead to huge deviations, resulting in poor operation results of the ebullated bed hydro-modification stable industrial device, that is, the aromatic saturation depth is seriously insufficient. The following analysis points out the insurmountable shortcomings of the ebullated bed hydro-modification reaction mode:

[0341] ① First, in the ebullated bed hydroprocessing reaction zone, there are short-circuit channels between the catalyst particles, and some crude oil passes through the ebullated bed reaction zone without contact or with less contact with the hydroprocessing stabilization catalyst, forming a short-circuit, that is, the average catalyst reaction time of the crude oil is not equal;

[0342] However, the downflow fixed bed hydro-modification reaction zone does not have the above problems;

[0343] ②Secondly, in the ebullated bed hydroprocessing reaction zone, the cumulative concentration of ammonia produced during the reaction process becomes higher and higher as the reaction depth increases. Since a high hydrogen-to-oil ratio is not allowed, a high concentration of ammonia exists in the downstream section of the ebullated bed hydroprocessing reaction zone. The high concentration of ammonia forms a strong adsorption on the active surface of the ebullated bed hydroprocessing catalyst, thereby forming a strong spatial shielding effect on the adsorption of the feedstock oil on the active surface of the ebullated bed hydroprocessing catalyst, which greatly inhibits the activity of the ebullated bed hydroprocessing catalyst, that is, greatly reduces the hydroprocessing reaction rate and the hydroprocessing reaction depth;

[0344] The downflow fixed bed hydroprocessing reaction zone can use a very high hydrogen-to-oil ratio of 600 to 2000 (3 to 10 times the hydrogen-to-oil ratio at the outlet of the boiling bed hydroprocessing reaction zone), and the spatial shielding effect on the active surface of the hydrogenation stable catalyst caused by the above-mentioned ammonia adsorption can be greatly reduced.

[0345] Since the R10 raw material coal slurry in the coal hydrogenation direct liquefaction reaction process requires a suitable viscosity, it is usually impossible to use only heavy components (hydrocarbons with a conventional boiling point of >320°C or hydrocarbons with a conventional boiling point of >290°C) hydrogen supply solvent oil to prepare the coal slurry. It is necessary to use a portion of hydrocarbons with a conventional boiling point of <320°C or hydrocarbons with a conventional boiling point of <290°C, such as hydrogen supply solvent oil with a conventional boiling point of 250-320°C. Usually, this will inevitably lead to the hydrocarbons with a conventional boiling point of 250-320°C from the coal hydrogenation direct liquefaction product oil. Regarding the problem of joint processing of conventional hydrocarbons with a boiling point of 320-520°C, when the amount of hydrogen solvent oil for the overall coal slurry is small, in order to simplify the process and reduce investment, a mixed processing of conventional hydrocarbons with a boiling point of 250-320°C and conventional hydrocarbons with a boiling point of 320-520°C can be adopted. Of course, when the amount of hydrogen solvent oil for the overall coal slurry is large, conventional hydrocarbons with a boiling point of 250-320°C and conventional hydrocarbons with a boiling point of 320-520°C can be used independently for hydrogenation modification reactions.

[0346] The same-path mode of boiling bed hydrogenation modification reaction of full-fraction coal direct liquefaction oil or the same-path mode of stable hydrogenation in a downflow fixed bed recorded in document A01 "Coal Direct Liquefaction Technology and Engineering" is actually a same-path mixed hydrogenation modification reaction of 2-ring aromatics, 3-ring aromatics, 4-ring aromatics and even 5-ring aromatics. It is inevitable that the optimal hydrogenation modification reaction depth cannot be achieved simultaneously for aromatics with different ring numbers, and there are the following major disadvantages:

[0347] ① It is impossible to achieve universal optimization of the structure of the hydrogenation-stabilized catalyst carrier, and the reaction efficiency of the hydrogenation-stabilized catalyst is low

[0348] Because the molecular sizes of 2-ring carrier structure aromatics, 3-ring carrier structure aromatics, 4-ring carrier structure aromatics and even 5-ring carrier structure aromatics vary greatly; the pore diameter of the hydrogenation stable catalyst suitable for the diffusion of 2-ring carrier structure aromatics must be small, so as to form a high catalyst specific surface area and improve the catalyst activity; the pore diameter of the hydrogenation stable catalyst suitable for the diffusion of 3-ring carrier structure aromatics and 4-ring carrier structure aromatics must be of medium size, and the pore diameter of the hydrogenation stable catalyst suitable for the diffusion of 5-ring carrier structure aromatics must be of large size;

[0349] In order to realize the joint processing of 2-ring carrier structure aromatics, 3-ring carrier structure aromatics, 4-ring carrier structure aromatics and even 5-ring carrier structure aromatics, the boiling bed hydrogenation stable catalyst must be arranged with a variety of corresponding pore carrier structures, which makes it difficult for large molecules to diffuse in small-sized pores and seriously occupies small-sized pores, affecting the diffusion of small-molecule raw materials and products, and reducing the reaction rate of small-molecule raw materials; at the same time, large molecules diffuse rapidly in large-sized pores, preferentially occupy the active surface of large-sized pores, affecting the adsorption of large-sized molecules, reducing the reaction rate of large-molecule raw materials, and making their hydrogenation modification reaction depth much lower than the average hydrogenation modification reaction depth of the overall crude oil;

[0350] ② It is impossible to achieve the universal optimization of the active metal component ratio of the ebullating bed hydrogenation stable catalyst, and the catalyst activity is not ideal

[0351] Because the molecular size, donor properties, and super-delocalization energy of aromatic carbon in the structure of 2-ring aromatics, 3-ring aromatics, 4-ring aromatics, and even 5-ring aromatics vary greatly, the optimal active metal component ratio of catalysts for hydrogenation stabilization of aromatics with different ring numbers must be different.

[0352] ③ It is impossible to achieve universal optimization of the reaction hydrogen partial pressure

[0353] The suitable hydrogen partial pressure for hydrogenation saturation reaction of 2-ring aromatics, 3-ring aromatics, 4-ring aromatics and even 5-ring aromatics varies greatly. Usually, the suitable hydrogen partial pressure for hydrogenation saturation reaction of 2-ring aromatics is about 6.0-10.0 MPa, the suitable hydrogen partial pressure for hydrogenation saturation reaction of 3-ring aromatics and 4-ring aromatics is about 11.0-14.0 MPa, and the suitable hydrogen partial pressure for hydrogenation saturation reaction of 5-ring aromatics is about 15.0-18.0 MPa.

[0354] In this way, the hydrogen partial pressure of the reaction of hydrogenation saturation of aromatics is suitable for small molecular aromatics, but the hydrogen partial pressure of the reaction is too low for large molecular aromatics, so the reaction rate is too low, the limit hydrogenation saturation depth will be reduced, and the reasonable hydrogenation stability depth of large molecular aromatics cannot be achieved, and the expected increase in the hydrogen supply index of large molecular aromatics cannot be achieved;

[0355] Similarly, for large molecular aromatics, the appropriate hydrogen partial pressure for aromatic hydrogenation saturation reaction is too high for small molecular aromatics, so the reaction rate is too fast and the ultimate hydrogenation saturation depth will exceed expectations, causing small molecular aromatics to form excessive hydrogenation saturation and reduce the hydrogen supply index. For the goal of improving the hydrogen supply index of the overall hydrogen supply solvent oil, the two have a partial offsetting effect.

[0356] ④ It is impossible to achieve universal optimization of reaction temperature

[0357] The suitable aromatic hydrogenation saturation reaction temperatures for 2-ring aromatics, 3-ring aromatics, 4-ring aromatics and even 5-ring aromatics are very different;

[0358] When the reaction hydrogen partial pressure is about 6.0-9.0 MPa, the suitable aromatic hydrogenation saturation reaction temperature for 2-ring aromatics is usually about 250-330°C;

[0359] When the reaction hydrogen partial pressure is about 9.0-12.0 MPa, the suitable aromatic hydrogenation saturation reaction temperature of 3-ring aromatics is usually about 300-360°C;

[0360] When the reaction hydrogen partial pressure is about 12.0-14.0 MPa, the saturation reaction temperature of the hydrogenation of 4-ring aromatics is usually about 330-370°C;

[0361] When the reaction hydrogen partial pressure is about 14.0-18.0 MPa, the saturation reaction temperature of the aromatic hydrogenation of 5-ring aromatics is usually about 340-410°C;

[0362] In this way, the suitable aromatic hydrogenation saturation reaction temperature for small molecular aromatics is too low for large molecular aromatics, so the reaction rate is too low and the limit hydrogenation saturation depth is reduced. In this way, the suitable aromatic hydrogenation saturation reaction temperature conditions for small molecular aromatics cannot achieve the reasonable hydrogenation stability depth of large molecular aromatics, and cannot achieve the expected increase in the hydrogen supply index of large molecular aromatics.

[0363] Similarly, the appropriate hydrogenation saturation reaction temperature for large molecular aromatics is too high for small molecular aromatics, so the reaction speed is too fast, the ultimate hydrogenation saturation depth will exceed expectations, and the reaction heat will be released in a concentrated manner, causing the small molecular aromatics to be over-hydrogenated and saturated, thereby reducing the hydrogen supply index. For the goal of improving the hydrogen supply index of the overall hydrogen supply solvent oil, the two have a partial offsetting effect;

[0364] ⑤ It is impossible to achieve universal optimization of reaction time

[0365] Under the same conditions of hydrogen partial pressure, reaction temperature, catalyst structure, and catalyst active metal component ratio, the suitable reaction times of 2-ring aromatics, 3-ring aromatics, 4-ring aromatics, and even 5-ring aromatics are very different.

[0366] In this way, the appropriate aromatic hydrogenation saturation reaction time for small molecular aromatics is too short for large molecular aromatics, so the hydrogenation depth is too low and the limit hydrogenation saturation depth is too low, which makes it impossible to achieve a reasonable hydrogenation stability depth for large molecular aromatics and the expected increase in the hydrogen supply index for large molecular aromatics.

[0367] Similarly, the appropriate hydrogenation saturation reaction time for large molecular aromatics is too long for small molecular aromatics, so the reaction depth is too deep and the limit hydrogenation saturation depth will exceed expectations, causing the small molecular aromatics to form excessive hydrogenation saturation and reduce the hydrogen supply index, which in turn reduces the increase in the hydrogen supply index of small molecular aromatics. For the goal of increasing the hydrogen supply index of the overall hydrogen supply solvent oil, the two have a partial offsetting effect.

[0368] Document A01 records some of the existing coal hydrogenation direct liquefaction processes, the hydrogenation stabilization process of coal direct liquefaction oil to produce hydrogen supply solvent oil, and the hydrogenation modification process of coal direct liquefaction oil, including raw material properties, hydrogenation stabilization catalysts, reaction conditions, product distribution, product properties, and industrial unit operation data: Document A02 ① Publication name: "Coal Direct Liquefaction Technology and Engineering", pages 98 to 456; ② Book code for retrieval: ISBN code: 978-7-03-043082-3; ③ Editors: Wu Xiuzhang, Shu Geping, Li Kejian, Xie Shunmin; ④ Publisher: Science Press.

[0369] For the distribution of solid content in coal direct liquefaction oil, please refer to document A02: ① Publication name: Clean Coal Technology (published in November 2015, Vol. 21, No. 6), pages 63 to 66, page 71; ② Article name: The influence and prevention of coal powder drift on Shenhua coal direct liquefaction process; ③ Authors: Wang Xiwu, Liu Dongming, An Liang, Yang Dong, this document describes the pollution of coal powder drift on the top gas phase of the atmospheric distillation tower of Shenhua coal direct liquefaction unit and the oil generated by coal hydrogenation direct liquefaction (fractionation tower distillate), and records the technical The solid content of the narrow fractions of the coal direct liquefaction oil of each line of the improved Shenhua coal direct liquefaction unit is shown in Table 10. Document A02 records the flow rate of the narrow fractions of the coal direct liquefaction oil of the Shenhua coal direct liquefaction unit, which is summarized in Table 11. It is calculated that the overall solid weight content of the coal direct liquefaction oil of the Shenhua coal direct liquefaction unit after the technical improvement is about 0.024 weight%, i.e. 240 ppm. For the hydrogenation and modification reactor system of the coal direct liquefaction oil with such a high coal powder content, only an ebullating bed reactor system can be used to prevent potential bed clogging problems caused by solid particles.

[0370] Table 10 is a table showing the solid content of the narrow fraction of coal direct liquefaction oil from the Shenhua coal direct liquefaction unit.

[0371] Table 10 Solid content of narrow fractions of coal direct liquefaction oil from Shenhua coal direct liquefaction unit

[0372]

[0373] Table 11 Solid content of narrow fractions and overall liquefied oil from coal direct liquefaction of Shenhua coal direct liquefaction unit

[0374]

[0375] Usually, the weight flow rate of the feedstock R30F in the hydrogenation and upgrading reaction process accounts for 25-40% of the weight flow rate of conventional liquid hydrocarbons in the whole fraction distillate of the coal hydrogenation direct liquefaction product oil. If the distillation range separated in the fractionation process of the coal hydrogenation direct liquefaction product oil is suitable for being used as the light distillate oil KEY-1 with a conventional boiling point of <320°C or <290°C as the feedstock R30 in the hydrogenation and upgrading reaction process, the solid weight content is very low, for example, less than 20ppm, and the diameter of the solid particles contained is less than that of the hydrogenation catalyst bed in the downflow fixed bed hydrogenation reaction process. The interception particle diameter, that is, the solid particles can smoothly pass through the downflow fixed bed hydrogenation catalyst bed, then the coal direct liquefaction oil KEY-1 can directly enter the coal direct liquefaction oil hydrogenation upgrading reaction process R30 to produce deeply hydrogenated modified oil products without going through the hydrogenation modification reaction process R20. In this way, the processing volume of the hydrogenation modification reaction process R20 can be significantly reduced, the investment and energy consumption of the hydrogenation modification reaction process R20 can be reduced, and it is also beneficial to narrow the distillation range of the raw oil in the hydrogenation modification reaction process R20, which is beneficial to the optimization of the operating conditions of the hydrogenation modification reaction process R20.

[0376] For the three narrow-fraction oil products of the liquefied oil produced by Shenhua's coal direct liquefaction unit, the main function of the hydrogenation stabilization unit is to provide qualified hydrogen supply solvent oil for the coal hydrogenation direct liquefaction unit. By pre-hydrogenating the coal direct liquefaction oil in all fractions, a relatively mild hydrogenation refining reaction is carried out in the hydrogenation modification reactor to reduce the aromatic carbon in the circulating hydrogen supply solvent oil. Then, the hydrogenated coal direct liquefaction oil is divided into a fraction of >350℃, a fraction of 300℃~350℃ by a fractionation tower, and a fraction of 100℃~150℃. The fraction at ℃, the fraction at 220℃-300℃, the fraction at 145℃-220℃ and the fraction at <145℃, among which the fraction at <145℃, the fraction at 145℃-220℃ and part of the fraction at 220℃-350℃ are used as raw materials for the hydrogenation reforming unit; the fraction at >350℃ and part of the fraction at 220℃-350℃ are used as hydrogen supply solvent oil for the coal hydrogenation direct liquefaction unit, and play a key role in the overall process of the entire coal direct liquefaction process.

[0377] Since coal direct liquefaction oil contains a certain amount of coal powder and the concentration of the coal powder is in a state of fluctuation, with a weight content of about tens to thousands of ppm, in order to prevent the catalyst bed of the hydrogenation modification reaction process R20 from being blocked, the hydrogenation modification reaction process R20 usually adopts an ebullated bed hydrogenation reaction system, and uses a hydrogenation modification reaction product liquid phase circulation pump to circulate a certain amount of hydrogenation modification reaction liquid phase product to the reaction feed to control the expansion rate of the catalyst bed. Since the hydrogenation stabilization target reaction is a liquid phase reaction, in order to improve the liquid phase reaction efficiency of the hydrogenation modification reactor, it is necessary to reduce the gas holdup rate of the logistics in the hydrogenation modification reactor, so that the hydrogen flow rate should be as low as possible; on the other hand, in order to ensure that the catalysts in the ebullated bed hydrogenation modification reactor have as little "rigid collision" with each other as possible while maintaining the ebullated bed state, it is also necessary to reduce the gas holdup rate of the logistics; from the perspective of reducing the circulation amount of circulating hydrogen, it is naturally required to reduce the gas phase feed amount of the ebullated bed hydrogenation modification reactor as much as possible.

[0378] Referring to Example 1, a typical hydrogenation stabilization unit of a coal hydrogenation direct liquefaction project has a feed hydrogen gas phase standard volume / fresh feed oil weight ratio of only 320 Nm 3 / t, and the ratio of the standard volume of residual hydrogen gas phase to the weight of the net liquid phase product at the outlet of the ebullating bed hydrogenation reforming reactor is only 196Nm 3 / t. Since the reactor uses circulating oil with a weight flow rate of about 2.1 times the weight flow rate of the feed oil, the actual hydrogen / oil volume ratio inside the reactor is lower.

[0379] Generally, coal is a hydrocarbon material with a high organic nitrogen content and / or a high organic oxygen content. Coal direct liquefaction oil contains a large amount of organic nitrogen and / or organic oxygen. Therefore, the hydrogenation modification reaction process R20 of coal direct liquefaction oil produces a large amount of ammonia and / or water vapor. Moreover, the ebullated bed hydrogenation modification reactor cannot use a large amount of hydrogen to dilute the ammonia and / or water vapor (which will greatly reduce the liquid phase fraction of the reaction zone material and increase the reaction zone volume by multiples or even several times). This also causes the ammonia volume concentration and / or water vapor volume concentration of the reaction gas phase in the ebullated bed hydrogenation modification reaction process R20 to be abnormally high. The volume concentration of gaseous ammonia in the fixed-bed hydrorefining reaction process of conventional petroleum-based oils is tens or even hundreds of times higher than that of gaseous water vapor in the fixed-bed hydrorefining reaction process of conventional oils, which greatly limits the hydrogenation modification reaction process R20 of coal direct liquefaction oil, especially the catalyst performance of the middle and final reaction processes that control the final reaction depth. Therefore, it is necessary to weaken the accumulation effect of water vapor, ammonia and methane gas, the products of the hydrogenation modification reaction process of coal direct liquefaction oil, that is, to adopt the intermediate degassing and graded hydrogenation modification reaction method of coal direct liquefaction oil.

[0380] For the ebullated bed hydrogenation stabilized catalyst R20C used in the ebullated bed hydrogenation modification reaction process R20 of coal direct liquefaction oil, its anti-wear property is an important indicator. Since the catalyst in the ebullated bed hydrogenation modification reactor of coal direct liquefaction oil is in a boiling back-mixing state and the catalyst is added / unloaded online, the ebullated bed catalyst has high requirements for strength and wear to reduce the wear and breakage of the catalyst. Usually, the catalyst is required to have a certain strength and wear, especially the strength distribution, that is, the strength distribution cannot be dispersed, and the number of low-strength particles is guaranteed to be small to avoid the breakage of low-strength particles in the back-mixing state, which increases the agent consumption. For this reason, nanofiber alumina can be used in its carrier to improve the strength or wear resistance of the carrier.

[0381] The expanded bed reactor described in the present invention is a vertical upflow reactor. When a catalyst is used, it belongs to an expanded bed reactor, and the main reaction zone is usually a cylindrical area of ​​equal diameter; vertical means that the central axis of the reactor in the working state after installation is perpendicular to the ground; upflow means that the main flow direction of the reaction material passes through the reaction space or catalyst bed from bottom to top or flows in the same direction as the upward catalyst; expanded bed means that the catalyst bed is in an expanded state in the working state, and the expansion ratio of the catalyst bed of equal diameter is defined as the ratio KBED of the maximum height CWH of the catalyst bed in the working state when the reaction raw materials pass through the catalyst bed to the height CUH of the empty bed static state of the catalyst bed. Generally, when KBED is less than 1.10, it is called a micro-expanded bed, when KBED is between 1.25 and 1.55, it is called a boiling bed, and a suspended bed is considered to be the most extreme form of expanded bed.

[0382] The back-mixed flow expanded bed reaction zone described in the present invention refers to the operation mode of the reaction zone using the expanded bed reactor in which there is back-mixing of liquid flow or circulating liquid; the back-mixed flow or circulating liquid refers to at least a portion of the liquid phase XK-L in the intermediate product XK or the final product XK at the process point K returning to the upstream reaction zone of the material flow XK as the circulating liquid flow XK-LR, and the reaction product of the circulating liquid flow XK-LR flows through the K point and exists in XK. The way to form the back-mixed flow in the expanded bed reactor can be any suitable way, such as setting a built-in inner circulation tube, a built-in outer circulation tube, a built-in liquid collecting cup + guide tube + built-in circulation pump, a built-in liquid collecting cup + guide tube + external circulation pump, an external circulation tube, etc.

[0383] The liquid collecting cup or liquid collecting vessel provided in the reactor of the present invention refers to a container arranged in the reactor for collecting liquid, which is usually opened at the top or the upper side, and has a guide pipe installed at the bottom or the lower side for discharging the collected liquid; the top liquid collecting vessel of the expanded bed reactor is usually installed in the deliquidation zone of the gas-liquid material to obtain a liquid and gas-liquid mixed phase flow or a liquid and a gas.

[0384] The hot high separator described in the present invention refers to a gas-liquid separation device used to separate hot gas-liquid mixed phase materials of hydrogenation reaction intermediate products or final products.

[0385] Application No. 202310229274.7 A control method for a communicating vessel in a hydrocarbon material upstream expanded bed staged series hydrogenation reaction process, relates to a control method for a front separation zone in which the reaction products of the separation front reaction zone are front separation gas and front separation liquid, the front separation gas is combined with the adjacent rear separation gas of the reaction product of the adjacent rear reaction zone to form a communicating vessel reaction system, and an internal throttling channel for one phase discharge, such as a front separation liquid delivery channel, is selected to only use a static throttling element to deliver the front separation liquid to an adjacent downstream reaction zone, while an adjustable throttling channel for another phase discharge, such as a front separation gas delivery channel, uses a dynamic throttling system with a minimum opening flow rate that is not zero, and the liquid level adjustment in the front separation zone is achieved by manipulating the opening of the dynamic throttling element of the front separation gas delivery channel; the process control system of the front separator of the invention has a simple structure, low cost, and high safety, and is a basic control technology required for a staged series oil-coal slurry suspension bed hydrogenation direct liquefaction reaction process with lower operating pressure and higher liquid phase reaction efficiency.

[0386] The present invention provides an intermediate degassing and graded hydrogenation modification reaction method for direct coal liquefaction oil. When the operating pressure of the intermediate separator is higher than the operating pressure of the downstream reaction zone, the upstream reaction zone and the downstream reaction zone are essentially connecting device-type liquid series reaction zones. Therefore, the liquid level control method of the intermediate separator can adopt the control method of the connecting device for the upstream expanded bed graded series hydrogenation reaction process of hydrocarbon materials of application number 202310229274.7.

[0387] The suitable raw material coal for the coal hydrogenation direct liquefaction reaction process R10 of the present invention usually has a higher volatile matter, a higher hydrogen content, and also has a higher organic oxygen content, a certain range of organic nitrogen content, and an organic sulfur content.

[0388] The coal direct liquefaction oil mentioned in this article refers to the liquefied oil produced by the coal hydrogenation direct liquefaction reaction process R10, which is usually a mixed hydrocarbon rich in dicyclic aromatics, tricyclic aromatics, and tetracyclic aromatics. It can also be a narrow fraction oil mainly composed of aromatics with a specific number of rings, such as a narrow fraction oil mainly composed of 2-ring, 3-ring, or 4-ring aromatics. Since coal contains a large amount of organic oxygen and organic nitrogen with high bond energy, coal direct liquefaction oil usually contains more organic oxygen and organic nitrogen. Since coal contains a large amount of aromatic structural carbon, coal direct liquefaction oil usually has a higher aromatic carbon rate, a lower hydrogen content, and a lower hydrogen supply index.

[0389] For the coal hydrogenation direct liquefaction reaction process R10 with certain operating conditions (operating pressure, operating temperature, residence time, catalyst type and concentration in the liquid phase, reactor form, etc.), the fluctuation of the raw coal properties (hydrogen content, volatile matter content, organic oxygen content, organic nitrogen content, organic sulfur content, ash content) directly leads to the fluctuation of the properties of the target product of the coal hydrogenation direct liquefaction reaction, namely the coal direct liquefaction oil (such as hydrogen content, aromatic carbon rate, hydrogen supply index, hydrocarbon group composition, organic nitrogen content, organic oxygen content, organic sulfur content). Therefore, it is usually required to keep the properties of the raw coal for coal hydrogenation direct liquefaction as stable as possible. However, since the properties of raw coal, a natural product, cannot be stable and unchanged, on the contrary, even the coal at different depths at the same plane position in the same coal mine or the coal at different plane positions at the same depth usually have differences or even large differences, which will inevitably lead to fluctuations or even large fluctuations in the properties of the coal direct liquefaction oil.

[0390] Under the condition that the operating conditions (process mode, processing load, total operating pressure, operating temperature, catalyst space velocity) of the hydrogenation modification reaction process remain unchanged, the fluctuation of the properties of the coal direct liquefaction oil will inevitably lead to the fluctuation of the properties of the oil generated by the hydrogenation modification reaction of the coal direct liquefaction oil (aromatic carbon rate, hydrogen supply index, hydrocarbon group composition, etc.) or even larger fluctuations. For example, with the increase of organic nitrogen content, organic oxygen content and decrease of hydrogen content in the coal hydrogenation direct liquefaction feedstock, the organic nitrogen content and organic oxygen content of the coal direct liquefaction oil will increase and the hydrogen content will decrease. Due to the properties of the suitable hydrogen supply solvent oil, the organic nitrogen content of the coal direct liquefaction oil will increase. There are restrictive boundary values ​​for the quality indicators (hydrogen content, aromatic carbon rate, hydrogen supply index, hydrocarbon family composition, etc.) (for example, the hydrogen supply index cannot be lower than 22). When the properties of the raw coal for direct liquefaction of coal by hydrogenation deteriorate (this involves the source range of liquefied coal or the utilization rate of coal resources in coal mines), the properties of the coal direct liquefaction oil deteriorate (for example, the hydrogen content decreases, the aromatic carbon rate increases, the hydrogen supply index decreases, the organic nitrogen content increases, and the organic oxygen content increases), for the hydrogenation modification reaction process of the coal direct liquefaction oil with certain operating conditions, the properties of the hydrogen supply solvent oil will inevitably deteriorate (for example, the hydrogen content decreases, the aromatic carbon rate increases, The deterioration of the properties of the hydrogen supply solvent oil in turn leads to further deterioration of the properties of the oil produced by coal hydrogenation direct liquefaction. The final result of the comprehensive reaction equilibrium is that the properties of the coal direct liquefaction oil and the oil produced by the hydrogenation modification reaction are greatly deteriorated. The degree of deterioration is a superposition effect, that is, the deterioration of the properties of the raw coal for coal hydrogenation direct liquefaction will inevitably lead to the simultaneous deterioration of the properties of the hydrogen supply solvent oil. In the end, the degree of deterioration of the effect of the coal hydrogenation direct liquefaction reaction is far greater than the deterioration of the properties of the raw coal for coal hydrogenation direct liquefaction while the properties of the hydrogen supply solvent oil remain unchanged. In other words, in order to maintain the smoothness of system operation, it is necessary to propose a hydrogenation modification reaction method with strong resistance to deterioration fluctuations in the properties of coal for direct liquefaction of raw materials, that is, it is necessary to propose a method that can reduce the deterioration fluctuations of coal direct liquefaction oil properties (such as hydrogen content, aromatic carbon rate, hydrogen supply index, hydrocarbon group composition, organic nitrogen content, organic oxygen content, organic sulfur content) on the final effect of the hydrogenation modification reaction, that is, the magnitude of the deterioration of the property indicators of hydrogen supply solvent oil (hydrogen content, aromatic carbon rate, hydrogen supply index, hydrocarbon group composition, etc.) while having good economic efficiency.

[0391] The deteriorating fluctuations in the properties of coal direct liquefaction oil are mainly manifested in one or more of the following: reduced hydrogen content, increased aromatic carbon rate, increased average carbon number of hydrocarbons, increased organic nitrogen content, increased organic oxygen content, increased organic sulfur content, and reduced hydrogen supply index. This fluctuation factor is transmitted to the hydrogenation modification reaction process. In order to maintain the stability of the hydrogen supply index, a key indicator of hydrogen supply solvent oil, it is necessary to specifically increase the hydrogenation saturation depth, increase the hydrogenation saturation range of the aromatic carbon rate, and increase the increase in the hydrogen supply index (this requires increased hydrogen consumption, extended reaction time, and increased catalyst dosage), which will inevitably lead to an increase in the organic nitrogen removal rate, an increase in the organic oxygen removal rate, and an increase in the methane gas yield. In order to maintain the established reaction hydrogen partial pressure and catalyst efficiency, this requires compensatory weakening of the cumulative effect of the product ammonia, water vapor and methane gas (reducing the gas phase hydrogen partial pressure will also enhance the adsorption of ammonia and water vapor on the active surface of the hydrogenation stable catalyst, thereby reducing the adsorption of the target reactants and the hydrogenation reaction efficiency). Since the properties of the feed oil in the initial reaction process of the hydrogenation modification reaction cannot be changed, and the mid-term and final reaction processes of the hydrogenation modification reaction determine the properties of the hydrogen supply solvent oil that is finally generated by the hydrogenation modification reaction, therefore, optimizing and changing the feed properties in the mid-term and final reaction processes of the hydrogenation modification reaction becomes an inevitable choice. The present invention is proposed based on this analysis.

[0392] As shown in Table 5, the properties of the coal direct liquefaction oil (ebulbed hydromodification reaction raw oil) involved in the coal hydro-direct liquefaction project of China Shenhua Group are summarized. When the properties of the ebulbed hydromodification reaction raw oil fluctuate due to deterioration, resulting in a significant decrease in hydrogen content, a significant increase in aromatic carbon rate, and a significant increase in organic nitrogen content, in order to ensure that the hydrogen supply index of the hydrogen supply solvent oil remains basically unchanged (that is, the aromatic carbon rate remains basically unchanged), the unit hydrogen consumption of the ebulbed hydromodification reaction process R20 of the ebulbed hydromodification reaction raw oil after deterioration will increase from 1.2 wt% to about 2.0 wt%, an increase of 67%, and the total temperature rise of the ebulbed hydromodification reaction will increase from about 65°C to about 105°C, an increase of 62%. Since the hydrogen content of the ebulbed hydromodification reaction raw oil decreases significantly, it is necessary not only to extend the reaction time, but also to require an upstream ebulbed hydromodification reaction process R20 with a lower reaction temperature, that is, it is necessary to reduce the starting reaction temperature of the overall ebulbed hydromodification reaction process R20, which has at least the following advantages:

[0393] ① Lowering the temperature of the feed in the hydrotreating reaction is conducive to reducing the fuel consumption of the heating furnace;

[0394] ② For hydrocarbon components with low hydrogen content and low initial hydrorefining reaction temperature, it can reduce the adverse effects of concentrated hydrogenation reaction, local release of a large amount of reaction heat and induction of rapid coking on the catalyst surface, which is conducive to the smooth operation of R20 in the ebullated bed hydrogenation modification reaction process and prolongs the life of the ebullated bed hydrogenation stable catalyst;

[0395] ③ The downstream ebullated bed hydrogenation modification reaction process R20 can be operated at a temperature appropriately higher than that of the upstream ebullated bed hydrogenation modification reaction process, so as to increase the reaction rate of the catalyst in the downstream ebullated bed hydrogenation modification reaction process R20, thereby reducing the amount of catalyst used in the downstream ebullated bed hydrogenation modification reaction process R20 and increasing the reaction depth of the downstream ebullated bed hydrogenation modification reaction process R20. At the same time, a downstream ebullated bed hydrogenation modification reaction process R20 with a higher reaction temperature is required to increase the activity of the downstream ebullated bed hydrogenation stable catalyst and reduce the amount of catalyst used.

[0396] The single-stage ebullating bed hydro-modification reaction method has the following common problems: As the properties of the raw oil in the single-stage ebullating bed hydro-modification reaction deteriorate, the equilibrium gas phase composition of the material at the reactor outlet of the single-stage ebullating bed hydro-modification reaction process R20 will inevitably deteriorate greatly. The deterioration trend is: the volume concentration of ammonia increases significantly, the volume concentration of water vapor increases significantly, and the volume concentration of methane gas increases significantly, which causes at least 3 problems:

[0397] First, the water vapor partial pressure and ammonia partial pressure at the reactor outlet (i.e., the downstream reaction zone) of the single-stage ebullated bed hydromodification reaction process R20 are too high, which means that the amount of ammonia adsorbed on the active surface of the hydrogenation-stabilized catalyst in the catalyst reaction space in the second half of the single-stage ebullated bed hydromodification reactor is larger, and the efficiency of the hydrogenation-stabilized catalyst is lower;

[0398] Second, the hydrogen partial pressure at the reactor outlet (i.e., the downstream reaction zone) of the single-stage ebullated bed hydromodification reaction process R20 is too low, which means that the thermal condensation reaction on the active surface of the hydrogenation-stabilized catalyst in the catalyst reaction space in the second half of the single-stage ebullated bed hydromodification reactor will increase, the coking rate on the surface of the hydrogenation-stabilized catalyst will increase, and the activity loss rate of the hydrogenation-stabilized catalyst will accelerate; or the total operating pressure of the device needs to be increased;

[0399] The hydrogen partial pressure at the outlet of the R20 reactor in the single-stage ebullating bed hydro-modification reaction process is too low, which will also reduce the reasonable hydro-modification reaction depth and reduce the increase in the hydrogen supply index of the oil produced by the hydro-modification reaction;

[0400] Third, the reactor of the single-stage fluidized bed hydrogenation modification process R20 is basically operated at one reaction temperature, which cannot adapt to the natural demand of low reaction temperature in the initial stage of the hydrogenation stabilization reaction of the deteriorated crude oil and high reaction temperature in the final stage of the reaction.

[0401] Based on the above analysis, compared with the single-stage fluidized bed hydrogenation modification reaction process R20, the reasonable coal direct liquefaction oil hydrogenation modification reaction method is the intermediate degassing graded hydrogenation modification reaction method, which has better technical and economic indicators. It is suitable for the hydrogenation modification reaction process of inferior coal direct liquefaction oil, or it has strong resistance to the impact of fluctuations in the properties of coal direct liquefaction oil. Through the intermediate degassing process, the adverse effects of the increase in ammonia yield, the increase in water gas yield, the increase in the volume concentration of non-hydrogen gas caused by the fluctuation of the properties of coal direct liquefaction oil are limited to the upper limit of the intermediate degassing process. The operating temperature of the upstream reaction process and the downstream reaction process of the staged reaction process can be flexibly adjusted in reverse. When the properties of the coal direct liquefaction oil tend to be deteriorating, the reaction temperature of the upstream reaction process of the staged hydrogenation modification reaction process can be reduced, and the reaction temperature of the downstream reaction process of the staged reaction process can be increased. These advantages cannot be achieved by the single-stage fluidized bed hydrogenation modification reaction method. This is also a major reason for the unsatisfactory operation of the hydrogenation stabilization device supporting the China Shenhua Group's coal hydrogenation direct liquefaction project.

[0402] Generally speaking, the fluctuation or even large fluctuation of the raw coal properties of the coal hydrogenation direct liquefaction device is inevitable. The key of the present invention is to objectively face up to the fact that the raw coal properties of the coal hydrogenation direct liquefaction are bound to fluctuate or even fluctuate greatly. It points out that the deterioration of coal quality will have a complex deteriorating effect on the coal hydrogenation direct liquefaction reaction process R10, and keeping the properties of the oil generated by the hydrogenation modification reaction from deteriorating (such as maintaining its hydrogen supply index from decreasing) or improving (such as improving the hydrogen supply index) is the key basic condition for achieving smooth operation of the coal hydrogenation direct liquefaction reaction process R10. For the first time, the necessity and significant technical and economic benefits of the intermediate degassing and graded hydrogenation modification reaction method for coal direct liquefaction oil are pointed out. This method has a significant inhibitory effect on the amplitude of the fluctuation of the properties of the liquefied raw coal, which leads to the fluctuation of the properties of the coal direct liquefaction oil, and then leads to the fluctuation of the properties of the oil generated by the boiling bed hydrogenation modification reaction, thereby ultimately improving the adaptability of the coal hydrogenation direct liquefaction reaction process R10 to the fluctuation of the properties of the liquefied raw coal.

[0403] The present invention changes the conventional thinking of adopting a single-stage reaction mode in the direct coal liquefaction oil hydrogenation modification reaction method, and provides an effective technical approach for rationally expanding the source of liquefied coal raw materials and improving the coal utilization rate of coal mines. It has great economic value because it is the first time to introduce the concept of intermediate degassing and graded hydrogenation modification reaction into the hydrogenation modification reaction process of hydrogenated liquefied oil, and points out the effect of this method on the coal hydrogenation direct liquefaction reaction process R10, so it is creative.

[0404] Compared with the existing single hydrogenation reforming reactor reaction system, the present invention is mainly proposed based on the following reasons and / or objectives. Usually, the coal direct liquefaction oil processed by the present invention contains solid particles:

[0405] ① With the increase in the amount of coal processed in the coal hydro-direct liquefaction process, the amount of raw oil in the hydro-modification reaction process, i.e., coal direct liquefaction oil, will inevitably increase, and the volume of its hydro-modification reactor will inevitably increase. When it reaches a certain scale, for example, the raw oil in the hydro-modification reaction process is greater than 900t / h, due to the upper limit of the equipment manufacturing capacity, the upper limit of the equipment transportation capacity, or the high cost of repairing the equipment once it is damaged, it is impossible to prepare a single hydro-modification reactor reaction system that meets the needs of the project, or the manufacturing cost of a single hydro-modification reactor reaction system is too high and uneconomical, and two or more hydro-modification reactors operated in series must be used;

[0406] ② The existing single hydrogenation reactor reaction system has an unsatisfactory operating effect under the designed load and needs to increase the amount of catalyst (extend the catalytic reaction time), and accordingly increase the hydrogenation reactor;

[0407] Alternatively, in order to increase the processing capacity of the existing device, it is necessary to increase the amount of catalyst used and increase the number of hydrogenation reactors accordingly;

[0408] ③ When processing low-quality coal direct liquefaction oil with low hydrogen content and / or high organic nitrogen content, due to the high unit hydrogen consumption and huge reaction heat of the low-quality coal direct liquefaction oil, in order to achieve a reasonable reaction temperature distribution, it is necessary to use two or more hydrogenation reforming reactors operated in series to achieve an operation mode in which the reaction temperature is gradually increased;

[0409] ④ Due to the fact that the properties of raw coal in the direct liquefaction reaction of coal hydrogenation are unstable and even fluctuate widely, when the hydrogen content and / or organic nitrogen content of the direct liquefied coal oil fluctuates widely, in order to adapt to the fluctuation, the working conditions of the direct liquefied coal oil with high harshness become high. At this time, the unit hydrogen consumption of the direct liquefied coal oil with low quality is high and the reaction heat is huge. In order to achieve a reasonable reaction temperature distribution, it is necessary to use two or more hydrogenation reactors operated in series to realize an operation mode in which the reaction temperature is gradually increased;

[0410] ⑤ For conventional coal direct liquefaction oil, the intermediate degassing graded ebullated bed hydromodification reaction method can effectively reduce the volume concentration of non-hydrogen gas in the gas phase of R20 in the downstream ebullated bed hydromodification reaction process, that is, increase the hydrogen concentration, reduce the total operating pressure of the hydromodification reaction process to reduce device investment and energy consumption, and also increase the limit depth of the overall hydromodification reaction;

[0411] ⑥ For conventional coal direct liquefaction oil, the intermediate degassing graded ebullated bed hydro-modification reaction method can effectively reduce the volume concentration of ammonia in the gas phase of R20 in the downstream ebullated bed hydro-modification reaction process, that is, reduce the adsorption amount of ammonia on the surface of the ebullated bed hydro-stabilization catalyst, weaken the shielding effect of ammonia on the surface of the ebullated bed hydro-stabilization catalyst, and improve the reaction activity of the ebullated bed hydro-stabilization catalyst. It can reduce the catalyst loading amount in the hydro-modification reaction process, reduce the catalyst deactivation rate, and thus reduce the consumption of the ebullated bed hydro-stabilization catalyst. In addition, it can increase the limit depth of the overall hydro-modification reaction;

[0412] ⑦ For conventional coal direct liquefaction oil, the intermediate degassing graded ebullated bed hydrogenation modification reaction method is adopted, which can separate the low-boiling point components in the intermediate products of the ebullated bed hydrogenation modification reaction from the ebullated bed hydrogenation modification reaction system in advance, avoiding excessive hydrogenation leading to a decrease in the hydrogen supply index, and at the same time reducing the load of the downstream ebullated bed hydrogenation modification reaction process R20, that is, reducing the investment and energy consumption of the downstream ebullated bed hydrogenation modification reaction process R20;

[0413] ⑧ For conventional coal direct liquefaction oil, the intermediate degassing graded ebullated bed hydro-modification reaction method can be used to form a downstream ebullated bed hydro-modification reaction process R20DEEP-R environment with low ammonia partial pressure and high hydrogen partial pressure. In this way, the polycyclic aromatic hydrocarbon fraction KEY-L with a low hydrogen supply index obtained by separating the ebullated bed hydro-modification reaction product oil can be returned to the downstream ebullated bed hydro-modification reaction process R20DEEP-R for efficient deep hydro-modification reaction. With a simple process, its hydrogen supply index can be efficiently improved, which is equivalent to using a simple process to extend the ebullated bed hydro-modification reaction time of the polycyclic aromatic hydrocarbon fraction KEY-L;

[0414] ⑨ For young coals suitable for liquefaction with high hydrogen content and high volatile matter, which have short hydrogenation direct liquefaction reaction time and high organic nitrogen content in raw materials, the coal direct liquefaction oil contains higher organic nitrogen, organic oxygen and lower hydrogen content because of the short hydrogenation direct liquefaction reaction time. At this time, the intermediate degassing graded ebullating bed hydrogenation modification reaction method of the present invention has significant adaptability and technical advantages;

[0415] ⑩ Hydrogen resources can be used rationally to reduce the scale of the circulating hydrogen system. The intermediate separation liquid is pumped to the downstream hydrogenation and reforming reaction zone, and the low-ammonia and hydrogen-rich separation gas of the downstream hydrogenation and reforming reaction stage can be connected to the upstream hydrogenation and reforming reaction zone for secondary use;

[0416] The liquid level control of the intermediate separator can adopt the control method of the communicating vessel for the hydrocarbon material upflow expanded bed staged series hydrogenation reaction process of application number 202310229274.7.

[0417] According to the solid content of different narrow fractions separated from coal hydrogenation direct liquefaction oil, the raw material oil R20F of the ebullated bed hydro-modification reaction is selected. If the light fractions with a conventional boiling point below 300°C separated in the fractionation process of coal hydrogenation direct liquefaction oil have a high solid weight content, such as higher than 100 ppm, these light fractions can be used as the raw material oil R20F of the ebullated bed hydro-modification reaction and enter the ebullated bed hydro-modification reaction process R20 for treatment. The hydro-modification reaction products are treated with solids in the fractionation part of the hydrogenation stable oil to become fractions with low solid weight content and can be used as the raw material oil of the hydro-upgrading reaction process.

[0418] Usually, the weight flow rate of the feedstock oil in the hydrogenation and upgrading reaction process R30 accounts for 25-40% of the weight flow rate of conventional liquid hydrocarbons in the full-fraction distillate oil of the coal hydrogenation direct liquefaction product oil. If the solid weight content of the light distillate oil with a conventional boiling point below 300°C separated in the distillation process of the coal hydrogenation direct liquefaction product oil is very low, for example, below 20 ppm, then these light distillate oils can directly enter the coal direct liquefaction oil hydrogenation and upgrading reaction process R30 to produce deeply hydrogenated and modified oil products without going through the ebullated bed hydrogenation and modification reaction process R20, which can significantly reduce the processing volume of the ebullated bed hydrogenation and modification reaction process R20, reduce the investment and energy consumption of the ebullated bed hydrogenation and modification reaction process R20, and is also conducive to the optimization of the operating conditions of the ebullated bed hydrogenation and modification reaction process R20.

[0419] For coal direct liquefaction oil with an extremely large flow rate, such as 900 tons / hour, the optimal operation can be carried out by adopting the most optimized operating conditions according to the different numbers of aromatic rings therein. For example, the light hydrocarbon stream R20AF (containing monocyclic aromatic hydrocarbons, dicyclic aromatic hydrocarbons, and very few polycyclic aromatic hydrocarbons) derived from coal hydrogenation direct liquefaction oil, which is mainly composed of hydrocarbons with a conventional boiling point below 310°C, enters the first ebullated bed hydrogenation modification reaction stage U210, and the heavy hydrocarbon stream R20BF (containing dicyclic aromatic hydrocarbons, polycyclic aromatic hydrocarbons, and very few monocyclic aromatic hydrocarbons) derived from coal hydrogenation direct liquefaction oil, which is mainly composed of hydrocarbons with a conventional boiling point above 310°C, enters the second ebullated bed hydrogenation modification reaction stage U220 for classified hydrogenation stabilization. The energy consumption of the fractionation process of the oil generated by the hydro-modification reaction can be greatly reduced by treating the oil instead of mixing them together for the mixed oil hydro-stabilization treatment. This is because at least a part or even most of the oil generated by the hydro-modification reaction of the light hydrocarbon stream R20AF does not need to be flashed into steam and then condensed and separated, but only needs to be stripped to remove the light components to be used as the bottom oil of the fractionation tower. In this way, the hot high-fraction oil of the reaction effluent of the first ebullated bed hydro-modification reaction stage U210 or part of the heat of the stream after its pressure reduction can be used to preheat the hydrogen feed of the first ebullated bed hydro-modification reaction stage U210 and / or preheat the crude oil feed of the first ebullated bed hydro-modification reaction stage U210.

[0420] The hydrogenation modification reaction mode of coal hydrogenation direct liquefaction to generate oil classified according to the fraction range is suitable for ultra-large-scale coal hydrogenation direct liquefaction projects. For example, the total output of coal hydrogenation liquefied oil is as high as 6 million tons / year, of which the output of hydrocarbons with a conventional boiling point below 280°C accounts for 40%, i.e. 2.4 million tons / year, the output of hydrocarbons with a conventional boiling point of 280-400°C accounts for 50%, i.e. 3 million tons / year, and the output of hydrocarbons with a conventional boiling point above 400°C accounts for 10%, i.e. 600,000 tons / year.

[0421] Separately processing hydrocarbons with conventional boiling points higher than 400°C, i.e., heavy distillate oil and over-vaporized oil from the vacuum tower of a coal hydrogenation direct liquefaction unit, can select suitable large-pore hydrogenation stabilizing catalysts for four-ring aromatics and more ring aromatics and colloids, and optimize operations with suitable high hydrogenation modification reaction hydrogen partial pressure, suitable high hydrogenation modification reaction temperature and liquid phase product circulation ratio, which is also beneficial to reducing the fractionation energy consumption of the overall hydrogenation stable generated oil, because the evaporation ratio of the overall hydrogenation stable generated oil can be reduced; at the same time, the hydrogenation reaction conditions of the light hydrocarbon stream R20F11 and the medium hydrocarbon stream R20F12 are optimized, for example, suitable small-pore and medium-pore hydrogenation stabilizing catalysts can be selected to increase the active surface area per unit weight of the hydrogenation stabilizing catalyst, reduce the hydrogenation modification reaction hydrogen partial pressure, reduce the hydrogenation modification reaction temperature, and reduce the liquid phase product circulation ratio. At the same time, the coking rate of the catalyst is greatly reduced, which can reduce the overall consumption and regeneration ratio of the hydrogenation stabilizing catalyst, and is also beneficial to the metal recovery of the spent hydrogenation stabilizing catalyst.

[0422] The characteristic parts of the present invention are described below.

[0423] The intermediate degassing graded ebullating bed hydrogenation modification reaction method of coal direct liquefaction oil of the present invention is characterized by:

[0424] The feedstock oil R20F of the ebullated bed hydro-modification reaction process R20 is a hydrocarbon stream containing organic nitrogen and organic oxygen, including dicyclic aromatic hydrocarbons and / or polycyclic aromatic hydrocarbons, and at least a hydrocarbon stream containing distillate oil generated by direct coal liquefaction, with or without carbonaceous solid particles;

[0425] In the ebullated bed hydro-modification reaction process R20, in the presence of hydrogen, liquid hydrocarbons, an ebullated bed hydro-modification catalyst, and in the presence or absence of carbon-containing solid particles, a stream containing hydrocarbon liquid based on the feedstock oil R20F undergoes an ebullated bed hydro-modification reaction to be converted into hydrocarbons with a lower aromatic carbon content to obtain a hydro-modification reaction effluent R20P;

[0426] In the ebullating bed hydro-modification reaction process R20, at least a portion of the organic nitrogen component of the logistics containing hydrocarbon liquid based on the feedstock oil R20F undergoes a hydrogenation hydrogenolysis reaction to produce ammonia, at least a portion of the organic oxygen component of the logistics containing hydrocarbon liquid based on the feedstock oil R20F undergoes a hydrogenation hydrogenolysis reaction to produce water, and at least a portion of the bicyclic aromatic hydrocarbons and / or polycyclic aromatic hydrocarbons of the logistics containing hydrocarbon liquid based on the feedstock oil R20F undergo a hydrogenation saturation reaction to be converted into aromatic hydrocarbons with a lower aromatic carbon rate;

[0427] A hydrocarbon hydro-modification reaction stage, comprising a hydrocarbon hydro-modification reaction process and a gas-liquid separation process of the reaction effluent;

[0428] A hydrocarbon ebullated bed hydro-modification reaction stage, comprising an ebullated bed hydro-modification reaction process and a gas-liquid separation process of the reaction effluent;

[0429] The ebullated bed hydromodification reaction process R20 comprises at least two adjacent ebullated bed hydromodification reaction stages, a hydromodification reactor of other forms using or not using a stream containing hydrocarbon liquid based on the feedstock oil R20F, and a reaction stage of a hydromodification reactor of other forms using or not using a stream containing hydrocarbon liquid based on the feedstock oil R20F, wherein the other forms of hydromodification reactor are selected from one or more of the following:

[0430] ① Micro-expanded bed with process fluid upflow;

[0431] ② Fixed bed with process fluid upflow;

[0432] ③ Fixed bed with downward flow of process fluid;

[0433] ④Suspended bed or slurry bed;

[0434] The ebullated bed hydroprocessing reaction process R20 comprises two or more ebullated bed hydroprocessing reaction stages connected in series for a flow containing hydrocarbon liquid based on the feedstock oil R20F, and is divided into an upstream ebullated bed hydroprocessing reaction stage and a downstream ebullated bed hydroprocessing reaction stage according to the main flow direction of the ebullated bed hydroprocessing reaction process of the feedstock oil R20F, wherein the most downstream ebullated bed hydroprocessing reaction stage is called a final ebullated bed hydroprocessing reaction stage;

[0435] The intermediate product separation process refers to the gas-liquid separation process of the upstream hydro-modification reaction product between two adjacent hydro-modification reaction stages. The intermediate product separation process separates the intermediate product separation gas and the intermediate product separation liquid;

[0436] The average volume concentration of gaseous ammonia in the ebullated bed hydro-modification reaction process refers to the arithmetic mean of the volume concentration of gaseous ammonia at the starting reaction point of the catalyst bed and the volume concentration of gaseous ammonia at the end reaction point of the catalyst bed in the ebullated bed hydro-modification reaction process;

[0437] The average volumetric concentration of ammonia in the gas phase of the ebullated bed hydro-modification reaction process UR2N of any downstream ebullated bed hydro-modification reaction stage is lower than the average volumetric concentration of ammonia in the gas phase of the ebullated bed hydro-modification reaction process UR2M of the adjacent upstream ebullated bed hydro-modification reaction stage;

[0438] The aromatic carbon ratio of all hydrocarbons with a conventional boiling point higher than 220° C. in the reaction effluent of any ebullated bed hydromodification reaction process UR2N is lower than the aromatic carbon ratio of all hydrocarbons with a conventional boiling point higher than 220° C. in the reaction feed of the ebullated bed hydromodification reaction process UR2N;

[0439] In an intermediate product separation process MS of the reaction effluent of any upstream ebullating bed hydro-modification reaction stage, ammonia and water are stripped from the liquid phase separated from the hydro-modification reaction effluent of the stage with or without using a stripping hydrogen stream;

[0440] The ebullated bed hydro-modification reaction process R20 comprises at least a first ebullated bed hydro-modification reaction stage U210 and a second ebullated bed hydro-modification reaction stage U220;

[0441] (1) The first ebullated bed hydro-modification reaction stage U210, comprising the first ebullated bed hydro-modification reaction process UR210 and the first gas-liquid separation process US210;

[0442] A hydrocarbon liquid-containing stream based on the feedstock oil R20F is used as the hydrocarbon-containing feedstock UR210F of the first ebullated bed hydro-modification reaction process UR210;

[0443] In the first ebullated bed hydro-modification reaction process UR210, the hydrocarbon-containing feedstock UR210F is subjected to the first ebullated bed hydro-modification reaction and converted into the first ebullated bed hydro-modification reaction effluent UR210P;

[0444] In the first gas-liquid separation process US210, the gas-liquid mixed phase flow of the first ebullated bed hydro-modification reaction effluent UR210P is separated into a first separated gas containing ammonia and water and a first separated liquid, and part of the ammonia component and part of the water component in the first ebullated bed hydro-modification reaction effluent UR210P enter the first separated gas;

[0445] In the first gas-liquid separation process US210, the liquid phase separated from the gas-liquid mixed phase stream of the first ebullated bed hydro-modification reaction effluent UR210P is stripped with or without the use of the hydrogen-rich gas stream to reduce the ammonia content and water content in the liquid phase after stripping;

[0446] When the first stripping process UB210 is used, the first hydrogen-rich stripping gas contacts the first separation liquid-based stream, i.e., the first stripping liquid, at least once and completes separation, the low-boiling point components in the first stripping liquid enter the gas phase to form the first stripped gas, and the unvaporized first stripping liquid forms the first stripped liquid; the weight content of ammonia in the first stripped liquid is lower than the weight content of ammonia in the first separation liquid; the weight content of ammonia in the first stripped gas is higher than the weight content of ammonia in the first hydrogen-rich stripping gas;

[0447] (2) The second ebullated bed hydroprocessing reaction stage U220, comprising a second ebullated bed hydroprocessing reaction process UR220 and a second gas-liquid separation process US220;

[0448] The hydrocarbon-containing stream based on the first separated liquid is used as the hydrocarbon-containing feedstock UR220F of the second ebullated bed hydro-modification reaction process UR220;

[0449] In the second ebullated bed hydro-modification reaction process UR220, the hydrocarbon-containing feedstock UR220F is subjected to a second ebullated bed hydro-modification reaction and converted into a second ebullated bed hydro-modification reaction effluent UR220P;

[0450] The average volume concentration of ammonia in the gas phase of the second ebullated bed hydro-modification reaction process UR220 is lower than the average volume concentration of ammonia in the gas phase of the first ebullated bed hydro-modification reaction process UR210;

[0451] In the second gas-liquid separation process US220, the gas-liquid mixed phase flow based on the second ebullated bed hydro-modification reaction effluent UR220P is separated into a second separated gas and a second separated liquid, and part of the ammonia component in the second ebullated bed hydro-modification reaction effluent UR220P enters the second separated gas;

[0452] The final ebullated bed hydroprocessing reaction stage U290 includes a final ebullated bed hydroprocessing reaction process UR290 and a final gas-liquid separation process US290;

[0453] A hydrocarbon liquid-containing stream based on the intermediate product separation liquid of the adjacent upstream ebullated bed hydro-modification reaction stage is used as a hydrocarbon-containing feedstock UR290F for the final ebullated bed hydro-modification reaction process UR290;

[0454] In the final ebullated bed hydroprocessing reaction stage U290, the hydrocarbon-containing feedstock UR290F of the final ebullated bed hydroprocessing reaction process UR290 is subjected to the final ebullated bed hydroprocessing reaction and converted into the final ebullated bed hydroprocessing reaction effluent UR290P;

[0455] In the final gas-liquid separation process US290, the gas-liquid mixed phase flow based on the final ebullating bed hydrogenation modification reaction effluent UR290P is separated into the final separation gas and the final separation liquid.

[0456] In the present invention, usually, in the generated oil fractionation process of the ebullated bed hydroprocessing reaction process R20, a heavy fraction KEYL mainly composed of hydrocarbons with a conventional boiling point higher than 320°C is separated from a hydrocarbon flow containing at least a final separation liquid, and a hydrocarbon-containing flow based on part of the heavy fraction KEYL is returned as a circulating reaction material KEYL-R to the ebullated bed hydroprocessing reaction process of any downstream ebullated bed hydroprocessing reaction stage of the ebullated bed hydroprocessing reaction process R20 to carry out a circulating hydrogenation reaction for reducing the aromatic carbon rate.

[0457] In the present invention, usually, in the intermediate product separation process of the reaction effluent of any upstream ebullating bed hydroprocessing reaction stage, the liquid phase separated from the hydroprocessing reaction effluent of this stage is subjected to two or more countercurrent contacts with the liquid phase using a stripping hydrogen flow to strip ammonia and water therein.

[0458] In the present invention, generally, the intermediate product separation process of the reaction effluent of any upstream ebullating bed hydroprocessing reaction stage and the hydrogen stripping process of the liquid phase separated from the hydroprocessing reaction effluent of this stage are completed in the same high-pressure container pressure shell.

[0459] In the present invention, generally, the separated gas obtained in the gas-liquid separation process of the ebullated bed hydro-modification reaction effluent of any ebullated bed hydro-modification reaction stage contains more than 70% of the ammonia component in the ebullated bed hydro-modification reaction effluent of the ebullated bed hydro-modification reaction stage;

[0460] The average volume concentration of gas-phase ammonia in any downstream ebullated bed hydroprocessing reaction process UR2N is lower than 40% of the average volume concentration of gas-phase ammonia at the terminal reaction of the adjacent upstream ebullated bed hydroprocessing reaction process UR2M.

[0461] In the present invention, generally, the separated gas obtained in the gas-liquid separation process of the ebullated bed hydro-modification reaction effluent of any ebullated bed hydro-modification reaction stage contains more than 85% of the ammonia component in the ebullated bed hydro-modification reaction effluent of the ebullated bed hydro-modification reaction stage;

[0462] The average volume concentration of gas-phase ammonia in any downstream ebullated bed hydroprocessing reaction process UR2N is 20% lower than the average volume concentration of gas-phase ammonia at the terminal reaction of the adjacent upstream ebullated bed hydroprocessing reaction process UR2M.

[0463] In the present invention, generally, the source and composition of the raw oil R20F are selected from one or more of the following:

[0464] ① The distillate stream from the fractionation process of coal direct liquefaction to generate oil, mainly composed of hydrocarbons with a conventional boiling point of 200 to 280°C;

[0465] ② The distillate stream from the fractionation process of coal direct liquefaction to generate oil, mainly composed of hydrocarbons with a conventional boiling point of 280 to 370°C;

[0466] ③ The distillate stream from the fractionation process of coal direct liquefaction to generate oil, mainly composed of hydrocarbons with a conventional boiling point of 370 to 470°C;

[0467] ④ The distillate stream from the fractionation process of coal direct liquefaction to generate oil, mainly composed of hydrocarbons with a conventional boiling point of 470 to 525°C;

[0468] ⑤ The distillate stream from the fractionation process of coal direct liquefaction to produce oil, mainly composed of hydrocarbons with a conventional boiling point of 525 to 550°C;

[0469] ⑥ The distillate oil stream from the fractionation process of direct coal liquefaction to produce oil is mainly composed of hydrocarbons with a conventional boiling point of 550 to 650°C.

[0470] In the present invention, the feedstock oil R20F may include one or more of the following, and their overall proportion in the feedstock oil R20F is less than 30% by weight:

[0471] ① The distillate stream from the fractionation process of coal tar, mainly composed of hydrocarbons with a conventional boiling point of 200 to 330°C;

[0472] ② The distillate stream from the fractionation process of coal tar, mainly composed of hydrocarbons with a conventional boiling point of 330 to 400°C;

[0473] ③ The distillate oil stream from the fractionation process of coal tar is mainly composed of hydrocarbons with a conventional boiling point of 400 to 540°C.

[0474] In the present invention, generally, the operating conditions of the ebullated bed hydro-modification reaction zone used in the ebullated bed hydro-modification reaction process R20 are: temperature of 250-440°C, pressure of 8.0-25.0 MPa, hydrogen / feedstock oil volume ratio of 100-400 Nm 3 / m 3 , the weight chemical hydrogen consumption per unit weight of raw oil is 0.4~3.5%.

[0475] In the present invention, generally, the operating conditions of the ebullated bed hydro-modification reaction zone used in the ebullated bed hydro-modification reaction process R20 are: temperature of 300-400°C, pressure of 13.0-20.0 MPa, hydrogen / feedstock oil volume ratio of 200-350 Nm 3 / m 3 , the weight chemical hydrogen consumption per unit weight of crude oil is 1.0~2.5%.

[0476] In the present invention, generally, the solid particle content in the feedstock oil R20F in the ebullated bed hydro-modification reaction is greater than 100 ppm.

[0477] In the present invention, the ebullated bed hydroprocessing reaction process R20 may include two ebullated bed hydroprocessing reaction stages connected in series, and the operation objectives thereof are selected from one or more of the following:

[0478] ① The organic nitrogen hydrodenitrification rate of the first ebullated bed hydromodification reaction stage U210 is 60-95% of the overall denitrification rate of the ebullated bed hydromodification reaction process R20;

[0479] The organic nitrogen hydrodenitrification rate of the second ebullated bed hydromodification reaction stage U220 is 5 to 40% of the overall denitrification rate of the ebullated bed hydromodification reaction process R20;

[0480] ② The aromatic carbon hydroremoval rate of the first ebullated bed hydromodification reaction stage U210 is 60-80% of the overall aromatic carbon hydroremoval rate of the ebullated bed hydromodification reaction process R20;

[0481] The aromatics hydrogenation removal rate of the second ebullated bed hydromodification reaction stage U220 is 20-40% of the overall aromatics hydrogenation removal rate of the ebullated bed hydromodification reaction process R20;

[0482] ③ The reaction temperature rise of the first ebullated bed hydro-modification reaction stage U210 is 40-70% of the overall reaction temperature rise of the ebullated bed hydro-modification reaction process R20;

[0483] The reaction temperature rise of the second ebullated bed hydro-modification reaction stage U220 is 40-60% of the overall reaction temperature rise of the ebullated bed hydro-modification reaction process R20;

[0484] ④ The chemical hydrogen consumption of the first ebullated bed hydroprocessing reaction stage U210 is 40-70% of the overall chemical hydrogen consumption of the ebullated bed hydroprocessing reaction process R20;

[0485] The chemical hydrogen consumption of the second ebullated bed hydro-modification reaction stage U220 is 40-60% of the overall chemical hydrogen consumption of the ebullated bed hydro-modification reaction process R20;

[0486] ⑤ The growth value of the hydrogen supply index of the feedstock R20F produced in the first ebullated bed hydro-modification reaction stage U210 is 40-70% of the growth value of the overall hydrogen supply index of R20 in the ebullated bed hydro-modification reaction process;

[0487] The growth value of the hydrogen supply index generated by the second ebullated bed hydroprocessing reaction stage U220 is 30-60% of the growth value of the overall hydrogen supply index of the ebullated bed hydroprocessing reaction process R20.

[0488] In the present invention, generally, the feedstock oil R20F in the ebullated bed hydro-modification reaction contains carbonaceous solid particles;

[0489] The ebullated bed hydromodification reaction process R20 may include two series-connected hydromodification reaction stages: a first ebullated bed hydromodification reaction stage U210 and a second ebullated bed hydromodification reaction stage U220;

[0490] The second ebullated bed hydro-modification reaction stage U220 can be provided with a liquid product circulation pump to transport the liquid product of the second ebullated bed hydro-modification reaction stage U220, and the working mode is selected from one or more of the following:

[0491] ① delivering the circulating reaction liquid to the second ebullated bed hydro-modification reaction process UR220, and this part of the circulating reaction liquid does not pass through the first ebullated bed hydro-modification reaction process UR210;

[0492] ② Transport circulating reaction liquid to the first ebullated bed hydrogenation modification reaction process UR210.

[0493] In the present invention, generally, the feedstock oil R20F in the ebullated bed hydro-modification reaction contains carbonaceous solid particles;

[0494] The ebullated bed hydromodification reaction process R20 includes two series-connected hydromodification reaction stages: a first ebullated bed hydromodification reaction stage U210 and a second ebullated bed hydromodification reaction stage U220;

[0495] Each ebullated bed hydroprocessing reaction stage can be provided with a liquid reaction product circulation pump, so that part of the liquid product of this reaction stage can be circulated and reacted in the ebullated bed hydroprocessing reaction process of this stage.

[0496] In the present invention, generally, the feedstock oil R20F in the ebullated bed hydro-modification reaction contains carbonaceous solid particles;

[0497] The ebullated bed hydromodification reaction process R20 includes two series-connected hydromodification reaction stages: a first ebullated bed hydromodification reaction stage U210 and a second ebullated bed hydromodification reaction stage U220;

[0498] The first ebullated bed hydro-modification reaction stage U210 can be provided with a first separation liquid delivery pump, and its working mode is selected from one or more of the following:

[0499] ① Transporting circulating reaction liquid to the first ebullated bed hydro-modification reaction process UR210;

[0500] ②Transporting reaction feed liquid to the second ebullated bed hydro-modification reaction process UR220;

[0501] ③ The operating pressure of the second ebullated bed hydrogenation modification reaction stage U220 is higher than the operating pressure of the first ebullated bed hydrogenation modification reaction stage U210, and part or all of the second separated gas enters the first ebullated bed hydrogenation modification reaction process UR210 by relying on its own pressure, and / or, a part of the second separated liquid enters the first ebullated bed hydrogenation modification reaction process UR210 by relying on its own pressure, and a part of the second separated liquid is used as the second separated liquid net product.

[0502] In the present invention, generally, the ebullated bed hydroprocessing reaction process R20 may include three ebullated bed hydroprocessing reaction stages connected in series, and the operation objectives thereof are selected from one or more of the following:

[0503] ① The organic nitrogen hydrodenitrification rate of the first ebullated bed hydromodification reaction stage U210 is 40-70% of the overall denitrification rate of the ebullated bed hydromodification reaction process R20;

[0504] The organic nitrogen hydrodenitrification rate of the second ebullated bed hydromodification reaction stage U220 is 25-40% of the overall denitrification rate of the ebullated bed hydromodification reaction process R20;

[0505] The organic nitrogen hydrodenitrification rate of the third ebullated bed hydromodification reaction stage U230 is 10-20% of the overall denitrification rate of the ebullated bed hydromodification reaction process R20;

[0506] ② The aromatic carbon hydroremoval rate of the first ebullated bed hydromodification reaction stage U210 is 40-70% of the overall aromatic carbon hydroremoval rate of the ebullated bed hydromodification reaction process R20;

[0507] The aromatics hydrogenation removal rate of the second ebullated bed hydromodification reaction stage U220 is 25-40% of the overall aromatics hydrogenation removal rate of the ebullated bed hydromodification reaction process R20;

[0508] The aromatic carbon hydroremoval rate of the third ebullated bed hydromodification reaction stage U230 is 10-20% of the overall aromatic carbon hydroremoval rate of the ebullated bed hydromodification reaction process R20;

[0509] ③ The reaction temperature rise of the first ebullated bed hydro-modification reaction stage U210 is 40-70% of the overall reaction temperature rise of the ebullated bed hydro-modification reaction process R20;

[0510] The reaction temperature rise of the second ebullated bed hydro-modification reaction stage U220 is 25-40% of the overall reaction temperature rise of the ebullated bed hydro-modification reaction process R20;

[0511] The reaction temperature rise of the third ebullated bed hydro-modification reaction stage U230 is 10-20% of the overall reaction temperature rise of the ebullated bed hydro-modification reaction process R20;

[0512] ④ The chemical hydrogen consumption of the first ebullated bed hydroprocessing reaction stage U210 is 40-70% of the overall chemical hydrogen consumption of the ebullated bed hydroprocessing reaction process R20;

[0513] The chemical hydrogen consumption of the second ebullated bed hydro-modification reaction stage U220 is 25-40% of the overall chemical hydrogen consumption of the ebullated bed hydro-modification reaction process R20;

[0514] The chemical hydrogen consumption of the third ebullated bed hydro-modification reaction stage U230 is 10-20% of the overall chemical hydrogen consumption of the ebullated bed hydro-modification reaction process R20;

[0515] ⑤ The growth value of the hydrogen supply index of the feedstock R20F produced in the first ebullated bed hydro-modification reaction stage U210 is 40-70% of the growth value of the overall hydrogen supply index of R20 in the ebullated bed hydro-modification reaction process;

[0516] The growth value of the hydrogen supply index generated by the second ebullated bed hydroprocessing reaction stage U220 is 25-40% of the growth value of the overall hydrogen supply index of the ebullated bed hydroprocessing reaction process R20;

[0517] The increase value of the hydrogen supply index generated by the third ebullated bed hydroprocessing reaction stage U230 is 10-20% of the increase value of the overall hydrogen supply index of the ebullated bed hydroprocessing reaction process R20.

[0518] In the present invention, generally, the feedstock oil R20F contains carbonaceous solid particles;

[0519] In the ebullated bed hydroprocessing reaction process R20, a liquid product circulation pump is provided in any ebullated bed hydroprocessing reaction stage to transport the liquid product of the ebullated bed hydroprocessing reaction stage. The working mode can be selected from one or more of the following:

[0520] ① Transporting circulating reaction liquid to the ebullated bed hydrogenation and modification reaction process at this stage;

[0521] ②Transporting circulating reaction liquid to the existing downstream hydrogenation and modification reaction process

[0522] ③ Transporting circulating reaction liquid to any existing upstream boiling bed hydrogenation modification reaction process.

[0523] In the present invention, generally, the feedstock oil R20F contains carbonaceous solid particles;

[0524] The ebullating bed hydroprocessing reaction process R20 comprises a plurality of hydroprocessing reaction stages connected in series;

[0525] Each ebullated bed hydroprocessing reaction stage can be provided with a liquid reaction product circulation pump, so that part of the liquid product of this reaction stage can be circulated and reacted in the ebullated bed hydroprocessing reaction process of this stage.

[0526] In the present invention, generally, the feedstock oil R20F for the ebullated bed hydro-modification reaction contains carbonaceous solid particles;

[0527] The ebullating bed hydroprocessing reaction process R20 may include three hydroprocessing reaction stages connected in series;

[0528] The first ebullated bed hydro-modification reaction stage U210 is provided with a first separation liquid delivery pump, and its working mode is selected from one or more of the following:

[0529] ① Transporting circulating reaction liquid to the first ebullated bed hydro-modification reaction process UR210;

[0530] ②Transporting reaction feed liquid to the second ebullated bed hydro-modification reaction process UR220;

[0531] ③ The operating pressure of the second ebullated bed hydro-modification reaction stage U220 is higher than the operating pressure of the first ebullated bed hydro-modification reaction stage U210, and the second separated gas partially or completely enters the first ebullated bed hydro-modification reaction process UR210 by its own pressure, and / or a part of the second separated liquid enters the first ebullated bed hydro-modification reaction process UR210 by its own pressure;

[0532] And / or, the second ebullated bed hydro-modification reaction stage U220 is provided with a second separation liquid delivery pump, and its working mode is selected from one or more of the following:

[0533] ① Transporting circulating reaction liquid to the first ebullated bed hydro-modification reaction process UR210;

[0534] ②Transporting the cyclic reaction liquid to the second ebullated bed hydrogenation modification reaction process UR220;

[0535] ③ Transporting reaction feed liquid to the third ebullated bed hydrogenation modification reaction process UR230;

[0536] ④ The operating pressure of the third ebullated bed hydrogenation modification reaction stage U230 is higher than the operating pressure of the second ebullated bed hydrogenation modification reaction stage U220, and the third separated gas partially or completely enters the second ebullated bed hydrogenation modification reaction process UR220 by relying on its own pressure, and / or, a part of the third separated liquid enters the second ebullated bed hydrogenation modification reaction process UR220 by relying on its own pressure, and a part of the third separated liquid is used as the third separated liquid net product.

[0537] In the present invention, generally, the ebullated bed hydroprocessing reaction process R20 comprises two or more hydroprocessing reaction stages connected in series;

[0538] Two or more ebullated bed hydro-modification reaction stages connected in series realize an operation mode of increasing reaction temperature, and the average reaction temperature of the downstream ebullated bed hydro-modification reaction stage is 5 to 30°C higher than the average reaction temperature of the upstream ebullated bed hydro-modification reaction stage;

[0539] The average reaction temperature of the ebullated bed hydroprocessing reaction stage refers to the sum of the product of the arithmetic mean of the process fluid reaction temperature at the starting reaction of the catalyst bed layer and the process fluid reaction temperature at the end reaction of the catalyst bed layer in each reaction zone of the ebullated bed hydroprocessing reaction stage and the volume coefficient of the sub-reaction zone under normal operation;

[0540] The volume coefficient of a sub-reaction zone of the ebullated bed hydroprocessing reaction stage under normal operating conditions refers to the ratio of the volume of the sub-reaction zone to the total volume of all sub-reaction zones of the ebullated bed hydroprocessing reaction stage under normal operating conditions.

[0541] In the present invention, usually, in the generated oil fractionation process of the ebullated bed hydromodification reaction process R20, a heavy fraction KXL is separated from a hydrocarbon flow containing at least the final separation liquid, and part of the heavy fraction KXL is returned as a circulating reaction material KXL-R to any downstream ebullated bed hydromodification reaction stage of the ebullated bed hydromodification reaction process R20 for a cyclic hydrogenation reaction to reduce the aromatic carbon rate. The working mode can be selected from one or more of the following:

[0542] ① In the generated oil fractionation process of the ebullated bed hydromodification reaction process R20, a heavy fraction KXL1 mainly composed of hydrocarbons with a conventional boiling point of 280 to 520° C. is separated from the hydrocarbon flow containing at least the final separation liquid, and part of the heavy fraction KXL1 is returned as a circulating reaction material KXL1-R to any downstream hydromodification reaction process of the ebullated bed hydromodification reaction process R20 for a cyclic hydrogenation reaction to reduce the aromatic carbon rate;

[0543] ② In the generated oil fractionation process of the ebullated bed hydromodification reaction process R20, a heavy fraction KXL2 mainly composed of hydrocarbons with a conventional boiling point of 320 to 520° C. is separated from the hydrocarbon flow containing at least the final separation liquid, and a part of the heavy fraction KXL2 is returned as a circulating reaction material KXL2-R to any downstream hydromodification reaction process of the ebullated bed hydromodification reaction process R20 for a cyclic hydrogenation reaction to reduce the aromatic carbon rate;

[0544] ③ In the generated oil fractionation process of the ebullated bed hydromodification reaction process R20, a heavy fraction KXL3 mainly composed of hydrocarbons with a conventional boiling point of 410-520°C is separated from the hydrocarbon flow at least containing the final separation liquid, and part of the heavy fraction KXL3 is returned as the circulating reaction material KXL3-R to any downstream hydromodification reaction process of the ebullated bed hydromodification reaction process R20 for a circulating hydrogenation reaction to reduce the aromatic carbon rate.

[0545] In the present invention, usually, in the generated oil fractionation process of the ebullated bed hydromodification reaction process R20, a heavy fraction KYL is separated from a hydrocarbon stream containing at least the final separation liquid, and part of the heavy fraction KYL is returned as a circulating reaction material KYL-R to any downstream ebullated bed hydromodification reaction stage of the ebullated bed hydromodification reaction process R20 for a circulating hydrogenation reaction to reduce the aromatic carbon rate. The method for producing the circulating reaction material KYL-R can be selected from one or more of the following:

[0546] ① In the first hot low-pressure separation process based on the logistics of the final separation liquid, the logistics based on the final separation liquid is depressurized and separated into a first hot low-pressure separation gas and a first hot low-pressure separation liquid;

[0547] Part of the first hot low-pressure separation liquid is used as circulating reaction material KYL-R;

[0548] The operating conditions of the first hot low-pressure separation process are: temperature of 320-420°C and pressure of 1.5-4.0 MPa;

[0549] ② In the first hot low-pressure separation process based on the logistics of the final separation liquid, the logistics based on the final separation liquid is depressurized and separated into a first hot low-pressure separation gas and a first hot low-pressure separation liquid;

[0550] In the second hot low-pressure separation process, the first hot low-pressure separation liquid is depressurized and separated into a second hot low-pressure separation gas and a second hot low-pressure separation liquid;

[0551] Part of the second hot low-pressure separation liquid is used as circulating reaction material KYL-R;

[0552] The operating conditions of the first hot low-pressure separation process are: temperature of 320-420°C and pressure of 1.5-4.0 MPa;

[0553] The operating conditions of the second hot low-pressure separation process are: temperature of 320-420°C and pressure of 0.10-0.50 MPa.

[0554] The present invention generally separates the first fractionation tower bottom oil in the first fractionation tower system based on the logistics of the first hot low-pressure separation liquid and / or the second hot low-pressure separation liquid;

[0555] a first fractionation column system, with or without a sidestream distillation column;

[0556] A portion of the bottom oil of the first fractionation tower is used as circulating reaction material KYL-R;

[0557] The operating pressure of the distillation tower is 0.05~0.45MPa.

[0558] In the present invention, generally, in the second fractionation tower system, the second fractionation tower bottom oil is separated based on the logistics of the first fractionation tower bottom oil;

[0559] a second fractionator system, with or without a sidestream distillation column;

[0560] A portion of the bottom oil of the second fractionation tower is used as circulating reaction material KYL-R;

[0561] The second distillation tower is a vacuum distillation tower, and the operating pressure of the second distillation tower is -0.03 to -0.090 MPa.

[0562] In the present invention, usually, in the generated oil fractionation process of the ebullated bed hydromodification reaction process R20, a heavy fraction KEYL mainly composed of hydrocarbons with a conventional boiling point higher than 320° C. is separated from a hydrocarbon stream containing at least a final separation liquid, and a hydrocarbon stream based on part of the heavy fraction KEYL is returned as a circulating reaction material KEYL-R to an ebullated bed hydromodification reaction process of any downstream ebullated bed hydromodification reaction stage of the ebullated bed hydromodification reaction process R20 to carry out a circulating hydrogenation reaction for reducing the aromatic carbon rate;

[0563] The ratio of the weight flow rate of the circulating reaction material KEYL-R to the weight flow rate of the heavy fraction KEYL net product is 0.15 to 7.00;

[0564] The circulating reaction material KEYL-R is returned to the ebullated bed hydrogenation modification reaction process R20 for the cyclic hydrogenation reaction to reduce the aromatic carbon rate, so that the hydrogen supply index of the heavy fraction KEYL net product is increased by 0.5 to 12.0.

[0565] In the present invention, generally, the ratio of the weight flow rate of the circulating reaction material KEYL-R to the weight flow rate of the heavy fraction KEYL net product is 1.00 to 3.0;

[0566] The circulating reaction material KEYL-R is returned to the ebullated bed hydrogenation modification reaction process R20 for the cyclic hydrogenation reaction to reduce the aromatic carbon rate, so that the hydrogen supply index of the heavy fraction KEYL net product is increased by 1.5 to 6.0.

[0567] In the present invention, the ebullated bed hydro-modification reaction process R20 can use two or more parallel ebullated bed hydro-modification reaction series to process narrow fraction oils of different boiling ranges from coal direct liquefaction oil respectively;

[0568] Any ebullated bed hydro-modification reaction series, including two or more ebullated bed hydro-modification reaction stages of its feedstock oil liquid phase connected in series, the intermediate product separation liquid separated in any intermediate product separation process enters the ebullated bed hydro-modification reaction process of the adjacent downstream ebullated bed hydro-modification reaction stage;

[0569] In the gas-liquid separation process of the reaction effluent of any ebullated bed hydro-modification reaction stage, for the liquid phase separated from the ebullated bed hydro-modification reaction effluent of this stage, stripping the ammonia component therein with or without stripping hydrogen;

[0570] The average volumetric concentration of ammonia in the gas phase of any downstream ebullated bed hydroprocessing reaction process is lower than the average volumetric concentration of ammonia in the gas phase of the adjacent upstream ebullated bed hydroprocessing reaction process;

[0571] The aromatic carbon ratio of all hydrocarbons with a normal boiling point higher than 200°C in the reaction effluent of any downstream ebullated-bed hydromodification reaction process is lower than the aromatic carbon ratio of all hydrocarbons with a normal boiling point higher than 200°C in the reaction effluent of the adjacent upstream ebullated-bed hydromodification reaction process.

[0572] The present invention can adopt two parallel series to process the light hydrocarbon stream R20F11A and the medium hydrocarbon stream R20F12A respectively.

[0573] The light hydrocarbon stream R20F11A from coal direct liquefaction oil is mainly composed of hydrocarbons with a conventional boiling point below 280°C;

[0574] The medium hydrocarbon stream R20F12A from the oil generated from direct coal liquefaction is mainly composed of hydrocarbons with a conventional boiling point of 280 to 470°C.

[0575] The present invention can adopt two parallel series to process the light hydrocarbon stream R20F11B and the medium hydrocarbon stream R20F12B of the oil produced by direct coal liquefaction respectively;

[0576] The light hydrocarbon stream R20F11B from the oil produced by direct coal liquefaction is mainly composed of hydrocarbons with a conventional boiling point below 280°C;

[0577] The medium hydrocarbon stream R20F12B from the oil generated from direct coal liquefaction is mainly composed of hydrocarbons with a conventional boiling point of 280 to 520°C.

[0578] The present invention can adopt three parallel series to process light hydrocarbon stream R20F11C from coal direct liquefaction oil, medium hydrocarbon stream R20F12C from coal direct liquefaction oil, and heavy hydrocarbon stream R20F13C from coal direct liquefaction oil respectively;

[0579] The light hydrocarbon stream R20F11C from the oil produced by direct coal liquefaction is mainly composed of hydrocarbons with a conventional boiling point below 280°C;

[0580] The medium hydrocarbon stream R20F12C from the oil produced by direct coal liquefaction is mainly composed of hydrocarbons with a conventional boiling point of 280 to 400°C;

[0581] The heavy hydrocarbon stream R20F13C produced from direct coal liquefaction is mainly composed of hydrocarbons with a conventional boiling point of 400 to 525°C.

[0582] In the present invention, generally, when the ebullated bed hydromodification reaction process R20 processes hydrocarbons mainly composed of conventional boiling points below 320°C, the ebullated bed hydromodification reaction process R20 and the hydromodification reaction process R30 are carried out in series, the reaction effluent of the ebullated bed hydromodification reaction process R20 enters the hydromodification reaction process R30, and / or the hot high-pressure separation gas separated from the reaction effluent of the ebullated bed hydromodification reaction process R20 in its hot high-pressure separation process enters the hydromodification reaction process R30, and / or the hot high-pressure separation liquid separated from the reaction effluent of the ebullated bed hydromodification reaction process R20 in its hot high-pressure separation process, and the hydrocarbon oil mainly composed of hydrocarbons with conventional boiling points below 250°C separated based on the hot high-pressure separation liquid enters the hydromodification reaction process R30.

[0583] In the present invention, generally, the ebullated bed hydroprocessing reaction process R20 comprises two or more ebullated bed hydroprocessing reaction stages connected in series;

[0584] The operating pressure of the ebullated bed hydrogenation modification reaction stage gradually decreases along the process. The operating pressure of the gas-liquid separation process of the reaction product of the upstream ebullated bed hydrogenation modification reaction stage is higher than the operating pressure of the adjacent downstream ebullated bed hydrogenation modification reaction stage. The reaction zone of the downstream ebullated bed hydrogenation modification reaction process and the reaction zone of the upstream ebullated bed hydrogenation modification reaction process are essentially interconnected liquid phase reaction zones of the interconnector type. The liquid level control method of the intermediate gas-liquid separation process adopts the control method of the communicating vessel for the upstream expanded bed staged series hydrogenation reaction process of hydrocarbon materials of Application No. 202310229274.7.

[0585] The present invention, generally, in the final gas-liquid separation process US290, the gas-liquid mixed phase flow of the final ebullating bed hydro-modification reaction effluent is separated into a final separation gas and a final separation liquid;

[0586] In the warm and high pressure separation process, the logistics based on the final separation gas is separated into warm and high pressure gas and warm and high pressure oil. The operating conditions of the warm and high pressure separation process are: temperature of 160-280°C and pressure of 10.0-25.0MPa;

[0587] The degassed oil stream obtained after the high temperature oil fractionation stream is depressurized and degassed enters the fractionation tower of the final stage ebullating bed hydro-modification reaction to generate the oil fractionation process;

[0588] In the hot low-pressure separation process of the final separation liquid, the logistics of the final separation liquid is depressurized and separated into hot low-pressure separation gas and hot low-pressure separation liquid. The operating conditions of the hot low-pressure separation process of the final separation liquid are: temperature of 320-400°C and pressure of 0.40-4.0MPa;

[0589] The hot low-pressure separation liquid is fed into a fractionation tower for the fractionation of the oil produced by the final ebullating bed hydro-modification reaction;

[0590] In the temperature and low pressure separation process, the hot low pressure separation gas is condensed and separated into temperature and low pressure gas and temperature and low pressure oil. The operating conditions of the temperature and low pressure separation process are: temperature 150-300℃, pressure 0.40-4.0MPa;

[0591] The logistics based on low temperature oil separation enters the distillation tower of the final boiling bed hydro-modification reaction to generate oil for the distillation process.

[0592] In the present invention, generally, in the cold high-pressure separation process, the cold high-fraction gas and the cold high-fraction oil are separated after the flow of the warm high-fraction gas is condensed. The operating conditions of the cold high-pressure separation process are: temperature of 20 to 80° C. and pressure of 10.0 to 25.0 MPa;

[0593] In the cold low-pressure separation process, the cold high-fraction oil-based logistics is depressurized and separated into cold low-fraction gas and cold low-fraction oil. The operating conditions of the cold low-pressure separation process are: temperature of 20-80°C and pressure of 0.4-4.0MPa;

[0594] The logistics based on the cold low-fraction oil enters the distillation tower of the final boiling bed hydro-modification reaction to generate the oil in the distillation process.

[0595] In the present invention, generally, in the ebullating bed hydrogenation modification reaction process R20, in the intermediate separation gas cooling high pressure separation process, the intermediate separation gas is separated into the intermediate separation gas cooling high fraction gas and the intermediate separation gas cooling high fraction oil;

[0596] In the cold high-pressure separation process, cold high-fraction gas and cold high-fraction oil are separated after the logistics of the final separation gas is condensed;

[0597] At least a portion of the intermediate separated gas cooled high-fraction gas and / or at least a portion of the intermediate separated gas cooled high-fraction gas and / or the cold high-fraction gas enters the cold high-fraction gas of the ebullated bed hydrogenation modification reaction process R20, and enters the ebullated bed hydrogenation modification reaction process of any ebullated bed hydrogenation modification reaction stage of the ebullated bed hydrogenation modification reaction process R20.

[0598] In the present invention, in the ebullating bed hydrogenation modification reaction process R20, the intermediate separation gas can be separated into intermediate separation gas cooling high-fraction gas and intermediate separation gas cooling high-fraction oil in the intermediate separation gas cooling high-fraction separation process;

[0599] In the cold high-pressure separation process, cold high-fraction gas and cold high-fraction oil are separated after the logistics of the final separation gas is condensed;

[0600] At least a portion of the intermediate separated gas cooled high fraction gas and the final stage cooled high fraction gas enters the ebullated bed hydro-modification reaction process of any ebullated bed hydro-modification reaction stage of the ebullated bed hydro-modification reaction process R20;

[0601] The intermediate separated gas cooled high-fraction gas and / or the final stage cooled high-fraction gas enters the coal hydrogenation direct liquefaction reaction process R10 as exhaust gas and is used as hydrogen raw material.

[0602] In the present invention, in the ebullating bed hydrogenation modification reaction process R20, the intermediate separation gas can be separated into intermediate separation gas cooling high-fraction gas and intermediate separation gas cooling high-fraction oil in the intermediate separation gas cooling high-fraction separation process;

[0603] In the cold high-pressure separation process, cold high-fraction gas and cold high-fraction oil are separated after the logistics of the final separation gas is condensed;

[0604] At least a portion of the intermediate separated gas cooled high fraction gas and the final stage cooled high fraction gas enters the ebullated bed hydro-modification reaction process of any ebullated bed hydro-modification reaction stage of the ebullated bed hydro-modification reaction process R20;

[0605] At least a portion of the intermediate separated gas cooled high-fraction gas and / or at least a portion of the final stage cooled high-fraction gas is used as exhaust gas to enter the membrane separation system of the cooled high-fraction gas of the coal hydrogenation direct liquefaction reaction process R10 and be used as membrane separation feed gas.

[0606] In the present invention, generally, in the ebullated bed hydroprocessing reaction process R20, at least a portion of the new hydrogen enters the ebullated bed hydroprocessing reaction process of the most downstream ebullated bed hydroprocessing reaction stage.

[0607] In the present invention, generally, in the generated oil fractionation process of the ebullated bed hydro-modification reaction process R20, a hydrogen-donating solvent oil DS mainly composed of hydrocarbons having a conventional boiling point between 200 and 550° C. is separated from a hydrocarbon stream containing at least a final separation liquid;

[0608] Coal slurry DS-TM is prepared from hydrogen-donating solvent oil DS and coal powder;

[0609] The material based on coal slurry DS-TM is converted into coal hydrogenation direct liquefaction reaction effluent R10P through coal hydrogenation direct liquefaction reaction process R10;

[0610] Separating the coal hydrogenation direct liquefaction reaction effluent R10P to obtain the coal direct liquefaction product oil distillate R10P-SP;

[0611] The stream based on distillate oil R10P-SP is used as feedstock oil R20F for the ebullated-bed hydro-modification reaction.

[0612] The present invention, generally, in the fractionation process of the product oil in the ebullated bed hydro-modification reaction process R20, a fraction R20P-SP1 mainly composed of hydrocarbons with a conventional boiling point between 200 and 350°C and a heavy fraction R20P-SP2 composed of hydrocarbons with a conventional boiling point higher than 320°C are separated from a hydrocarbon stream containing at least a final separation liquid;

[0613] Part of the material based on fraction R20P-SP1 is used as feedstock for the hydro-upgrading reaction process R30;

[0614] A material based partly on fraction R20P-SP1 and at least partly on heavy fraction R20P-SP2, used alone or in combination as hydrogen supply solvent oil DS;

[0615] Coal slurry DS-TM is prepared from hydrogen-donating solvent oil DS and coal powder;

[0616] The material based on coal slurry DS-TM is converted into coal hydrogenation direct liquefaction reaction effluent R10P through coal hydrogenation direct liquefaction reaction process R10;

[0617] Separating the coal hydrogenation direct liquefaction reaction effluent R10P to obtain the coal direct liquefaction product oil distillate R10P-SP;

[0618] The distillate oil R10P-SP was used as the feed oil R20F for the ebullated bed hydro-modification reaction.

[0619] In the present invention, in the ebullated bed hydrogenation modification reaction process R20, any ebullated bed hydrogenation modification reaction process can be a slurry bed-ebullated bed combined hydrogenation modification reaction mode using a slurry bed hydrogenation catalyst at the same time.

[0620] In the present invention, generally, the feedstock oil R20F of the ebullated bed hydro-modification reaction process R20 has an organic nitrogen content of 0.20 to 1.5 wt % and an organic oxygen content of 0.4 to 9.0 wt %.

[0621] In the present invention, generally, in the produced oil fractionation process of the ebullated bed hydro-modification reaction process R20, a first heavy fraction KEYL1 mainly composed of hydrocarbons with a normal boiling point of 320 to 470° C. and a second heavy fraction KEYL2 mainly composed of hydrocarbons with a normal boiling point of >470° C. are separated from a hydrocarbon stream containing at least a final separation liquid;

[0622] Based on the hydrocarbon-containing flow of part of the second heavy fraction KEYL2 as the circulating reaction material KEYL2-R, the circulating reaction material is returned to any downstream boiling bed hydro-modification reaction stage U2-77 of the boiling bed hydro-modification reaction process R20 to carry out a circulating hydrogenation reaction to reduce the aromatic carbon rate;

[0623] Based on a part of the hydrocarbon-containing flow of the first heavy fraction KEYL1 as a circulating reaction material KEYL1-R, the hydrocarbon-containing flow is returned to any downstream ebullated bed hydro-modification reaction stage U2-88 of the ebullated bed hydro-modification reaction process R20 to carry out a circulating hydrogenation reaction for reducing the aromatic carbon rate;

[0624] The process flow direction of gradually increasing the hydrogenation depth of the feedstock R20F in the ebullated bed hydrogenation modification reaction process R20 is forward flow, and the ebullated bed hydrogenation modification reaction stage U2-88 is located downstream of the ebullated bed hydrogenation modification reaction stage U2-77.

[0625] Example

[0626] Example 1

[0627] According to the present invention, the hydrogenation modification reaction process R20 adopts an intermediate degassing two-stage hydrogenation modification reaction method, using a first hydrogenation modification reaction process and a second hydrogenation modification reaction process; each ebullated bed hydrogenation modification reaction stage uses an ebullated bed hydrogenation modification reactor, and is provided with a liquid reaction product circulation pump, so that part of the liquid product of this reaction stage is circulated in the ebullated bed hydrogenation modification reaction process of this stage; by reducing the volume concentration of non-hydrogen components ammonia and water vapor in the gas phase of the second hydrogenation modification reaction process, the hydrogenation stable catalyst reaction rate of the second hydrogenation modification reaction process is increased, and the first separated gas and the second separated gas are mixed into a mixed hot high-fraction gas.

[0628] Table 12 shows the properties of R20 feedstock oil, the first hydrogenation-modified oil, and the second hydrogenation-modified oil in the hydrogenation-modified reaction process of Example 1.

[0629] Compared with the space velocity of 1.7h in the second hydrogenation reaction process in the single-stage hydrogenation reaction method, -1 In comparison, the space velocity of the second hydrogenation reaction process in Example 1 is 1.89h -1 That is, it is increased by about 35%. Accordingly, the amount of the hydrogenation catalyst used in the second hydrogenation reaction process of Example 1 is reduced by about 26%.

[0630] Table 13 is the material balance of the step-by-step reaction and the overall reaction of the hydrogenation modification reaction process R20 of Example 1.

[0631] The goal of the hydrogenation modification reaction process R20 is to reduce the aromatic carbon content (Fa) of the crude oil from 54.1 mol% to 29.7 mol%, that is, to reduce it by 24.4 mol%, and to increase the hydrogen supply index of the mixed raw material from 17.2 to about 23.7, that is, to increase it by 6.5.

[0632] The specific process flow is described below.

[0633] The specific process is as follows:

[0634] The fresh raw oil, i.e., the first hydro-modification reaction raw oil, is heat-exchanged with the mixed hot high-fraction gas, and then mixed with the first liquid sulfur and the first hot mixed hydrogen to form the first hydro-modification reaction mixed feed, which is then heated in the first hydro-modification reaction mixed feed heating furnace to become the hot first hydro-modification reaction mixed feed, and then enters the first hydro-modification reactor from the bottom to be converted into the first hydro-modification reaction effluent;

[0635] In the first gas-liquid separation process US210, the gas-liquid mixed phase flow of the first hydro-modification reaction effluent is separated into a first separated gas and a first separated liquid;

[0636] In the first gas stripping process, a first hydrogen stripping tower with 10 sieve trays is set, the descending first separated liquid is countercurrently contacted with the ascending first stripping gas to strip off low-boiling components such as ammonia and water, the first stripping gas is discharged from the top of the first hydrogen stripping tower, and the first stripping liquid is discharged from the bottom of the first hydrogen stripping tower;

[0637] The first lifted gas is mixed with the first separated gas for treatment;

[0638] The first gas-liquid separation process US210 and the first gas stripping process can be arranged in one pressure-bearing shell;

[0639] The second hot mixed hydrogen passes through the second hot mixed hydrogen heating furnace to become the feed temperature-adjusting hydrogen gas for the second hydro-modification reactor, and is mixed with the first separation liquid and the second liquid sulfur to become the total feed for the second hydro-modification reaction, and enters the second hydro-modification reactor from the bottom to be converted into the second hydro-modification reaction effluent;

[0640] In the second hydro-modification reaction effluent gas-liquid separation process US220, the second hydro-modification reaction effluent is separated into a second separated gas and a second separated liquid;

[0641] The first separated gas and the second separated gas are mixed into a mixed hot high-fraction gas. The mixed hot high-pressure separated gas is heat exchanged with the first hydrogenation reforming reaction raw oil and the total temperature mixed hydrogen, and then injected with washing water, and then heat exchanged with the cold mixed hydrogen. Then, it is cooled by a high-pressure air cooler and enters a cold high-pressure separator to be separated into cold high-fraction gas, cold high-fraction oil, and cold high-fraction water.

[0642] The new hydrogen had a hydrogen concentration of 99.9 mol% and a methane concentration of 0.01 mol%.

[0643] After the cold high-fraction gas is pressurized by the circulating hydrogen compressor, it is mixed with new hydrogen to form mixed hydrogen. The cold mixed hydrogen is heat-exchanged with the mixed hot high-fraction gas after water injection to form warm mixed hydrogen. The warm mixed hydrogen is heat-exchanged with the mixed hot high-fraction gas to form hot mixed hydrogen. The hot mixed hydrogen is divided into two paths: a first path of hot mixed hydrogen mixed with the first hydrogenation reforming reaction raw oil, and a second path of hot mixed hydrogen mixed with the first separation liquid.

[0644] The second separated liquid enters the hot low-pressure separator after depressurization and is separated into hot low-pressure gas and hot low-pressure oil;

[0645] After the hot low-pressure gas is cooled, it enters the warm low-pressure separator with a temperature of 250°C and a pressure of 2.6MPa to be separated into warm low-pressure gas and warm low-pressure oil.

[0646] After the cold high-pressure oil is depressurized, it enters the cold low-pressure separator and is separated into cold low-pressure gas and cold low-pressure oil;

[0647] After the warm low fraction gas is mixed with the washing water, it is cooled by the warm low fraction gas air cooler and then enters the cold low pressure separator with a temperature of 54℃ and a pressure of 2.55MPa to separate the cold low fraction gas and cold low pressure fraction oil.

[0648] Hot low-pressure oil separators, warm low-pressure oil separators and cold low-pressure oil separators enter the distillation tower to separate narrow-fraction oil products.

[0649] Table 14 shows the material composition of the first gas-liquid separation process US210 and the first separated liquid gas stripping process UB210 in Example 1.

[0650] From Table 14 we can see that:

[0651] ① In the first gas-liquid separation process US210, 82.52 mol% of the ammonia component, 62.61 mol% of the water component, 75.23 mol% of the methane component, more than 36.62 mol% of the conventional liquid hydrocarbons of C5 to NBP135, and more than 26.43 mol% of the conventional liquid hydrocarbons of NBP140 to NBP185 in the first hydrogenation stabilization reaction effluent enter the first separation gas;

[0652] ② In the first separated liquid gas stripping process, 6.25 mol% of ammonia components, 47.7 mol% of water components, 61.0 mol% of methane components, 82.59 mol% of conventional liquid hydrocarbons of C5 to NBP135, and more than 88.71 mol% of conventional liquid hydrocarbons of NBP140 to NBP185 in the first separated liquid entered the first stripped liquid;

[0653] The molar flow rate of the ammonia component in the first extracted liquid is 1.15 Kgmol / h, which is only 1.09% of the molar flow rate of the ammonia component in the first hydrogenation stabilization reaction effluent of 105.25 Kgmol / h;

[0654] ③ The gas phase ammonia molar concentration at the start of the second hydro-modification reaction (process simulation calculation value) is 0.179 mol%, which is only 0.0775 times the gas phase ammonia molar concentration at the end of the first hydro-modification reaction (process simulation calculation value) of 2.31 mol%;

[0655] ④ The molar concentration of gaseous ammonia at the end of the second hydrogenation reaction (process simulation calculated value) is 0.632 mol%, which is only 0.274 times the molar concentration of gaseous ammonia at the end of the first hydrogenation reaction (process simulation calculated value) of 2.31 mol%, which is beneficial to the improvement of the activity of the second hydrogenation catalyst.

[0656] Table 12 Properties of R20 feedstock oil, first hydro-modified oil, and second hydro-modified oil during the hydro-modification reaction process of Example 1

[0657]

[0658]

[0659] Table 13 Material balance of stepwise reaction and overall reaction of R20 in Example 1 hydrogenation modification reaction process

[0660]

[0661] Table 14 Material composition of the first gas-liquid separation process US210 and the first separated liquid stripping process UB210 in Example 1

[0662]

[0663] Example 2

[0664] Based on Example 1, part of the liquid phase product at the outlet of the second ebullated bed hydro-modification reactor is circulated to the mixing chamber at the bottom of the first ebullated bed hydro-modification reactor for circulation reaction.

[0665] Example 3

[0666] Based on Example 1, the liquid product circulation pump of the first ebullated bed hydro-modification reactor system is cancelled, and the liquid product circulation pump of the second ebullated bed hydro-modification reactor system is used to circulate part of the liquid phase product at the outlet of the second ebullated bed hydro-modification reactor to the mixing chamber at the bottom of the first ebullated bed hydro-modification reactor for circulation reaction, and the circulation oil flow rate is adjusted to control the expansion rate of the hydrogenation stable catalyst bed of the first ebullated bed hydro-modification reactor and the second ebullated bed hydro-modification reactor to be within 30 volume %;

[0667] Compared with Example 1, one circulating pump is reduced;

[0668] At this time, the circulating oil flow rate of the first reaction stage and the circulating oil flow rate of the second reaction stage are equal.

[0669] Example 4

[0670] Based on Example 1, the circulating pump RPUMP-1 at the bottom of the first ebullated bed hydro-modification reactor is not provided, and the circulating pump RPUMP-2 at the bottom of the second ebullated bed hydro-modification reactor is not provided. The first hydro-modification reaction stage is provided with a first intermediate separation liquid delivery pump PUMP1TO2, and its working mode is selected from one or more of the following:

[0671] ① The first separated liquid is pumped by the delivery pump PUMP1TO2 to increase the operating pressure to 0.6MPaABS and enters the mixing chamber at the bottom of the second ebullated bed hydro-modification reactor;

[0672] The second hydro-modification reaction process raw oil is delivered to the second hydro-modification reaction process UR220, that is, the first intermediate separation liquid net product is delivered;

[0673] The operating pressure of the second gas-liquid separation process US220 is specified to be higher than the operating pressure of the first hydro-reforming reaction process UR210, so that all the second separated gas can enter the mixing chamber at the bottom of the first ebullated bed hydro-reforming reactor by its own pressure for secondary use in a cyclic reaction;

[0674] Allowing part of the second separated liquid to enter the mixing chamber at the bottom of the first ebullated bed hydro-modification reactor by its own pressure for circulation reaction;

[0675] At the same time, part of the net product of the second separated liquid enters the separation and fractionation process of the hydrogenated stable generated oil;

[0676] ② According to the need, part of the first intermediate separation liquid is transported to the first hydrogenation and modification reaction process UR210 for circulation reaction;

[0677] The whole new hydrogen of the device passes through the second ebullated bed hydrogenation reactor, and the second separated gas passes through the first ebullated bed hydrogenation reactor.

[0678] Example 5

[0679] Based on Example 1, the first hydromodification reaction process UR210 and the second hydromodification reaction process UR220 can achieve an optimized operation mode of increasing reaction temperature, that is, the average reaction temperature of the first hydromodification reaction zone is relatively low (the mixed feed temperature at the reactor inlet is 305°C, the outlet temperature of the bottom mixing chamber in the reactor is 346°C, the outlet temperature of the upper part of the reactor is 365°C, and the average temperature of the reaction zone is 365°C), while the average reaction temperature of the second hydromodification reaction zone is relatively high (the mixed feed temperature at the reactor inlet is 305°C, the outlet temperature of the bottom mixing chamber in the reactor is 367°C, the outlet temperature of the upper part of the reactor is 385°C, and the average temperature of the reaction zone is about 385°C). At the same time, the catalyst loading amount is adjusted, which has the following advantages:

[0680] ① The first hydro-modification reaction zone of the low-boiling-point hydrocarbon component carries out hydro-deoxygenation, hydro-desulfurization, hydro-denitrogenation, olefin hydrogenation saturation, and hydrogenation aromatic saturation reactions at a relatively low temperature with a suitable reaction rate, thereby avoiding the concentrated hydro-refining exothermic reaction of the reactive components;

[0681] At the same time, the high-boiling-point polycyclic aromatic hydrocarbon components are first converted into polycyclic aromatic hydrocarbon components stabilized by shallow hydrogenation at a low temperature in the first hydrogenation modification reaction zone, which can reduce the thermal condensation reaction of polycyclic aromatic hydrocarbons under high temperature conditions;

[0682] ② The polycyclic aromatic hydrocarbon components after shallow hydrogenation stabilization undergo efficient hydrogenation aromatic saturation reaction at a higher temperature in the second hydrogenation modification reaction zone (the rate of aromatic hydrogenation saturation is fast). Due to the reduction in ammonia concentration, the adsorption competitiveness of the polycyclic aromatic hydrocarbon components on the active surface of the hydrogenation stabilization catalyst is enhanced, thereby improving the selectivity of the polycyclic aromatic hydrocarbon hydrogenation aromatic saturation reaction in the second hydrogenation modification reaction zone.

[0683] Example 6

[0684] Based on Example 1, a portion of the heavy fraction (distillate oil with a conventional boiling point higher than 320°C) separated from the second separated liquid net product (the weight ratio to the flow rate of the heavy fraction net product is usually 50-400%, generally 150-250%) is returned to the second ebullated bed hydro-modification reactor for a cyclic reaction to carry out efficient hydrogenation and dearomatization, and the hydrogen supply index of the heavy fraction net product is increased by a value of usually 0.5-7.0, generally 1.5-4.5.

[0685] Example 7

[0686] Based on Example 1, the first gas-liquid separation process US210 makes the operating pressure of the first intermediate separator higher than the operating pressure of the downstream second ebullated bed hydrogenation modification reactor. The upstream reaction zone, the intermediate separation zone, and the downstream reaction zone contained in the second ebullated bed hydrogenation modification reactor, the first intermediate separator, and the second ebullated bed hydrogenation modification reactor are essentially interconnected liquid phase reaction zones. The liquid level control method of the first intermediate separator adopts the control method of the communicating vessel for the upstream expanded bed staged series hydrogenation reaction process of hydrocarbon materials of application number 202310229274.7.

[0687] Example 8

[0688] Based on Example 1, a three-stage hydro-modification reaction method with intermediate degassing is adopted, and the tasks of each hydro-modification reaction process are allocated as follows:

[0689] The organic nitrogen hydroremoval rate of the first hydromodification reaction stage is 55% of the overall denitrification rate;

[0690] The organic nitrogen hydroremoval rate of the second hydromodification reaction stage is 30% of the overall denitrification rate;

[0691] The organic nitrogen hydroremoval rate of the third hydromodification reaction stage is 15% of the overall denitrification rate.

[0692] Example 9

[0693] Based on Examples 1 to 8, 1 to 5% of the cold high-pressure separation gas is discharged as waste hydrogen from the methane in the exhaust circulating hydrogen and enters the cold high-gas membrane separation system of the coal hydrogenation direct liquefaction reaction process for gas separation to obtain membrane separation permeate hydrogen and membrane separation tail gas.

Claims

1. A method for the intermediate degassing and graded ebullated bed hydrogenation modification of coal direct liquefaction oil, characterized in that: The feedstock oil R20F of the ebullated bed hydro-modification reaction process R20 is a hydrocarbon stream containing organic nitrogen and organic oxygen, including dicyclic aromatic hydrocarbons and / or polycyclic aromatic hydrocarbons, and at least a hydrocarbon stream containing distillate oil generated by direct coal liquefaction, with or without carbonaceous solid particles; In the ebullated bed hydro-modification reaction process R20, in the presence of hydrogen, liquid hydrocarbons, an ebullated bed hydro-modification catalyst, and in the presence or absence of carbon-containing solid particles, a stream containing hydrocarbon liquid based on the feedstock oil R20F undergoes an ebullated bed hydro-modification reaction to be converted into hydrocarbons with a lower aromatic carbon content to obtain a hydro-modification reaction effluent R20P; In the ebullating bed hydro-modification reaction process R20, at least a portion of the organic nitrogen component of the logistics containing hydrocarbon liquid based on the feedstock oil R20F undergoes a hydrogenation hydrogenolysis reaction to produce ammonia, at least a portion of the organic oxygen component of the logistics containing hydrocarbon liquid based on the feedstock oil R20F undergoes a hydrogenation hydrogenolysis reaction to produce water, and at least a portion of the bicyclic aromatic hydrocarbons and / or polycyclic aromatic hydrocarbons of the logistics containing hydrocarbon liquid based on the feedstock oil R20F undergo a hydrogenation saturation reaction to be converted into aromatic hydrocarbons with a lower aromatic carbon rate; A hydrocarbon hydro-modification reaction stage, comprising a hydrocarbon hydro-modification reaction process and a gas-liquid separation process of the reaction effluent; A hydrocarbon ebullated bed hydro-modification reaction stage, comprising an ebullated bed hydro-modification reaction process and a gas-liquid separation process of the reaction effluent; The ebullated bed hydromodification reaction process R20 comprises at least two adjacent ebullated bed hydromodification reaction stages, a hydromodification reactor of other forms using or not using a stream containing hydrocarbon liquid based on the feedstock oil R20F, and a reaction stage of a hydromodification reactor of other forms using or not using a stream containing hydrocarbon liquid based on the feedstock oil R20F, wherein the other forms of hydromodification reactor are selected from one or more of the following: ① Micro-expanded bed with process fluid upflow; ② Fixed bed with process fluid upflow; ③ Fixed bed with downward flow of process fluid; ④Suspended bed or slurry bed; The ebullated bed hydroprocessing reaction process R20 comprises two or more ebullated bed hydroprocessing reaction stages connected in series for a flow containing hydrocarbon liquid based on the feedstock oil R20F, and is divided into an upstream ebullated bed hydroprocessing reaction stage and a downstream ebullated bed hydroprocessing reaction stage according to the main flow direction of the ebullated bed hydroprocessing reaction process of the feedstock oil R20F, wherein the most downstream ebullated bed hydroprocessing reaction stage is called a final ebullated bed hydroprocessing reaction stage; The intermediate product separation process refers to the gas-liquid separation process of the upstream hydro-modification reaction product between two adjacent hydro-modification reaction stages. The intermediate product separation process separates the intermediate product separation gas and the intermediate product separation liquid; The average volume concentration of gaseous ammonia in the ebullated bed hydro-modification reaction process refers to the arithmetic mean of the volume concentration of gaseous ammonia at the starting reaction point of the catalyst bed and the volume concentration of gaseous ammonia at the end reaction point of the catalyst bed in the ebullated bed hydro-modification reaction process; The average volumetric concentration of ammonia in the gas phase of the ebullated bed hydro-modification reaction process UR2N of any downstream ebullated bed hydro-modification reaction stage is lower than the average volumetric concentration of ammonia in the gas phase of the ebullated bed hydro-modification reaction process UR2M of the adjacent upstream ebullated bed hydro-modification reaction stage; The aromatic carbon ratio of all hydrocarbons with a conventional boiling point higher than 220° C. in the reaction effluent of any ebullated bed hydromodification reaction process UR2N is lower than the aromatic carbon ratio of all hydrocarbons with a conventional boiling point higher than 220° C. in the reaction feed of the ebullated bed hydromodification reaction process UR2N; In an intermediate product separation process MS of the reaction effluent of any upstream ebullating bed hydro-modification reaction stage, ammonia and water are stripped from the liquid phase separated from the hydro-modification reaction effluent of the stage with or without using a stripping hydrogen stream; The ebullated bed hydro-modification reaction process R20 comprises at least a first ebullated bed hydro-modification reaction stage U210 and a second ebullated bed hydro-modification reaction stage U220; (1) The first ebullated bed hydro-modification reaction stage U210, comprising the first ebullated bed hydro-modification reaction process UR210 and the first gas-liquid separation process US210; A hydrocarbon liquid-containing stream based on the feedstock oil R20F is used as the hydrocarbon-containing feedstock UR210F of the first ebullated bed hydro-modification reaction process UR210; In the first ebullated bed hydro-modification reaction process UR210, the hydrocarbon-containing feedstock UR210F is subjected to the first ebullated bed hydro-modification reaction and converted into the first ebullated bed hydro-modification reaction effluent UR210P; In the first gas-liquid separation process US210, the gas-liquid mixed phase flow of the first ebullated bed hydro-modification reaction effluent UR210P is separated into a first separated gas containing ammonia and water and a first separated liquid, and part of the ammonia component and part of the water component in the first ebullated bed hydro-modification reaction effluent UR210P enter the first separated gas; In the first gas-liquid separation process US210, the liquid phase separated from the gas-liquid mixed phase stream of the first ebullated bed hydro-modification reaction effluent UR210P is stripped with or without the use of the hydrogen-rich gas stream to reduce the ammonia content and water content in the liquid phase after stripping; When the first stripping process UB210 is used, the first hydrogen-rich stripping gas contacts the first separation liquid-based stream, i.e., the first stripping liquid, at least once and completes separation, the low-boiling point components in the first stripping liquid enter the gas phase to form the first stripped gas, and the unvaporized first stripping liquid forms the first stripped liquid; the weight content of ammonia in the first stripped liquid is lower than the weight content of ammonia in the first separation liquid; the weight content of ammonia in the first stripped gas is higher than the weight content of ammonia in the first hydrogen-rich stripping gas; (2) The second ebullated bed hydroprocessing reaction stage U220, comprising a second ebullated bed hydroprocessing reaction process UR220 and a second gas-liquid separation process US220; The hydrocarbon-containing stream based on the first separated liquid is used as the hydrocarbon-containing feedstock UR220F of the second ebullated bed hydro-modification reaction process UR220; In the second ebullated bed hydro-modification reaction process UR220, the hydrocarbon-containing feedstock UR220F is subjected to a second ebullated bed hydro-modification reaction and converted into a second ebullated bed hydro-modification reaction effluent UR220P; The average volume concentration of ammonia in the gas phase of the second ebullated bed hydro-modification reaction process UR220 is lower than the average volume concentration of ammonia in the gas phase of the first ebullated bed hydro-modification reaction process UR210; In the second gas-liquid separation process US220, the gas-liquid mixed phase flow based on the second ebullated bed hydro-modification reaction effluent UR220P is separated into a second separated gas and a second separated liquid, and part of the ammonia component in the second ebullated bed hydro-modification reaction effluent UR220P enters the second separated gas; The final ebullated bed hydroprocessing reaction stage U290 includes a final ebullated bed hydroprocessing reaction process UR290 and a final gas-liquid separation process US290; A hydrocarbon liquid-containing stream based on the intermediate product separation liquid of the adjacent upstream ebullated bed hydro-modification reaction stage is used as a hydrocarbon-containing feedstock UR290F for the final ebullated bed hydro-modification reaction process UR290; In the final ebullated bed hydroprocessing reaction stage U290, the hydrocarbon-containing feedstock UR290F of the final ebullated bed hydroprocessing reaction process UR290 is subjected to the final ebullated bed hydroprocessing reaction and converted into the final ebullated bed hydroprocessing reaction effluent UR290P; In the final gas-liquid separation process US290, the gas-liquid mixed phase flow based on the final ebullating bed hydrogenation modification reaction effluent UR290P is separated into the final separation gas and the final separation liquid.

2. The method according to claim 1, characterized in that: In the generated oil fractionation process of the ebullated bed hydroprocessing reaction process R20, a heavy fraction KEYL mainly composed of hydrocarbons with a conventional boiling point higher than 320°C is separated from the hydrocarbon flow containing at least the final separation liquid, and a hydrocarbon-containing flow based on part of the heavy fraction KEYL is returned as a circulating reaction material KEYL-R to the ebullated bed hydroprocessing reaction process of any downstream ebullated bed hydroprocessing reaction stage of the ebullated bed hydroprocessing reaction process R20 for a circulating hydrogenation reaction to reduce the aromatic carbon rate.

3. The method according to claim 1, characterized in that: In the intermediate product separation process of the reaction effluent of any upstream ebullating bed hydroprocessing reaction stage, the liquid phase separated from the hydroprocessing reaction effluent of this stage is subjected to two or more countercurrent contacts with the liquid phase using a stripping hydrogen flow to strip ammonia and water therein.

4. The method according to claim 1, characterized in that: The intermediate product separation process of the reaction effluent of any upstream ebullating bed hydroprocessing reaction stage and the hydrogen stripping process of the liquid phase separated from the hydroprocessing reaction effluent of this stage are completed in the same high-pressure vessel pressure shell.

5. The method according to claim 2, characterized in that: In the intermediate product separation process of the reaction effluent of any upstream ebullating bed hydroprocessing reaction stage, the liquid phase separated from the hydroprocessing reaction effluent of this stage is subjected to two or more countercurrent contacts with the liquid phase using a stripping hydrogen flow to strip ammonia and water therein.

6. The method according to claim 2, characterized in that: The intermediate product separation process of the reaction effluent of any upstream ebullating bed hydroprocessing reaction stage and the hydrogen stripping process of the liquid phase separated from the hydroprocessing reaction effluent of this stage are completed in the same high-pressure vessel pressure shell.

7. The method according to claim 1 or 2 or 3 or 4 or 5 or 6, characterized in that: The separated gas obtained in the gas-liquid separation process of the ebullated bed hydro-modification reaction effluent of any ebullated bed hydro-modification reaction stage contains more than 70% of the ammonia component in the ebullated bed hydro-modification reaction effluent of the stage; The average volume concentration of gas-phase ammonia in any downstream ebullated bed hydroprocessing reaction process UR2N is lower than 40% of the average volume concentration of gas-phase ammonia at the terminal reaction of the adjacent upstream ebullated bed hydroprocessing reaction process UR2M.

8. The method according to claim 1 or 2 or 3 or 4 or 5 or 6, characterized in that: The separated gas obtained in the gas-liquid separation process of the ebullated bed hydro-modification reaction effluent in any ebullated bed hydro-modification reaction stage contains more than 85% of the ammonia component in the ebullated bed hydro-modification reaction effluent of the stage; The average volume concentration of gas-phase ammonia in any downstream ebullated bed hydroprocessing reaction process UR2N is 20% lower than the average volume concentration of gas-phase ammonia at the terminal reaction of the adjacent upstream ebullated bed hydroprocessing reaction process UR2M.

9. The method according to claim 1, characterized in that: The raw material oil R20F, its source and composition are selected from one or more of the following: ① The distillate stream from the fractionation process of coal direct liquefaction to generate oil, mainly composed of hydrocarbons with a conventional boiling point of 200 to 280°C; ② The distillate stream from the fractionation process of coal direct liquefaction to generate oil, mainly composed of hydrocarbons with a conventional boiling point of 280 to 370°C; ③ The distillate stream from the fractionation process of coal direct liquefaction to generate oil, mainly composed of hydrocarbons with a conventional boiling point of 370 to 470°C; ④ The distillate stream from the fractionation process of coal direct liquefaction to generate oil, mainly composed of hydrocarbons with a conventional boiling point of 470 to 525°C; ⑤ The distillate stream from the fractionation process of coal direct liquefaction to produce oil, mainly composed of hydrocarbons with a conventional boiling point of 525 to 550°C; ⑥ The distillate oil stream from the fractionation process of direct coal liquefaction to produce oil is mainly composed of hydrocarbons with a conventional boiling point of 550 to 650°C.

10. The method according to claim 9, characterized in that: The feedstock oil R20F comprises one or more of the following, the total proportion of which in the feedstock oil R20F is less than 30% by weight: ① The distillate stream from the fractionation process of coal tar, mainly composed of hydrocarbons with a conventional boiling point of 200 to 330°C; ② The distillate stream from the fractionation process of coal tar, mainly composed of hydrocarbons with a conventional boiling point of 330 to 400°C; ③ The distillate oil stream from the fractionation process of coal tar is mainly composed of hydrocarbons with a conventional boiling point of 400 to 540°C.

11. The method according to claim 1 or 2 or 3 or 4 or 5 or 6, characterized in that: The operating conditions of the ebullated bed hydro-modification reaction zone used in the ebullated bed hydro-modification reaction process R20 are: temperature of 250-440°C, pressure of 8.0-25.0 MPa, hydrogen / feedstock volume ratio of 100-400 Nm 3 / m 3 , the weight chemical hydrogen consumption per unit weight of raw oil is 0.4~3.5%.

12. The method according to claim 1 or 2 or 3 or 4 or 5 or 6, characterized in that: The operating conditions of the ebullated bed hydro-modification reaction zone used in the ebullated bed hydro-modification reaction process R20 are: temperature of 300-400°C, pressure of 13.0-20.0 MPa, hydrogen / feedstock volume ratio of 200-350 Nm 3 / m 3 , the weight chemical hydrogen consumption per unit weight of crude oil is 1.0~2.5%.

13. The method according to claim 1 or 2 or 3 or 4 or 5 or 6, characterized in that: The solid particle content in the feedstock oil R20F of the ebullated bed hydro-modification reaction is greater than 100 ppm.

14. The method according to claim 1, characterized in that: The ebullated bed hydroprocessing reaction process R20 comprises two ebullated bed hydroprocessing reaction stages connected in series, and its operation objectives are selected from one or more of the following: ① The organic nitrogen hydrodenitrification rate of the first ebullated bed hydromodification reaction stage U210 is 60-95% of the overall denitrification rate of the ebullated bed hydromodification reaction process R20; The organic nitrogen hydrodenitrification rate of the second ebullated bed hydromodification reaction stage U220 is 5 to 40% of the overall denitrification rate of the ebullated bed hydromodification reaction process R20; ② The aromatic carbon hydroremoval rate of the first ebullated bed hydromodification reaction stage U210 is 60-80% of the overall aromatic carbon hydroremoval rate of the ebullated bed hydromodification reaction process R20; The aromatics hydrogenation removal rate of the second ebullated bed hydromodification reaction stage U220 is 20-40% of the overall aromatics hydrogenation removal rate of the ebullated bed hydromodification reaction process R20; ③ The reaction temperature rise of the first ebullated bed hydro-modification reaction stage U210 is 40-70% of the overall reaction temperature rise of the ebullated bed hydro-modification reaction process R20; The reaction temperature rise of the second ebullated bed hydro-modification reaction stage U220 is 40-60% of the overall reaction temperature rise of the ebullated bed hydro-modification reaction process R20; ④ The chemical hydrogen consumption of the first ebullated bed hydroprocessing reaction stage U210 is 40-70% of the overall chemical hydrogen consumption of the ebullated bed hydroprocessing reaction process R20; The chemical hydrogen consumption of the second ebullated bed hydro-modification reaction stage U220 is 40-60% of the overall chemical hydrogen consumption of the ebullated bed hydro-modification reaction process R20; ⑤ The growth value of the hydrogen supply index of the feedstock R20F produced in the first ebullated bed hydro-modification reaction stage U210 is 40-70% of the growth value of the overall hydrogen supply index of R20 in the ebullated bed hydro-modification reaction process; The growth value of the hydrogen supply index generated by the second ebullated bed hydroprocessing reaction stage U220 is 30-60% of the growth value of the overall hydrogen supply index of the ebullated bed hydroprocessing reaction process R20.

15. The method according to claim 1 or 2 or 3 or 4 or 5 or 6, characterized in that: The feedstock oil R20F in the ebullated bed hydro-modification reaction contains carbonaceous solid particles; The ebullated bed hydromodification reaction process R20 includes two series-connected hydromodification reaction stages: a first ebullated bed hydromodification reaction stage U210 and a second ebullated bed hydromodification reaction stage U220; The second ebullated bed hydro-modification reaction stage U220 is provided with a liquid product circulation pump to transport the liquid product of the second ebullated bed hydro-modification reaction stage U220. The working mode is selected from one or more of the following: ① delivering the circulating reaction liquid to the second ebullated bed hydro-modification reaction process UR220, and this part of the circulating reaction liquid does not pass through the first ebullated bed hydro-modification reaction process UR210; ② Transport circulating reaction liquid to the first ebullated bed hydrogenation modification reaction process UR210.

16. The method according to claim 1 or 2 or 3 or 4 or 5 or 6, characterized in that: The feedstock oil R20F in the ebullated bed hydro-modification reaction contains carbonaceous solid particles; The ebullated bed hydromodification reaction process R20 includes two series-connected hydromodification reaction stages: a first ebullated bed hydromodification reaction stage U210 and a second ebullated bed hydromodification reaction stage U220; Each ebullated bed hydroprocessing reaction stage is provided with a liquid reaction product circulation pump, so that part of the liquid product of this reaction stage can be circulated and reacted in the ebullated bed hydroprocessing reaction process of this stage.

17. The method according to claim 1 or 2 or 3 or 4 or 5 or 6, characterized in that: The feedstock oil R20F in the ebullated bed hydro-modification reaction contains carbonaceous solid particles; The ebullated bed hydromodification reaction process R20 includes two series-connected hydromodification reaction stages: a first ebullated bed hydromodification reaction stage U210 and a second ebullated bed hydromodification reaction stage U220; The first ebullated bed hydro-modification reaction stage U210 is provided with a first separation liquid delivery pump, and its working mode is selected from one or more of the following: ① Transporting circulating reaction liquid to the first ebullated bed hydro-modification reaction process UR210; ②Transporting reaction feed liquid to the second ebullated bed hydro-modification reaction process UR220; ③ The operating pressure of the second ebullated bed hydrogenation modification reaction stage U220 is higher than the operating pressure of the first ebullated bed hydrogenation modification reaction stage U210, and part or all of the second separated gas enters the first ebullated bed hydrogenation modification reaction process UR210 by relying on its own pressure, and / or, a part of the second separated liquid enters the first ebullated bed hydrogenation modification reaction process UR210 by relying on its own pressure, and a part of the second separated liquid is used as the second separated liquid net product.

18. The method according to claim 1 or 2 or 3 or 4 or 5 or 6, characterized in that: The ebullated bed hydroprocessing reaction process R20 comprises three ebullated bed hydroprocessing reaction stages connected in series, and its operation objectives are selected from one or more of the following: ① The organic nitrogen hydrodenitrification rate of the first ebullated bed hydromodification reaction stage U210 is 40-70% of the overall denitrification rate of the ebullated bed hydromodification reaction process R20; The organic nitrogen hydrodenitrification rate of the second ebullated bed hydromodification reaction stage U220 is 25-40% of the overall denitrification rate of the ebullated bed hydromodification reaction process R20; The organic nitrogen hydrodenitrification rate of the third ebullated bed hydromodification reaction stage U230 is 10-20% of the overall denitrification rate of the ebullated bed hydromodification reaction process R20; ② The aromatic carbon hydroremoval rate of the first ebullated bed hydromodification reaction stage U210 is 40-70% of the overall aromatic carbon hydroremoval rate of the ebullated bed hydromodification reaction process R20; The aromatics hydrogenation removal rate of the second ebullated bed hydromodification reaction stage U220 is 25-40% of the overall aromatics hydrogenation removal rate of the ebullated bed hydromodification reaction process R20; The aromatic carbon hydroremoval rate of the third ebullated bed hydromodification reaction stage U230 is 10-20% of the overall aromatic carbon hydroremoval rate of the ebullated bed hydromodification reaction process R20; ③ The reaction temperature rise of the first ebullated bed hydro-modification reaction stage U210 is 40-70% of the overall reaction temperature rise of the ebullated bed hydro-modification reaction process R20; The reaction temperature rise of the second ebullated bed hydro-modification reaction stage U220 is 25-40% of the overall reaction temperature rise of the ebullated bed hydro-modification reaction process R20; The reaction temperature rise of the third ebullated bed hydro-modification reaction stage U230 is 10-20% of the overall reaction temperature rise of the ebullated bed hydro-modification reaction process R20; ④ The chemical hydrogen consumption of the first ebullated bed hydroprocessing reaction stage U210 is 40-70% of the overall chemical hydrogen consumption of the ebullated bed hydroprocessing reaction process R20; The chemical hydrogen consumption of the second ebullated bed hydro-modification reaction stage U220 is 25-40% of the overall chemical hydrogen consumption of the ebullated bed hydro-modification reaction process R20; The chemical hydrogen consumption of the third ebullated bed hydro-modification reaction stage U230 is 10-20% of the overall chemical hydrogen consumption of the ebullated bed hydro-modification reaction process R20; ⑤ The growth value of the hydrogen supply index of the feedstock R20F produced in the first ebullated bed hydro-modification reaction stage U210 is 40-70% of the growth value of the overall hydrogen supply index of R20 in the ebullated bed hydro-modification reaction process; The growth value of the hydrogen supply index generated by the second ebullated bed hydroprocessing reaction stage U220 is 25-40% of the growth value of the overall hydrogen supply index of the ebullated bed hydroprocessing reaction process R20; The increase value of the hydrogen supply index generated by the third ebullated bed hydroprocessing reaction stage U230 is 10-20% of the increase value of the overall hydrogen supply index of the ebullated bed hydroprocessing reaction process R20.

19. The method according to claim 1 or 2 or 3 or 4 or 5 or 6, characterized in that: The feedstock oil R20F contains carbonaceous solid particles; In the ebullated bed hydroprocessing reaction process R20, a liquid product circulation pump is provided in any ebullated bed hydroprocessing reaction stage to transport the liquid product of the ebullated bed hydroprocessing reaction stage, and the working mode is selected from one or more of the following: ① Transporting circulating reaction liquid to the ebullated bed hydrogenation and modification reaction process at this stage; ②Transporting circulating reaction liquid to the existing downstream hydrogenation and modification reaction process ③ Transporting circulating reaction liquid to any existing upstream boiling bed hydrogenation modification reaction process.

20. The method according to claim 1 or 2 or 3 or 4 or 5 or 6, characterized in that: The feedstock oil R20F contains carbonaceous solid particles; The ebullating bed hydroprocessing reaction process R20 comprises a plurality of hydroprocessing reaction stages connected in series; Each ebullated bed hydroprocessing reaction stage is provided with a liquid reaction product circulation pump, so that part of the liquid product of this reaction stage can be circulated and reacted in the ebullated bed hydroprocessing reaction process of this stage.

21. The method according to claim 1 or 2 or 3 or 4 or 5 or 6, characterized in that: The feedstock oil R20F for the ebullated bed hydro-modification reaction contains carbonaceous solid particles; The ebullating bed hydroprocessing reaction process R20 includes three hydroprocessing reaction stages connected in series; The first ebullated bed hydro-modification reaction stage U210 is provided with a first separation liquid delivery pump, and its working mode is selected from one or more of the following: ① Transporting circulating reaction liquid to the first ebullated bed hydro-modification reaction process UR210; ②Transporting reaction feed liquid to the second ebullated bed hydro-modification reaction process UR220; ③ The operating pressure of the second ebullated bed hydrogenation modification reaction stage U220 is higher than the operating pressure of the first ebullated bed hydrogenation modification reaction stage U210, and the second separated gas partially or completely enters the first ebullated bed hydrogenation modification reaction process UR210 by its own pressure, and / or, a part of the second separated liquid enters the first ebullated bed hydrogenation modification reaction process UR210 by its own pressure; and / or, the second ebullated bed hydrogenation modification reaction stage U220 is provided with a second separated liquid delivery pump, and its working mode is selected from one or more of the following: ① Transporting circulating reaction liquid to the first ebullated bed hydro-modification reaction process UR210; ②Transporting the cyclic reaction liquid to the second ebullated bed hydrogenation modification reaction process UR220; ③ Transporting reaction feed liquid to the third ebullated bed hydrogenation modification reaction process UR230; ④ The operating pressure of the third ebullated bed hydrogenation modification reaction stage U230 is higher than the operating pressure of the second ebullated bed hydrogenation modification reaction stage U220, and the third separated gas partially or completely enters the second ebullated bed hydrogenation modification reaction process UR220 by relying on its own pressure, and / or, a part of the third separated liquid enters the second ebullated bed hydrogenation modification reaction process UR220 by relying on its own pressure, and a part of the third separated liquid is used as the third separated liquid net product.

22. The method according to claim 1 or 2 or 3 or 4 or 5 or 6, characterized in that: The ebullated bed hydroprocessing reaction process R20 comprises two or more hydroprocessing reaction stages connected in series; Two or more ebullated bed hydro-modification reaction stages connected in series realize an operation mode of increasing reaction temperature, and the average reaction temperature of the downstream ebullated bed hydro-modification reaction stage is 5 to 30°C higher than the average reaction temperature of the upstream ebullated bed hydro-modification reaction stage; The average reaction temperature of the ebullated bed hydroprocessing reaction stage refers to the sum of the product of the arithmetic mean of the process fluid reaction temperature at the starting reaction of the catalyst bed layer and the process fluid reaction temperature at the end reaction of the catalyst bed layer in each reaction zone of the ebullated bed hydroprocessing reaction stage and the volume coefficient of the sub-reaction zone under normal operation; The volume coefficient of a sub-reaction zone of the ebullated bed hydroprocessing reaction stage under normal operating conditions refers to the ratio of the volume of the sub-reaction zone to the total volume of all sub-reaction zones of the ebullated bed hydroprocessing reaction stage under normal operating conditions.

23. The method according to claim 1 or 2 or 3 or 4 or 5 or 6, characterized in that: In the generated oil fractionation process of the ebullated bed hydromodification reaction process R20, a heavy fraction KXL is separated from the hydrocarbon flow at least containing the final separation liquid, and part of the heavy fraction KXL is returned as a circulating reaction material KXL-R to any downstream ebullated bed hydromodification reaction stage of the ebullated bed hydromodification reaction process R20 for a cyclic hydrogenation reaction to reduce the aromatic carbon rate, and its working mode is selected from one or more of the following: ① In the generated oil fractionation process of the ebullated bed hydromodification reaction process R20, a heavy fraction KXL1 mainly composed of hydrocarbons with a conventional boiling point of 280 to 520° C. is separated from the hydrocarbon flow containing at least the final separation liquid, and part of the heavy fraction KXL1 is returned as a circulating reaction material KXL1-R to any downstream hydromodification reaction process of the ebullated bed hydromodification reaction process R20 for a cyclic hydrogenation reaction to reduce the aromatic carbon rate; ② In the generated oil fractionation process of the ebullated bed hydromodification reaction process R20, a heavy fraction KXL2 mainly composed of hydrocarbons with a conventional boiling point of 320 to 520° C. is separated from the hydrocarbon flow containing at least the final separation liquid, and a part of the heavy fraction KXL2 is returned as a circulating reaction material KXL2-R to any downstream hydromodification reaction process of the ebullated bed hydromodification reaction process R20 for a cyclic hydrogenation reaction to reduce the aromatic carbon rate; ③ In the generated oil fractionation process of the ebullated bed hydromodification reaction process R20, a heavy fraction KXL3 mainly composed of hydrocarbons with a conventional boiling point of 410-520°C is separated from the hydrocarbon flow at least containing the final separation liquid, and part of the heavy fraction KXL3 is returned as the circulating reaction material KXL3-R to any downstream hydromodification reaction process of the ebullated bed hydromodification reaction process R20 for a circulating hydrogenation reaction to reduce the aromatic carbon rate.

24. The method according to claim 1 or 2 or 3 or 4 or 5 or 6, characterized in that: In the generated oil fractionation process of the ebullated bed hydromodification reaction process R20, a heavy fraction KYL is separated from the hydrocarbon stream containing at least the final separation liquid, and part of the heavy fraction KYL is returned as a circulating reaction material KYL-R to any downstream ebullated bed hydromodification reaction stage of the ebullated bed hydromodification reaction process R20 for a circulating hydrogenation reaction to reduce the aromatic carbon rate. The method for producing the circulating reaction material KYL-R is selected from one or more of the following: ① In the first hot low-pressure separation process based on the logistics of the final separation liquid, the logistics based on the final separation liquid is depressurized and separated into a first hot low-pressure separation gas and a first hot low-pressure separation liquid; Part of the first hot low-pressure separation liquid is used as circulating reaction material KYL-R; The operating conditions of the first hot low-pressure separation process are: temperature of 320-420°C and pressure of 1.5-4.0 MPa; ② In the first hot low-pressure separation process based on the logistics of the final separation liquid, the logistics based on the final separation liquid is depressurized and separated into a first hot low-pressure separation gas and a first hot low-pressure separation liquid; In the second hot low-pressure separation process, the first hot low-pressure separation liquid is depressurized and separated into a second hot low-pressure separation gas and a second hot low-pressure separation liquid; Part of the second hot low-pressure separation liquid is used as circulating reaction material KYL-R; The operating conditions of the first hot low-pressure separation process are: temperature of 320-420°C and pressure of 1.5-4.0 MPa; The operating conditions of the second hot low-pressure separation process are: temperature of 320-420°C and pressure of 0.10-0.50 MPa.

25. The method according to claim 23 or 24, characterized in that: In the first fractionation tower system, separating the first fractionation tower bottom oil based on the stream of the first hot low-pressure separated liquid and / or the second hot low-pressure separated liquid; a first fractionation column system, with or without a sidestream distillation column; A portion of the bottom oil of the first fractionation tower is used as circulating reaction material KYL-R; The operating pressure of the distillation tower is 0.05~0.45MPa.

26. The method according to claim 25, characterized in that: In the second fractionation tower system, based on the stream of the first fractionation tower bottom oil, a second fractionation tower bottom oil is separated; a second fractionator system, with or without a sidestream distillation column; A portion of the bottom oil of the second fractionation tower is used as circulating reaction material KYL-R; The second distillation tower is a vacuum distillation tower, and the operating pressure of the second distillation tower is -0.03 to -0.090 MPa.

27. The method according to claim 2, characterized in that: In the generated oil fractionation process of the ebullated bed hydromodification reaction process R20, a heavy fraction KEYL mainly composed of hydrocarbons having a conventional boiling point higher than 320° C. is separated from the hydrocarbon stream containing at least the final separation liquid, and a hydrocarbon stream based on part of the heavy fraction KEYL is returned as a circulating reaction material KEYL-R to the ebullated bed hydromodification reaction process of any downstream ebullated bed hydromodification reaction stage of the ebullated bed hydromodification reaction process R20 for a circulating hydrogenation reaction to reduce the aromatic carbon rate; The ratio of the weight flow rate of the circulating reaction material KEYL-R to the weight flow rate of the heavy fraction KEYL net product is 0.15 to 7.00; The circulating reaction material KEYL-R is returned to the ebullated bed hydrogenation modification reaction process R20 for the cyclic hydrogenation reaction to reduce the aromatic carbon rate, so that the hydrogen supply index of the heavy fraction KEYL net product is increased by 0.5 to 12.

0.

28. The method according to claim 27, characterized in that: The ratio of the weight flow rate of the circulating reaction material KEYL-R to the weight flow rate of the heavy fraction KEYL net product is 1.00 to 3.0; The circulating reaction material KEYL-R is returned to the ebullated bed hydrogenation modification reaction process R20 for the cyclic hydrogenation reaction to reduce the aromatic carbon rate, so that the hydrogen supply index of the heavy fraction KEYL net product is increased by 1.5 to 6.

0.

29. The method according to claim 1, characterized in that: The ebullated bed hydro-modification reaction process R20 uses two or more parallel ebullated bed hydro-modification reaction series to process narrow fraction oils of different boiling ranges from coal direct liquefaction oil; Any ebullated bed hydro-modification reaction series, including two or more ebullated bed hydro-modification reaction stages of its feedstock oil liquid phase connected in series, the intermediate product separation liquid separated in any intermediate product separation process enters the ebullated bed hydro-modification reaction process of the adjacent downstream ebullated bed hydro-modification reaction stage; In the gas-liquid separation process of the reaction effluent of any ebullated bed hydro-modification reaction stage, for the liquid phase separated from the ebullated bed hydro-modification reaction effluent of this stage, stripping the ammonia component therein with or without stripping hydrogen; The average volumetric concentration of ammonia in the gas phase of any downstream ebullated bed hydroprocessing reaction process is lower than the average volumetric concentration of ammonia in the gas phase of the adjacent upstream ebullated bed hydroprocessing reaction process; The aromatic carbon ratio of all hydrocarbons with a normal boiling point higher than 200°C in the reaction effluent of any downstream ebullated-bed hydromodification reaction process is lower than the aromatic carbon ratio of all hydrocarbons with a normal boiling point higher than 200°C in the reaction effluent of the adjacent upstream ebullated-bed hydromodification reaction process.

30. The method according to claim 29, characterized in that: Two parallel trains are used to process light hydrocarbon stream R20F11A and medium hydrocarbon stream R20F12A respectively. The light hydrocarbon stream R20F11A from coal direct liquefaction oil is mainly composed of hydrocarbons with a conventional boiling point below 280°C; The medium hydrocarbon stream R20F12A from the oil generated from direct coal liquefaction is mainly composed of hydrocarbons with a conventional boiling point of 280 to 470°C.

31. The method according to claim 29, characterized in that: Two parallel trains are used to process the light hydrocarbon stream R20F11B and the medium hydrocarbon stream R20F12B respectively. The light hydrocarbon stream R20F11B from the oil produced by direct coal liquefaction is mainly composed of hydrocarbons with a conventional boiling point below 280°C; The medium hydrocarbon stream R20F12B from the oil generated from direct coal liquefaction is mainly composed of hydrocarbons with a conventional boiling point of 280 to 520°C.

32. The method according to claim 29, characterized in that: Three parallel series are used to process light hydrocarbon stream R20F11C from coal direct liquefaction oil, medium hydrocarbon stream R20F12C from coal direct liquefaction oil, and heavy hydrocarbon stream R20F13C from coal direct liquefaction oil respectively; The light hydrocarbon stream R20F11C from the oil produced by direct coal liquefaction is mainly composed of hydrocarbons with a conventional boiling point below 280°C; The medium hydrocarbon stream R20F12C from the oil produced by direct coal liquefaction is mainly composed of hydrocarbons with a conventional boiling point of 280 to 400°C; The heavy hydrocarbon stream R20F13C produced from direct coal liquefaction is mainly composed of hydrocarbons with a conventional boiling point of 400 to 525°C.

33. The method according to claim 1, characterized in that: When the ebullated bed hydromodification reaction process R20 processes mainly hydrocarbons with conventional boiling points below 320°C, the ebullated bed hydromodification reaction process R20 and the hydromodification reaction process R30 are carried out in series, and the reaction effluent of the ebullated bed hydromodification reaction process R20 enters the hydromodification reaction process R30, and / or the hot high-pressure separation gas separated from the reaction effluent of the ebullated bed hydromodification reaction process R20 in its hot high-pressure separation process enters the hydromodification reaction process R30, and / or the hot high-pressure separation liquid separated from the reaction effluent of the ebullated bed hydromodification reaction process R20 in its hot high-pressure separation process, and the hydrocarbon oil mainly composed of hydrocarbons with conventional boiling points below 250°C separated based on the hot high-pressure separation liquid enters the hydromodification reaction process R30.

34. The method according to claim 1, characterized in that: The ebullated bed hydroprocessing reaction process R20 comprises two or more ebullated bed hydroprocessing reaction stages connected in series; The operating pressure of the ebullated bed hydrogenation modification reaction stage gradually decreases along the process. The operating pressure of the gas-liquid separation process of the reaction product of the upstream ebullated bed hydrogenation modification reaction stage is higher than the operating pressure of the adjacent downstream ebullated bed hydrogenation modification reaction stage. The reaction zone of the downstream ebullated bed hydrogenation modification reaction process and the reaction zone of the upstream ebullated bed hydrogenation modification reaction process are essentially interconnected liquid phase reaction zones of the interconnector type. The liquid level control method of the intermediate gas-liquid separation process adopts the control method of the communicating vessel for the upstream expanded bed staged series hydrogenation reaction process of hydrocarbon materials of Application No. 202310229274.

7.

35. The method according to claim 1, characterized in that: In the final gas-liquid separation process US290, the gas-liquid mixed phase flow of the effluent from the final ebullating bed hydro-modification reaction is separated into a final separation gas and a final separation liquid; In the warm and high pressure separation process, the logistics separation based on the final separation gas is warm and high pressure gas and warm and high pressure oil. The operating conditions of the warm and high pressure separation process are: temperature of 160-280°C and pressure of 10.0-25.0MPa; The degassed oil stream obtained after the high temperature oil fractionation stream is depressurized and degassed enters the fractionation tower of the final stage ebullating bed hydro-modification reaction to generate the oil fractionation process; In the hot low-pressure separation process of the final separation liquid, the logistics of the final separation liquid is depressurized and separated into hot low-pressure separation gas and hot low-pressure separation liquid. The operating conditions of the hot low-pressure separation process of the final separation liquid are: temperature of 320-400°C and pressure of 0.40-4.0MPa; The hot low-pressure separation liquid is fed into a fractionation tower for the fractionation of the oil produced by the final ebullating bed hydro-modification reaction; In the temperature and low pressure separation process, the hot low pressure separation gas is condensed and separated into temperature and low pressure gas and temperature and low pressure oil. The operating conditions of the temperature and low pressure separation process are: temperature 150-300℃, pressure 0.40-4.0MPa; The logistics based on low temperature oil separation enters the distillation tower of the final boiling bed hydro-modification reaction to generate oil for the distillation process.

36. The method according to claim 35, characterized in that: In the cold high-pressure separation process, the cold high-fraction gas and the cold high-fraction oil are separated after the flow of the warm high-fraction gas is condensed. The operating conditions of the cold high-pressure separation process are: temperature of 20-80°C and pressure of 10.0-25.0MPa; In the cold low-pressure separation process, the cold high-fraction oil-based logistics is depressurized and separated into cold low-fraction gas and cold low-fraction oil. The operating conditions of the cold low-pressure separation process are: temperature of 20-80°C and pressure of 0.4-4.0MPa; The logistics based on the cold low-fraction oil enters the distillation tower of the final boiling bed hydro-modification reaction to generate the oil in the distillation process.

37. The method according to claim 1, characterized in that: In the ebullating bed hydrogenation modification reaction process R20, in the intermediate separation gas cooling high pressure separation process, the intermediate separation gas is separated into intermediate separation gas cooling high fraction gas and intermediate separation gas cooling high fraction oil; In the cold high-pressure separation process, cold high-fraction gas and cold high-fraction oil are separated after the logistics of the final separation gas is condensed; At least a portion of the intermediate separated gas cooled high-fraction gas and / or at least a portion of the intermediate separated gas cooled high-fraction gas and / or the cold high-fraction gas enters the cold high-fraction gas of the ebullated bed hydrogenation modification reaction process R20, and enters the ebullated bed hydrogenation modification reaction process of any ebullated bed hydrogenation modification reaction stage of the ebullated bed hydrogenation modification reaction process R20.

38. The method according to claim 1, characterized in that: In the ebullating bed hydrogenation modification reaction process R20, in the intermediate separation gas cooling high pressure separation process, the intermediate separation gas is separated into intermediate separation gas cooling high fraction gas and intermediate separation gas cooling high fraction oil; In the cold high-pressure separation process, cold high-fraction gas and cold high-fraction oil are separated after the logistics of the final separation gas is condensed; At least a portion of the intermediate separated gas cooled high fraction gas and the final stage cooled high fraction gas enters the ebullated bed hydro-modification reaction process of any ebullated bed hydro-modification reaction stage of the ebullated bed hydro-modification reaction process R20; The intermediate separated gas cooled high-fraction gas and / or the final stage cooled high-fraction gas enters the coal hydrogenation direct liquefaction reaction process R10 as exhaust gas and is used as hydrogen raw material.

39. The method according to claim 1, characterized in that: In the ebullating bed hydrogenation modification reaction process R20, in the intermediate separation gas cooling high pressure separation process, the intermediate separation gas is separated into intermediate separation gas cooling high fraction gas and intermediate separation gas cooling high fraction oil; In the cold high-pressure separation process, cold high-fraction gas and cold high-fraction oil are separated after the logistics of the final separation gas is condensed; At least a portion of the intermediate separated gas cooled high fraction gas and the final stage cooled high fraction gas enters the ebullated bed hydro-modification reaction process of any ebullated bed hydro-modification reaction stage of the ebullated bed hydro-modification reaction process R20; At least a portion of the intermediate separated gas cooled high-fraction gas and / or at least a portion of the final stage cooled high-fraction gas is used as exhaust gas to enter the membrane separation system of the cooled high-fraction gas of the coal hydrogenation direct liquefaction reaction process R10 and be used as membrane separation feed gas.

40. The method according to claim 1, characterized in that: In the ebullated bed hydroprocessing reaction process R20, at least a portion of the new hydrogen enters the ebullated bed hydroprocessing reaction process of the most downstream ebullated bed hydroprocessing reaction stage.

41. The method according to claim 1, characterized in that: In the generated oil fractionation process of the ebullated bed hydro-modification reaction process R20, a hydrogen-donating solvent oil DS mainly composed of hydrocarbons having a conventional boiling point of 200 to 550° C. is separated from a hydrocarbon stream containing at least a final separation liquid; Coal slurry DS-TM is prepared from hydrogen-donating solvent oil DS and coal powder; The material based on coal slurry DS-TM is converted into coal hydrogenation direct liquefaction reaction effluent R10P through coal hydrogenation direct liquefaction reaction process R10; Separating the coal hydrogenation direct liquefaction reaction effluent R10P to obtain the coal direct liquefaction product oil distillate R10P-SP; The stream based on distillate oil R10P-SP is used as feed oil R20F for the ebullated-bed hydro-modification reaction.

42. The method according to claim 1, characterized in that: In the produced oil fractionation process of the ebullated bed hydro-modification reaction process R20, a fraction R20P-SP1 mainly composed of hydrocarbons with a normal boiling point between 200 and 350° C. and a heavy fraction R20P-SP2 composed of hydrocarbons with a normal boiling point higher than 320° C. are separated from the hydrocarbon stream containing at least the final separation liquid; Part of the material based on fraction R20P-SP1 is used as feedstock for the hydro-upgrading reaction process R30; A material based partly on fraction R20P-SP1 and at least partly on heavy fraction R20P-SP2, used alone or in combination as hydrogen supply solvent oil DS; Coal slurry DS-TM is prepared from hydrogen-donating solvent oil DS and coal powder; The material based on coal slurry DS-TM is converted into coal hydrogenation direct liquefaction reaction effluent R10P through coal hydrogenation direct liquefaction reaction process R10; Separating the coal hydrogenation direct liquefaction reaction effluent R10P to obtain the coal direct liquefaction product oil distillate R10P-SP; The distillate oil R10P-SP was used as the feed oil R20F for the ebullated bed hydro-modification reaction.

43. The method according to claim 1, characterized in that: In the ebullated bed hydroprocessing reaction process R20, any ebullated bed hydroprocessing reaction process is a slurry bed-ebullated bed combined hydroprocessing reaction mode using a slurry bed hydrogenation catalyst at the same time.

44. The method according to claim 1 or 2 or 3 or 4 or 5 or 6, characterized in that: The feedstock oil R20F of the ebullated bed hydro-modification reaction process R20 has an organic nitrogen content of 0.20 to 1.5 wt % and an organic oxygen content of 0.4 to 9.0 wt %.

45. The method according to claim 2 or 3 or 4 or 5 or 6, characterized in that: In the produced oil fractionation process of the ebullated bed hydro-modification reaction process R20, a first heavy fraction KEYL1 mainly composed of hydrocarbons with a normal boiling point of 320 to 470° C. and a second heavy fraction KEYL2 mainly composed of hydrocarbons with a normal boiling point of more than 470° C. are separated from a hydrocarbon stream containing at least the final separation liquid; Based on the hydrocarbon-containing flow of part of the second heavy fraction KEYL2 as the circulating reaction material KEYL2-R, the circulating reaction material is returned to any downstream boiling bed hydro-modification reaction stage U2-77 of the boiling bed hydro-modification reaction process R20 to carry out a circulating hydrogenation reaction to reduce the aromatic carbon rate; Based on a part of the hydrocarbon-containing flow of the first heavy fraction KEYL1 as a circulating reaction material KEYL1-R, the hydrocarbon-containing flow is returned to any downstream ebullated bed hydro-modification reaction stage U2-88 of the ebullated bed hydro-modification reaction process R20 to carry out a circulating hydrogenation reaction for reducing the aromatic carbon rate; The process flow direction of gradually increasing the hydrogenation depth of the feedstock R20F in the ebullated bed hydrogenation modification reaction process R20 is forward flow, and the ebullated bed hydrogenation modification reaction stage U2-88 is located downstream of the ebullated bed hydrogenation modification reaction stage U2-77.

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