Hydrogenation method and system for hydrocarbon oil

Abstract

The present invention relates to the field of petroleum refining and chemical industry, and discloses a method and system for hydrogenating hydrocarbon oil. The method includes the steps of: (1) carrying out a gas-phase desulfurization reaction of a hydrocarbon oil feedstock in a gas-phase hydrogenation reactor in the presence of hydrogen gas to obtain a gas-phase desulfurization reaction product; (2) boosting the pressure of the gas-phase desulfurization reaction product to obtain a boosted stream; and (3) sending the boosted stream to a liquid-phase hydrogenation reactor, and carrying out a liquid-phase hydrogenation reaction of the liquid-phase components in the boosted stream in the liquid-phase hydrogenation reactor to obtain a liquid-phase hydrogenation reaction product. The method and system according to the present invention can achieve the effect of high hydrogenation, and also simplify the overall process flow, reduce the severity of the reaction, and improve the efficiency of the chemical reaction.

Description

[Technical field]

[0001] [CROSS REFERENCE TO RELATED APPLICATIONS] This application claims the benefit of Chinese patent applications 202210008433.6, 202210008420.9 and 202210014492.4, filed on January 6, 2022, the contents of which are incorporated herein by reference.

[0002] [Technical field] The present invention relates to the field of petroleum refining and chemical industry, and more particularly to a method and system for hydrogenating hydrocarbon oils. [Background technology]

[0003] Emissions from the combustion of sulfur and polycyclic aromatic hydrocarbons in diesel pollute the air environment on which mankind depends, so countries are constantly accelerating the pace of improving diesel quality standards. China's national V diesel standard, which came into force in 2017, stipulates that the sulfur content must not exceed 10 mg / kg. The national VI diesel quality standard proposed in 2019 requires polycyclic aromatic hydrocarbons to be ≦11%, and the national VIB standard to be implemented in 2023 requires polycyclic aromatic hydrocarbons to be ≦5%. In addition, China's demand for secondary processing raw materials is also increasing day by day, and low-quality raw materials such as catalytic diesel contain as much as 60% aromatic hydrocarbons, which places higher demands on catalytic activity. However, from the perspective of the reaction mechanism of advanced desulfurization and advanced dearomatization, there is a big difference between the reaction environment requirements of the two. In the desulfurization reaction, the removal of low-molecular-weight sulfur is mainly carried out by the direct desulfurization route, that is, hydrocracking desulfurization. For low-reactivity polymer sulfides, the aromatic ring is hydrogenated, and then hydrocracking and desulfurization are carried out by the hydrodesulfurization reaction route. Therefore, in the relatively low temperature and high hydrogen partial pressure environment at the top of the reactor, the hydrocracking of low molecular sulfides (endothermic) and the hydrogenation reaction of aromatic ring-containing substances (massive exothermic) mainly occur. At the bottom of the reactor, the reaction environment is high temperature and low hydrogen partial pressure due to the accumulation of heat and hydrogen sulfide. This reaction environment is conducive to further hydrocracking of polymer sulfides after hydrogenation, but is very unfavorable for further saturation of aromatic hydrocarbons, since it is severely limited by the thermodynamics of aromatic hydrocarbon hydrogenation. Especially at the end of the reaction, the catalytic activity is reduced, and there is no good operation method other than increasing the temperature, which further affects the dearomatization effect. In addition to the various requirements for both reaction environments, the competitive adsorption of aromatic hydrocarbons on the catalyst surface also inhibits deep desulfurization, making it difficult for traditional hydrogenation technology to balance the two requirements of ultra-deep desulfurization and efficient saturation of aromatic hydrocarbons. There is further demand for the necessity and urgency of upgrading diesel cleaning technology.

[0004] In the conventional technology, in order to further advance dearomatization in addition to advanced desulfurization, the existing catalyst system can be used to reduce the reaction space velocity, that is, to reduce the processing volume or to add more reactors, but this is not very reasonable from an economic point of view. The second method is to use a two-stage process technology in which the produced oil is stripped after conventional hydrogenation to remove hydrogen sulfide, and then fed into a precious metal hydrogenation reactor, which significantly increases the cost of using the catalyst and complicates the process, and is not the best solution.

[0005] CN108085058B discloses a method for the advanced dearomatization of hydrocarbon oils. In this method, the feedstock oil and hydrogen gas are passed through a highly dispersed Pt-Pd / Al2O3 catalyst using relatively mild temperature and pressure conditions. The gas phase after the reaction is compressed and recycled, while the liquid phase is a product with a low aromatic hydrocarbon content. However, the Pt-Pd / Al2O3 hydrogenation catalyst is mainly suitable for the dearomatization of low-sulfur diesel feedstocks, but the effect of desulfurization and dearomatization of low-quality diesel is not sufficient.

[0006] CN109926067A discloses a platinum-palladium-cobalt trimetallic hydrodearomatization catalyst and its preparation method. This method adopts a stepwise impregnation method of active metal precursors, so that the prepared catalyst has a high utilization rate of platinum and palladium precious metals, high synergistic catalytic ability, and the introduction of platinum and palladium leads to an improvement in the hydrogenation performance of non-precious metal cobalt to aromatic hydrocarbons. However, this catalyst is intended for hydrocarbon oil after the basic removal of sulfur-containing compounds, in order to avoid the influence of hydrogen sulfide on the advanced dearomatization by precious metals, and cannot achieve the desulfurization and dearomatization of low-quality diesel. Summary of the Invention [Problem to be solved by the invention]

[0007] In view of the shortcomings of the prior art, the present invention provides a method and system for hydrogenating hydrocarbon oil, which can achieve the effect of high hydrogenation, and can simplify the overall process flow, reduce the severity of the reaction, and improve the efficiency of the chemical reaction. [Means for solving the problem]

[0008] The first aspect of the present invention is (1) performing a gas-phase desulfurization reaction of a hydrocarbon oil feedstock in a gas-phase hydrogenation reactor in the presence of hydrogen gas to obtain a gas-phase desulfurization reaction product; (2) pressurizing the gas-phase desulfurization reaction product to obtain an pressurized stream; and (3) sending the pressurized stream to a liquid-phase hydrogenation reactor, and carrying out a liquid-phase hydrogenation reaction of a liquid phase component in the pressurized stream in the liquid-phase hydrogenation reactor, thereby obtaining a liquid-phase hydrogenation reaction product.

[0009] Preferably, the conditions for the gas-phase desulfurization reaction are a pressure of 0.1 to 2.8 MPa, preferably 0.5 to 2 MPa, a temperature of 260 to 400 ° C, preferably 320 to 390 ° C, a hydrogen / oil volume ratio of 100 to 900, preferably 300 to 700, and a space velocity of 0.5 to 3 h -1 , preferably 0.8 to 2 hours -1 Includes.

[0010] Preferably, the conditions for the liquid phase hydrogenation reaction are a pressure of 2 to 8 MPa, preferably 3 to 6 MPa, a temperature of 200 to 400 ° C, preferably 260 to 360 ° C, and a space velocity of 0.1 to 3 h -1 , preferably 0.5 to 1 h -1 Includes.

[0011] A second aspect of the present invention is a method for producing a hydrogen-containing gas-phase hydrogenation reactor comprising: a gas phase hydrogenation reactor packed with a first hydrogenation catalyst; a pressure booster; and a liquid phase hydrogenation reactor packed with a second hydrogenation catalyst, the liquid phase hydrogenation reactor being connected in series; The gas-phase hydrogenation reactor performs a gas-phase desulfurization reaction of a hydrocarbon oil feedstock and hydrogen gas to obtain a gas-phase desulfurization reaction product, the booster boosts the gas-phase desulfurization reaction product to obtain a boosted stream; The liquid-phase hydrogenation reactor brings the pressurized stream into contact with a second hydrogenation catalyst to carry out a liquid-phase hydrogenation reaction, thereby obtaining a liquid-phase hydrogenation reaction product, thereby providing a system for hydrogenating a hydrocarbon oil. Effect of the Invention

[0012] Compared with the prior art, the hydrogenation method and system of the present invention have the following advantages:

[0013] (1) In the hydrogenation method and system of the present invention, the easily reactive low molecular weight components are removed in the gas phase hydrogenation reactor, the unreacted high molecular weight components are liquefied by a slight pressure increase and enter the liquid phase hydrogenation reactor, and the easily liquefied heavy components undergo advanced hydrorefining reactions. In this way, advanced desulfurization and dearomatization are performed in the same reaction system, avoiding the drawback of the prior art that the reaction conditions are not compatible. Through research, the inventors have found that by subjecting the hydrocarbon oil to gas phase hydrodesulfurization, the competitive adsorption of other substances in the hydrocarbon oil, such as aromatic hydrocarbons, can be greatly reduced, which is helpful for the targeted desulfurization reaction, and by linking with the liquid phase hydrogenation reactor, the advanced removal of other substances in the hydrocarbon oil, such as subsequent dearomatization, can be made easier.

[0014] (2) In the hydrogenation method and system of the present invention, the gas-phase desulfurization reaction product is pressurized to promote the simultaneous liquefaction of hydrogen gas and oil. Moreover, since the dissolution rules of hydrogen gas and hydrogen sulfide in petroleum products are different, the influence of hydrogen sulfide on the catalytic activity when entering the subsequent liquid-phase hydrogenation reactor can be avoided, and the inhibiting effect of hydrogen sulfide on the deep desulfurization in the conventional liquid-phase hydrogenation technology can be fully avoided, and the need for hydrogen sulfide stripping between the two reactors can be eliminated.

[0015] (3) In the present invention, it is possible to realize hydrorefining of hydrocarbon oils under milder operating conditions and a more simplified process flow, such as advanced desulfurization and dearomatization using low-quality diesel as a raw material. Among the gas-phase desulfurization reaction products, the reacted low-molecular weight compounds are not liquefied during the pressure boosting process, but are liquefied when they are separated at high pressure through a heat exchanger. This liquefaction method is advantageous for separating hydrogen gas from the raw material, and a large amount of hydrogen gas can be recovered and recycled, thereby improving the efficiency of hydrogen utilization. The hydrogenated light components that have undergone high-pressure separation are mixed with the hydrogenated heavy components and then enter the next stripping and fractionation system. In the entire reaction system, the hydrogen gas compressor of the fixed-bed reaction system and the circulating oil pump of the liquid-phase hydrogenation reaction system are not required, which reduces investment costs, simplifies the process steps, improves reaction efficiency, and reduces the severity of the reaction. [Brief description of the drawings]

[0016] [Figure 1] FIG. 1 is a schematic diagram of a method and system for hydrogenating a hydrocarbon oil according to a particular embodiment of the present invention. [Diagram 2] FIG. 2 is a schematic diagram of a method and system for hydrogenating a hydrocarbon oil according to another specific embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] The range endpoints and any values ​​disclosed herein are not intended to be limiting to the exact ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. In the case of numerical ranges, the individual range endpoints, the individual range endpoints and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be considered to be specifically disclosed herein.

[0018] The description of the exemplary embodiments is intended to be read with reference to the drawings, which are considered to be part of the entire written description. In the specification, relative terms such as "lower", "upper", "horizontal", "vertical", "upper", "lower", "upward", "downward", "top", and "bottom" and their derivatives (e.g., "horizontally", "under", "above", etc.) should be interpreted as the orientation shown in the drawings being described at the time. These relative terms are for ease of description and do not require that the devices be constructed or operated in a particular orientation. Unless otherwise specified, the "connection" of the present invention refers to a relationship in which structures are fixed or connected to each other directly or indirectly through intermediate structures.

[0019] The first aspect of the present invention is (1) performing a gas-phase desulfurization reaction of a hydrocarbon oil feedstock in a gas-phase hydrogenation reactor in the presence of hydrogen gas to obtain a gas-phase desulfurization reaction product; (2) pressurizing the gas-phase desulfurization reaction product to obtain an pressurized stream; and (3) sending the pressurized stream to a liquid-phase hydrogenation reactor, and carrying out a liquid-phase hydrogenation reaction of a liquid phase component in the pressurized stream in the liquid-phase hydrogenation reactor, thereby obtaining a liquid-phase hydrogenation reaction product.

[0020] The hydrogen gas in step (1) of the present invention can be any hydrogen-containing gas containing hydrogen gas, and can be fresh hydrogen gas, recycled hydrogen, or hydrogen-rich gas. Those skilled in the art can clearly understand the hydrogen-containing gas of the present invention after understanding the technical solution of the present invention.

[0021] In the present invention, the range of the hydrocarbon oil raw material to be selected is wide, and the method according to the present invention is suitable for any hydrocarbon oil, including at least one of low-quality diesel, aviation kerosene, wax oil, and naphtha, which need to simultaneously remove low-molecular-weight sulfides and other polymeric impurities. The method according to the present invention mainly removes low-molecular-weight sulfides in a gas-phase hydrogenation reactor, and the unreacted polymer is liquefied by a slight pressure increase and enters a liquid-phase hydrogenation reactor, and the heavy components that are easy to liquefy undergo an advanced hydrorefining reaction.

[0022] In the present invention, the range of properties of the hydrocarbon oil raw material is wide, and preferably, the low-quality diesel has an initial boiling point of 150 to 200 ° C, a final boiling point of 320 to 400 ° C, an S content of ≦ 20000 μg / g, preferably ≦ 15000 μg / g, an N content of ≦ 1000 μg / g, preferably ≦ 800 μg / g, and a polycyclic aromatic hydrocarbon content of ≦ 50 wt %. For example, the S content of the low-quality diesel includes, but is not limited to, 8000 μg / g, 9000 μg / g, 10000 μg / g, and 11500 μg / g, and the N content includes, but is not limited to, 500 μg / g, 600 μg / g, and 700 μg / g, and the polycyclic aromatic hydrocarbon content includes, but is not limited to, 25 wt %, 30 wt %, 35 wt %, 40 wt %, and 45 wt %.

[0023] Preferably, the aviation kerosene has an initial boiling point of 80 to 150° C., a final boiling point of 200 to 300° C., an S content of ≦8000 μg / g, preferably ≦4000 μg / g, and an N content of ≦100 μg / g, preferably ≦20 μg / g. For example, the S content of the aviation kerosene may be, but is not limited to, 500 μg / g, 1000 μg / g, 2000 μg / g, 3000 μg / g, and the N content may be, but is not limited to, 5 μg / g, 10 μg / g, 15 μg / g, and the like.

[0024] Preferably, the wax oil has an initial boiling point of 160 to 220° C., a final boiling point of 300 to 400° C., an S content of ≦30000 μg / g, preferably ≦20000 μg / g, an N content of ≦2000 μg / g, preferably ≦1500 μg / g, and a polycyclic aromatic hydrocarbon content of ≦60 wt%. For example, the S content of the wax oil may be, but is not limited to, 500 μg / g, 1000 μg / g, 2000 μg / g, 5000 μg / g, 8000 μg / g, 9000 μg / g, 10000 μg / g, and 15000 μg / g, and the N content may be, but is not limited to, 500 μg / g, 700 μg / g, 1000 μg / g, and 1200 μg / g. The content of polycyclic aromatic hydrocarbons may be, but is not limited to, 10 wt%, 20 wt%, 30 wt%, 40 wt%, 50 wt%, and the like.

[0025] In the present invention, the symbol "≦" means less than or equal to and the symbol "≧" means greater than or equal to.

[0026] According to one preferred embodiment of the present invention, the gas-phase desulfurization reaction is carried out in the presence of a first hydrogenation catalyst, and the first hydrogenation catalyst is a catalyst having a hydrodesulfurization function. In the present invention, the catalyst having a hydrodesulfurization function can be selected from a wide range of options and may be selected from the ordinary options in the field. For example, the catalyst having a hydrodesulfurization function includes a support and a hydrogenation active metal, where the support is an inorganic refractory oxide, generally one or more selected from alumina, amorphous silicon aluminum, silica, titanium oxide, etc., and the hydrogenation active metal includes a Group VIB metal component and / or a Group VIII metal component. In the catalyst having a hydrodesulfurization function, the Group VIB metal component is preferably selected from tungsten and / or molybdenum, and the content in the catalyst in terms of oxide mass is 5% to 30%, preferably 15% to 30%. The Group VIII metal component is preferably selected from nickel and / or cobalt, and the content in the catalyst in terms of oxide mass is 1% to 6%, preferably 2% to 6%. The catalyst having hydrodesulfurization function may further contain an auxiliary component such as at least one of phosphorus, silicon, boron, magnesium, fluorine, etc., and the mass content of this auxiliary component in the catalyst having hydrodesulfurization function is generally 6 wt% or less.

[0027] The catalyst having hydrodesulfurization function may be prepared by any method, and may be a commercially available catalyst, such as at least one of FHUDS-5, FHUDS-6, and FHUDS-7 catalysts developed by Sinopec Fushun Petrochemical Industry Research Institute (FRIPP).

[0028] According to the method of the present invention, the conditions of the gas-phase desulfurization reaction are preferably a pressure of 0.1 to 2.8 MPa, preferably 0.5 to 2 MPa, a temperature of 260 to 400°C, preferably 320 to 390°C, a hydrogen / oil volume ratio of 100 to 900, preferably 300 to 700, and a space velocity of 0.5 to 3 h -1 , preferably 0.8 to 2 hours -1In the method according to the present invention, when the gas-phase hydrodesulfurization reaction is carried out at this preferred hydrogen / oil volume ratio, it is further helpful to reduce the partial pressure of the feedstock and achieve complete vaporization of the feedstock. In addition, the gas-phase desulfurization reaction of the present invention may be carried out at a lower pressure, thereby greatly saving energy consumption.

[0029] In the gas-phase desulfurization reaction in step (1), not only is the sulfur content in the hydrocarbon oil feedstock removed, but the nitrogen content is also inevitably removed.

[0030] In the present invention, the type of the gas phase hydrogenation reactor is particularly limited, and preferably, the gas phase hydrogenation reactor is a fixed bed reactor.

[0031] In step (2) of the present invention, the gas-phase desulfurization reaction product is pressurized, and the pressurization may be performed by a pressure booster, for example, a compressor, and the type of the compressor is not particularly limited and may be, for example, a reciprocating compressor or a centrifugal compressor.

[0032] In the present invention, the pressure boosting range of the gas phase desulfurization reaction product is widely selected, and it is preferable to boost the product so as to ensure normal supply to the liquid phase hydrogenation reactor and meet the operating pressure requirements of the liquid phase hydrogenation reactor. In the present invention, the pressure boosting of the gas phase desulfurization reaction product promotes the simultaneous liquefaction of hydrogen gas and oil. In addition, the dissolution rules of hydrogen gas and hydrogen sulfide in oil products are different, that is, under high temperature conditions, the solubility of hydrogen gas is high and the solubility of hydrogen sulfide is low, so the concentration of hydrogen gas in the liquefied liquid phase is high and the concentration of hydrogen sulfide is low. When entering the subsequent liquid phase hydrogenation reactor, the influence of hydrogen sulfide on the catalytic activity is avoided, and the need to strip hydrogen sulfide between the two reactors is also eliminated.

[0033] According to one preferred embodiment of the present invention, in step (2), the gas-phase desulfurization reaction product is pressurized to 2-10 MPa, preferably 2.5-7.5 MPa. The pressure range may vary depending on the hydrocarbon feedstock and the requirements of various products.

[0034] Preferably, the hydrocarbon oil feedstock is low-quality diesel, and in step (2), the gas-phase desulfurization reaction product is pressurized to 4.5-6.5 MPa. In this preferred embodiment, the liquid-phase hydrogenation reaction is carried out in the presence of a second hydrogenation catalyst, and the second hydrogenation catalyst is a hydro-dearomatization catalyst. When the hydrocarbon oil feedstock is low-quality diesel, the method of the present invention carries out advanced desulfurization and dearomatization in the same reaction system, thereby avoiding the drawback of incompatible reaction conditions. By controlling the reaction conditions of the gas-phase hydrogenation reactor, aromatic ring-containing substances are less likely to be adsorbed on the catalyst surface, and the competitive adsorption of aromatic hydrocarbon substances is significantly reduced, contributing to the desired desulfurization reaction. In addition, the reaction conditions of the gas-phase hydrogenation reactor are controlled to more appropriately cooperate with the liquid-phase hydrogenation reactor to more appropriately promote not only gas-phase desulfurization but also the subsequent advanced dearomatization.

[0035] According to another preferred embodiment of the present invention, the hydrocarbon oil feedstock is low-quality diesel, and in step (2), the gas-phase desulfurization reaction product is pressurized to 4-7 MPa. In this preferred embodiment, the liquid-phase hydrogenation reaction is carried out in the presence of a second hydrogenation catalyst, and the second hydrogenation catalyst is an advanced hydrodesulfurization catalyst. In this preferred embodiment, the method of the present invention can effectively remove high molecular weight sulfides at a relatively low temperature and appropriate pressure. If it is necessary to further remove polycyclic aromatic hydrocarbons, the production of high-quality diesel products can be realized by selecting an advanced hydrodesulfurization catalyst (e.g., Mo-Ni catalyst) that also has the function of removing polycyclic aromatic hydrocarbons.

[0036] According to another preferred embodiment of the present invention, the hydrocarbon oil feedstock is aviation kerosene, and in step (2), the gas-phase desulfurization reaction product is pressurized to 2.5-4 MPa. In this preferred embodiment, the liquid-phase hydrogenation reaction is carried out in the presence of a second hydrogenation catalyst, and the second hydrogenation catalyst is a hydrodearomatization catalyst. When the hydrocarbon oil feedstock is aviation kerosene, the method of the present invention can effectively remove aromatic hydrocarbons in aviation kerosene and improve the smoke point of aviation kerosene. In particular, when heavy components are cut from aviation kerosene fractions to increase the aromatic hydrocarbon content in the feedstock in order to increase the production amount of aviation kerosene, a reaction environment suitable for removing aromatic hydrocarbons is more preferable, and the production of high smoke point aviation kerosene can be realized.

[0037] According to another preferred embodiment of the present invention, the hydrocarbon oil feedstock is aviation kerosene, and in step (2), the gas-phase desulfurization reaction product is pressurized to 2.5-4 MPa. In this preferred embodiment, the liquid-phase hydrogenation reaction is carried out in the presence of a second hydrogenation catalyst, and the second hydrogenation catalyst is a hydroisomerization catalyst. When the hydrocarbon oil feedstock is aviation kerosene, the method of the present invention can effectively isomerize branched alkanes in aviation kerosene. In particular, when heavy components are removed from aviation kerosene fractions to increase the content of long-chain alkanes in the feedstock in order to increase the production of aviation kerosene, a reaction environment suitable for alkane isomerization is more preferable, and the production of aviation kerosene with a low freezing point can be realized.

[0038] According to another preferred embodiment of the present invention, the hydrocarbon oil feedstock is a wax oil, and in step (2), the gas phase desulfurization reaction product is pressurized to 5-10 MPa. In this preferred embodiment, the liquid phase hydrogenation reaction is carried out in the presence of a second hydrogenation catalyst, and the second hydrogenation catalyst is an isomerization pour point depressing catalyst. In this preferred embodiment, the method of the present invention can improve the viscosity index of a specialty oil product by isomerizing long chain alkanes in a wax oil fraction. When the hydrocarbon oil feedstock is a wax oil, preferably, the method may further include a step of moving the gas phase components in the pressurized stream upwardly and discharging them from a liquid phase hydrogenation reactor, optionally carrying out a de-impurity treatment to obtain a hydrogenated light component, and then mixing the hydrogenated light component with the liquid phase hydrogenation reaction product and carrying out a hydrodearomatization reaction to obtain a specialty oil product such as white oil. The hydrodearomatization reaction may be carried out in the presence of a hydrodearomatization catalyst in a third hydrogenation reactor, and the form of the third hydrogenation reactor in the present invention is not particularly limited and may be a fixed-bed hydrogenation reactor. The reaction conditions may be selected in a wide range, as long as the hydrodearomatization can be smoothly carried out.

[0039] In the present invention, the type of the second hydrogenation catalyst may be selected from a wide range of types, provided that the above-mentioned object can be achieved. For example, the second hydrogenation catalyst may be a hydrodearomatization catalyst having a hydrodearomatization hydrocarbon function, a hydroisomerization catalyst having a hydroisomerization function, an advanced hydrodesulfurization catalyst having an advanced hydrodesulfurization function, or an isomerization pour point depressing catalyst having an isomerization pour point depressing function.

[0040] According to one preferred embodiment of the present invention, the hydrodearomatization catalyst may be a non-precious metal catalyst or a precious metal catalyst, and the non-precious metal catalyst may include a carrier and a hydrogenation active metal, where the carrier is an inorganic refractory oxide, generally one or more selected from alumina, amorphous silicon aluminum, silica, and titanium oxide, etc., and preferably alumina, and the hydrogenation active metal includes a group VIB metal component and / or a group VIII metal component. In the hydrodearomatization catalyst, the group VIB metal component is preferably selected from tungsten and / or molybdenum, and the content in the catalyst by oxide mass is 5% to 30%, preferably 15% to 30%. The group VIII metal component is preferably selected from nickel and / or cobalt, and the content in the catalyst by oxide mass is 1% to 6%, preferably 2% to 5%. The hydrodearomatization catalyst may further contain an auxiliary component such as at least one of phosphorus, silicon, boron, magnesium, fluorine, etc., and the mass content of this auxiliary component in the catalyst having hydrodesulfurization function is generally 6wt% or less. The hydrodearomatization catalyst is preferably a Mo-Ni type catalyst.

[0041] The hydrodearomatization catalyst may be prepared by any method, and may be a commercially available catalyst, such as at least one of FHUDS-10, FHUDS-6, and FHUDS-8 developed by Sinopec Fushun Petrochemical Industry Research Institute (FRIPP).

[0042] The noble metal catalyst preferably has Pt, Pd, etc. as active metal, and may be prepared by any method or may be a commercially available catalyst, such as FHDA-10 catalyst developed by Sinopec Fushun Petrochemical Industry Research Institute (FRIPP).

[0043] According to one preferred embodiment of the present invention, the hydroisomerization catalyst may be any catalyst capable of performing hydroisomerization function, preferably, the catalyst is alumina doped with molecular sieve (including but not limited to at least one of ZSM-5, Y, β molecular sieve) as the support and a Group VIII metal as the active component (including but not limited to Ni), and may be prepared by any method, or may be a commercially available catalyst, such as FDW-3 catalyst developed by Sinopec Fushun Petrochemical Industry Research Institute (FRIPP).

[0044] According to one preferred embodiment of the present invention, the advanced hydrodesulfurization catalyst can be any catalyst that can perform the function of polymer desulfurization, the support of the catalyst is preferably alumina, the active component is a group VIB metal, a group VIII metal, and the group VIB metal, the group VIII metal can be selected as above. The catalyst can be prepared by any method, and can be a commercially available catalyst, such as FHUDS-5, FHUDS-7 catalyst developed by Sinopec Fushun Petrochemical Industry Research Institute (FRIPP).

[0045] In the present invention, the isomerization pour point depressing catalyst is not particularly limited and may be any of various isomerization pour point depressing catalysts commonly used in the prior art. The active components and carriers thereof may be selected in the same range as those of the hydroisomerization catalyst described above, but are not described in detail in the present invention.

[0046] In the present invention, the catalyst having the specific function does not only exhibit that function, but mainly exhibits that function. For example, the hydrodesulfurization catalyst does not only exhibit the hydrodesulfurization action, but mainly exhibits the hydrodesulfurization action in its application environment.

[0047] According to one preferred embodiment of the present invention, the pressure of the liquid phase hydrogenation reaction is at least 1 MPa, preferably 1.5-7 MPa, more preferably 2.5-6 MPa higher than the pressure of the gas phase hydrodesulfurization reaction. The method according to the present invention can carry out the reaction under low or medium pressure, thereby greatly reducing the severity of the reaction and saving energy consumption.

[0048] According to the method of the present invention, the conditions of the liquid phase hydrogenation reaction are preferably a pressure of 2 to 8 MPa, preferably 3 to 6 MPa, a temperature of 200 to 400°C, preferably 260 to 360°C, and a space velocity of 0.1 to 3 h -1 , preferably 0.5 to 1 h -1 Includes.

[0049] In the present invention, the type of the liquid phase hydrogenation reactor is not particularly limited, and preferably, the liquid phase hydrogenation reactor is a fixed bed reactor.

[0050] According to one preferred embodiment of the present invention, the liquid phase hydrogenation reactor is a fixed bed reactor equipped with a gas-liquid separation zone. The gas-liquid separation zone can be any zone capable of achieving separation, for example, in the case of a flash zone, the liquid phase hydrogenation reactor is a fixed bed reactor equipped with a flash zone.

[0051] Specifically, a flash zone is provided in the liquid-phase hydrogenation reactor, and no catalyst is packed in the flash zone or above, and the area below the flash zone is a liquid-phase hydrogenation reaction zone. A flow (gas-liquid mixed phase) obtained by pressurizing the gas-phase desulfurization reaction product is supplied to the flash zone of the liquid-phase hydrogenation reactor, the resulting gas-phase component moves upward and is discharged from the liquid-phase hydrogenation reactor, the resulting liquid-phase component moves downward and causes a liquid-phase hydrogenation reaction, and the resulting liquid-phase hydrogenation reaction product, the hydrogenated heavy component, is discharged from the bottom of the liquid-phase hydrogenation reactor.

[0052] According to one preferred embodiment of the invention, the gas phase components in the boosted stream are allowed to move upwardly and discharged from the liquid phase hydrogenation reactor, and are optionally subjected to a de-impurity treatment to obtain hydrogenated light components.

[0053] In the present invention, the selection range of the impurity removal treatment is wide, including but not limited to desulfurization treatment. Preferably, the impurity removal treatment includes desulfurization treatment, preferably heat exchange of the gas phase component, followed by high-pressure separation to obtain the hydrogenated light component and hydrogen sulfide-containing hydrogen gas. In the method according to the present invention, the gas phase desulfurization reaction product contains reacted low molecules that are not liquefied during pressure increase, but are liquefied by heat exchange and high-pressure separation, and such liquefaction means is advantageous for separating hydrogen gas from the raw material, allowing hydrogen gas to be recovered and recycled in large quantities, and increasing the utilization rate of hydrogen gas. The hydrogenated light component separated at high pressure is mixed with the hydrogenated heavy component and fed to the subsequent stripping and fractionation system. The entire reaction system does not require a hydrogen gas compressor in a fixed bed reaction system or a circulating oil pump in a liquid phase hydrogenation reaction system, which can reduce investment costs, simplify the flow of the chemical process, increase reaction efficiency, and reduce the severity of the reaction.

[0054] The heat exchange may be performed in a heat exchanger. The high-pressure separation may be performed in a high-pressure separator. In the present invention, the conditions of the heat exchange and high-pressure separation are not particularly limited as long as the above object is achieved.

[0055] Preferably, the gas phase component is cooled to 100 to 200°C, preferably 120 to 150°C, by the heat exchange.

[0056] According to one preferred embodiment of the present invention, the method may further comprise the step of mixing the liquid-phase hydrogenation reaction product (also referred to as hydrogenated heavy component) and the hydrogenated light component to obtain a hydrogenation product.

[0057] According to one preferred embodiment of the present invention, the method may further include stripping (hydrogen desulfurization) and fractionating the hydrogenated product to obtain a target product. The specific conditions of the stripping and fractionating are not particularly limited and can be operated according to the requirements of the feedstock and the performance of the target product. For example, when the hydrocarbon oil feedstock is low-quality diesel, the hydrogenated product is stripped and fractionated to cut off the naphtha fraction and obtain a diesel refinery product.

[0058] Preferably, the hydrogenation product is a diesel refinery product having an aromatic hydrocarbon content of 5 wt% or less and an S content of 10 μg / g or less.

[0059] Preferably, the hydrogenation product is an aviation grade kerosene refinery having a smoke point of 26 mm or more and / or a freezing point of -50°C or less.

[0060] Preferably, the hydrogenation product is a specialty oil product having an aromatic hydrocarbon content of 5 wt% or less and an S content of 10 μg / g or less.

[0061] A second aspect of the present invention is a process for producing a gas phase hydrogenation reactor packed with a first hydrogenation catalyst, a pressure booster, and a liquid phase hydrogenation reactor packed with a second hydrogenation catalyst, the process being connected in series; The gas-phase hydrogenation reactor performs a gas-phase desulfurization reaction of a hydrocarbon oil feedstock and hydrogen gas to obtain a gas-phase desulfurization reaction product, the booster boosts the gas-phase desulfurization reaction product to obtain a boosted stream; The liquid-phase hydrogenation reactor brings the pressurized stream into contact with a second hydrogenation catalyst to carry out a liquid-phase hydrogenation reaction, thereby obtaining a liquid-phase hydrogenation reaction product, thereby providing a system for hydrogenating a hydrocarbon oil.

[0062] Preferably, the pressure booster boosts the gas-phase desulfurization reaction product to 2 to 10 MPa, preferably 2.5 to 7.5 MPa. In the present invention, the type of the pressure booster is not particularly limited and may be, for example, a compressor, and the type of the compressor is not particularly limited and may be, for example, a reciprocating compressor or a centrifugal compressor.

[0063] In the system according to the present invention, the types of the first hydrogenation catalyst and the second hydrogenation catalyst may be selected according to the type of the hydrocarbon oil feedstock, specifically, they can be selected according to the contents described in the first aspect, and therefore will not be described in detail here.

[0064] Preferably, the hydrocarbon oil feedstock is diesel, the first hydrogenation catalyst is a hydrodesulfurization catalyst, and the second hydrogenation catalyst is a hydrodearomatization catalyst; or the hydrocarbon feedstock is diesel, the first hydrogenation catalyst is a hydrodesulfurization catalyst, and the second hydrogenation catalyst is an advanced hydrodesulfurization catalyst; or the hydrocarbon oil feedstock is aviation kerosene, the first hydrogenation catalyst is a hydrodesulfurization catalyst, and the second hydrogenation catalyst is a hydrodearomatization catalyst; or the hydrocarbon oil feedstock is aviation kerosene, the first hydrogenation catalyst is a hydrodesulfurization catalyst, and the second hydrogenation catalyst is a hydroisomerization catalyst; or The hydrocarbon oil feedstock is a waxy oil, the first hydrogenation catalyst is a hydrodesulfurization catalyst, and the second hydrogenation catalyst is an isomerization pour point reducing catalyst.

[0065] The selection of the first hydrogenation catalyst and the second hydrogenation catalyst is specifically similar to that described in the first embodiment, and therefore will not be described in detail here.

[0066] According to the system of the present invention, preferably, said gas phase hydrogenation reactor is a fixed bed reactor.

[0067] According to one preferred embodiment of the present invention, the liquid-phase hydrogenation reactor is provided at its top with an outlet for gaseous components and at its bottom with an outlet for liquid-phase hydrogenation reaction products.

[0068] According to the system of the present invention, the liquid-phase hydrogenation reactor is preferably a fixed bed reactor, preferably a fixed bed reactor provided with a gas-liquid separation zone. Specifically, the gas-liquid separation zone may be any zone capable of realizing separation, for example, in the case of a flash zone, the liquid-phase hydrogenation reactor is a fixed bed reactor provided with a flash zone. Specifically, the liquid-phase hydrogenation reactor is provided with a flash zone, and the flash zone and above are not filled with catalyst, and the area below the flash zone is a liquid-phase hydrogenation reaction zone, that is, preferably, the gas-liquid separation zone is above the liquid-phase reaction zone. A stream (gas-liquid mixed phase) obtained by increasing the pressure of the gas-phase desulfurization reaction product is supplied to the flash zone of the liquid-phase hydrogenation reactor, the obtained gas phase component moves upward and is discharged from the upper outlet of the liquid-phase hydrogenation reactor, and the obtained liquid phase component moves downward to cause a liquid-phase hydrogenation reaction, and the obtained liquid-phase hydrogenation reaction product, the hydrogenated heavy component, is discharged from the bottom outlet of the liquid-phase hydrogenation reactor.

[0069] According to a preferred embodiment of the present invention, the system further includes a removal apparatus, the inlet of which is connected to the outlet of the gas phase component of the liquid-phase hydrogenation reactor, and the removal apparatus performs an impurity removal treatment on the gas phase component in the pressurized stream discharged from the liquid-phase hydrogenation reactor to obtain a hydrogenated light component.

[0070] Preferably, the impurity removal device is a hydrogen desulfurization device.

[0071] Preferably, the desulfurization unit includes a heat exchange unit and a high pressure separation unit in communication.

[0072] In the system according to the present invention, preferably, the gas phase component outlet of the liquid phase hydrogenation reactor is connected to the inlet of a heat exchanger, and the outlet of the heat exchanger is connected to the inlet of the high-pressure separation device. The gas phase component is subjected to heat exchange and high-pressure separation to obtain the hydrogenated light component and hydrogen sulfide-containing hydrogen gas. The hydrogen-rich gas obtained by treating the hydrogen sulfide-containing hydrogen gas can be recycled.

[0073] Preferably, the heat exchanger reduces the temperature of the gas phase components to a temperature of preferably 100 to 200°C, more preferably 120 to 150°C.

[0074] According to one preferred embodiment of the present invention, the system further comprises a mixer for receiving and mixing the liquid-phase hydrogenated reaction product and the hydrogenated light component to obtain a hydrogenated product.

[0075] Specifically, the gas phase component outlet of the liquid phase hydrogenation reactor is connected in sequence to a heat exchanger and a high-pressure separator, and the pipeline of the liquid phase outlet at the bottom of the liquid phase hydrogenation reactor is connected to the pipeline of the liquid phase outlet at the bottom of the high-pressure separator, which jointly supply the mixing device.

[0076] According to one preferred embodiment of the present invention, the system further includes a stripping and fractionation device, which strips (dehydrogenates) and fractionates the hydrogenation product. The specific conditions of the stripping and fractionation are not particularly limited and can be operated according to the requirements of the raw material and the performance of the target product. The specific conditions are as described above.

[0077] When the hydrocarbon oil feedstock is a wax oil, preferably, the system further includes a third hydrogenation reactor filled with a third hydrogenation catalyst (preferably a hydrodearomatization catalyst), and the third hydrogenation reactor has an inlet connected to the liquid-phase hydrogenation reaction product outlet of the liquid-phase hydrogenation reactor and the hydrogenated light component outlet of the impurity removal device, and performs a hydrodearomatization reaction of the hydrogenated light component and the liquid-phase hydrogenation reaction product.

[0078] The embodiments and effects of the present invention will be further described below with reference to examples.

[0079] In the present invention, percentages and percentage contents are by weight unless otherwise stated.

[0080] The method and system of the present invention will be described in detail below with reference to FIG. 1. The hydrocarbon oil feedstock is diesel as an example. The diesel feedstock and hydrogen gas 1 are fed into a gas-phase hydrogenation reactor 2 (also called the first hydrogenation reactor) to carry out a gas-phase desulfurization reaction, and obtain a gas-phase desulfurization reaction product 3. The feedstock is fed into a pressure booster 4 (compressor), and is then boosted by the compressor before being fed into a liquid-phase hydrogenation reactor 5 (also called the second hydrogenation reactor) equipped with a flash zone. The liquid phase component moves downward and enters the reaction zone, where it undergoes a hydrodearomatization reaction to obtain a liquid-phase hydrogenation reaction product 6 (hydrogenated heavy component), and the gas phase component 7 moves upward and is discharged from the liquid-phase hydrogenation reactor, enters a heat exchanger 8, and then enters a high-pressure separator 9 to be separated into a hydrogenated light component 11 and a hydrogen sulfide-containing hydrogen gas 10. The liquid-phase hydrogenation reaction product 6 and the hydrogenated light component 11 are mixed and fed into a stripping and fractionation device 12, and finally a diesel refined product 13 is obtained. Examples 1 to 3

[0081] The flow diagram shown in Figure 1 was followed. Two 100 mL fixed-bed hydrogenation reactors, a gas-phase hydrogenation reactor and a liquid-phase hydrogenation reactor, were connected in series. A reciprocating compressor of normal power was provided between the reactors. The gas-phase hydrogenation reactor was filled with 50 mL of Mo-Co type diesel hydrogenation catalyst A, and the liquid-phase hydrogenation reactor was filled with 50 mL of Mo-Ni type diesel hydrogenation catalyst B, with a flash zone provided above it. A gas phase component outlet was provided above the liquid-phase hydrogenation reactor, which was connected in sequence to a heat exchanger (cooled down to 130 ° C) and a high-pressure separator, and a liquid phase outlet was provided at the bottom of the liquid-phase hydrogenation reactor. The liquid phase outlet pipeline and the liquid phase outlet pipeline at the bottom of the high-pressure separator were connected and entered the subsequent stripping and fractionation device together, the naphtha fraction was cut, and a diesel refined product (initial boiling point 150 ° C) was obtained. The mixture of straight-run diesel, coked diesel and catalytic diesel was used as the feedstock. The catalyst properties are shown in Table 1, the feedstock properties in Table 2, and the reaction process conditions and results in Table 3. Comparative Example 1

[0082] A conventional diesel fixed-bed hydrogenation process flow was used, and one hydrogenation reactor, namely the first hydrogenation reactor, was arranged. According to the conventional blending system of catalysts, the Mo-Ni type catalyst B was packed at the top and the Mo-Co type catalyst A was packed at the bottom, with a packing volume of 50 mL each. In general, high-pressure separation, low-pressure separation, stripping and other processes were set up after the reactor to obtain diesel products. Hydrogen sulfide was removed from the hydrogen gas, and the hydrogen was pressurized by a cycle hydrogen compressor for recycling. The properties of the raw material and catalyst were the same as those of Examples 1 to 3, and the conditions and results of the reaction process are shown in Table 3. Comparative Example 2

[0083] A typical diesel fixed-bed hydrogenation process flow was used, and one hydrogenation reactor, i.e., the first hydrogenation reactor, was arranged. According to the same catalyst blending order as in Examples 1 to 3, Mo-Co type catalyst A was packed at the top and Mo-Ni type catalyst B was packed at the bottom, with a packed volume of 50 mL each. In general, high-pressure separation, low-pressure separation, stripping and other processes were set up after the reactor to obtain diesel products. Hydrogen sulfide was removed from the hydrogen gas, and the hydrogen was pressurized by a cycle hydrogen compressor for recycling. The raw materials and catalysts were the same as in Examples 1 to 3, and the reaction process conditions and results are shown in Table 3. Comparative Example 3

[0084] A typical diesel fixed-bed hydrogenation process flow was used, and two hydrogenation reactors, the first reactor and the second reactor, were connected in series, and a stripping tower was installed between the two reactors. Reactor 1 was filled with 50 mL of Mo-Co type diesel hydrogenation catalyst A, and reactor 2 was filled with 50 mL of Mo-Ni type diesel hydrogenation catalyst B. In general, processes such as high-pressure separation, low-pressure separation, and stripping were set up after the reactor to obtain diesel products. Hydrogen sulfide was removed from the hydrogen gas, and the hydrogen was pressurized by a cycle hydrogen compressor and recycled. The raw materials and catalysts were the same as those in Examples 1 to 3, and the reaction process conditions and results are shown in Table 3. Comparative Example 4

[0085] Except for the installation of a high-power reciprocating compressor between the first and second hydrogenation reactors and the control of the process conditions, the hydrogenation process steps were the same as those in Examples 1 to 3. The reaction process conditions and results are shown in Table 3.

[0086] [Table 1]

[0087] [Table 2]

[0088] [Table 3]

[0089] As can be seen from Table 3, in Comparative Example 1, in which a conventional fixed bed hydrogenation technology and a conventional catalyst packing system were used, hydrogenation of polycyclic aromatic hydrocarbons occurred in the upper part of the reactor, and advanced desulfurization occurred in the lower part of the reactor. In order to obtain the effect of advanced desulfurization, it is difficult to balance the reaction conditions for hydrogenation of aromatic hydrocarbons, and as a result, the removal effect of polycyclic aromatic hydrocarbons is poor. On the other hand, in the present invention, the pressure of the reaction system is significantly lowered, and since desulfurization and dearomatization are performed in two reaction systems, the reaction conditions can be optimized separately, and a better dearomatization effect can be obtained. In Comparative Example 2, the fixed bed hydrogenation technology adopts the same catalyst packing order as in the Example, and the sulfide is removed at the top of the reactor, and the hydrogenation saturation reaction of aromatic hydrocarbons occurs at the bottom. The temperature at the bottom of the reactor increases significantly, so the hydrogenation of aromatic hydrocarbons is thermodynamically limited, and both the sulfide removal effect and the aromatic hydrocarbon hydrogenation effect are poor.

[0090] Both of the two reactors used in Comparative Example 3 are conventional fixed-bed hydrogenation reactors, which have relatively harsh reaction conditions, high hydrogen consumption, and high energy consumption. In addition, the effluent from the first reactor all enters the second reactor, which increases the space velocity of aromatic hydrocarbon hydrogenation in the second reactor and deteriorates the removal effect of polycyclic aromatic hydrocarbons.

[0091] In Comparative Example 4, the hydrogen / oil ratio in the gas-phase hydrogenation reactor was too high, which reduced the partial pressure of the feed oil, affecting the adsorption of sulfides onto the catalyst surface and resulting in insufficient desulfurization. In addition, the difficulty of liquefying the vaporized gas-phase reactor effluent was significantly increased, and even at a reaction pressure of 10 MPa, it was difficult to liquefy all of the heavy components, adversely affecting the removal effect of polycyclic aromatic hydrocarbons. Example 4

[0092] The flow diagram shown in Figure 1 is adopted. Two 100 mL fixed-bed hydrogenation reactors, which are a gas-phase hydrogenation reactor and a liquid-phase hydrogenation reactor, respectively, were connected in series. A reciprocating compressor of normal power was provided between the reactors. The gas-phase hydrogenation reactor was filled with 50 mL of Mo-Ni type hydrogenation catalyst A, and the liquid-phase hydrogenation reactor was filled with 50 mL of isomerization catalyst B (grade FDW-3), and a flash zone was provided above it. A gas phase outlet was provided above the liquid-phase hydrogenation reactor, and this gas phase outlet was connected to a heat exchanger (which lowered the temperature of the gas phase components to 130°C) and a high-pressure separator, and a liquid phase outlet was provided at the bottom of the liquid-phase hydrogenation reactor, and the pipeline of the liquid phase outlet and the pipeline of the liquid phase outlet at the bottom of the high-pressure separator were connected to enter the subsequent stripping and fractionation device together. The properties of the catalyst are shown in Table 4, the properties of the feedstock are shown in Aviation Kerosene 1 in Table 5, and the reaction process conditions and results are shown in Table 6. Example 5

[0093] The flow diagram shown in Figure 1 is adopted. Two 100mL fixed-bed hydrogenation reactors are connected in series, and a reciprocating compressor is provided between the reactors. The first reactor is a gas-phase hydrogenation reactor filled with 50mL of Mo-Ni type diesel hydrogenation catalyst A, and the second reactor is a liquid-phase hydrogenation reactor filled with 50mL of Ni-based hydrogenation catalyst C, with a flash zone provided above it. A gas phase outlet is provided above the second reactor, and this gas phase component outlet is connected in sequence to a heat exchanger (cooled down to 130°C) and a high-pressure separator, and the pipeline of the bottom liquid phase outlet of the second reactor and the pipeline of the bottom liquid phase outlet of the high-pressure separator are connected and enter the subsequent stripping and fractionation device together. The properties of the catalyst are shown in Table 4, the properties of the feedstock are shown in Table 5 for aviation kerosene 2, and the reaction process conditions and results are shown in Table 6. Example 6

[0094] The flow diagram shown in Figure 1 is adopted. Two 100 mL fixed-bed hydrogenation reactors, the first and second reactors respectively, were connected in series. A reciprocating compressor of normal power was provided between the reactors. The first reactor was a gas-phase desulfurization reactor packed with 50 mL of Mo-Ni type diesel hydrodesulfurization catalyst D, and the second reactor was a liquid-phase desulfurization reactor packed with 50 mL of Mo-Co type diesel hydrodesulfurization catalyst E, with a flash zone provided above it. A gas-phase outlet was provided above the second reactor, and this gas-phase component outlet was connected in sequence to a heat exchanger (cooled down to 130 ° C) and a high-pressure separator, and the pipeline of the bottom liquid-phase outlet of the second reactor and the pipeline of the bottom liquid-phase outlet of the high-pressure separator were connected together and entered the subsequent stripping and fractionation device, the naphtha fraction was cut, and a low-sulfur diesel product (initial boiling point 180 ° C) was obtained. The catalyst properties are shown in Table 4, the feedstock properties are diesel in Table 5, and the reaction process conditions and results are shown in Table 6. Example 7

[0095] The flow diagram shown in Figure 2 is adopted. Three 100 mL fixed-bed hydrogenation reactors, the first reactor, the second reactor, and the third reactor, were connected in series. A reciprocating compressor of normal power was provided between the first and second reactors. The first reactor was a gas-phase hydrogenation reactor filled with 50 mL of Mo-Co type diesel hydrogenation catalyst E, and the second reactor was a liquid-phase hydrogenation reactor filled with 50 mL of Ni type isomerization pour point depressing catalyst B, with a flash zone provided above it. A gas phase outlet was provided above the second reactor, and this gas phase component outlet was connected in sequence to a heat exchanger (cooled down to 130 ° C) and a high-pressure separator, and the pipeline of the bottom liquid phase outlet of the second reactor and the pipeline of the bottom liquid phase outlet of the high-pressure separator were connected and entered the third reactor together, which was filled with 50 mL of Mo-Ni type advanced hydrogenation catalyst D. A special oil product was finally obtained. The catalyst properties are shown in Table 4, the feedstock properties are the wax oils in Table 5, and the reaction process conditions and results are shown in Table 6.

[0096] [Table 4]

[0097] [Table 5]

[0098] [Table 6]

[0099] Although the preferred embodiment of the present invention has been described in detail above, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, including combining each technical feature in other suitable ways, and these simple modifications and combinations should also be regarded as the contents disclosed in the present invention, and all belong to the protection scope of the present invention. [Explanation of symbols]

[0100] In FIG. 1. Diesel feedstock and hydrogen gas 2. Gas Phase Hydrogenation Reactor 3. Gas-phase desulfurization reaction products 4. Pressure booster 5 Liquid Phase Hydrogenation Reactor 6 Liquid phase hydrogenation reaction products 7 Gas Phase Components 8 Heat exchange equipment 9. High-pressure separator 10 Hydrogen gas containing hydrogen sulfide 11 Hydrogenated light components 12 Stripping and fractionation equipment 13 Diesel refined products In FIG. 1. Wax oil raw material and hydrogen gas 2. Gas Phase Hydrogenation Reactor 3. Gas-phase desulfurization reaction products 4. Pressure booster 5 Liquid Phase Hydrogenation Reactor 6 Liquid phase hydrogenation reaction products 7 Gas Phase Components 8 Heat exchange equipment 9. High-pressure separator 10 Hydrogenated light components 11 Hydrogen gas containing hydrogen sulfide 12 Third hydrogenation reactor 13 Special oil products

Claims

1. A method for hydrogenating a hydrocarbon oil, comprising the steps of: (1) performing a gas-phase desulfurization reaction of a hydrocarbon oil feedstock in a gas-phase hydrogenation reactor in the presence of hydrogen gas to obtain a gas-phase desulfurization reaction product; (2) pressurizing the gas-phase desulfurization reaction product to obtain an pressurized stream; and (3) sending the pressurized stream to a liquid-phase hydrogenation reactor, and subjecting a liquid phase component in the pressurized stream to a liquid-phase hydrogenation reactor to a liquid-phase hydrogenation reaction to obtain a liquid-phase hydrogenation reaction product.

2. The hydrocarbon oil feedstock is at least one selected from low-quality diesel, aviation kerosene, wax oil, and naphtha; Preferably, the low-quality diesel has an initial boiling point of 150 to 200°C, a final boiling point of 320 to 400°C, an S content of ≦20000 μg / g, preferably ≦15000 μg / g, an N content of ≦1000 μg / g, preferably ≦800 μg / g, and a polycyclic aromatic hydrocarbon content of ≦50 wt%; Preferably, the aviation kerosene has an initial boiling point of 80 to 150°C, a final boiling point of 200 to 300°C, an S content of ≦8000μg / g, preferably ≦4000μg / g, and an N content of ≦100μg / g, preferably ≦20μg / g; The method according to claim 1, wherein the wax oil has an initial boiling point of 160 to 220°C, a final boiling point of 300 to 400°C, an S content of ≦30000 μg / g, preferably ≦20000 μg / g, an N content of ≦2000 μg / g, preferably ≦1500 μg / g, and a polycyclic aromatic hydrocarbon content of ≦60 wt%.

3. The gas-phase desulfurization reaction is carried out in the presence of a first hydrogenation catalyst, and the first hydrogenation catalyst is a catalyst having a hydrodesulfurization function; Preferably, the conditions of the gas phase desulfurization reaction are a pressure of 0.1 to 2.8 MPa, preferably 0.5 to 2 MPa, a temperature of 260 to 400 ° C, preferably 320 to 390 ° C, a hydrogen / oil volume ratio of 100 to 900, preferably 300 to 700, and a space velocity of 0.5 to 3 h －１, preferably 0.8 to 2 h －１ Includes 3. The process according to claim 1 or 2, wherein the gas phase hydrogenation reactor is a fixed bed reactor.

4. The method according to any one of claims 1 to 3, wherein in step (2), the gas-phase desulfurization reaction product is pressurized to 2 to 10 MPa, preferably 2.5 to 7.5 MPa.

5. The hydrocarbon oil feedstock is low-quality diesel, and in step (2), the gas-phase desulfurization reaction product is pressurized to 4.5 to 6.5 MPa; The process according to any one of claims 1 to 4, wherein the liquid phase hydrogenation reaction is carried out in the presence of a second hydrogenation catalyst, the second hydrogenation catalyst being a hydrodearomatization catalyst.

6. The hydrocarbon oil feedstock is low-quality diesel, and in step (2), the gas-phase desulfurization reaction product is pressurized to 4-7 MPa; 5. The process according to any one of claims 1 to 4, wherein the liquid phase hydrogenation reaction is carried out in the presence of a second hydrogenation catalyst, the second hydrogenation catalyst being an advanced hydrodesulfurization catalyst.

7. The hydrocarbon oil feedstock is aviation kerosene, and in step (2), the gas-phase desulfurization reaction product is pressurized to 2.5 to 4 MPa; The process according to any one of claims 1 to 4, wherein the liquid phase hydrogenation reaction is carried out in the presence of a second hydrogenation catalyst, the second hydrogenation catalyst being a hydrodearomatization catalyst.

8. The hydrocarbon oil feedstock is aviation kerosene, and in step (2), the gas-phase desulfurization reaction product is pressurized to 2.5 to 4 MPa; The process according to any one of claims 1 to 4, wherein the liquid phase hydrogenation reaction is carried out in the presence of a second hydrogenation catalyst, the second hydrogenation catalyst being a hydroisomerization catalyst.

9. The hydrocarbon oil feedstock is wax oil, and in step (2), the gas-phase desulfurization reaction product is pressurized to 5 to 10 MPa; Preferably, the liquid phase hydrogenation reaction is carried out in the presence of a second hydrogenation catalyst, the second hydrogenation catalyst being an isomerization pour point reducing catalyst; The method according to any one of claims 1 to 4, further comprising the steps of discharging the gas phase component in the pressurized stream from above outside the liquid-phase hydrogenation reactor, optionally removing impurities to obtain a hydrogenated light component, and then mixing the hydrogenated light component with a liquid-phase hydrogenation reaction product to carry out a hydrodearomatization reaction.

10. 10. The method according to any one of claims 1 to 9, wherein the pressure of the liquid phase hydrogenation reaction is at least 1 MPa, preferably 1.5 to 7 MPa, more preferably 2.5 to 6 MPa higher than the pressure of the gas phase hydrodesulfurization.

11. The liquid phase hydrogenation reactor is a fixed bed reactor, preferably a fixed bed reactor provided with a gas-liquid separation zone, Preferably, the conditions of the liquid phase hydrogenation reaction are a pressure of 2 to 8 MPa, preferably 3 to 6 MPa, a temperature of 200 to 400 ° C, preferably 260 to 360 ° C, and a space velocity of 0.1 to 3 h －１ , preferably 0.5 to 1 h －１ The method according to any one of claims 1 to 10, comprising:

12. a gaseous component in the pressurized stream is allowed to move upwardly out of the liquid-phase hydrogenation reactor and is optionally subjected to a de-impurity treatment to obtain a hydrogenated light component; Preferably, the removal of impurities includes a desulfurization process, preferably a process for heat exchange of the gas phase components, followed by high-pressure separation to obtain the hydrogenated light components and hydrogen sulfide-containing hydrogen gas; The method according to any one of claims 1 to 11, wherein the heat exchange reduces the temperature of the gas phase components to between 100 and 200°C, preferably between 120 and 150°C.

13. The method further comprises the step of mixing the liquid-phase hydrogenation reaction product with the hydrogenated light component to obtain a hydrogenation product; Preferably, the hydrogenation product is a diesel refinery product having a polycyclic aromatic hydrocarbon content of 5 wt % or less and a S content of 10 μg / g or less; Preferably, the hydrogenation product is an aviation kerosene refinery product having a smoke point of 26 mm or more and / or a freezing point of −50° C. or less; 13. The method of claim 12, wherein the hydrogenation product is a specialty oil product having an aromatics content of 5 wt% or less and an S content of 10 μg / g or less.

14. A system for hydrogenating a hydrocarbon oil, comprising: a gas phase hydrogenation reactor packed with a first hydrogenation catalyst, a pressure booster, and a liquid phase hydrogenation reactor packed with a second hydrogenation catalyst, the gas phase hydrogenation reactor being connected in series; The gas-phase hydrogenation reactor performs a gas-phase desulfurization reaction of a hydrocarbon oil feedstock and hydrogen gas to obtain a gas-phase desulfurization reaction product, the booster boosts the gas-phase desulfurization reaction product to obtain a boosted stream; The liquid-phase hydrogenation reactor is configured to contact the pressurized stream with a second hydrogenation catalyst to carry out a liquid-phase hydrogenation reaction and obtain a liquid-phase hydrogenation reaction product.

15. The hydrogenation system according to claim 14, wherein the pressure booster boosts the gas-phase desulfurization reaction product to 2 to 10 MPa.

16. the hydrocarbon oil feedstock is diesel, the first hydrogenation catalyst is a hydrodesulfurization catalyst, and the second hydrogenation catalyst is a hydrodearomatization catalyst; or the hydrocarbon feedstock is diesel, the first hydrogenation catalyst is a hydrodesulfurization catalyst, and the second hydrogenation catalyst is an advanced hydrodesulfurization catalyst; or the hydrocarbon oil feedstock is aviation kerosene, the first hydrogenation catalyst is a hydrodesulfurization catalyst, and the second hydrogenation catalyst is a hydrodearomatization catalyst; or the hydrocarbon oil feedstock is aviation kerosene, the first hydrogenation catalyst is a hydrodesulfurization catalyst, and the second hydrogenation catalyst is a hydroisomerization catalyst; or 16. The hydrogenation system of claim 14 or 15, wherein the hydrocarbon oil feedstock is a waxy oil, the first hydrogenation catalyst is a hydrodesulfurization catalyst, and the second hydrogenation catalyst is an isomerization pour point reducing catalyst.

17. The gas phase hydrogenation reactor is a fixed bed reactor, The hydrogenation system according to any one of claims 14 to 16, wherein the liquid phase hydrogenation reactor is a fixed bed reactor, preferably a fixed bed reactor provided with a gas-liquid separation zone.

18. the method further includes a removal of impurities, the removal of impurities having an inlet connected to an outlet for the gas phase component of the liquid-phase hydrogenation reactor, and performing a removal of impurities on the gas phase component in the pressurized stream discharged from the liquid-phase hydrogenation reactor to obtain a hydrogenated light component; Preferably, the impurity removal device is a hydrogen desulfurization device, A hydrogenation system according to any one of claims 14 to 17, wherein the desulfurization unit preferably comprises a heat exchange unit and a high pressure separation unit in communication.

19. 20. The hydrogenation system of claim 18, further comprising a mixer for receiving and mixing the liquid-phase hydrogenated reaction product and the hydrogenated light components to obtain a hydrogenated product.

20. 19. The hydrogenation system according to claim 18, wherein the hydrocarbon oil feedstock is a wax oil, and the system further comprises a third hydrogenation reactor filled with a third hydrogenation catalyst, and the third hydrogenation reactor has an inlet connected to a liquid-phase hydrogenation reaction product outlet of the liquid-phase hydrogenation reactor and a hydrogenated light component outlet of the impurity removal device, and performs a hydrodearomatization reaction of the hydrogenated light component and the liquid-phase hydrogenation reaction product.

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