A method for producing special oil raw materials from heavy fuel oil

Abstract

The present invention relates to a process for producing special oil raw materials from heavy fuel oil; the present invention combines fixed-bed hydrogenation, delayed coking, hydrorefining and atmospheric and vacuum distillation processes, with a simple process flow and low investment; a steam generator is provided at the bottom of the coking fractionation tower of the present invention, and the bottom temperature of the tower is controlled by heat exchange while generating steam; alternatively, the atmospheric and vacuum distillation fraction products can be used to exchange heat with the residue fixed-bed hydrogenation raw materials to meet the demand for raw material preheating and reduce energy consumption; during the sulfidation process of the present invention, the succinic acid / cobalt / ruthenium complex and phosphoric acid groups on the MCM-41 molecular sieve react with hydrogen sulfide to form a more active hydrodesulfurization active center, which can catalyze the hydrodesulfurization reaction of sulfides and improve the desulfurization efficiency.

Description

Technical Field

[0001] The present invention relates to the technical field of petrochemical engineering, and particularly to a method for producing special oil raw materials from heavy fuel oil. Background Art

[0002] The demand for fine petrochemical products is strong and is developing towards the high-end, special and dedicated directions. To adapt to the rapid development of the automotive and machinery industries and strict environmental protection requirements, the upgrading speed of special oil products has significantly accelerated. The increasing market demand for special oils has also driven the continuous increase in the demand for special oil raw materials.

[0003] Traditional Class II and Class III high-quality lubricating oil base oil raw materials are usually produced from paraffinic crude oil. Due to the worldwide deterioration of crude oil, the quantity of paraffinic crude oil suitable for producing high-viscosity index lubricating oil base oil raw materials by traditional processes has gradually decreased. Therefore, the technology for producing lubricating oil raw materials by the hydrogenation method has developed very rapidly. The hydrogenation process refers to the process of producing lubricating oil base oil raw materials by using a hydrotreating or hydrocracking process - hydrodewaxing or isodewaxing - hydrofining combined process. Its advantages include large raw material flexibility, high yield of base oil raw materials, and high by-product value, etc.

[0004] Delayed coking is a commonly used means for upgrading residue oil. The coking process is a secondary processing process that uses residue oil as a raw material for deep thermal cracking at high temperatures to produce distillate oil and petroleum coke. Most of them adopt the delayed coking process. Its advantages are that it can process various inferior residue oils, the process is simple, and the investment and operating costs are low. Its disadvantages are that the content of unsaturated hydrocarbons in coker gasoline and coker diesel is high, and the content of non-hydrocarbon compounds such as sulfur and nitrogen is also high, which brings great difficulties to further processing. Against this background, the processing technologies for distillate oils such as gasoline and diesel, especially the processing technologies for secondary processed gasoline and diesel distillates, have received increasing attention. The raw materials of secondary processed gasoline and diesel distillates generally adopt a processing method of separately performing hydrogenation or mixing for hydrogenation, and each method has its own characteristics and deficiencies.

[0005] Chinese Patent CN103059997A discloses a combined process method for residue oil hydrotreating and delayed coking. In this method, a fluidized bed process is used to hydrotreat the residue oil, including: the liquid phase product after the residue oil raw material is hydrotreated by the fluidized bed is directly fed into the coking fractionation tower without fractionation, and countercurrently contacts with the gas phase generated by coking. The light components generated by hydrogenation and the light components generated by coking are taken out of the unit together, and the fractions above wax oil are recycled back to the delayed coking unit. This technology combines a fluidized bed coking unit with delayed coking. Due to the insufficient depth of residue oil hydrogenation and low impurity removal rate in the fluidized bed hydrogenation process, and at the same time, the bottom temperature of the coking fractionation tower in the process cannot be effectively controlled, the wide application of this process is restricted.

[0006] Chinese patent CN0109671.6 discloses a method for hydrofining of coking whole fraction oil. Under medium pressure conditions, coking whole fraction oil is contacted with a hydrofining catalyst, and the reaction product is separated into gas and liquid phases through high separation. The gas phase product is circulated to the coking whole fraction oil hydrofining reactor as circulating hydrogen; the liquid phase product enters the fractionation tower to separate gasoline, diesel and wax oil. This process technology has the disadvantage of large temperature rise of the reaction bed, and cold hydrogen is required between the reaction beds to cool down.

[0007] Chinese patent CN200610045708.4 discloses a method for producing high-quality diesel from coking whole fraction oil, wherein the coking whole fraction oil is separated into coking light fraction oil and coking heavy fraction oil, wherein the light fraction oil contains part of the light diesel fraction, and the heavy fraction oil is a heavy diesel fraction with a higher dry point. The coking heavy fraction oil is subjected to hydro-refining, and the hydro-refining product is mixed with the coking light fraction oil for hydro-refining treatment. This method can obtain high-quality clean diesel in the largest amount, and can also obtain high-quality naphtha, but the necessity of hydro-refining treatment after hydro-refining of the coking heavy fraction oil is not obvious, and the coking wax oil fraction needs to be further processed by other processes.

[0008] In the prior art, the residual oil hydrotreatment and gasoline and diesel hydrofining processes are operated separately. Although they can meet the purpose requirements, they are bound to lead to high total investment costs and high operating costs due to the complete independence of several processing units, each with independent equipment and pipelines. Therefore, providing a simpler, more reasonable and efficient combined process flow that combines heavy oil hydrotreatment-delayed coking-hydrofining to produce special oil raw materials is a technical problem that needs to be solved urgently. Summary of the invention

[0009] In view of the deficiencies in the prior art, the present invention provides a combined process for residual oil hydroprocessing, delayed coking reaction and distillate oil hydrofining, which has the characteristics of simple process, strong raw material adaptability, multiple product types and flexible production scheme, and can efficiently and stably produce special oil raw materials with excellent performance, realize the full utilization of heavy oil resources and produce high value-added products such as low-sulfur petroleum coke. The present invention can make full use of the high-temperature fraction product of the atmospheric and vacuum distillation tower to preheat the residual oil hydroprocessing raw material, thereby minimizing construction investment and production costs.

[0010] The present invention provides a method for producing special oil raw material from heavy fuel oil, and the operating steps are as follows:

[0011] S1: The heavy fuel oil as raw material passes through the raw material buffer tank and the first feed pump. A part of it is sent to the first heating furnace for heating and then fed into the coking fractionating tower; another part is mixed with hydrogen, where the volume ratio of hydrogen to heavy fuel oil is 300 - 1000, preferably 500 - 800; after being heated by the second heating furnace, it is sent to the fixed bed reactor for reaction;

[0012] S2: The mixture after reaction in the fixed bed reactor is subjected to gas - liquid separation in a first - stage hot high - pressure separator. The gas phase is further separated in a first - stage cold high - pressure separator, and the liquid phase is stripped in a first - stage medium - pressure stripper; after the stripped gas phase is mixed with the liquid phase from the first - stage cold high - pressure separator, it is subjected to gas - liquid separation in a first - stage cold low - pressure separator; the separated liquid phase is sent to the coking fractionating tower; the liquid phase of the first - stage medium - pressure stripper is sent to the first heating furnace;

[0013] S3: The bottom liquid of the coking fractionating tower is heated by the first circulation pump and the steam generator and then returned to the bottom of the coking fractionating tower;

[0014] S4: The bottom liquid of the coking fractionating tower is sent through the second feed pump, the first heating furnace, and the coking tower for delayed coking reaction and then returned to the coking fractionating tower;

[0015] S5: The top gas phase of the coking fractionating tower passes through the reflux drum. A part of the liquid phase is returned to the coking fractionating tower through the second circulation pump; another part, together with the coking diesel oil from the coking fractionating tower, is sent through the third feed pump, mixed with hydrogen, and then fed into the third heating furnace;

[0016] S6: The coking wax oil from the coking fractionating tower is sent through the fourth feed pump and the fourth heating furnace into the first hydrofining reactor for reaction. After that, it is mixed with the material from the third heating furnace in S5 and then sent together into the second hydrofining reactor for reaction;

[0017] S7: After the reaction in the second hydrofining reactor is completed, it is sent to a second - stage hot high - pressure separator for separation. The gas phase is further separated in a second - stage cold high - pressure separator; the liquid phase of the second - stage hot high - pressure separator is separated in a second - stage hot low - pressure separator, and the gas phase and the liquid phase from the second - stage cold high - pressure separator are sent together into the second - stage cold low - pressure separator; the liquid phase of the second - stage cold low - pressure separator and the gas - liquid phase from the second - stage hot low - pressure separator are sent together into the second - stage stripper;

[0018] S8: After being stripped in the second - stage stripper, high - quality foamer raw material is obtained at the top of the tower. The bottom oil phase is sent through the fifth feed pump and the fifth heating furnace to the atmospheric distillation tower for fractionation; after the heavy fraction at the bottom of the atmospheric distillation tower is admixed with Fischer - Tropsch wax oil, it is sent through the sixth feed pump and the sixth heating furnace to the vacuum distillation tower for fractionation, and the vacuum degree of the vacuum tower is - 70~ - 80 kPa.

[0019] Preferably, chemical light oil is fractionated at the top of the atmospheric distillation tower, and 4# jet fuel, 3# white oil raw material, transformer oil raw material, and 10# white oil raw material are fractionated successively from the side lines.

[0020] Preferably, the 15# white oil raw material is fractionated from the top of the vacuum tower, the 100N and 250N base oil raw materials are fractionated from the side lines of the tower in sequence, and the 500N base oil raw material is fractionated from the bottom of the tower.

[0021] Preferably, the temperature of the fixed-bed hydrogenation reaction is 300 - 500 °C, preferably 370 - 403 °C; the reaction pressure is 5 - 30 MPa, preferably 15 - 25 MPa; the liquid hourly space velocity is 0.05 - 1.5 h -1 , preferably 0.1 - 0.8 h -1 ; the sulfur content in the oil phase after hydrogenation is 0.1 - 0.9%, preferably 0.4 - 0.5%.

[0022] Preferably, the temperature at the bottom of the coking fractionation tower is controlled at 350 - 400 °C, preferably 360 - 365 °C; the temperature of the steam generator is controlled at 360 - 400 °C, preferably 385 - 395 °C.

[0023] Preferably, the outlet temperatures of the first, second, third, fourth, fifth, and sixth heating furnaces are 450 - 550 °C, preferably 480 - 510 °C.

[0024] Preferably, the feed temperature of the coking tower is controlled at 350 - 400 °C, preferably 350 - 370 °C; the reaction temperature of the coking tower is 390 - 460 °C, preferably 400 - 430 °C; the top pressure is 0.1 - 0.7 MPa, preferably 0.35 - 0.55 MPa; the recycle ratio is less than 0.3, preferably 0.15 - 0.3; the temperature of the oil and gas at the top of the coking tower is 400 - 450 °C, preferably 410 - 430 °C.

[0025] Preferably, the operating conditions of the first hydrofining reactor are: the hydrogen-oil volume ratio is 300 - 1000, preferably 600 - 800; the reaction temperature is 350 - 450 °C, preferably 390 - 415 °C; the reaction pressure is 5 - 30 MPa, preferably 15 - 25 MPa; the liquid hourly space velocity is 0.5 - 1.5 h -1 , preferably 0.9 - 1.1 h -1 .

[0026] Preferably, the operating conditions of the second hydrofining reactor are: the hydrogen-oil volume ratio is 300 - 800, preferably 400 - 600; the reaction temperature is 300 - 400 °C, preferably 350 - 370 °C; the reaction pressure is 5 - 30 MPa, preferably 15 - 25 MPa; the liquid hourly space velocity is 1.0 - 2.0 h -1 , preferably 1.4 - 1.6 h -1 .

[0027] Preferably, the first-stage hydrofining catalyst is hydrotreating agent RL-2; the theoretical filling volume is 2-5 L / kg;

[0028] Preferably, the theoretical filling volume of the second-stage hydrofining catalyst is 1-4 L / kg, and its preparation method is as follows:

[0029] T1: By mass, in the first stirring kettle, add 100-150 parts of MCM-41 molecular sieve to 1000-1200 parts of water and 3-6 parts of silane coupling agent KH-560, stir at 30-50 °C for 40-80 min, discharge, filter, and dry to obtain epoxy MCM-41 molecular sieve;

[0030] T2: Add 12-23 parts of cobalt acetate, 28-56 parts of ruthenium acetate, 18-36 parts of dimercaptosuccinic acid, and 1000-1200 parts of DMF to the second stirring kettle, heat up to 70-80 °C, stir for 120-180 min, and distill off water to obtain dimercaptosuccinic acid / cobalt / ruthenium complex;

[0031] T3: Add 2-7 parts of dimercaptosuccinic acid / cobalt / ruthenium complex, 0.02-0.2 parts of diethyl allyl phosphate, and 1000-1200 parts of toluene to the first stirring kettle, heat up to 70-80 °C, stir for 40-80 min, then add 100-160 parts of epoxy MCM-41 molecular sieve, heat up to 70-80 °C, stir for 120-180 min, discharge, filter, and dry to obtain the second-stage hydrofining catalyst.

[0032] Reaction mechanism

[0033] The MCM-41 molecular sieve reacts with the silane coupling agent KH-560 to obtain epoxy MCM-41 molecular sieve; cobalt acetate, ruthenium acetate, and dimercaptosuccinic acid react to obtain dimercaptosuccinic acid / cobalt / ruthenium complex; the dimercaptosuccinic acid / cobalt / ruthenium complex undergoes a thiol-allyl addition reaction with diethyl allyl phosphate; the dimercaptosuccinic acid / cobalt / ruthenium complex undergoes a thiol-epoxy reaction with epoxy MCM-41 molecular sieve, and the above reactions obtain the second-stage hydrofining catalyst.

[0034] Technical effect

[0035] The method for producing special oil raw materials from heavy fuel oil in the present invention has the following remarkable effects compared with the prior art:

[0036] 1. The present invention combines fixed-bed hydrogenation, delayed coking, hydrofining, and atmospheric and vacuum distillation processes, featuring originality and advancement in terms of simple process flow and low investment. By reasonably matching three catalysts and continuously optimizing process conditions, appropriate process conditions are determined to achieve the purpose of producing high-quality special oil raw materials.

[0037] 2. The present invention uses low-cost production to obtain high-quality petroleum coke with low sulfur and low ash content, which meets the requirements of raw materials for battery-grade anode materials.

[0038] 3. A steam generator is provided at the bottom of the coking fractionation tower of the present invention to control the bottom temperature through heat exchange and generate steam simultaneously. Alternatively, heat exchange between atmospheric and vacuum distillation products and residue fixed-bed hydrogenation raw materials can be utilized to meet the demand for raw material preheating and reduce energy consumption.

[0039] 4. Through reasonable process layout in the present invention, when the fixed-bed hydrogenation unit fails, the raw materials directly enter the delayed coking reaction without the need for a full-system shutdown for maintenance. At the same time, as the cold oil circulation process of the fixed bed during system startup, it has advantages such as a large operating flexibility in production.

[0040] 5. During the sulfidation process of the present invention, the succinic acid / cobalt / ruthenium complex and phosphoric acid group on the MCM-41 molecular sieve react with hydrogen sulfide to form a more active hydrodesulfurization active center, which can catalyze the hydrodesulfurization reaction of sulfides and improve the desulfurization efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 It is a schematic diagram of the process flow described in the present invention.

[0042] Among them, 1 is the raw material buffer tank; 2 is the first-stage hot high-pressure separator; 3 is the first-stage cold high-pressure separator; 4 is the first-stage medium-pressure stripping column; 5 is the first-stage cold low-pressure separator; 6 is the coking fractionation tower; 7 is the first heating furnace; 8 is the coking tower; 9 is the second heating furnace; 10 is the fixed-bed reactor; 11 is the first feed pump; 12 is the second feed pump; 13 is the first circulation pump; 14 is the second circulation pump; 15 is the steam generator; 16 is the first valve; 17 is the second valve; 18 is the third valve; 19 is the reflux tank; 20 is the third feed pump; 21 is the third heating furnace; 22 is the fourth feed pump; 23 is the fourth heating furnace; 24 is the first hydrofining reactor; 25 is the second hydrofining reactor; 26 is the second-stage hot high-pressure separator; 27 is the second-stage cold high-pressure separator; 28 is the second-stage hot low-pressure separator; 29 is the second-stage cold low-pressure separator; 30 is the fifth feed pump; 31 is the fifth heating furnace; 32 is the sixth feed pump; 33 is the sixth heating furnace; 34 is the second-stage stripping column; 35 is the atmospheric separation tower; 36 is the vacuum separation tower. DETAILED DESCRIPTION OF THE INVENTION

[0043] To further elaborate on the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the following will, in conjunction with the accompanying drawings and preferred embodiments, detail the specific implementation manners, structures, features and their effects of the present invention as follows.

[0044] It is determined by using the elemental analysis method.

[0045] Main properties of the raw heavy oil:

[0046] Heavy oil Analysis data <![CDATA[Density, 20 °C, g / cm 3 > 0.9931 S, Wt% ≤5 N, μg / g ≤3000 CCR, Wt% ≤15.0 Ni+V, μg / g ≤120

[0047] Example 1

[0048] A method for producing special oil raw materials from heavy fuel oil, the operation steps of which are as follows:

[0049] S1: A part of the raw heavy fuel oil is sent to the first heating furnace for heating through the raw material buffer tank and the first feed pump, and then sent to the coking fractionation tower; another part is mixed with hydrogen, and the volume ratio of hydrogen to heavy fuel oil is 500; after being heated by the second heating furnace, it is sent to the fixed bed reactor for reaction;

[0050] S2: The mixture after the reaction in the fixed bed reactor is subjected to gas-liquid separation in the first-stage hot high-pressure separator. The gas phase is further separated in the first-stage cold high-pressure separator, and the liquid phase is stripped in the first-stage medium-pressure stripper; after the gas phase after stripping is mixed with the liquid phase in the first-stage cold high-pressure separator, it is subjected to gas-liquid separation in the first-stage cold low-pressure separator; the separated liquid phase is sent to the coking fractionation tower; the liquid phase in the first-stage medium-pressure stripper is sent to the first heating furnace;

[0051] S3: The bottom liquid of the coking fractionation tower is heated by the first circulation pump and the steam generator and returned to the bottom of the coking fractionation tower;

[0052] S4: The bottom liquid of the coking fractionation tower is sent to the coking tower through the second feed pump, the first heating furnace for delayed coking reaction, and then returned to the coking fractionation tower;

[0053] S5: The gas phase at the top of the coking fractionation tower passes through the reflux drum. A part of the liquid phase is returned to the coking fractionation tower through the second circulation pump; another part and the coking diesel oil in the coking fractionation tower are sent through the third feed pump, mixed with hydrogen, and then sent to the third heating furnace;

[0054] S6: The coking wax oil in the coking fractionation tower is sent to the first hydrofining reactor for reaction through the fourth feed pump and the fourth heating furnace, and then mixed with the material from the third heating furnace in S5 and sent to the second hydrofining reactor for reaction;

[0055] S7: After the reaction in the second hydrofining reactor is completed, it is sent to the second-stage hot high-pressure separator for separation. The gas phase is further separated in the second-stage cold high-pressure separator. The liquid phase in the second-stage hot high-pressure separator is separated in the second-stage hot low-pressure separator, and the gas phase is sent to the second-stage cold low-pressure separator together with the liquid phase in the second-stage cold high-pressure separator. The liquid phase in the second-stage cold low-pressure separator and the gas-liquid phase in the second-stage hot low-pressure separator are sent to the second-stage stripping column together.

[0056] S8: After being stripped in the second-stage stripping column, high-quality foamer raw materials are obtained at the top of the column. The bottom oil phase is sent to the atmospheric distillation column for fractionation through the fifth feed pump and the fifth heating furnace. After the heavy fraction at the bottom of the atmospheric distillation column is admixed with Fischer-Tropsch wax oil, it is sent to the vacuum distillation column for fractionation through the sixth feed pump and the sixth heating furnace. The vacuum degree of the vacuum column is -70 kPa.

[0057] The chemical light oil is fractionated at the top of the atmospheric distillation column described above, and 4# jet fuel hot feedstock, 3# white oil raw material, transformer oil raw material, and 10# white oil raw material are fractionated successively from the side lines.

[0058] The 15# white oil raw material is fractionated at the top of the vacuum column described above, 100N and 250N base oil raw materials are fractionated successively from the side lines of the column, and 500N base oil raw material is fractionated at the bottom of the column.

[0059] The fixed-bed hydrogenation reaction temperature is 370 °C; the reaction pressure is 15 MPa; the liquid hourly space velocity is 0.1 h -1 ; the sulfur content in the oil phase after hydrogenation is 0.4%.

[0060] The bottom temperature of the coking fractionation column is controlled at 360 °C; the temperature of the steam generator is controlled at 385 °C.

[0061] The outlet temperature of the first, second, third, fourth, fifth, and sixth heating furnaces is 480 °C.

[0062] The feed temperature of the coking column is controlled at 350 °C; the reaction temperature of the coking column is 400 °C; the top pressure is 0.35 MPa; the recycle ratio is 0.15; the temperature of the oil and gas at the top of the coking column is 410 °C.

[0063] The operating conditions of the first hydrofining reactor are: the hydrogen-oil volume ratio is 600; the reaction temperature is 390 °C; the reaction pressure is 15 MPa; the liquid hourly space velocity is 0.9 h -1 .

[0064] The operating conditions of the second hydrofining reactor are: the hydrogen-oil volume ratio is 400; the reaction temperature is 350 °C; the reaction pressure is 15 MPa; the liquid hourly space velocity is 1.4 h -1 .

[0065] The first-stage hydrofining catalyst is the hydrotreating agent RL-2; the theoretical packing volume is 2 L / kg;

[0066] The theoretical packing volume of the second-stage hydrofining catalyst described above is 1 L / kg, and its preparation method is as follows:

[0067] T1: In the first stirring kettle, add 100 kg of MCM-41 molecular sieve into 1000 kg of water and 3 kg of silane coupling agent KH-560, stir at 30 °C for 40 min, discharge the material, filter, and dry to obtain epoxy MCM-41 molecular sieve.

[0068] T2: Add 12 kg of cobalt acetate, 28 kg of ruthenium acetate, 18 kg of dimercaptosuccinic acid, and 1000 kg of DMF into the second stirring kettle, heat up to 70 °C, stir for 120 min, and distill off water to obtain dimercaptosuccinic acid / cobalt / ruthenium complex.

[0069] T3: Add 2 kg of dimercaptosuccinic acid / cobalt / ruthenium complex, 0.02 kg of diethyl allyl phosphate, and 1000 kg of toluene into the first stirring kettle, heat up to 70 °C, stir for 40 min, then add 100 kg of epoxy MCM-41 molecular sieve, heat up to 70 °C, stir for 120 min, discharge the material, filter, and dry to obtain the second-stage hydrofining catalyst.

[0070] Example 2

[0071] A method for producing special oil raw materials from heavy fuel oil, and its operation steps are as follows:

[0072] S1: The raw heavy fuel oil passes through the raw material buffer tank and the first feed pump. Part of it is sent to the first heating furnace for heating and then sent to the coking fractionating tower; another part is mixed with hydrogen, and the volume ratio of hydrogen to heavy fuel oil is 600; after being heated by the second heating furnace, it is sent to the fixed-bed reactor for reaction.

[0073] S2: The mixture after the reaction in the fixed-bed reactor is subjected to gas-liquid separation in the first-stage hot high-pressure separator. The gas phase is further separated in the first-stage cold high-pressure separator, and the liquid phase is stripped in the first-stage medium-pressure stripper; after the gas phase after stripping is mixed with the liquid phase in the first-stage cold high-pressure separator, it is subjected to gas-liquid separation in the first-stage cold low-pressure separator; the separated liquid phase is sent to the coking fractionating tower; the liquid phase of the first-stage medium-pressure stripper is sent to the first heating furnace.

[0074] S3: The bottom liquid of the coking fractionating tower is heated by the first circulation pump and the steam generator and returned to the bottom of the coking fractionating tower.

[0075] S4: The bottom liquid of the coking fractionating tower is sent to the coking tower through the second feed pump, the first heating furnace for delayed coking reaction, and then returned to the coking fractionating tower.

[0076] S5: The gas phase at the top of the coking fractionating column passes through the reflux drum. Part of the liquid phase returns to the coking fractionating column via the second circulation pump. The other part, together with the coking diesel oil from the coking fractionating column, is sent to the third feed pump, mixed with hydrogen, and then fed into the third heating furnace.

[0077] S6: The coking wax oil from the coking fractionating column is sent to the first hydrofining reactor through the fourth feed pump and the fourth heating furnace. After the reaction, it is mixed with the material from the third heating furnace in S5 and then sent to the second hydrofining reactor for reaction together.

[0078] S7: After the reaction in the second hydrofining reactor is completed, it is sent to the second-stage hot high-pressure separator for separation. The gas phase is further separated through the second-stage cold high-pressure separator. The liquid phase in the second-stage hot high-pressure separator is separated through the second-stage hot low-pressure separator. The gas phase and the liquid phase in the second-stage cold high-pressure separator are sent to the second-stage cold low-pressure separator together. The liquid phase in the second-stage cold low-pressure separator and the gas-liquid phase in the second-stage hot low-pressure separator are sent to the second-stage stripping column together.

[0079] S8: After being stripped in the second-stage stripping column, high-quality foamer raw materials are obtained at the top of the column. The bottom oil phase is sent to the atmospheric distillation column for fractionation through the fifth feed pump and the fifth heating furnace. After the heavy fraction at the bottom of the atmospheric distillation column is mixed with the Fischer-Tropsch wax oil, it is sent to the vacuum distillation column for fractionation through the sixth feed pump and the sixth heating furnace. The vacuum degree of the vacuum column is -75 kPa.

[0080] The chemical light oil is fractionated at the top of the described atmospheric distillation column, and 4# jet fuel hot material, 3# white oil raw material, transformer oil raw material, and 10# white oil raw material are fractionated successively from the side lines.

[0081] The 15# white oil raw material is fractionated at the top of the described vacuum column, 100N and 250N base oil raw materials are fractionated successively from the side lines of the column, and the 500N base oil raw material is fractionated at the bottom of the column.

[0082] The fixed-bed hydrogenation reaction temperature is 380 °C; the reaction pressure is 18 MPa; the liquid hourly space velocity is 0.3 h -1 ; the sulfur content in the hydrogenated oil phase is 0.45%.

[0083] The bottom temperature of the described coking fractionating column is controlled at 362 °C; the temperature of the steam generator is controlled at 388 °C.

[0084] The outlet temperature of the first, second, third, fourth, fifth, and sixth heating furnaces is 495 °C.

[0085] The feed temperature of the described coking tower is controlled at 355 °C; the reaction temperature of the coking tower is 410 °C; the top pressure is 0.4 MPa; the recycle ratio is 0.2; the temperature of the oil and gas at the top of the coking tower is 415 °C.

[0086] The operating conditions of the first hydrofining reactor are as follows: the hydrogen-oil volume ratio is 650; the reaction temperature is 400 °C; the reaction pressure is 18 MPa; the liquid hourly space velocity is 1.0 h -1 .

[0087] The operating conditions of the second hydrofining reactor are as follows: the hydrogen-oil volume ratio is 450; the reaction temperature is 355 °C; the reaction pressure is 18 MPa; the liquid hourly space velocity is 1.5 h -1 .

[0088] The first-stage hydrofining catalyst described above is a hydrotreating agent RL-2; the theoretical loading volume is 3 L / kg;

[0089] The theoretical loading volume of the second-stage hydrofining catalyst described above is 2 L / kg, and its preparation method is as follows:

[0090] T1: In the first stirring kettle, add 110 kg of MCM-41 molecular sieve to 1050 kg of water and 4 kg of silane coupling agent KH-560, stir at 35 °C for 50 min, discharge, filter, and dry to obtain epoxy-functionalized MCM-41 molecular sieve;

[0091] T2: Add 16 kg of cobalt acetate, 36 kg of ruthenium acetate, 24 kg of dimercaptosuccinic acid, and 1050 kg of DMF to the second stirring kettle, heat up to 75 °C, stir for 140 min, and distill off water to obtain dimercaptosuccinic acid / cobalt / ruthenium complex;

[0092] T3: Add 3 kg of dimercaptosuccinic acid / cobalt / ruthenium complex, 0.1 kg of diethyl allyl phosphate, and 1050 kg of toluene to the first stirring kettle, heat up to 75 °C, stir for 50 min, then add 110 kg of epoxy-functionalized MCM-41 molecular sieve, heat up to 75 °C, stir for 140 min, discharge, filter, and dry to obtain the second-stage hydrofining catalyst.

[0093] Example 3

[0094] A method for producing special oil raw materials from heavy fuel oil, and its operating steps are as follows:

[0095] S1: The raw heavy fuel oil passes through the raw material buffer tank and the first feed pump. A part is sent to the first heating furnace for heating and then sent to the coking fractionating tower; another part is mixed with hydrogen, where the volume ratio of hydrogen to heavy fuel oil is 700; after being heated by the second heating furnace, it is sent to the fixed-bed reactor for reaction;

[0096] S2: The mixture after the reaction in the fixed-bed reactor is separated by gas-liquid separation in a first-stage hot high-pressure separator. The gas phase is further separated in a first-stage cold high-pressure separator, and the liquid phase is stripped in a first-stage medium-pressure stripper. After the stripped gas phase is mixed with the liquid phase from the first-stage cold high-pressure separator, it is separated by gas-liquid separation in a first-stage cold low-pressure separator. The separated liquid phase is sent to the coking fractionating column, and the liquid phase of the first-stage medium-pressure stripper is sent to the first heating furnace.

[0097] S3: The bottom liquid of the coking fractionating column is heated by the first circulation pump and the steam generator and then returned to the bottom of the coking fractionating column.

[0098] S4: The bottom liquid of the coking fractionating column is pumped by the second feed pump, passed through the first heating furnace and the coking tower for delayed coking reaction, and then returned to the coking fractionating column.

[0099] S5: The gas phase at the top of the coking fractionating column passes through the reflux drum. Part of the liquid phase is pumped back to the coking fractionating column by the second circulation pump. The other part, together with the coking diesel oil from the coking fractionating column, is pumped by the third feed pump, mixed with hydrogen, and then sent to the third heating furnace.

[0100] S6: The coking wax oil from the coking fractionating column is pumped by the fourth feed pump, passed through the fourth heating furnace, and sent to the first hydrofining reactor for reaction. After that, it is mixed with the material from the third heating furnace in S5 and then sent to the second hydrofining reactor for reaction together.

[0101] S7: After the reaction in the second hydrofining reactor is completed, it is sent to the second-stage hot high-pressure separator for separation. The gas phase is further separated in the second-stage cold high-pressure separator. The liquid phase of the second-stage hot high-pressure separator is separated in the second-stage hot low-pressure separator. The gas phase and the liquid phase from the second-stage cold high-pressure separator are sent to the second-stage cold low-pressure separator together. The liquid phase of the second-stage cold low-pressure separator and the gas-liquid phases from the second-stage hot low-pressure separator are sent to the second-stage stripper together.

[0102] S8: After being stripped in the second-stage stripper, high-quality foamer raw materials are obtained at the top of the tower. The bottom oil phase is pumped by the fifth feed pump, passed through the fifth heating furnace, and sent to the atmospheric distillation column for fractionation. After the heavy fraction at the bottom of the atmospheric distillation column is admixed with the Fischer-Tropsch wax oil, it is pumped by the sixth feed pump, passed through the sixth heating furnace, and sent to the vacuum distillation column for fractionation. The vacuum degree of the vacuum column is -75 kPa.

[0103] The chemical light oil is fractionated at the top of the atmospheric distillation column, and 4# jet fuel hot material, 3# white oil raw material, transformer oil raw material, and 10# white oil raw material are fractionated successively from the side lines.

[0104] The 15# white oil raw material is fractionated at the top of the vacuum column, 100N and 250N base oil raw materials are fractionated successively from the side lines of the column, and the 500N base oil raw material is fractionated at the bottom of the column.

[0105] The temperature of the fixed-bed hydrogenation reaction is 400 °C; the reaction pressure is 23 MPa; the liquid hourly space velocity is 0.6 h -1 ; the sulfur content in the oil phase after hydrogenation is 0.45%.

[0106] The bottom temperature of the coking fractionating tower is controlled at 364 °C; the temperature of the steam generator is controlled at 392 °C.

[0107] The outlet temperatures of the first, second, third, fourth, fifth, and sixth heating furnaces are 500 °C.

[0108] The feed temperature of the coking tower is controlled at 365 °C; the reaction temperature of the coking tower is 420 °C; the top pressure is 0.5 MPa; the recycle ratio is 0.25; the temperature of the oil and gas at the top of the coking tower is 420 °C.

[0109] The operating conditions of the first hydrofining reactor are as follows: the hydrogen-oil volume ratio is 750; the reaction temperature is 410 °C; the reaction pressure is 23 MPa; the liquid hourly space velocity is 1.0 h -1 .

[0110] The operating conditions of the second hydrofining reactor are as follows: the hydrogen-oil volume ratio is 550; the reaction temperature is 365 °C; the reaction pressure is 23 MPa; the liquid hourly space velocity is 1.5 h -1 .

[0111] The first-stage hydrofining catalyst is a hydrotreating agent RL-2; the theoretical packed volume is 4 L / kg;

[0112] The theoretical packed volume of the second-stage hydrofining catalyst is 3 L / kg, and its preparation method is as follows:

[0113] T1: In the first stirring kettle, add 140 kg of MCM-41 molecular sieve to 1150 kg of water and 5 kg of silane coupling agent KH-560, stir at 45 °C for 70 min, discharge, filter, and dry to obtain epoxy MCM-41 molecular sieve;

[0114] T2: Add 20 kg of cobalt acetate, 50 kg of ruthenium acetate, 30 kg of dimercaptosuccinic acid, and 1150 kg of DMF to the second stirring kettle, heat up to 75 °C, stir for 160 min, and distill off water to obtain dimercaptosuccinic acid / cobalt / ruthenium complex;

[0115] T3: Add 6 kg of dimercaptosuccinic acid / cobalt / ruthenium complex, 0.15 kg of diethyl allyl phosphate, and 1150 kg of toluene to the first stirring kettle, heat up to 75 °C, stir for 70 min, then add 150 kg of epoxy MCM-41 molecular sieve, heat up to 75 °C, stir for 160 min, discharge, filter, and dry to obtain the second-stage hydrofining catalyst.

[0116] Example 4

[0117] A method for producing special oil raw materials from heavy fuel oil, the operation steps of which are as follows:

[0118] S1: Part of the raw heavy fuel oil is sent to the first heating furnace for heating through the raw material buffer tank and the first feed pump, and then sent to the coking fractionating tower; another part is mixed with hydrogen, and the volume ratio of hydrogen to heavy fuel oil is 800; after being heated by the second heating furnace, it is sent to the fixed bed reactor for reaction;

[0119] S2: The mixture after the reaction in the fixed bed reactor is subjected to gas-liquid separation in the first-stage hot high-pressure separator. The gas phase is further separated in the first-stage cold high-pressure separator, and the liquid phase is stripped in the first-stage medium-pressure stripper; after the stripped gas phase is mixed with the liquid phase in the first-stage cold high-pressure separator, it is subjected to gas-liquid separation in the first-stage cold low-pressure separator; the separated liquid phase is sent to the coking fractionating tower; the liquid phase in the first-stage medium-pressure stripper is sent to the first heating furnace;

[0120] S3: The bottom liquid of the coking fractionating tower is heated and returned to the bottom of the coking fractionating tower through the first circulation pump and the steam generator;

[0121] S4: The bottom liquid of the coking fractionating tower is sent to the coking tower through the second feed pump, the first heating furnace for delayed coking reaction, and then returned to the coking fractionating tower;

[0122] S5: The top gas phase of the coking fractionating tower passes through the reflux drum. Part of the liquid phase is returned to the coking fractionating tower through the second circulation pump; another part, together with the coking diesel oil in the coking fractionating tower, is sent to the third feed pump, mixed with hydrogen, and then sent to the third heating furnace;

[0123] S6: The coking wax oil in the coking fractionating tower is sent to the first hydrofining reactor for reaction through the fourth feed pump and the fourth heating furnace, and then mixed with the material from the third heating furnace in S5 and sent to the second hydrofining reactor for reaction together;

[0124] S7: After the reaction in the second hydrofining reactor is completed, it is sent to the second-stage hot high-pressure separator for separation. The gas phase is further separated in the second-stage cold high-pressure separator; the liquid phase in the second-stage hot high-pressure separator is separated in the second-stage hot low-pressure separator, and the gas phase and the liquid phase in the second-stage cold high-pressure separator are sent to the second-stage cold low-pressure separator together; the liquid phase in the second-stage cold low-pressure separator and the gas-liquid phase in the second-stage hot low-pressure separator are sent to the second-stage stripper together;

[0125] S8: After being stripped in the second-stage stripper, high-quality foamer raw materials are obtained at the top of the tower, and the bottom oil phase is sent to the atmospheric distillation tower for fractionation through the fifth feed pump and the fifth heating furnace; after the heavy fraction at the bottom of the atmospheric distillation tower is admixed with Fischer-Tropsch wax oil, it is sent to the vacuum distillation tower for fractionation through the sixth feed pump and the sixth heating furnace, and the vacuum degree of the vacuum tower is -80 kPa.

[0126] The chemical light oil is fractionated at the top of the atmospheric distillation tower, and 4# jet fuel, 3# white oil raw material, transformer oil raw material, and 10# white oil raw material are fractionated in sequence at the side lines.

[0127] The 15# white oil raw material is fractionated at the top of the vacuum tower, and the 100N and 250N base oil raw materials are fractionated successively from the side lines of the tower. The 500N base oil raw material is fractionated at the bottom of the tower.

[0128] The temperature of the fixed-bed hydrogenation reaction is 403 °C; the reaction pressure is 25 MPa; the liquid hourly space velocity is 0.8 h -1 ; the sulfur content in the oil phase after hydrogenation is 0.5%.

[0129] The temperature at the bottom of the coking fractionation tower is controlled at 365 °C; the temperature of the steam generator is controlled at 395 °C.

[0130] The outlet temperatures of the first, second, third, fourth, fifth, and sixth heating furnaces are 510 °C.

[0131] The feed temperature of the coking tower is controlled at 370 °C; the reaction temperature of the coking tower is 430 °C; the top pressure is 0.55 MPa; the recycle ratio is 0.3; the temperature of the oil and gas at the top of the coking tower is 430 °C.

[0132] The operating conditions of the first hydrofining reactor are as follows: the hydrogen-oil volume ratio is 800; the reaction temperature is 415 °C; the reaction pressure is 25 MPa; the liquid hourly space velocity is 1.1 h -1 .

[0133] The operating conditions of the second hydrofining reactor are as follows: the hydrogen-oil volume ratio is 600; the reaction temperature is 370 °C; the reaction pressure is 25 MPa; the liquid hourly space velocity is 1.6 h -1 .

[0134] The first-stage hydrofining catalyst is the hydrotreating agent RL-2; the theoretical packing volume is 5 L / kg;

[0135] The theoretical packing volume of the second-stage hydrofining catalyst is 4 L / kg, and its preparation method is as follows:

[0136] T1: In the first stirring kettle, 150 kg of MCM-41 molecular sieve is added to 1200 kg of water and 6 kg of silane coupling agent KH-560, stirred at 50 °C for 80 min, discharged, filtered, and dried to obtain epoxy MCM-41 molecular sieve;

[0137] T2: 23 kg of cobalt acetate, 56 kg of ruthenium acetate, 36 kg of dimercaptosuccinic acid, and 1200 kg of DMF are added to the second stirring kettle, heated to 80 °C, stirred for 180 min, and water is distilled off to obtain dimercaptosuccinic acid / cobalt / ruthenium complex;

[0138] T3: Add 7 kg of dimercaptosuccinic acid / cobalt / ruthenium complex, 0.2 kg of diethyl allyl phosphate, and 1,200 kg of toluene into the first stirring kettle. Heat up to 80 °C and stir for 80 min. Then add 160 kg of epoxy MCM-41 molecular sieve, heat up to 80 °C and stir for 180 min. Discharge the material, filter, and dry to obtain the second-stage hydrofining catalyst.

[0139] Comparative Example 1

[0140] In this example, ruthenium acetate is not added, and the others are the same as in Example 1.

[0141] Comparative Example 2

[0142] In this example, dimercaptosuccinic acid is not added, and the others are the same as in Example 1.

[0143]

[0144]

[0145] Comparative Example 3

[0146] In this example, diethyl allyl phosphate is not added, and the others are the same as in Example 1.

[0147] Through the data analysis of the above examples and comparative examples, the present invention can prepare high-quality special oil raw materials that can meet the requirements of battery-grade anode materials; the second-stage hydrofining catalyst prepared by the present invention has a high desulfurization efficiency.

[0148] The above is only a preferred embodiment of the present invention, and it does not impose any form of limitation on the present invention. Although the present invention has been disclosed as above with preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some changes or modifications to the above-disclosed technical content to form equivalent embodiments within the scope of the technical solution of the present invention. However, as long as it does not depart from the content of the technical solution of the present invention, any brief modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A method for producing special oil raw materials from heavy fuel oil, and its operation steps are as follows: S1: The raw heavy fuel oil passes through the raw material buffer tank and the first feed pump. A part of it is sent to the first heating furnace for heating and then sent to the coking fractionating tower; another part is mixed with hydrogen, where the volume ratio of hydrogen to heavy fuel oil is 500 - 800; after being heated by the second heating furnace, it is sent to the fixed-bed reactor for reaction; S2: The mixture after the reaction in the fixed-bed reactor undergoes gas-liquid separation in the first-stage hot high-pressure separator. The gas phase is further separated in the first-stage cold high-pressure separator, and the liquid phase is stripped in the first-stage medium-pressure stripping tower; after the stripped gas phase is mixed with the liquid phase in the first-stage cold high-pressure separator, it undergoes gas-liquid separation in the first-stage cold low-pressure separator; the separated liquid phase is sent to the coking fractionating tower; the liquid phase of the first-stage medium-pressure stripping tower is sent to the first heating furnace; S3: A part of the bottom liquid of the coking fractionating tower is heated by the first circulation pump and the steam generator and returned to the bottom of the coking fractionating tower; S4: Another part of the bottom liquid of the coking fractionating tower undergoes delayed coking reaction through the second feed pump, the first heating furnace, and the coking tower, and then returns to the coking fractionating tower; S5: The top gas phase of the coking fractionating tower passes through the reflux drum. A part of the liquid phase is returned to the coking fractionating tower through the second circulation pump; another part, together with the coking diesel oil in the coking fractionating tower, is sent to the third feed pump, mixed with hydrogen, and then sent to the third heating furnace; S6: The coking wax oil in the coking fractionating tower is sent to the first hydrofining reactor for reaction through the fourth feed pump and the fourth heating furnace, and then mixed with the material from the third heating furnace in S5 and sent to the second hydrofining reactor for reaction together; S7: After the reaction in the second hydrofining reactor is completed, it is sent to the second-stage hot high-pressure separator for separation. The gas phase is further separated in the second-stage cold high-pressure separator; the liquid phase in the second-stage hot high-pressure separator is separated in the second-stage hot low-pressure separator, and the gas phase and the liquid phase in the second-stage cold high-pressure separator are sent to the second-stage cold low-pressure separator together; the liquid phase in the second-stage cold low-pressure separator and the gas-liquid phase in the second-stage hot low-pressure separator are sent to the second-stage stripping tower together; S8: After being stripped in the second-stage stripping tower, high-quality foamer raw materials are obtained at the top of the tower. The bottom oil phase is sent to the atmospheric separation tower for fractionation through the fifth feed pump and the fifth heating furnace; after the heavy fraction at the bottom of the atmospheric separation tower is mixed with Fischer-Tropsch wax oil, it is sent to the vacuum separation tower for fractionation through the sixth feed pump and the sixth heating furnace. The vacuum degree of the vacuum separation tower is -70 to -80 kPa.

2. A method for producing special oil raw materials from heavy fuel oil according to claim 1, characterized in that: The chemical light oil is fractionated at the top of the atmospheric separation tower, and 4# jet fuel, 3# white oil raw material, transformer oil raw material, and 10# white oil raw material are fractionated at the side lines in sequence; 15# white oil raw material is fractionated at the top of the vacuum tower, 100N and 250N base oil raw materials are fractionated at the side lines of the tower in sequence, and 500N base oil raw material is fractionated at the bottom of the tower.

3. A method for producing special oil raw materials from heavy fuel oil according to claim 1, characterized in that: The fixed-bed hydrogenation reaction temperature is 370 - 403 °C; the reaction pressure is 15 - 25 MPa; the liquid hourly space velocity is 0.1 - 0.8 h -1 ; the sulfur content in the oil phase after hydrogenation is 0.4 - 0.5%.

4. A method for producing special oil raw materials from heavy fuel oil according to claim 1, characterized in that: The bottom temperature of the coking fractionating tower is controlled at 360 - 365 °C; the temperature of the steam generator is controlled at 385 - 395 °C.

5. A method for producing special oil raw materials from heavy fuel oil according to claim 1, characterized in that: The outlet temperatures of the first, second, third, fourth, fifth, and sixth heating furnaces are 480 - 510 °C.

6. A method for producing special oil raw materials from heavy fuel oil according to claim 1, characterized in that: The feed temperature of the coking tower is controlled at 350 - 370 °C; the reaction temperature of the coking tower is 400 - 430 °C; the top pressure is 0.35 - 0.55 MPa; the circulation ratio is 0.15 - 0.3; the temperature of the oil and gas at the top of the coking tower is 410 - 430 °C.

7. A method for producing special oil raw materials from heavy fuel oil according to claim 1, characterized in that: The operating conditions of the first hydrofining reactor are as follows: the hydrogen-oil volume ratio is 600 - 800; the reaction temperature is 390 - 415 °C; the reaction pressure is 15 - 25 MPa; the liquid hourly space velocity is 0.9 - 1.1 h -1 .

8. A method for producing special oil raw materials from heavy fuel oil according to claim 1, characterized in that: The operating conditions of the second hydrofining reactor are as follows: the hydrogen-oil volume ratio is 400 - 600; the reaction temperature is 350 - 370 °C; the reaction pressure is 15 - 25 MPa; the liquid hourly space velocity is 1.4 - 1.6 h -1 .

9. A method for producing special oil raw materials from heavy fuel oil according to claim 1, characterized in that: The first-stage hydrofining catalyst is the hydrotreating agent RL-2; the theoretical packing volume is 2-5 L / kg.

10. A method for producing special oil raw materials from heavy fuel oil according to claim 1, characterized in that: The theoretical packing volume of the second-stage hydrofining catalyst is 1-4 L / kg, and its preparation method is as follows: T1: According to the mass parts, add 100-150 parts of MCM-41 molecular sieve into 1000-1200 parts of water and 3-6 parts of silane coupling agent KH-560 in the first stirring kettle, stir at 30-50 °C for 40-80 min, discharge, filter, and dry to obtain epoxy MCM-41 molecular sieve; T2: Add 12-23 parts of cobalt acetate, 28-56 parts of ruthenium acetate, 18-36 parts of dimercaptosuccinic acid, and 1000-1200 parts of DMF into the second stirring kettle, heat up to 70-80 °C, stir for 120-180 min, distill off water to obtain dimercaptosuccinic acid / cobalt / ruthenium complex; T3: Add 2-7 parts of dimercaptosuccinic acid / cobalt / ruthenium complex, 0.02-0.2 parts of diethyl allyl phosphate, and 1000-1200 parts of toluene into the first stirring kettle, heat up to 70-80 °C, stir for 40-80 min, then add 100-160 parts of epoxy MCM-41 molecular sieve, heat up to 70-80 °C, stir for 120-180 min, discharge, filter, and dry to obtain the second-stage hydrofining catalyst.

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