A method for producing petroleum coke

Abstract

The present invention proposes a method for producing petroleum coke, which belongs to the technical field of petroleum coke. Residual oil raw material is mixed with hydrogen, and reacted under the action of a catalyst and a desulfurizing agent after heating to generate low-sulfur petroleum coke and an oil-gas mixture, and the oil-gas mixture is treated with water to remove hydrogen sulfide, and hydrogen is recovered; the catalyst is a zirconium-based metal organic framework material with amino groups modified by polydopamine loaded with rhodium, molybdenum and nickel; the desulfurizing agent is a zinc / manganese-based mesoporous molecular sieve modified by polydopamine. The method for producing petroleum coke of the present invention is simple, has mild conditions, and has low production cost. The catalyst and the desulfurizing agent can be reused, and it is easy to realize large-scale industrial production, and has broad application prospects.

Description

Technical Field

[0001] The invention relates to the technical field of petroleum coke, and in particular to a method for producing petroleum coke. Background Art

[0002] Petroleum coke is a byproduct of petroleum refining. It is generally produced from various residual oils, asphalt or heavy oils through delayed coking process. It is widely used in metallurgy and chemical industries. According to different processing methods, petroleum coke can be divided into green coke and cooked coke. Cooked coke, also known as calcined coke, is a product obtained by calcining green coke at 1300℃.

[0003] The sulfur content of petroleum coke mainly depends on the raw materials, and the coking process has little effect on the sulfur content of petroleum coke. With the global crude oil quality becoming heavier and inferior, the output of petroleum coke continues to increase, but it is mainly high-sulfur coke. In the future, the demand for low-sulfur coke will grow rapidly, and the gap may gradually expand. It is mainly reflected in the following aspects: ① Affected by the continuous introduction of environmental protection regulations, the use of high-sulfur coke products is obviously limited, and the rigid demand of the fuel industry will shift to low-sulfur coke and or alternative fuels. ② The demand for low-sulfur coke in traditional fields such as high-end prebaked anodes and graphite electrodes downstream of petroleum coke continues to rise. The trend of short-process replacement of long-process in steel is established, the proportion of electric furnaces will continue to increase, the demand for ultra-high power graphite electrodes will increase, and the proportion of ordinary power graphite electrodes will decrease. However, due to the continuous growth in the absolute amount of electric furnaces, the demand for low-sulfur coke for graphite electrodes will continue to grow. ③ The demand for lithium battery negative electrodes has great potential, and the gap in low-sulfur coke will continue to expand. New energy vehicles continue to develop rapidly, with both high-end and low-end routes given equal importance in the future; under the demand for electricity peak regulation, the development of power storage has entered the fast lane, and the demand for lithium battery negative electrode materials is strong, which will further open up growth space for low-sulfur coke.

[0004] CN1676573A discloses a hydrogenation delayed coking method, wherein the coking raw material and the optional coking circulating oil are contacted with hydrogen and a catalyst before entering the coke tower, the hydrogenation generated oil is depressurized and then enters the coking heating furnace to be heated to the coking temperature and then enters the coke tower, the generated coke is retained in the coke tower, and the coking oil gas is separated to obtain coking gas, coking gasoline, coking diesel oil, and coking wax oil. The method improves the yield of liquid products, reduces the sulfur content of coke, reduces the coking tendency of furnace tubes, and prolongs the operation cycle of the heating furnace.

[0005] US4919793A discloses an improved coking method, which includes adding a soaking pipe in front of a heating furnace, injecting hydrogen-rich gas or hydrogen into the soaking pipe, and subjecting the residual oil raw material in front of the coking heating furnace to hydrogenation and modification in the soaking pipe, thereby improving the liquid yield and properties of the coking product and reducing the coke and gas yields by improving the coking raw materials.

[0006] US4394250A discloses a catalytic coking method, in which hydrogen and a catalyst are injected at the inlet of a heating furnace to increase the yield of coking distillate oil and reduce the yield of coke.

[0007] CN101600781A discloses the selective cracking and coking of unwanted components in coking circulating materials and diesel. The invention injects an additive into the steam produced by the traditional coking process in the coking container before fractionation to selectively crack or coke the unwanted diesel components.

[0008] At present, the production method of low-sulfur petroleum coke is complicated and costly. Therefore, there is an urgent need to develop an efficient, simple and low-cost production method for petroleum coke. Summary of the invention

[0009] The purpose of the present invention is to provide a method for producing petroleum coke, which is simple, has mild conditions, low production cost, and the catalyst and desulfurizer can be reused, is easy to realize industrial large-scale production, and has broad application prospects.

[0010] The technical solution of the present invention is achieved in this way:

[0011] The present invention provides a method for producing petroleum coke, wherein residual oil raw material is mixed with hydrogen, and the mixture is heated to react under the action of a catalyst and a desulfurizer to generate low-sulfur petroleum coke and an oil-gas mixture, and hydrogen sulfide is removed from the oil-gas mixture by water, and hydrogen is recovered;

[0012] The catalyst is a zirconium-based metal organic framework material with amino groups modified by polydopamine loaded with rhodium, molybdenum and nickel;

[0013] The desulfurizing agent is a polydopamine-modified zinc / manganese-based mesoporous molecular sieve.

[0014] As a further improvement of the present invention, the preparation method of the catalyst is as follows:

[0015] S1. Dissolve zirconium chloride and 2-aminoterephthalic acid in N,N-dimethylformamide, add acetic acid with stirring, heat the reaction, cool to room temperature, filter, wash the solid, and dry to obtain a carrier;

[0016] S2. The carrier is added to water, dopamine hydrochloride and a catalyst are added, the reaction is heated and stirred, filtered, washed, and dried to obtain a modified carrier;

[0017] S3. Add the modified carrier into water, add rhodium salt, molybdenum salt and nickel salt, irradiate with ultraviolet light, stir and react, filter, wash and dry to obtain a catalyst.

[0018] As a further improvement of the present invention, the molar ratio of zirconium chloride to 2-aminoterephthalic acid in step S1 is 1:1, the temperature of the heating reaction is 120-130° C., and the time is 20-24 hours.

[0019] As a further improvement of the present invention, the mass ratio of the carrier, dopamine hydrochloride and catalyst in step S2 is 10:2-3:0.1-0.2, the catalyst is a Tris-HCl solution with a pH of 8.5-9.5, the temperature of the heating and stirring reaction is 40-50°C, and the time is 2-4h.

[0020] As a further improvement of the present invention, the mass ratio of the modified carrier, rhodium salt, molybdenum salt and nickel salt in step S3 is 200:6-8:15-20:17-22, the rhodium salt is rhodium nitrate, the molybdenum salt is molybdenum chloride or molybdenum nitrate, the nickel salt is nickel chloride or nickel nitrate, and the ultraviolet light irradiation stirring reaction time is 1-2h.

[0021] As a further improvement of the present invention, the preparation method of the desulfurizing agent is as follows:

[0022] T1. Prepare mesoporous nano-silica into a suspension, dissolve potassium permanganate in water, add dropwise to the mesoporous nano-silica suspension, stir at room temperature for reaction, centrifuge, wash, resuspend, adjust the pH value of the solution, heat and stir for reaction, centrifuge, wash, and dry to obtain hollow mesoporous nano-MnO2 spheres;

[0023] T2. Dissolve the porogen, sodium silicate and sodium aluminate in water, add zinc acetate and thioacetamide, stir and mix evenly, add hollow mesoporous nano MnO2 balls, adjust the pH value of the solution, stir the reaction, heat the hydrothermal reaction, centrifuge, wash, dry and calcine to obtain a zinc / manganese-based mesoporous molecular sieve;

[0024] T3. Add zinc / manganese-based mesoporous molecular sieve into water, add dopamine hydrochloride and a catalyst, heat and stir to react, centrifuge, wash, and dry to obtain a desulfurizer; the catalyst is a Tris-HCl solution with a pH of 8.5-9.5.

[0025] As a further improvement of the present invention, the average particle size of the mesoporous nano-silica in step T1 is 100-200 nm, the mass ratio of the mesoporous nano-silica to potassium permanganate is 10-12:4-6, the time of the room temperature stirring reaction is 10-12 hours, the pH value of the adjusted solution is 9-10, the temperature of the heated stirring reaction is 40-50°C, and the time is 8-10 hours.

[0026] As a further improvement of the present invention, the molar ratio of the porogen, sodium silicate, sodium aluminate, zinc acetate and thioacetamide in step T2 is 0.1-0.3:1:0.02-0.04:0.3-0.4:0.9-1.2, and the molar mass ratio of the sodium silicate and the hollow mesoporous nano MnO2 spheres is 1 mol:10 g; the pH value of the adjusted solution is 9.5-10.5, the stirring reaction time is 3-5h, the heating hydrothermal reaction temperature is 75-85°C, the time is 1-3h, the calcination temperature is 600-700°C, the time is 1-3h, and the porogen is hexadecyltrimethylammonium chloride.

[0027] As a further improvement of the present invention, the mass ratio of the zinc / manganese-based mesoporous molecular sieve, dopamine hydrochloride and catalyst in step T3 is 10:2-3:0.5-1, and the temperature of the heating and stirring reaction is 40-50°C and the time is 2-4h.

[0028] As a further improvement of the present invention, the residual oil raw material is at least one of atmospheric residual oil, vacuum residual oil, catalytic cracking slurry, and visbreaking oil. Based on the residual oil raw material, the added amount of the catalyst is 0.1-1wt%, the added amount of the desulfurizer is 1-2wt%, the heating temperature is 400-500°C, and the reaction hydrogen pressure is 0.5-2Mpa.

[0029] The present invention has the following beneficial effects:

[0030] The invention prepares a catalyst, which is a zirconium-based metal organic framework material with amino groups modified by polydopamine loaded with rhodium, molybdenum and nickel. The zirconium-based metal organic framework material with amino groups is prepared by a hydrothermal method, and 2-aminoterephthalic acid is used as a reactant. The prepared carrier is a novel organic-inorganic hybrid porous material, whose crystal structure consists of metal clusters and organic connectors, has a large specific surface area, high porosity, and adjustable pore size and functional groups. The surface of the carrier carries organic molecular groups amino groups, which is easy to further load polydopamine on the surface for modification, thereby greatly improving the specific surface area of ​​the material. At the same time, its rich multi-active group structure is conducive to the enrichment and reaction of metal ions, and the light-induced reaction is used to prepare the zirconium-based metal organic framework material with amino groups modified by polydopamine loaded with rhodium, molybdenum and nickel. In this catalyst, by doping a small amount of rhodium metal, the catalytic activity of the catalyst is greatly improved. The molybdenum / nickel bimetallic catalytic hydrogenation improves the hydrogenation activity under the synergistic effect, reduces the reaction activation energy, reduces the use of precious metals, and is not prone to catalyst poisoning due to repeated use, so it has good application prospects.

[0031] The desulfurizer prepared by the present invention is a zinc / manganese-based mesoporous molecular sieve modified by polydopamine, which takes metal zinc and manganese as main materials. The two materials have good affinity for sulfur and have high sulfur adsorption capacity. At the same time, the mesoporous structure provides a large specific surface area and a multi-pore structure, which is convenient for fully absorbing sulfur impurities. The surface is further coated with polydopamine, which further greatly improves the specific surface area of ​​the material. The rich amino structure is easy to fix sulfur elements, thereby greatly improving the desulfurization efficiency, and low-sulfur petroleum coke can be quickly and effectively prepared.

[0032] The petroleum coke production method of the present invention is simple, has mild conditions, has low production cost, and the catalyst and desulfurizer can be reused, is easy to realize industrialized large-scale production, and has broad application prospects. DETAILED DESCRIPTION

[0033] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0034] The average particle size of mesoporous nano-silica was 150 nm and was purchased from Jiangsu Xianfeng Nanomaterial Technology Co., Ltd.

[0035] Preparation Example 1 Preparation of Catalyst

[0036] Here’s how:

[0037] S1. Dissolve 0.2 mmol zirconium chloride and 0.2 mmol 2-aminoterephthalic acid in 50 mL N,N-dimethylformamide, add 5 mL acetic acid with stirring, heat to 120°C, stir and react for 20 hours, cool to room temperature, filter, wash the solid, and dry to obtain a carrier;

[0038] S2. Add 1 g of the carrier to 200 mL of water, add 0.2 g of dopamine hydrochloride and 0.01 g of the catalyst, heat to 40°C, stir and react for 2 h, filter, wash, and dry to obtain a modified carrier;

[0039] The catalyst is a Tris-HCl solution with a pH of 8.5;

[0040] S3. Add 200 mg of the modified carrier into 100 mL of water, add 6 mg of rhodium nitrate, 15 mg of molybdenum nitrate and 17 mg of nickel nitrate, stir for 1 hour, irradiate with ultraviolet light and stir to react for 1 hour, filter, wash and dry to obtain a catalyst.

[0041] Preparation Example 2 Preparation of Catalyst

[0042] Here’s how:

[0043] S1. Dissolve 0.2 mmol zirconium chloride and 0.2 mmol 2-aminoterephthalic acid in 50 mL N,N-dimethylformamide, add 5 mL acetic acid with stirring, heat to 130°C, stir and react for 24 hours, cool to room temperature, filter, wash the solid, and dry to obtain a carrier;

[0044] S2. Add 1 g of the carrier to 200 mL of water, add 0.3 g of dopamine hydrochloride and 0.02 g of the catalyst, heat to 50°C, stir and react for 4 hours, filter, wash, and dry to obtain a modified carrier;

[0045] The catalyst is a Tris-HCl solution with a pH of 9.5;

[0046] S3. Add 200 mg of the modified carrier into 100 mL of water, add 8 mg of rhodium nitrate, 20 mg of molybdenum nitrate and 22 mg of nickel nitrate, stir for 1 hour, irradiate with ultraviolet light and stir to react for 2 hours, filter, wash and dry to obtain a catalyst.

[0047] Preparation Example 3 Preparation of Catalyst

[0048] Here’s how:

[0049] S1. Dissolve 0.2 mmol zirconium chloride and 0.2 mmol 2-aminoterephthalic acid in 50 mL N,N-dimethylformamide, add 5 mL acetic acid with stirring, heat to 125°C, stir and react for 22 hours, cool to room temperature, filter, wash the solid, and dry to obtain a carrier;

[0050] S2. Add 1 g of the carrier to 200 mL of water, add 0.25 g of dopamine hydrochloride and 0.015 g of the catalyst, heat to 45°C, stir and react for 3 h, filter, wash, and dry to obtain a modified carrier;

[0051] The catalyst is a Tris-HCl solution with a pH of 9;

[0052] S3. Add 200 mg of the modified carrier into 100 mL of water, add 7 mg of rhodium nitrate, 17 mg of molybdenum nitrate and 20 mg of nickel nitrate, stir for 1 hour, irradiate with ultraviolet light and stir to react for 1.5 hours, filter, wash and dry to obtain a catalyst.

[0053] Comparative Preparation Example 1:

[0054] Compared with Preparation Example 3, the difference is that terephthalic acid is used instead of 2-aminoterephthalic acid in step S1.

[0055] The details are as follows:

[0056] S1. Dissolve 0.2 mmol zirconium chloride and 0.2 mmol terephthalic acid in 50 mL N,N-dimethylformamide, add 5 mL acetic acid with stirring, heat to 125°C, stir and react for 22 hours, cool to room temperature, filter, wash the solid, and dry to obtain a carrier.

[0057] Comparative Preparation Example 2:

[0058] Compared with Preparation Example 3, the difference is that step S2 is not performed.

[0059] The details are as follows:

[0060] S1. Dissolve 0.2 mmol zirconium chloride and 0.2 mmol 2-aminoterephthalic acid in 50 mL N,N-dimethylformamide, add 5 mL acetic acid with stirring, heat to 125°C, stir and react for 22 hours, cool to room temperature, filter, wash the solid, and dry to obtain a carrier;

[0061] S2. Add 200 mg of the carrier into 100 mL of water, add 7 mg of rhodium nitrate, 17 mg of molybdenum nitrate and 20 mg of nickel nitrate, stir for 1 hour, irradiate with ultraviolet light and stir to react for 1.5 hours, filter, wash and dry to obtain a catalyst.

[0062] Comparative Preparation Example 3:

[0063] Compared with Preparation Example 3, the difference is that rhodium nitrate is not added in step S3.

[0064] The details are as follows:

[0065] S3. Add 200 mg of the modified carrier into 100 mL of water, add 17 mg of molybdenum nitrate and 20 mg of nickel nitrate, stir for 1 hour, irradiate with ultraviolet light and stir to react for 1.5 hours, filter, wash, and dry to obtain a catalyst.

[0066] Comparative Preparation Example 4:

[0067] Compared with Preparation Example 3, the difference is that platinum nitrate is not added in step S3.

[0068] The details are as follows:

[0069] S3. Add 200 mg of the modified carrier into 100 mL of water, add 7 mg of rhodium nitrate and 37 mg of nickel nitrate, stir for 1 hour, irradiate with ultraviolet light and stir to react for 1.5 hours, filter, wash and dry to obtain a catalyst.

[0070] Comparative Preparation Example 5:

[0071] Compared with Preparation Example 3, the difference is that nickel nitrate is not added in step S3.

[0072] The details are as follows:

[0073] S3. Add 200 mg of the modified carrier into 100 mL of water, add 7 mg of rhodium nitrate and 37 mg of molybdenum nitrate, stir for 1 hour, irradiate with ultraviolet light and stir to react for 1.5 hours, filter, wash and dry to obtain a catalyst.

[0074] Test Example 1:

[0075] The specific surface area and pore volume parameters of the catalysts prepared in Preparation Examples 1-3 and Comparative Preparation Examples 1-5 were measured using an ASAP2460 fully automatic specific surface and porosity analyzer produced by Micromeritics Instruments, Inc., USA. The results are shown in Table 1.

[0076] Table 1:

[0077] .

[0078] It can be seen from the above table that the catalysts prepared in Preparation Examples 1-3 of the present invention have larger specific surface areas and total pore volumes.

[0079] Preparation Example 4 Preparation of desulfurizing agent

[0080] Here’s how:

[0081] T1. Prepare 10g of mesoporous nano-silica into 100mL suspension, dissolve 4g of potassium permanganate in 100mL of water, add dropwise to the mesoporous nano-silica suspension, stir and react at room temperature for 10h, centrifuge, wash, resuspend, adjust the solution pH to 9, heat to 40°C, stir and react for 8h, centrifuge, wash, and dry to obtain hollow mesoporous nano-MnO2 spheres;

[0082] T2. Dissolve 10mmol of porogen, 100mmol of sodium silicate and 2mmol of sodium aluminate in 100mL of water, add 30mmol of zinc acetate and 90mmol of thioacetamide, stir and mix evenly, add 1g of hollow mesoporous nano-MnO2 balls, adjust the pH value of the solution to 9.5, stir and react for 3h, heat to 75℃, hydrothermally react for 1h, centrifuge, wash, dry, and calcine at 600℃ for 1h to obtain zinc / manganese-based mesoporous molecular sieve;

[0083] T3. Add 1g of zinc / manganese-based mesoporous molecular sieve to 200mL of water, add 0.2g of dopamine hydrochloride and 0.05g of catalyst, heat to 40°C, stir and react for 2h, centrifuge, wash, and dry to obtain a desulfurizer;

[0084] The catalyst is a Tris-HCl solution with a pH of 8.5.

[0085] Preparation Example 5 Preparation of desulfurizing agent

[0086] Here’s how:

[0087] T1. Prepare 12g of mesoporous nano-silica into 100mL suspension, dissolve 6g of potassium permanganate in 100mL of water, add dropwise to the mesoporous nano-silica suspension, stir and react at room temperature for 12h, centrifuge, wash, resuspend, adjust the solution pH to 10, heat to 50°C, stir and react for 10h, centrifuge, wash, and dry to obtain hollow mesoporous nano-MnO2 spheres;

[0088] T2. Dissolve 30mmol hexadecyltrimethylammonium chloride, 100mmol sodium silicate, and 4mmol sodium aluminate in 100mL water, add 40mmol zinc acetate and 120mmol thioacetamide, stir and mix evenly, add 1g hollow mesoporous nano MnO2 balls, adjust the solution pH to 10.5, stir and react for 5h, heat to 85℃, hydrothermally react for 3h, centrifuge, wash, dry, and calcine at 700℃ for 3h to obtain zinc / manganese-based mesoporous molecular sieve;

[0089] T3. Add 1g of zinc / manganese-based mesoporous molecular sieve to 200mL of water, add 0.3g of dopamine hydrochloride and 0.1g of catalyst, heat to 50°C, stir and react for 4h, centrifuge, wash, and dry to obtain a desulfurizer;

[0090] The catalyst is a Tris-HCl solution with a pH of 9.5.

[0091] Preparation Example 6 Preparation of desulfurizing agent

[0092] Here’s how:

[0093] T1. Prepare 11g of mesoporous nano-silica into 100mL suspension, dissolve 5g of potassium permanganate in 100mL of water, add dropwise to the mesoporous nano-silica suspension, stir and react at room temperature for 11h, centrifuge, wash, resuspend, adjust the solution pH to 9.5, heat to 45°C, stir and react for 9h, centrifuge, wash, and dry to obtain hollow mesoporous nano-MnO2 spheres;

[0094] T2. Dissolve 20mmol hexadecyltrimethylammonium chloride, 100mmol sodium silicate, and 3mmol sodium aluminate in 100mL water, add 35mmol zinc acetate and 110mmol thioacetamide, stir and mix evenly, add 1g hollow mesoporous nano MnO2 balls, adjust the solution pH to 10, stir and react for 4h, heat to 80℃, hydrothermally react for 2h, centrifuge, wash, dry, and calcine at 650℃ for 2h to obtain zinc / manganese-based mesoporous molecular sieve;

[0095] T3. Add 1g of zinc / manganese-based mesoporous molecular sieve to 200mL of water, add 0.25g of dopamine hydrochloride and 0.07g of catalyst, heat to 45°C, stir and react for 3h, centrifuge, wash, and dry to obtain a desulfurizer;

[0096] The catalyst is a Tris-HCl solution with a pH of 9.

[0097] Comparative Preparation Example 6:

[0098] Compared with Preparation Example 6, the difference is that hollow mesoporous nano-MnO2 spheres are not added in step T2.

[0099] The details are as follows:

[0100] T1. Dissolve 20mmol hexadecyltrimethylammonium chloride, 100mmol sodium silicate, and 3mmol sodium aluminate in 100mL water, add 35mmol zinc acetate and 110mmol thioacetamide, stir and mix evenly, adjust the solution pH to 10, stir and react for 4h, heat to 80℃, hydrothermally react for 2h, centrifuge, wash, dry, and calcine at 650℃ for 2h to obtain a zinc-based mesoporous molecular sieve;

[0101] T2. Add 1g of zinc-based mesoporous molecular sieve to 200mL of water, add 0.25g of dopamine hydrochloride and 0.07g of catalyst, heat to 45°C, stir and react for 3h, centrifuge, wash and dry to obtain a desulfurizer;

[0102] The catalyst is a Tris-HCl solution with a pH of 9.

[0103] Comparative Preparation Example 7:

[0104] Compared with Preparation Example 6, the difference is that step T2 is not performed.

[0105] The details are as follows:

[0106] T1. Prepare 11g of mesoporous nano-silica into 100mL suspension, dissolve 5g of potassium permanganate in 100mL of water, add dropwise to the mesoporous nano-silica suspension, stir and react at room temperature for 11h, centrifuge, wash, resuspend, adjust the solution pH to 9.5, heat to 45°C, stir and react for 9h, centrifuge, wash, and dry to obtain hollow mesoporous nano-MnO2 spheres;

[0107] T2. Add 1g of hollow mesoporous nano-MnO2 balls to 200mL of water, add 0.25g of dopamine hydrochloride and 0.07g of catalyst, heat to 45°C, stir and react for 3h, centrifuge, wash and dry to obtain a desulfurizer;

[0108] The catalyst is a Tris-HCl solution with a pH of 9.

[0109] Comparative Preparation Example 8:

[0110] Compared with Preparation Example 6, the difference is that step T3 is not performed.

[0111] The details are as follows:

[0112] T1. Prepare 11g of mesoporous nano-silica into 100mL suspension, dissolve 5g of potassium permanganate in 100mL of water, add dropwise to the mesoporous nano-silica suspension, stir and react at room temperature for 11h, centrifuge, wash, resuspend, adjust the solution pH to 9.5, heat to 45°C, stir and react for 9h, centrifuge, wash, and dry to obtain hollow mesoporous nano-MnO2 spheres;

[0113] T2. Dissolve 20mmol hexadecyltrimethylammonium chloride, 100mmol sodium silicate and 3mmol sodium aluminate in 100mL water, add 35mmol zinc acetate and 110mmol thioacetamide, stir and mix evenly, add 1g hollow mesoporous nano MnO2 balls, adjust the pH value of the solution to 10, stir and react for 4h, heat to 80℃, hydrothermally react for 2h, centrifuge, wash, dry, and calcine at 650℃ for 2h to obtain zinc / manganese-based mesoporous molecular sieve, which is the desulfurizer.

[0114] Test Example 2:

[0115] The specific surface area and pore volume parameters of the desulfurizers prepared in Preparation Examples 4-6 and Comparative Preparation Examples 6-8 were measured using an ASAP2460 fully automatic specific surface and porosity analyzer produced by Micromeritics Instruments, Inc., USA. The results are shown in Table 2.

[0116] Table 2

[0117] .

[0118] It can be seen from the above table that the desulfurizers prepared in Preparation Examples 1-3 of the present invention have larger specific surface areas and total pore volumes.

[0119] Embodiment 1:

[0120] This embodiment provides a method for producing petroleum coke, wherein vacuum residue oil is mixed with hydrogen, the reaction hydrogen pressure is 1 MPa, and the mixture is heated to 400° C., and reacted under the action of the catalyst prepared in Preparation Example 1 and the desulfurizer prepared in Preparation Example 4 to generate low-sulfur petroleum coke and an oil-gas mixture, and the oil-gas mixture is used to remove hydrogen sulfide with water, and hydrogen is recovered, and coking gas, coking gasoline, coking diesel and coking wax oil are obtained through separation;

[0121] Based on the vacuum residue, the added amount of the catalyst is 0.5wt%, and the added amount of the desulfurizer is 1wt%.

[0122] The basic properties of vacuum residue are shown in Table 3.

[0123] Table 3:

[0124] .

[0125] Embodiment 2:

[0126] This embodiment provides a method for producing petroleum coke, wherein vacuum residue oil is mixed with hydrogen, the reaction hydrogen pressure is 2 MPa, and the mixture is heated to 500° C., and reacted under the action of the catalyst prepared in Preparation Example 2 and the desulfurizer prepared in Preparation Example 5 to generate low-sulfur petroleum coke and an oil-gas mixture, and the oil-gas mixture is used to remove hydrogen sulfide with water, and hydrogen is recovered, and coking gas, coking gasoline, coking diesel and coking wax oil are obtained through separation;

[0127] Based on the vacuum residue oil, the added amount of the catalyst is 1wt%, and the added amount of the desulfurizer is 2wt%.

[0128] Embodiment 3:

[0129] This embodiment provides a method for producing petroleum coke, wherein vacuum residue oil is mixed with hydrogen, the reaction hydrogen pressure is 1.5 MPa, and the mixture is heated to 450° C., and reacted under the action of the catalyst prepared in Preparation Example 3 and the desulfurizer prepared in Preparation Example 6 to generate low-sulfur petroleum coke and an oil-gas mixture, and the oil-gas mixture is treated with water to remove hydrogen sulfide, and hydrogen is recovered, and coking gas, coking gasoline, coking diesel and coking wax oil are obtained through separation;

[0130] Based on the vacuum residue, the added amount of the catalyst is 0.7wt%, and the added amount of the desulfurizer is 1.5wt%.

[0131] Comparative Example 1:

[0132] Compared with Example 3, the difference is that the catalyst is prepared by Comparative Preparation Example 1.

[0133] Comparative Example 2:

[0134] Compared with Example 3, the difference is that the catalyst is prepared by Comparative Preparation Example 2.

[0135] Comparative Example 3:

[0136] Compared with Example 3, the difference is that the catalyst is prepared by Comparative Preparation Example 3.

[0137] Comparative Example 4:

[0138] Compared with Example 3, the difference is that the catalyst is prepared by Comparative Preparation Example 4.

[0139] Comparative Example 5:

[0140] Compared with Example 3, the difference is that the catalyst is prepared by Comparative Preparation Example 5.

[0141] Comparative Example 6:

[0142] Compared with Example 3, the difference is that the desulfurizing agent is prepared by Comparative Preparation Example 6.

[0143] Comparative Example 7:

[0144] Compared with Example 3, the difference is that the desulfurizing agent is prepared by Comparative Preparation Example 7.

[0145] Comparative Example 8:

[0146] Compared with Example 3, the difference is that the desulfurizing agent is prepared by Comparative Preparation Example 8.

[0147] Test Example 3:

[0148] The sulfur content and the yield of the petroleum cokes obtained in Examples 1-3 and Comparative Examples 1-8 were tested. The results are shown in Table 4.

[0149] Table 4:

[0150] .

[0151] It can be seen from the above table that the petroleum coke obtained by the methods in Examples 1-3 of the present invention has a high yield and a low sulfur content.

[0152] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for producing petroleum coke, characterized in that: The residual oil raw material is mixed with hydrogen, and reacted under the action of a catalyst and a desulfurizer after heating to generate low-sulfur petroleum coke and an oil-gas mixture. The oil-gas mixture is then used to remove hydrogen sulfide with water, and hydrogen is recovered; The catalyst is a zirconium-based metal organic framework material with amino groups modified by polydopamine loaded with rhodium, molybdenum and nickel; The desulfurizing agent is a polydopamine-modified zinc / manganese-based mesoporous molecular sieve; The preparation method of the catalyst is as follows: S1. Dissolve zirconium chloride and 2-aminoterephthalic acid in N,N-dimethylformamide, add acetic acid with stirring, heat the reaction, cool to room temperature, filter, wash the solid, and dry to obtain a carrier; S2. The carrier is added to water, dopamine hydrochloride and a catalyst Tris-HCl solution are added, the reaction is heated and stirred, filtered, washed, and dried to obtain a modified carrier; S3. Add the modified carrier into water, add rhodium salt, molybdenum salt and nickel salt, irradiate with ultraviolet light to stir and react, filter, wash and dry to obtain a catalyst, wherein the mass ratio of the modified carrier, rhodium salt, molybdenum salt and nickel salt is 200:6-8:15-20:17-22, the rhodium salt is rhodium nitrate, the molybdenum salt is molybdenum chloride or molybdenum nitrate, the nickel salt is nickel chloride or nickel nitrate, and the ultraviolet light irradiation stirring reaction time is 1-2h.

2. The production method according to claim 1, characterized in that In step S1, the molar ratio of zirconium chloride to 2-aminoterephthalic acid is 1:1, the temperature of the heating reaction is 120-130° C., and the time is 20-24 hours.

3. The production method according to claim 1, characterized in that In step S2, the mass ratio of the carrier, dopamine hydrochloride and catalyst Tris-HCl solution is 10:2-3:0.1-0.2, the pH of the catalyst Tris-HCl solution is 8.5-9.5, the temperature of the heating and stirring reaction is 40-50° C., and the time is 2-4 hours.

4. The production method according to claim 1, characterized in that The preparation method of the desulfurizing agent is as follows: T1. Prepare mesoporous nano-silica into a suspension, dissolve potassium permanganate in water, add dropwise to the mesoporous nano-silica suspension, stir at room temperature for reaction, centrifuge, wash, resuspend, adjust the pH value of the solution, heat and stir for reaction, centrifuge, wash, and dry to obtain hollow mesoporous nano-MnO2 spheres; T2. Dissolve the porogen, sodium silicate and sodium aluminate in water, add zinc acetate and thioacetamide, stir and mix evenly, add hollow mesoporous nano MnO2 balls, adjust the pH value of the solution, stir the reaction, heat the hydrothermal reaction, centrifuge, wash, dry and calcine to obtain a zinc / manganese-based mesoporous molecular sieve; T3. Add zinc / manganese-based mesoporous molecular sieve into water, add dopamine hydrochloride and catalyst Tris-HCl solution, heat and stir to react, centrifuge, wash, and dry to obtain a desulfurizer; the pH of the catalyst Tris-HCl solution is 8.5-9.

5.

5. The production method according to claim 4, characterized in that: The average particle size of the mesoporous nano-silica in step T1 is 100-200 nm, the mass ratio of the mesoporous nano-silica to potassium permanganate is 10-12:4-6, the time of the room temperature stirring reaction is 10-12 hours, the pH value of the solution is adjusted to 9-10, the temperature of the heated stirring reaction is 40-50°C, and the time is 8-10 hours.

6. The production method according to claim 4, characterized in that: The molar ratio of the porogen, sodium silicate, sodium aluminate, zinc acetate and thioacetamide in step T2 is 0.1-0.3:1:0.02-0.04:0.3-0.4:0.9-1.2, and the molar mass ratio of the sodium silicate and the hollow mesoporous nano MnO2 spheres is 1 mol:10 g; the pH value of the adjusted solution is 9.5-10.5, the stirring reaction time is 3-5 h, the heating hydrothermal reaction temperature is 75-85 ° C, the time is 1-3 h, the calcination temperature is 600-700 ° C, the time is 1-3 h, and the porogen is hexadecyltrimethylammonium chloride.

7. The production method according to claim 4, characterized in that: In step T3, the mass ratio of the zinc / manganese-based mesoporous molecular sieve, dopamine hydrochloride and catalyst Tris-HCl solution is 10:2-3:0.5-1, and the temperature of the heating and stirring reaction is 40-50° C. and the time is 2-4 hours.

8. The production method according to claim 1, characterized in that: The residual oil raw material is at least one of atmospheric residual oil, vacuum residual oil, catalytic cracking slurry and visbreaking oil. Based on the residual oil raw material, the added amount of the catalyst is 0.1-1wt%, the added amount of the desulfurizer is 1-2wt%, the heating temperature is 400-500°C, and the reaction hydrogen pressure is 0.5-2PMa.