A method for processing high aromatics feedstock oil

Abstract

The present disclosure relates to a method for processing high-aromatic feedstock oil. The method realizes the reaction of multiple feedstock oils in one reactor at the same time, the utilization rate and conversion rate of the feedstock oils are both high, and the throw-out rate of unconverted feedstock is low; moreover, different feedstock oils are fed in layers and reacted in different zones, and the reaction degree of each feedstock oil can be accurately controlled by regulating the reaction conditions of each reaction zone, which can effectively prevent the occurrence of excessive hydrogenation, is conducive to improving the selectivity and yield of the target product and reducing hydrogen consumption.

Description

Technical Field

[0001] The present invention relates to the technical field of petrochemical industry, and in particular to a method for processing high aromatic feedstock oil. Background Art

[0002] Catalytic diesel and heavy aromatic oil have high aromatic content, and hydrocracking can produce more light aromatics. The aromatics contained in catalytic diesel are mainly dicyclic aromatics, which have high sulfur and nitrogen contents. When hydrocracking is carried out, it is necessary to first hydrodesulfurize and denitrogenate to saturate one of the benzene rings, and then dealkylate to generate light aromatics. The aromatics contained in heavy aromatic oil are mainly monocyclic aromatics with carbon content above nine, which have low sulfur and nitrogen contents. When hydrocracking is carried out, light aromatics can be directly dealkylated.

[0003] US7365252B1 discloses an LCO-X process for producing xylene and benzene using catalytic diesel. In the process, the catalytic diesel is first hydrogenated to remove impurities, followed by a hydrogenation reaction, and finally the maximum conversion of light aromatics is achieved through cycloalkane dehydrogenation and aromatic alkyl transfer. Xylene and benzene are mainly produced, with a designed maximum yield of 30w% and 11w%, and some low-sulfur diesel is produced as a byproduct. The process has harsh reaction conditions, poor aromatic selectivity, and poor diesel quality in the product.

[0004] CN103214332 discloses a method for producing light aromatics and high-quality oil products from catalytic cracking diesel. In the method, catalytic cracking diesel is firstly extracted with a solvent to obtain extracted oil rich in polycyclic aromatic hydrocarbons and raffinate oil rich in alkanes, and then the extracted oil is subjected to hydrorefining and hydrocracking under hydrogenation reaction conditions to produce light aromatics and high-octane gasoline fractions.

[0005] CN105647573A discloses a method for producing light aromatics and clean fuel oil by hydrocracking catalytically cracked diesel through a moving bed. In the method, the catalytically cracked diesel passes through a fixed bed hydrotreating reactor and a moving bed hydrocracking reactor in sequence, thereby obtaining light aromatics and high-octane clean gasoline and clean diesel components. The hydrogen partial pressure in the hydrotreating reactor is 4-8 MPa, the reaction temperature is 320-420°C, and the liquid hourly volume space velocity is 0.5-2 h -1 , the volume ratio of hydrogen to raw material is 300~1000Nm / m 3 The hydrogen partial pressure in the moving bed hydrocracking reactor is 4-8 MPa, the reaction temperature is 350-440°C, and the liquid hourly volume space velocity is 0.5-1.5 h -1 The volume ratio of hydrogen to raw material is 500~1500Nm / m 3 The method can improve the cracking performance of the reaction by regenerating the catalyst to restore its activity through the moving bed transfer.

[0006] CN105542849A discloses a method for producing clean diesel and light aromatics from low-quality diesel, in which the low-quality diesel is first subjected to medium-low pressure hydrogenation to remove sulfur, nitrogen, olefins and colloids, and the resulting refined diesel is subjected to simulated moving bed adsorption separation to remove aromatics and sulfides to obtain clean diesel and heavy aromatics, and then the heavy aromatics enter the lightening reactor and are hydrogenated at medium and low pressure to generate BTX, gasoline and a small amount of light hydrocarbons. The process is a combination of hydrofining, adsorption dearomatization and hydrocracking.

[0007] However, the feedstock oils used in the above methods are relatively simple, and there is a problem of excessive hydrogenation in the hydrogenation saturation and hydrocracking stages of the feedstock oil, resulting in a low yield of light aromatics. Summary of the invention

[0008] The purpose of the present invention is to solve the problems of single feedstock oil and low light aromatics yield caused by excessive hydrogenation in the existing hydrocracking technology for producing more light aromatics, and to provide a method for processing high aromatics feedstock oil.

[0009] In order to achieve the above object, the present disclosure provides a method for processing high aromatic feedstock oil, the method comprising the following operations:

[0010] The first mixed material is gasified and then enters the first reaction zone of the hydrocracking reactor to contact with the hydrocracking catalyst and undergo a first hydrocracking reaction to obtain a first reaction oil agent, wherein the first mixed material contains high aromatic feedstock oil and hydrogen;

[0011] The first reaction oil agent is allowed to enter the second reaction zone of the hydrocracking reactor to contact with the second mixed material and perform a second hydrocracking reaction to obtain a second reaction oil agent, wherein the second mixed material contains recycled oil and hydrogen;

[0012] The second reaction oil agent is allowed to enter the third reaction zone of the hydrocracking reactor to contact with the third mixed material and perform a third hydrocracking reaction to obtain a third reaction oil agent, wherein the third mixed material contains heavy aromatic oil and / or heavy gasoline and hydrogen;

[0013] The third reaction oil agent is subjected to gas-solid separation to obtain reaction oil gas and a catalyst to be generated.

[0014] Optionally, the method further comprises:

[0015] Separating the reaction oil and gas to obtain cracked gas, light aromatics, light gasoline, heavy gasoline and diesel;

[0016] At least part of the diesel is returned to the second reaction zone of the hydrocracking reactor for recycling as the recycled oil, and the heavy gasoline with a carbon number greater than 8 is returned to the third reaction zone of the hydrocracking reactor for recycling.

[0017] Optionally, the method further comprises:

[0018] The catalyst to be regenerated is stripped and then introduced into a regenerator for charring and regeneration to obtain a regenerated catalyst;

[0019] The regenerated catalyst is subjected to stripping and reduction treatments and then returned to the first reaction zone of the hydrocracking reactor for use as the hydrocracking catalyst.

[0020] Optionally, relative to 1 part by weight of the high aromatic feedstock oil, the amount of the recycled oil is 0.2 to 0.6 parts by weight, and the amount of the heavy aromatic oil and / or heavy gasoline is 0.1 to 0.4 parts by weight;

[0021] Relative to 1 volume part of hydrogen in the first mixed material, the amount of hydrogen in the second mixed material is 0.1 to 1.0 volume part, and the amount of hydrogen in the third mixed material is 0.05 to 0.5 volume part.

[0022] Optionally, the temperature of the first mixed material is 350-450° C.; the reaction conditions in the first reaction zone include: reaction pressure of 1.5-5.0 MPa, reaction temperature of 400-500° C., and hydrogen-to-oil volume ratio of 1000-5000;

[0023] The temperature of the second mixed material is 350-450°C; the reaction conditions in the second reaction zone include: the reaction temperature is 420-530°C, and the hydrogen-to-oil volume ratio is 1200-4500;

[0024] The temperature of the third mixed material is 300-450° C.; the reaction conditions in the third reaction zone include: the reaction temperature is 430-530° C., and the hydrogen-to-oil volume ratio is 1200-4500.

[0025] Optionally, the hydrocracking reactor is a pressurized fluidized bed reactor, and the pressurized fluidized bed reactor is a variable diameter or constant diameter reactor;

[0026] The feed inlet of the first reaction zone is located at the bottom of the hydrocracking reactor, the feed inlet of the second reaction zone is located at 20% to 50% of the height of the hydrocracking reactor, and the feed inlet of the third reaction zone is located at 30% to 70% of the height of the hydrocracking reactor.

[0027] Optionally, the pressurized fluidized bed reactor is a variable diameter reactor, and the ratio of the cross-sectional area of ​​the second reaction zone to the cross-sectional area of ​​the first reaction zone is (1.0-1.5):1.0, and the ratio of the cross-sectional area of ​​the third reaction zone to the cross-sectional area of ​​the first reaction zone is (1.0-2.0):1.0.

[0028] Optionally, the high aromatic feedstock oil includes at least one of catalytic diesel, hydrocatalytic diesel, coker diesel and heavy aromatic oil, and the total aromatic content in the high aromatic feedstock oil is greater than 50% by weight based on the total weight of the high aromatic feedstock oil.

[0029] Optionally, the hydrocracking catalyst includes a carrier and an active metal component supported on the carrier; the carrier includes a silica-alumina molecular sieve with a twelve-membered ring pore structure, a five-ring silica-alumina molecular sieve with an MFI structure, alumina and silica; the active metal component is selected from at least one of cobalt, nickel, iron, molybdenum, tungsten and manganese; based on the total weight of the hydrocracking catalyst, the content of the silica-alumina molecular sieve with a twelve-membered ring pore structure is 5 to 45 parts by weight, the content of the five-ring silica-alumina molecular sieve with an MFI structure is 3 to 35 parts by weight, the content of alumina is 3 to 45 parts by weight, the content of silica is 3 to 40 parts by weight, and the content of the active metal component is 10 to 25 parts by weight.

[0030] Optionally, the reduction treatment is performed at a pressure of 2.0 to 5.0 MPa, a temperature of 300 to 500° C., and a time of 0.2 to 2.0 h.

[0031] Through the above technical solution, the method disclosed in the present invention has the following advantages:

[0032] (1) It enables multiple raw materials to react in one reactor at the same time, with high utilization and conversion rates of the raw materials and low rejection rate of unconverted raw materials;

[0033] (2) Different feedstocks are fed in layers and reacted in different zones. By adjusting the reaction conditions in each reaction zone, the degree of reaction of each feedstock can be precisely controlled. This can effectively prevent excessive hydrogenation, improve the selectivity and yield of the target product, and reduce hydrogen consumption.

[0034] Other features and advantages of the present disclosure will be described in detail in the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] The accompanying drawings are used to provide a further understanding of the present disclosure and constitute a part of the specification. Together with the following specific embodiments, they are used to explain the present disclosure but do not constitute a limitation of the present disclosure. In the accompanying drawings:

[0036] Figure 1A flow chart of a method for processing high aromatic feedstock oil according to an embodiment of the present disclosure is schematically shown.

[0037] Description of Reference Numerals

[0038] 10 Fluidized bed reactor 11 Reactor settling section

[0039] 12 Filter 13 Product separation unit

[0040] 14 Lock hopper 15 Regenerator

[0041] 16 Lock hopper 17 Reducing device

[0042] 18 regulating valve 21 first reaction zone

[0043] 22 second reaction zone 23 third reaction zone DETAILED DESCRIPTION

[0044] The specific implementation of the present disclosure is described in detail below in conjunction with the accompanying drawings. It should be understood that the specific implementation described herein is only used to illustrate and explain the present disclosure, and is not used to limit the present disclosure.

[0045] The present disclosure provides a method for processing high aromatic feedstock oil, which comprises the following operations: gasifying a first mixed material and entering the first reaction zone of a hydrocracking reactor to contact with a hydrocracking catalyst and perform a first hydrocracking reaction to obtain a first reaction oil agent, wherein the first mixed material contains high aromatic feedstock oil and hydrogen; allowing the first reaction oil agent to enter the second reaction zone of the hydrocracking reactor to contact with a second mixed material and perform a second hydrocracking reaction to obtain a second reaction oil agent, wherein the second mixed material contains recycled oil and hydrogen; allowing the second reaction oil agent to enter the third reaction zone of the hydrocracking reactor to contact with a third mixed material and perform a third hydrocracking reaction to obtain a third reaction oil agent, wherein the third mixed material contains heavy aromatic oil and / or heavy gasoline and hydrogen; performing gas-solid separation on the third reaction oil agent to obtain reaction oil gas and a catalyst to be generated.

[0046] In the present disclosure, a variety of feedstock oils are fed into a hydrocracking reactor in layers, so that the multiple feedstock oils can react in one reactor at the same time, the utilization rate and conversion rate of the feedstock oils are high, and the throw-out rate of unconverted feedstock is low; at the same time, different feedstock oils are placed in different reaction zones for reaction, which is beneficial for setting appropriate reaction conditions for each reaction zone according to the type of feedstock oil, thereby accurately controlling the reaction degree of each feedstock oil, which can effectively prevent the occurrence of excessive hydrogenation, and is beneficial for improving the selectivity and yield of the target product and reducing hydrogen consumption.

[0047] Specifically, the hydrocracking of high aromatic feedstock oil requires first hydrogenation desulfurization and nitrogen, then hydrogenation to saturate a benzene ring, and then hydrodealkylation to generate light aromatics, so its reaction process is long and the hydrogenation depth is the highest; the sulfur and nitrogen content of recycled oil is low, and the content of monocyclic aromatics is high, so it needs shallow hydrogenation before hydrodealkylation, so its hydrogenation depth is lower than that of high aromatic feedstock oil; heavy aromatic oil and / or heavy gasoline have low sulfur and nitrogen content and can be directly subjected to hydrodealkylation, so its hydrogenation depth is the lowest. Therefore, in the present disclosure, high aromatic feedstock oil, recycled oil, heavy aromatic oil and / or heavy gasoline are added to different reaction zones of the reactor in sequence along the flow direction of the reactant stream, which can effectively avoid the situation where each feedstock oil is over-hydrogenated due to the influence of conditions such as hydrogen concentration and hydrogenation time.

[0048] In addition, as the reaction proceeds, a certain amount of carbon will gradually cover the fresh hydrocracking catalyst, causing some of the cracking active centers of the catalyst to be covered, the cracking activity of the catalyst to gradually decrease, and the cracking selectivity of the catalyst to gradually improve, which can effectively improve the selectivity and yield of the target product.

[0049] According to the present disclosure, the method may also include: separating the reaction oil and gas to obtain cracked gas, light aromatics, light gasoline, heavy gasoline and diesel; returning at least part of the diesel to the second reaction zone of the hydrocracking reactor for recycling as the recycled oil, and returning the heavy gasoline with a carbon atom number greater than 8 to the third reaction zone of the hydrocracking reactor for recycling.

[0050] According to the present disclosure, the method may further include: stripping the spent catalyst and introducing it into a regenerator for char regeneration to obtain a regenerated catalyst; stripping and reducing the regenerated catalyst and returning it to the first reaction zone of the hydrocracking reactor for use as the hydrocracking catalyst.

[0051] According to the present disclosure, the relative amount of hydrogen in each feedstock and each reaction zone can vary within a certain range. For example, relative to 1 part by weight of the high aromatic feedstock, the amount of the recycled oil can be 0.2 to 0.6 parts by weight, and the amount of the heavy aromatic oil and / or heavy gasoline can be 0.1 to 0.4 parts by weight; relative to 1 part by volume of hydrogen in the first mixed material, the amount of hydrogen in the second mixed material can be 0.1 to 1.0 part by volume, and the amount of hydrogen in the third mixed material can be 0.05 to 0.5 part by volume.

[0052] According to the present disclosure, in order to better control the hydrogenation depth of the feed oil in each reaction zone, preferably, the feed temperature and reaction conditions in each reaction zone can be accurately controlled. Specifically, the temperature of the first mixed material can be 350-450°C; the reaction conditions in the first reaction zone can include: reaction pressure of 1.5-5.0MPa, reaction temperature of 400-500°C, and hydrogen-to-oil volume ratio of 1000-5000; the temperature of the second mixed material can be 350-450°C; the reaction conditions in the second reaction zone can include: reaction temperature of 420-530°C, and hydrogen-to-oil volume ratio of 1200-4500; the temperature of the third mixed material can be 300-450°C; the reaction conditions in the third reaction zone can include: reaction temperature of 430-530°C, and hydrogen-to-oil volume ratio of 1200-4500.

[0053] In the present disclosure, specifically, as the reaction in each reaction zone in the reactor proceeds, the hydrogen-to-oil ratio and the reaction temperature in each reaction zone are dynamically adjusted, and the reaction conditions and reaction time in each reaction zone are accurately set according to the difficulty of converting the feedstock oil, thereby achieving moderate hydrogenation and rapid cracking of each feedstock oil while reducing the occurrence of secondary cracking, which can further improve the selectivity and yield of the target product and reduce hydrogen consumption.

[0054] According to the present disclosure, the hydrocracking reactor can be a pressurized fluidized bed reactor, and the pressurized fluidized bed reactor can be a variable diameter or equal diameter reactor; the feed inlet of the first reaction zone can be located at the bottom of the hydrocracking reactor, the feed inlet of the second reaction zone can be located at 20% to 50% of the height of the hydrocracking reactor, and the feed inlet of the third reaction zone can be located at 30% to 70% of the height of the hydrocracking reactor.

[0055] Preferably, the pressurized fluidized bed reactor is a variable diameter reactor, and the ratio of the cross-sectional area of ​​the second reaction zone to the cross-sectional area of ​​the first reaction zone can be (1.0-1.5):1.0, and the ratio of the cross-sectional area of ​​the third reaction zone to the cross-sectional area of ​​the first reaction zone can be (1.0-2.0):1.0.

[0056] According to the present disclosure, the high aromatic feedstock oil can be selected within a certain range. For example, the high aromatic feedstock oil can include at least one of catalytic diesel, hydrocatalytic diesel, coker diesel and heavy aromatic oil. Based on the total weight of the high aromatic feedstock oil, the total aromatic content in the high aromatic feedstock oil can be greater than 50% by weight.

[0057] According to the present disclosure, the hydrocracking catalyst can be selected within a certain range, for example, the hydrocracking catalyst may include a carrier and an active metal component loaded on the carrier; the carrier may include a silica-alumina molecular sieve having a twelve-membered ring pore structure, a five-ring silica-alumina molecular sieve having an MFI structure, aluminum oxide and silicon oxide; the active metal component may be selected from at least one of cobalt, nickel, iron, molybdenum, tungsten and manganese; based on the total weight of the hydrocracking catalyst, the content of the silica-alumina molecular sieve having a twelve-membered ring pore structure may be 5 to 45 parts by weight, the content of the five-ring silica-alumina molecular sieve having an MFI structure may be 3 to 35 parts by weight, the content of aluminum oxide may be 3 to 45 parts by weight, the content of silicon oxide may be 3 to 40 parts by weight, and the content of the active metal component may be 10 to 25 parts by weight.

[0058] Furthermore, the hydrocracking catalyst may be a solid microspherical catalyst.

[0059] In the present disclosure, specifically, in the hydrocracking catalyst, the silicon-aluminum-based carrier is loaded with oxides or sulfides of metals such as tungsten, cobalt, nickel, molybdenum, manganese, and iron, and has a catalytic effect on hydrocarbon hydrogenation reforming under certain hydrogen and pressure environments. The hydrogen-carbon chain structure of gasoline and light diesel fractions is relatively simple, so the activation energy of the hydrogenation reaction of these products is relatively low, and they already have a relatively high reaction equilibrium constant when the hydrogen pressure is 1.0 MPa. However, the hydrodesulfurization and denitrification reactions of sulfur-containing compounds and nitrogen-containing compounds can proceed smoothly, and have good desulfurization and denitrification effects within the reaction temperature range of 420 to 580°C.

[0060] According to the present disclosure, the conditions of the reduction treatment may vary within a certain range. For example, the pressure of the reduction treatment may be 2.0 to 5.0 MPa, the temperature may be 300 to 500° C., and the time may be 0.2 to 2.0 h.

[0061] Figure 1 A schematic diagram of a process for processing high aromatic feedstock oil according to an embodiment of the present disclosure is shown schematically. Figure 1As shown, after the high aromatic feedstock oil (catalytic diesel) is mixed with hydrogen, it is heated through a heat exchanger and a heating furnace, and after being completely gasified, it enters the first reaction zone 21 at the bottom of the fluidized bed reactor 10, contacts with the hot solid microsphere hydrocracking catalyst and undergoes a first hydrocracking reaction to obtain a first reaction oil agent; the first reaction oil agent moves upward along the fluidized bed reactor into the second reaction zone 22, contacts with a mixture of recycled oil (recycled diesel) and hydrogen entering from the bottom of the second reaction zone 22 and undergoes a second hydrocracking reaction to obtain a second reaction oil agent; the second reaction oil agent moves upward along the fluidized bed reactor into the third reaction zone 23, contacts with a mixture of recycled heavy gasoline and hydrogen entering from the bottom of the third reaction zone 23 and undergoes a third hydrocracking reaction to obtain a third reaction oil agent.

[0062] The third reaction oil leaves the reaction section and enters the reactor sedimentation section 11 with a larger diameter, where gas-solid separation is performed to obtain reaction oil gas and catalyst to be generated; after the reaction oil gas passes through the reaction filter 12 on the top of the reactor to achieve complete oil separation, it enters the product separation unit 13 to separate circulating hydrogen, cracked gas below C4, light gasoline, heavy gasoline, diesel and recycled diesel, heavy gasoline above C9 is used as recycled heavy gasoline, and most of the diesel is used as recycled oil.

[0063] The spent catalyst is drawn out from the upper part of the reactor 10, passes through the spent catalyst stripping and the lock hopper 14, and is transported to the regenerator 15. In the regenerator 15, the spent catalyst is burned to decarbonize and desulfurize to obtain a regenerated catalyst; the regenerated catalyst is transported to the reducer 17 through the spent catalyst stripping and the lock hopper 16, and is reduced with hydrogen in the reducer 17 to reduce the metal oxides therein to elemental metals. The reduced regenerated catalyst is transported to the bottom of the reactor 10 at a stable flow rate through the control valve 18 to be used as a hydrocracking catalyst.

[0064] The present disclosure is further described below by way of examples, but the present disclosure is not limited thereby. The raw materials, reagents, instruments and equipment involved in the examples of the present disclosure can all be purchased unless otherwise specified.

[0065] The composition and properties of the various feedstock oils involved in the embodiments of the present disclosure are shown in Table 1.

[0066] Table 1 Composition and properties of various feedstock oils

[0067]

[0068] Table 1 Composition and properties of various raw oils (continued)

[0069]

[0070] The composition and properties of the hydrocracking catalyst involved in the embodiments of the present disclosure are shown in Table 2.

[0071] Table 2 Composition and properties of hydrocracking catalyst

[0072]

[0073]

[0074] Example 1

[0075] (1) The mixture of catalytic diesel and hydrogen is gasified and then enters the first reaction zone from the bottom of the pressurized fluidized bed reactor, contacts with the hydrocracking catalyst and undergoes a first hydrocracking reaction to obtain a first reaction oil, wherein the operating pressure at the top of the fluidized bed reactor is 3.0 MPa (gauge pressure), the catalyst storage is 9.0 kg, and the total mass space velocity is 1.0 h -1 , relative to the catalytic diesel feedstock space velocity of 0.66h -1 The feed rate of catalytic diesel is 6.0 kg / h, and the feed rate of hydrogen is 14.2 Nm 3 / h, the volume ratio of hydrogen to oil is 2500v / v, the temperature of the mixture of catalytic diesel and hydrogen is 430℃, and the reaction temperature is 436℃;

[0076] (2) allowing the first reaction oil obtained in step (1) to move upward into the second reaction zone, contact with the mixture of recycled diesel 1 and hydrogen entering from the bottom of the second reaction zone and undergo a second hydrocracking reaction to obtain a second reaction oil, wherein the feed rate of recycled diesel 1 is 2.0 kg / h, and the feed rate of hydrogen is 5.0 Nm 3 / h, the volume ratio of hydrogen to oil is 2350v / v, the temperature of the mixture of recycled diesel 1 and hydrogen is 438℃, and the reaction temperature is 456℃;

[0077] (3) allowing the second reaction oil obtained in step (2) to move upward into the third reaction zone, contact with the mixture of recycled heavy gasoline and hydrogen entering from the bottom of the third reaction zone and undergo a third hydrocracking reaction to obtain a third reaction oil, wherein the feed rate of recycled heavy gasoline is 1.0 kg / h, and the feed rate of hydrogen is 1.6 Nm 3 / h, the hydrogen-to-oil volume ratio is 2000v / v, the temperature of the mixture of recycled heavy gasoline and hydrogen is 400℃, and the reaction temperature is 468℃;

[0078] (4) performing gas-solid separation on the third reaction oil obtained in step (3) to obtain reaction oil gas and a catalyst to be generated;

[0079] (5) The reaction oil and gas obtained in step (4) are separated and treated, and the distribution of the obtained products is shown in Table 3, wherein the properties of light gasoline are shown in Table 4, and the properties of heavy gasoline are shown in Table 5;

[0080] (6) The spent catalyst obtained in step (4) is stripped and introduced into a regenerator for char regeneration to obtain a regenerated catalyst, and the obtained regenerated catalyst is stripped and reduced and then returned to the first reaction zone in step (1) for recycling as a hydrocracking catalyst, wherein the carbon content of the regenerated catalyst is 0.5%, the residence time in the reducer is 1.0 h, and the circulation rate of the regenerated catalyst is 2.0 kg / h.

[0081] Example 2

[0082] (1) The mixture of catalytic diesel and hydrogen is gasified and then enters the first reaction zone from the bottom of the pressurized fluidized bed reactor, contacts with the hydrocracking catalyst and undergoes a first hydrocracking reaction to obtain a first reaction oil, wherein the operating pressure at the top of the fluidized bed reactor is 2.75 MPa (gauge pressure), the catalyst storage is 9.0 kg, and the total mass space velocity is 1.0 h -1 , relative to the catalytic diesel feedstock space velocity of 0.66h -1 The feed rate of catalytic diesel is 6.0 kg / h, and the feed rate of hydrogen is 14.2 Nm 3 / h, the hydrogen-to-oil volume ratio is 2500v / v, the temperature of the mixture of catalytic diesel and hydrogen is 430°C, and the reaction temperature is 445°C;

[0083] (2) allowing the first reaction oil obtained in step (1) to move upward into the second reaction zone, contact with the mixture of recycled diesel 2 and hydrogen entering from the bottom of the second reaction zone and undergo a second hydrocracking reaction to obtain a second reaction oil, wherein the feed rate of recycled diesel 2 is 2.0 kg / h, and the feed rate of hydrogen is 5.0 Nm 3 / h, the hydrogen-to-oil volume ratio is 2350v / v, the temperature of the mixture of recycled diesel 2 and hydrogen is 430°C, and the reaction temperature is 466°C;

[0084] (3) allowing the second reaction oil obtained in step (2) to move upward into the third reaction zone, contact with the mixture of recycled heavy gasoline and hydrogen entering from the bottom of the third reaction zone and undergo a third hydrocracking reaction to obtain a third reaction oil, wherein the feed rate of recycled heavy gasoline is 1.0 kg / h, and the feed rate of hydrogen is 1.6 Nm 3 / h, the volume ratio of hydrogen to oil is 2000v / v, the temperature of the mixture of recycled heavy gasoline and hydrogen is 410℃, and the reaction temperature is 475℃;

[0085] (4) performing gas-solid separation on the third reaction oil obtained in step (3) to obtain reaction oil gas and a catalyst to be generated;

[0086] (5) The reaction oil and gas obtained in step (4) are separated and treated, and the distribution of the obtained products is shown in Table 3, wherein the properties of light gasoline are shown in Table 4, and the properties of heavy gasoline are shown in Table 5;

[0087] (6) The regenerated catalyst obtained in step (4) is stripped and introduced into a regenerator for char regeneration to obtain a regenerated catalyst, and the regenerated catalyst is stripped and reduced and then returned to the first reaction zone in step (1) for recycling as a hydrocracking catalyst, wherein the carbon content of the regenerated catalyst is 0.48%, the residence time in the reducer is 1.0 h, and the circulation rate of the regenerated catalyst is 2.4 kg / h.

[0088] Example 3

[0089] (1) The mixture of catalytic diesel and hydrogen is gasified and then enters the first reaction zone from the bottom of the pressurized fluidized bed reactor, contacts with the hydrocracking catalyst and undergoes a first hydrocracking reaction to obtain a first reaction oil, wherein the operating pressure at the top of the fluidized bed reactor is 3.0 MPa (gauge pressure), the catalyst storage is 9.0 kg, and the total mass space velocity is 1.0 h -1 , relative to the catalytic diesel feedstock space velocity of 0.66h -1 The feed rate of catalytic diesel is 6.0 kg / h, and the feed rate of hydrogen is 17.6 Nm 3 / h, the volume ratio of hydrogen to oil is 2750v / v, the temperature of the mixture of catalytic diesel and hydrogen is 430℃, and the reaction temperature is 445℃;

[0090] (2) allowing the first reaction oil obtained in step (1) to move upward into the second reaction zone, contact with the mixture of recycled diesel 3 and hydrogen entering from the bottom of the second reaction zone and undergo a second hydrocracking reaction to obtain a second reaction oil, wherein the feed rate of recycled diesel 3 is 2.0 kg / h, and the feed rate of hydrogen is 5.5 Nm 3 / h, the volume ratio of hydrogen to oil is 2500v / v, the temperature of the mixture of recycled diesel 3 and hydrogen is 428℃, and the reaction temperature is 466℃;

[0091] (3) allowing the second reaction oil obtained in step (2) to move upward into the third reaction zone, contact with the mixture of recycled heavy gasoline and hydrogen entering from the bottom of the third reaction zone and undergo a third hydrocracking reaction to obtain a third reaction oil, wherein the feed rate of recycled heavy gasoline is 1.0 kg / h, and the feed rate of hydrogen is 1.0 Nm 3 / h, the hydrogen-to-oil volume ratio is 2200v / v, the temperature of the mixture of recycled heavy gasoline and hydrogen is 420℃, and the reaction temperature is 475℃;

[0092] (4) performing gas-solid separation on the third reaction oil obtained in step (3) to obtain reaction oil gas and a catalyst to be generated;

[0093] (5) The reaction oil and gas obtained in step (4) are separated and treated, and the distribution of the obtained products is shown in Table 3, wherein the properties of light gasoline are shown in Table 4, and the properties of heavy gasoline are shown in Table 5;

[0094] (6) The spent catalyst obtained in step (4) is stripped and introduced into a regenerator for char regeneration to obtain a regenerated catalyst, and the obtained regenerated catalyst is stripped and reduced and then returned to the first reaction zone in step (1) for recycling as a hydrocracking catalyst, wherein the carbon content of the regenerated catalyst is 0.45%, the residence time in the reducer is 1.0 h, and the circulation amount of the regenerated catalyst is 3.0 kg / h.

[0095] Example 4

[0096] (1) The mixture of catalytic diesel and hydrogen is gasified and then enters the first reaction zone from the bottom of the pressurized fluidized bed reactor, contacts with the hydrocracking catalyst and undergoes a first hydrocracking reaction to obtain a first reaction oil, wherein the operating pressure at the top of the fluidized bed reactor is 3.0 MPa (gauge pressure), the catalyst storage is 9.0 kg, and the total mass space velocity is 1.0 h -1 , relative to the catalytic diesel feedstock space velocity of 0.66h -1 The feed rate of catalytic diesel is 6.0 kg / h, and the feed rate of hydrogen is 14.5 Nm 3 / h, the volume ratio of hydrogen to oil is 2250v / v, the temperature of the mixture of catalytic diesel and hydrogen is 420℃, and the reaction temperature is 445℃;

[0097] (2) allowing the first reaction oil obtained in step (1) to move upward into the second reaction zone, contact with the mixture of recycled diesel 4 and hydrogen entering from the bottom of the second reaction zone and undergo a second hydrocracking reaction to obtain a second reaction oil, wherein the feed rate of recycled diesel 4 is 2.0 kg / h, and the feed rate of hydrogen is 4.1 Nm 3 / h, the hydrogen-to-oil volume ratio is 2000v / v, the temperature of the mixture of recycled diesel 4 and hydrogen is 418°C, and the reaction temperature is 466°C;

[0098] (3) allowing the second reaction oil obtained in step (2) to move upward into the third reaction zone, contact with the mixture of recycled heavy gasoline and hydrogen entering from the bottom of the third reaction zone and undergo a third hydrocracking reaction to obtain a third reaction oil, wherein the feed rate of recycled heavy gasoline is 1.0 kg / h, and the feed rate of hydrogen is 1.4 Nm 3 / h, the volume ratio of hydrogen to oil is 1800v / v, the temperature of the mixture of recycled heavy gasoline and hydrogen is 420℃, and the reaction temperature is 475℃;

[0099] (4) performing gas-solid separation on the third reaction oil obtained in step (3) to obtain reaction oil gas and a catalyst to be generated;

[0100] (5) The reaction oil and gas obtained in step (4) are separated and treated, and the distribution of the obtained products is shown in Table 3, wherein the properties of light gasoline are shown in Table 4, and the properties of heavy gasoline are shown in Table 5;

[0101] (6) stripping the spent catalyst obtained in step (4) and introducing it into a regenerator for char regeneration to obtain a regenerated catalyst, and stripping and reducing the obtained regenerated catalyst and returning it to the first reaction zone in step (1) for recycling as a hydrocracking catalyst, wherein the carbon content of the regenerated catalyst is 0.5%, the residence time in the reducer is 1.0 h, and the circulation rate of the regenerated catalyst is 3.0 kg / h.

[0102] Example 5

[0103] (1) The mixture of catalytic diesel and hydrogen is gasified and then enters the first reaction zone from the bottom of the pressurized fluidized bed reactor, contacts with the hydrocracking catalyst and undergoes a first hydrocracking reaction to obtain a first reaction oil, wherein the operating pressure at the top of the fluidized bed reactor is 2.50 MPa (gauge pressure), the catalyst storage is 9.0 kg, and the total mass space velocity is 1.0 h -1 , relative to the catalytic diesel feedstock space velocity of 0.66h -1 The feed rate of catalytic diesel is 6.0 kg / h, and the feed rate of hydrogen is 17.6 Nm 3 / h, the hydrogen-to-oil volume ratio is 2750v / v, the temperature of the mixture of catalytic diesel and hydrogen is 430°C, and the reaction temperature is 447°C;

[0104] (2) allowing the first reaction oil obtained in step (1) to move upward into the second reaction zone, contact with the mixture of recycled diesel 5 and hydrogen entering from the bottom of the second reaction zone and undergo a second hydrocracking reaction to obtain a second reaction oil, wherein the feed rate of recycled diesel 5 is 2.0 kg / h, and the feed rate of hydrogen is 5.5 Nm 3 / h, the volume ratio of hydrogen to oil is 2500v / v, the temperature of the mixture of recycled diesel 5 and hydrogen is 432℃, and the reaction temperature is 466℃;

[0105] (3) allowing the second reaction oil obtained in step (2) to move upward into the third reaction zone, contact with the mixture of recycled heavy gasoline and hydrogen entering from the bottom of the third reaction zone and undergo a third hydrocracking reaction to obtain a third reaction oil, wherein the feed rate of recycled heavy gasoline is 1.0 kg / h, and the feed rate of hydrogen is 1.0 Nm 3 / h, the hydrogen-to-oil volume ratio is 2200v / v, the temperature of the mixture of recycled heavy gasoline and hydrogen is 420℃, and the reaction temperature is 475℃;

[0106] (4) performing gas-solid separation on the third reaction oil obtained in step (3) to obtain reaction oil gas and a catalyst to be generated;

[0107] (5) The reaction oil and gas obtained in step (4) are separated and treated, and the distribution of the obtained products is shown in Table 3, wherein the properties of light gasoline are shown in Table 4, and the properties of heavy gasoline are shown in Table 5;

[0108] (6) stripping the spent catalyst obtained in step (4) and introducing it into a regenerator for char regeneration to obtain a regenerated catalyst, and stripping and reducing the obtained regenerated catalyst and returning it to the first reaction zone in step (1) for recycling as a hydrocracking catalyst, wherein the carbon content of the regenerated catalyst is 0.5%, the residence time in the reducer is 1.0 h, and the circulation rate of the regenerated catalyst is 3.0 kg / h.

[0109] Comparative Example 1

[0110] (1) Catalytic diesel and recycled diesel are fed into a first fixed bed reactor and contacted with 5 kg of a catalyst (Sinopec RN-21 hydrofining agent) for hydrofining to obtain hydrofined oil 1, wherein the feed rate of catalytic diesel is 4.5 kg / h, the feed rate of recycled diesel is 3.0 kg / h, the reaction pressure is 8.0 MPa, the hydrogen-to-oil volume ratio is 800 v / v, the average reaction temperature is 368°C, and the total mass space velocity is 1.5 h -1 , the mass space velocity relative to the raw material is 0.9h -1 ;

[0111] (2) The hydrorefined oil 1 and the recycled heavy gasoline were fed into a second fixed bed reactor to contact with 6 kg of a catalyst (Sinopec RHC-100 hydrocracking agent) for hydrocracking to obtain a reaction oil agent, wherein the feed rate of the recycled heavy gasoline was 1.5 kg / h, the reaction pressure was 5.0 MPa, the hydrogen-to-oil volume ratio was 1200 v / v, the average reaction temperature was 408 °C, and the mass space velocity was 1.5 h -1 The total mass space velocity of the catalytic diesel feed relative to the catalyst in the two reactors is 0.41h -1 ;

[0112] (3) The reaction oil and gas are separated and treated, and the distribution of the obtained products is shown in Table 3, among which the properties of light gasoline are shown in Table 4, and the properties of heavy gasoline are shown in Table 5.

[0113] Comparative Example 2

[0114] (1) Catalytic diesel and recycled diesel were fed into the first fixed bed reactor and contacted with 6 kg of catalyst (Sinopec RN-21 hydrofining agent) for hydrofining to obtain hydrofined oil 2, wherein the feed rate of catalytic diesel was 4.5 kg / h, the feed rate of recycled diesel was 3.0 kg / h, the reaction pressure was 6.0 MPa, the hydrogen-to-oil volume ratio was 800 v / v, the average reaction temperature was 368 °C, and the total mass space velocity was 1.25 h -1 , the mass space velocity relative to the raw material is 0.75h -1 ;

[0115] (2) The hydrorefined oil 2 and recycled heavy gasoline were fed into a second fixed bed reactor to contact with 6 kg of catalyst (Sinopec RHC-100 hydrocracking agent) for hydrocracking to obtain a reaction oil agent, wherein the feed rate of recycled heavy gasoline was 1.5 kg / h, the reaction pressure was 4.0 MPa, the hydrogen-to-oil volume ratio was 1200 v / v, the average reaction temperature was 418 °C, and the mass space velocity was 1.5 h -1 The total mass space velocity of the catalytic diesel feed relative to the catalyst in the two reactors is 0.38 h -1 ;

[0116] (3) The reaction oil and gas are separated and treated, and the distribution of the obtained products is shown in Table 3, among which the properties of light gasoline are shown in Table 4, and the properties of heavy gasoline are shown in Table 5.

[0117] Table 3 Product distribution

[0118]

[0119]

[0120] Note: Dry gas includes hydrogen sulfide, methane, ethane and ammonia.

[0121] Table 4 Light gasoline properties

[0122] Project Name Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 <![CDATA[Density (20 °C), g / cm 3 > 0.7830 0.7898 0.7935 0.7752 0.7837 0.7786 0.7841 <![CDATA[Refractive index, (n D 20 )]]> 1.4679 1.4689 1.4702 1.4621 1.4685 1.4652 1.4671 Initial distillation point, ℃ 30 30 31 32 30 31 30 Final distillation point, ℃ 169 170 171 172 171 170 169 Saturated hydrocarbons, w% 46.66 46.22 44.17 52.96 46.17 56.99 53.54 Olefins, w% 0.13 0.20 0.53 0.91 0.67 0.25 0.32 Benzene, w% 8.99 9.41 10.47 7.72 8.97 8.66 8.16 Toluene, w% 22.96 22.62 26.96 18.95 22.51 18.27 20.32 C8 aromatics, w% 21.25 21.55 24.03 19.46 21.69 15.82 17.66 S content, ppm 3 2 4 10 6 12 6 RON 98.5 98.7 99.2 96.3 97.4 95.6 96.7 MON 89.1 89.4 90.2 88.6 89.5 87.9 88.5

[0123] Table 5 Heavy gasoline properties

[0124] Project Name Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 <![CDATA[Density (20 °C), g / cm 3 > 0.8530 0.8578 0.8587 0.8463 0.8524 0.8412 0.8469 <![CDATA[Refractive index, (n D 20 )]]> 1.4829 1.4853 1.4860 1.4791 1.4821 1.4733 1.4795 Initial distillation point, ℃ 169 168 170 171 170 169 170 Final distillation point, ℃ 216 212 215 213 216 216 213 Saturated hydrocarbons, w% 13.2 14.0 11.7 14.8 10.6 19.5 16.1 Olefins, w% 0.4 0.6 0.9 1.0 1.1 0.3 0.5 Aromatics, w% 86.4 85.4 87.4 84.2 88.3 80.2 83.4 S,mg / kg 10 15 18 24 16 12 15 N,mg / kg 3 2 4 5 3 5 7 RON 94.3 94.7 95.2 93.6 94.6 93.1 94.3 MON 86.5 86.8 87.1 86.1 86.6 85.7 86.4

[0125] It can be seen that the method disclosed in the present invention significantly improves the selectivity and yield of gasoline and light aromatics, and has the advantages of low hydrogen consumption and less diesel rejection.

[0126] The preferred embodiments of the present disclosure are described in detail above in conjunction with the accompanying drawings; however, the present disclosure is not limited to the specific details in the above embodiments. Within the technical concept of the present disclosure, a variety of simple modifications can be made to the technical solution of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.

[0127] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present disclosure will not further describe various possible combinations.

[0128] In addition, various embodiments of the present disclosure may be arbitrarily combined, and as long as they do not violate the concept of the present disclosure, they should also be regarded as the contents disclosed by the present disclosure.

Claims

1. A method for processing high aromatics feedstock oil, characterized in that: The method includes the following operations: The first mixed material is gasified and then enters the first reaction zone of the hydrocracking reactor to contact with the hydrocracking catalyst and undergo a first hydrocracking reaction to obtain a first reaction oil agent, wherein the first mixed material contains high aromatic feedstock oil and hydrogen; The first reaction oil agent is allowed to enter the second reaction zone of the hydrocracking reactor to contact with the second mixed material and perform a second hydrocracking reaction to obtain a second reaction oil agent, wherein the second mixed material contains recycled oil and hydrogen; The second reaction oil agent is allowed to enter the third reaction zone of the hydrocracking reactor to contact with the third mixed material and perform a third hydrocracking reaction to obtain a third reaction oil agent, wherein the third mixed material contains heavy aromatic oil and / or heavy gasoline and hydrogen; Performing gas-solid separation on the third reaction oil to obtain reaction oil gas and a catalyst to be generated; The high aromatic feedstock oil includes at least one of catalytic diesel and coker diesel; Separating the reaction oil and gas to obtain cracked gas, light aromatics, light gasoline, heavy gasoline and diesel; The method further comprises: returning at least part of the diesel to the second reaction zone of the hydrocracking reactor for recycling as the recycled oil, and returning the heavy gasoline having a carbon number greater than 8 to the third reaction zone of the hydrocracking reactor for recycling; The reaction conditions in the first reaction zone include: reaction pressure of 1.5-5.0 MPa, reaction temperature of 400-500° C., and hydrogen-to-oil volume ratio of 1000-5000; The reaction conditions in the second reaction zone include: a reaction temperature of 420 to 530°C, a hydrogen to oil volume ratio of 1200 to 4500; The reaction conditions in the third reaction zone include: a reaction temperature of 430-530° C. and a hydrogen-to-oil volume ratio of 1200-4500.

2. The method according to claim 1, characterized in that The method further comprises: The catalyst to be regenerated is stripped and then introduced into a regenerator for charring and regeneration to obtain a regenerated catalyst; The regenerated catalyst is subjected to stripping and reduction treatments and then returned to the first reaction zone of the hydrocracking reactor for use as the hydrocracking catalyst.

3. The method according to claim 1, characterized in that Relative to 1 part by weight of the high aromatic feedstock oil, the amount of the recycled oil is 0.2 to 0.6 parts by weight, and the amount of the heavy aromatic oil and / or heavy gasoline is 0.1 to 0.4 parts by weight; Relative to 1 volume part of hydrogen in the first mixed material, the amount of hydrogen in the second mixed material is 0.1 to 1.0 volume part, and the amount of hydrogen in the third mixed material is 0.05 to 0.5 volume part.

4. The method according to claim 1, characterized in that: The temperature of the first mixed material is 350-450°C; the temperature of the second mixed material is 350-450°C; the temperature of the third mixed material is 300-450°C.

5. The method according to claim 1, characterized in that The hydrocracking reactor is a pressurized fluidized bed reactor, and the pressurized fluidized bed reactor is a variable diameter or constant diameter reactor; The feed inlet of the first reaction zone is located at the bottom of the hydrocracking reactor, the feed inlet of the second reaction zone is located at 20% to 50% of the height of the hydrocracking reactor, and the feed inlet of the third reaction zone is located at 30% to 70% of the height of the hydrocracking reactor.

6. The method according to claim 5, characterized in that The pressurized fluidized bed reactor is a variable diameter reactor, the ratio of the cross-sectional area of ​​the second reaction zone to the cross-sectional area of ​​the first reaction zone is (1.0-1.5):1.0, and the ratio of the cross-sectional area of ​​the third reaction zone to the cross-sectional area of ​​the first reaction zone is (1.0-2.0):1.

0.

7. The method according to claim 1, characterized in that The hydrocracking catalyst comprises a carrier and an active metal component supported on the carrier; the carrier comprises a silica-alumina molecular sieve with a twelve-membered ring pore structure, a five-ring silica-alumina molecular sieve with an MFI structure, aluminum oxide and silicon oxide; the active metal component is selected from at least one of cobalt, nickel, iron, molybdenum, tungsten and manganese; based on the total weight of the hydrocracking catalyst, the content of the silica-alumina molecular sieve with a twelve-membered ring pore structure is 5 to 45 parts by weight, the content of the five-ring silica-alumina molecular sieve with an MFI structure is 3 to 35 parts by weight, the content of aluminum oxide is 3 to 45 parts by weight, the content of silicon oxide is 3 to 40 parts by weight, and the content of the active metal component is 10 to 25 parts by weight.

8. The method according to claim 2, characterized in that: The reduction treatment is performed under a pressure of 2.0 to 5.0 MPa, a temperature of 300 to 500° C., and a time of 0.2 to 2.0 h.

9. The method according to claim 1, characterized in that: The catalytic diesel includes hydrogenated catalytic diesel.

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