Method and system for treating sulfur-containing hydrocarbon oil

Abstract

The invention relates to a method and system for treating sulfur-containing hydrocarbon oil, and the method comprises the following steps: contacting the sulfur-containing hydrocarbon oil with a catalyst in a desulfurization reactor, and carrying out a selective desulfurization reaction in the presence of hydrogen to obtain desulfurized hydrocarbon oil and a spent catalyst; and directly contacting the spent catalyst with a hydrogen donor to carry out a sulfur transfer reaction so as to obtain a sulfur-transferred catalyst, and returning at least one stream of the sulfur-transferred catalyst to a desulfurization reactor to carry out a selective desulfurization reaction. The hydrogen partial pressure is controlled to be higher than that of the desulfurization reactor when the spent catalyst is in contact with the hydrogen donor for the sulfur transfer reaction, so that deep conversion and transfer of sulfide on the catalyst can be realized, partial activity of the spent catalyst is recovered, and the spent catalyst can continuously participate in the desulfurization reaction; meanwhile, part of sulfur and carbon are loaded on the catalyst after the sulfur transfer reaction, so that the desulfurization selectivity is increased, and the octane number loss of a desulfurization refined product is less.

Description

Technical Field

[0001] The present application belongs to the field of petrochemical engineering, and in particular, relates to a method and system for treating sulfur-containing hydrocarbon oil. Background Art

[0002] As environmental problems become increasingly severe, restrictions on sulfur content in fuels are becoming increasingly stringent. For example, the National VI A Standard (GB-17930-2016) implemented in my country on January 1, 2019 stipulates that the sulfur content in gasoline shall not exceed 10 μg / g, and the volume fraction of olefins shall not exceed 18%; the National VI B Standard (GB-17930-2016) to be promoted and implemented nationwide on January 1, 2023 stipulates that the sulfur content in gasoline shall not exceed 10 μg / g, and the volume fraction of olefins shall not exceed 15%.

[0003] The S Zorb gasoline adsorption desulfurization process has been rapidly promoted in China due to its characteristics of high desulfurization depth, low hydrogen consumption and low octane number loss. In the methods disclosed in Chinese patents CN1382199A and CN1355727A, the sulfur content in catalytic cracking gasoline can be reduced to less than 10 μg / g by adsorption desulfurization of catalytic cracking gasoline; the desulfurization adsorbent used in the above method uses a mixture of zinc oxide, silica and aluminum oxide as a carrier, and the loaded active component is composed of one or more of cobalt, nickel, copper, iron, manganese, molybdenum, tungsten, silver, tin, vanadium, etc. The adsorbent is obtained by mixing, molding, drying and roasting the carrier and the active component.

[0004] However, the existing technology still has the problem of high octane number loss of hydrocarbon oil during desulfurization treatment of catalytic cracking gasoline. Summary of the invention

[0005] The object of the present invention is to further reduce the octane number loss of hydrocarbon oil in the desulfurization reaction.

[0006] In order to achieve the above object, a first aspect of the present invention provides a method for treating sulfur-containing hydrocarbon oil, the method comprising the following steps:

[0007] (1) contacting the sulfur-containing hydrocarbon oil with a catalyst in a desulfurization reactor and performing a selective desulfurization reaction under hydrogen conditions to obtain desulfurized hydrocarbon oil and a spent catalyst;

[0008] (2) directly contacting the spent catalyst with a hydrogen donor to carry out a sulfur transfer reaction to obtain a catalyst after sulfur transfer, and then returning at least one stream of the catalyst after sulfur transfer to step (1) to contact the sulfur-containing hydrocarbon oil and hydrogen to carry out a selective desulfurization reaction; the hydrogen partial pressure of the sulfur transfer is 0.1 to 3 MPa higher than the hydrogen partial pressure of the desulfurization reaction.

[0009] Optionally, the desulfurization reaction is carried out in a gas atmosphere containing hydrogen. The conditions of the desulfurization reaction include: a temperature of 300 to 550° C., a pressure of 0.5 to 5 MPa, a molar ratio of hydrogen in the hydrogen-containing gas to the sulfur-containing hydrocarbon oil of 0.1 to 5.0, and a weight hourly space velocity of the sulfur-containing hydrocarbon oil of 0.1 to 100 h -1 ;

[0010] Preferably, in the desulfurization reactor, the desulfurization reaction conditions include: a temperature of 350-500°C, a pressure of 1.0-3.5 MPa, a molar ratio of hydrogen in the hydrogen-containing gas to the sulfur-containing hydrocarbon oil of 0.3-2.5, a weight hourly space velocity of the sulfur-containing hydrocarbon oil of 1-10 h -1 ;

[0011] Preferably, the volume fraction of hydrogen in the hydrogen-containing gas is 30 to 100%, preferably 50 to 100%, and more preferably 70 to 100%;

[0012] Preferably, the hydrogen-containing gas is one or more of hydrogen, dry gas, catalytic cracking dry gas, coking dry gas and thermal cracking dry gas.

[0013] Optionally, the conditions of the sulfur transfer reaction include: a temperature of 350 to 550°C, a hydrogen partial pressure of the sulfur transfer of 1.0 to 6 MPa, preferably 1.5 to 4.5 MPa; the contact time between the spent catalyst and the hydrogen donor is 0.1 to 20 h, preferably 0.5 to 10 h; the volume fraction of hydrogen in the hydrogen donor is 70 to 100%, preferably 80 to 100%; the hydrogen donor is selected from one or more of hydrogen and dry gas.

[0014] Optionally, based on the weight of the spent catalyst, the mass fraction of sulfur in the spent catalyst is 1 to 12%, preferably 3 to 9%. The catalyst comprises a carrier and a metal active component supported on the carrier, based on the total weight of the carrier, the carrier contains 15 to 85 wt% of zinc oxide, 10 to 80 wt% of aluminum oxide and 5 to 75 wt% of silica; the weight of the metal active component accounts for 2 to 30% of the total weight of the catalyst; the metal active component is selected from one or more of cobalt, nickel, iron, manganese, copper, molybdenum, tungsten, silver, tin and vanadium.

[0015] Optionally, the sulfur-containing hydrocarbon oil is selected from one or more of liquefied gas, gasoline, diesel and narrow fractions of gasoline; the sulfur content in the sulfur-containing hydrocarbon oil is 30 to 5000 μg / g, preferably 50 to 3000 μg / g.

[0016] Optionally, based on the weight of the catalyst after the sulfur transfer, the mass fraction of sulfur in the catalyst after the sulfur transfer is 1 to 12%, preferably 3 to 9%.

[0017] Optionally, the method further comprises: subjecting another stream of the catalyst after the sulfur transfer to oxygen-containing coke regeneration and gas replacement and then returning the other stream to the desulfurization reactor of step (1) to participate in the selective desulfurization reaction.

[0018] Optionally, the catalyst after sulfur transfer is subjected to oxygen-containing charring in an oxygen-containing gas atmosphere, and the conditions for the oxygen-containing charring include: a temperature of 300-800°C, preferably 350-600°C; a pressure of 0.1-3.0 MPa, preferably 0.1-1.0 MPa; the oxygen-containing gas is one of air, a mixed gas of oxygen and nitrogen, and a mixed gas of air and nitrogen; the volume fraction of oxygen in the oxygen-containing gas is 5-50 volume %; and the gas replacement is carried out in a gas atmosphere containing hydrogen.

[0019] A second aspect of the present invention provides a system for treating sulfur-containing hydrocarbon oil, the system comprising a desulfurization reactor, a lock hopper and a regenerator; the desulfurization reactor is connected to a reactor receiver and a reactor feed tank; the regenerator is connected to a regenerator feed tank and a regenerator receiver;

[0020] The desulfurization reactor is provided with a material inlet for the premixed material to enter at the bottom, a catalyst inlet at the bottom, a hydrogen-containing gas inlet and a catalyst outlet to be produced at the top, and an oil and gas outlet at the top;

[0021] The reactor receiver is provided with a catalyst inlet to be produced, a catalyst outlet and a hydrogen-containing gas outlet;

[0022] The locking hopper is provided with a first material inlet, a first material outlet, a second material inlet, and a second material outlet;

[0023] The regenerator is provided with a flue gas outlet at the top, a catalyst inlet at the upper part, an oxygen-containing gas inlet at the lower part, and a regenerated catalyst outlet at the bottom;

[0024] The outlet of the catalyst to be regenerated of the desulfurization reactor is communicated with the inlet of the catalyst to be regenerated of the reactor receiver, and the outlet of the hydrogen-containing gas of the reactor receiver is communicated with the inlet of the hydrogen-containing gas of the desulfurization reactor;

[0025] The first material inlet of the lock hopper is connected to the catalyst outlet of the reactor receiver, the first material outlet of the lock hopper is switchably connected to the catalyst inlet of the reactor feed tank, and the catalyst outlet of the reactor feed tank is connected to the catalyst inlet of the desulfurization reactor;

[0026] The first material outlet of the lock hopper of the feed tank can also be switchably connected to the catalyst inlet of the regenerator feed tank, the catalyst outlet of the regenerator feed tank is connected to the catalyst inlet of the regenerator, the regenerated catalyst outlet of the regenerator is connected to the regenerated catalyst inlet of the regenerator receiver, the regenerated catalyst outlet of the regenerator receiver is connected to the second material inlet of the lock hopper, and the second material outlet of the lock hopper is connected to the catalyst inlet of the reactor feed tank.

[0027] Through the above technical scheme, the present invention controls the hydrogen partial pressure when the catalyst to be regenerated contacts with the hydrogen donor for the sulfur transfer reaction to be higher than that of the desulfurization reactor, thereby achieving deep conversion and transfer of sulfides on the catalyst, restoring part of the activity of the catalyst to be regenerated, and allowing it to continue to participate in the desulfurization reaction; at the same time, since part of the sulfur and carbon are loaded on the catalyst after the sulfur transfer reaction, its desulfurization selectivity is increased, and the octane number loss of the desulfurized refined product is less.

[0028] Other features and advantages of the present invention will be described in detail in the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] The accompanying drawings are used to provide a further understanding of the present invention and constitute a part of the specification. Together with the following specific embodiments, they are used to explain the present invention but do not constitute a limitation of the present invention. In the accompanying drawings:

[0030] Figure 1 It is a schematic structural diagram of a system for treating sulfur-containing hydrocarbon oil provided by the present invention.

[0031] Description of Reference Numerals

[0032] 1 pipeline 2 desulfurization reactor 3 pipeline 4 pipeline

[0033] 5 Reactor Receiver 6 Pipeline 7 Pipeline 8 Pipeline

[0034] 9 Lock hopper 10 Pipeline 11 Pipeline 12 Regenerator feed tank

[0035] 13 pipeline 14 pipeline 15 regenerator 16 pipeline

[0036] 17 pipeline 18 regenerator receiver 19 pipeline 20 pipeline

[0037] 21 Reactor feed tank 22 Pipeline DETAILED DESCRIPTION

[0038] The specific embodiments of the present invention are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention, and are not used to limit the present invention.

[0039] A first aspect of the present invention provides a method for treating sulfur-containing hydrocarbon oil, the method comprising the following steps:

[0040] (1) contacting the sulfur-containing hydrocarbon oil with a catalyst in a desulfurization reactor and performing a selective desulfurization reaction under hydrogen conditions to obtain desulfurized hydrocarbon oil and a spent catalyst;

[0041] (2) directly contacting the spent catalyst with a hydrogen donor to carry out a sulfur transfer reaction to obtain a catalyst after sulfur transfer, and then returning at least one stream of the catalyst after sulfur transfer to step (1) to contact the sulfur-containing hydrocarbon oil and hydrogen to carry out a selective desulfurization reaction; the hydrogen partial pressure of the sulfur transfer is 0.1 to 3 MPa higher than the hydrogen partial pressure of the desulfurization reaction.

[0042] The present invention controls the hydrogen partial pressure of the catalyst to be regenerated to be higher than that of the desulfurization reactor when the catalyst to be regenerated contacts with the hydrogen donor for the sulfur transfer reaction, thereby achieving deep conversion and transfer of sulfides on the catalyst, releasing the metal active center, and restoring part of the activity of the catalyst to be regenerated, so that the catalyst can continue to participate in the desulfurization reaction. Since part of the sulfur and carbon are loaded on the catalyst after the sulfur transfer reaction, its desulfurization selectivity is increased, and the octane number loss of the desulfurized refined product is less. In addition, the catalyst with partially restored activity continues to be returned to the desulfurization reactor for reaction, which can reduce the frequency of catalyst oxidation regeneration, reduce catalyst regeneration loss, and extend the service life of the catalyst.

[0043] In the present invention, "at least one" means part or all. For example, in one specific embodiment of the present invention, all the catalysts after sulfur transfer are returned to the desulfurization reactor of step (1) for selective desulfurization reaction. In another specific embodiment of the present invention, part of the catalysts after sulfur transfer are returned to the desulfurization reactor, and the remaining catalysts after sulfur transfer are subjected to oxygen-containing coke regeneration and reduction and then returned to the desulfurization reactor. The way in which the catalysts after sulfur transfer are returned to the desulfurization reactor is determined specifically according to the sulfur content and carbon content in the catalysts after sulfur transfer.

[0044] The desulfurization reaction is carried out in a gas atmosphere containing hydrogen. The conditions of the desulfurization reaction include: a temperature of 300 to 550°C, a pressure of 0.5 to 5 MPa, a molar ratio of hydrogen in the hydrogen-containing gas to the sulfur-containing hydrocarbon oil of 0.1 to 5.0, and a weight hourly space velocity of the sulfur-containing hydrocarbon oil of 0.1 to 100 h -1 .

[0045] Wherein, in the desulfurization reactor, the desulfurization reaction conditions include: temperature of 350-500°C, pressure of 1.0-3.5MPa, molar ratio of hydrogen in the hydrogen-containing gas to the sulfur-containing hydrocarbon oil of 0.3-2.5, weight hourly space velocity of the sulfur-containing hydrocarbon oil of 1-10h -1After the sulfur-containing hydrocarbon oil is reacted under the above-mentioned desulfurization conditions, the sulfur content in the refined product is reduced to below 10 ppm, and the loss of olefins is relatively small.

[0046] Preferably, the volume fraction of hydrogen in the hydrogen-containing gas is 30 to 100%, preferably 50 to 100%, and more preferably 70 to 100%.

[0047] Preferably, the hydrogen-containing gas is one or more of hydrogen, dry gas, catalytic cracking dry gas, coking dry gas and thermal cracking dry gas.

[0048] In the present invention, the desulfurization reactor can be a fluidized bed, a moving bed or a fixed bed, and the specific form of the reaction bed is adjusted according to the desulfurization depth and the reaction economy.

[0049] Among them, the conditions of the sulfur transfer reaction include: a temperature of 350 to 550°C, a hydrogen partial pressure of the sulfur transfer of 1.0 to 6 MPa, preferably 1.5 to 4.5 MPa; the contact time between the spent catalyst and the hydrogen donor is 0.1 to 20 hours, preferably 0.5 to 10 hours; the volume fraction of hydrogen in the hydrogen donor is 70 to 100%, preferably 80 to 100%; the hydrogen donor is selected from one or more of hydrogen and dry gas.

[0050] Wherein, based on the weight of the spent catalyst, the mass fraction of sulfur in the spent catalyst is 1-12%, preferably 3-9%. The catalyst comprises a carrier and a metal active component supported on the carrier, based on the total weight of the carrier, the carrier contains 15-85wt% of zinc oxide, 10-80wt% of aluminum oxide and 5-75wt% of silica; the weight of the metal active component accounts for 2-30% of the total weight of the catalyst; the metal active component is selected from one or more of cobalt, nickel, iron, manganese, copper, molybdenum, tungsten, silver, tin and vanadium.

[0051] In the present invention, when the desulfurization reactor is a fluidized bed reactor, the catalyst is preferably in microspherical form to facilitate catalyst fluidization. For example, in a specific embodiment of the present invention, the catalyst is in microspherical form, and the average particle size of the catalyst is 20 to 200 μm, preferably 40 to 100 μm.

[0052] The sulfur-containing hydrocarbon oil is selected from one or more of liquefied gas, gasoline, diesel and narrow fractions of gasoline; the sulfur content of the sulfur-containing hydrocarbon oil is 30 to 5000 μg / g, preferably 50 to 3000 μg / g.

[0053] Wherein, based on the weight of the catalyst after the sulfur transfer, the mass fraction of sulfur in the catalyst after the sulfur transfer is 1 to 12%, preferably 3 to 9%.

[0054] The method further comprises: subjecting the other stream of the catalyst after the sulfur transfer to oxygen-containing coke regeneration and gas replacement and then returning it to the desulfurization reactor of step (1) to participate in the selective desulfurization reaction.

[0055] The catalyst after sulfur transfer is subjected to oxygen-containing charring in an oxygen-containing gas atmosphere, and the conditions for the oxygen-containing charring include: a temperature of 300 to 800°C, preferably 350 to 600°C; a pressure of 0.1 to 3.0 MPa, preferably 0.1 to 1.0 MPa; the oxygen-containing gas is one of air, a mixed gas of oxygen and nitrogen, and a mixed gas of air and nitrogen; the volume fraction of oxygen in the oxygen-containing gas is 5 to 50% by volume; and the gas replacement is carried out in a gas atmosphere containing hydrogen.

[0056] A second aspect of the present invention provides a system for treating sulfur-containing hydrocarbon oil. Figure 1 The apparatus of a system for treating sulfur-containing hydrocarbon oil according to an embodiment of the present invention is schematically shown. It should be noted that: Figure 1 The device shown is merely an example of a device that can be applied to a method of an embodiment of the present invention, and does not mean that the method of the embodiment of the present invention cannot use other devices or equipment.

[0057] like Figure 1 As shown, the system includes a desulfurization reactor 2, a lock hopper 9 and a regenerator 15; the desulfurization reactor 2 is connected to a reactor receiver 5 and a reactor feed tank 21; the regenerator 15 is connected to a regenerator feed tank 12 and a regenerator receiver 18;

[0058] The desulfurization reactor 2 is provided with a material inlet for the premixed material to enter at the bottom, a catalyst inlet at the bottom, a hydrogen-containing gas inlet and a catalyst outlet to be produced at the top, and an oil and gas outlet at the top;

[0059] The reactor receiver 5 is provided with a catalyst inlet to be produced, a catalyst outlet and a hydrogen-containing gas outlet;

[0060] The locking hopper 9 is provided with a first material inlet, a first material outlet, a second material inlet, and a second material outlet;

[0061] The regenerator 15 is provided with a flue gas outlet at the top, a catalyst inlet at the upper part, an oxygen-containing gas inlet at the lower part, and a regenerated catalyst outlet at the bottom;

[0062] The outlet of the catalyst to be regenerated of the desulfurization reactor 2 is communicated with the inlet of the catalyst to be regenerated of the reactor receiver 5, and the outlet of the hydrogen-containing gas of the reactor receiver 5 is communicated with the inlet of the hydrogen-containing gas of the desulfurization reactor 2;

[0063] The first material inlet of the lock hopper 9 is connected to the catalyst outlet of the reactor receiver 5, and the first material outlet of the lock hopper 9 is switchably connected to the catalyst inlet of the reactor feed tank 21, and the catalyst outlet of the reactor feed tank 21 is connected to the catalyst inlet of the desulfurization reactor 2;

[0064] The first material outlet of the lock hopper 9 of the feed tank can also be switchably connected to the catalyst inlet of the regenerator feed tank 12, the catalyst outlet of the regenerator feed tank 12 is connected to the catalyst inlet of the regenerator 15, the regenerated catalyst outlet of the regenerator 15 is connected to the regenerated catalyst inlet of the regenerator receiver 18, the regenerated catalyst outlet of the regenerator receiver 18 is connected to the second material inlet of the lock hopper 9, and the second material outlet of the lock hopper 9 is connected to the catalyst inlet of the reactor feed tank 21.

[0065] In a specific embodiment of the present invention, the preheated sulfur-containing hydrocarbon oil feedstock and hydrogen enter from the bottom of the desulfurization reactor 2 through pipeline 1, contact with the catalyst in the desulfurization reactor 2 from bottom to top for selective desulfurization reaction, the oil and gas after the reaction and the sulfur-carrying catalyst enter the sedimentation separation section at the top of the desulfurization reactor for oil-agent separation, and the desulfurized oil and gas mixture is sent to the subsequent stabilization system through pipeline 3. The sulfur-carrying catalyst is sent to the reactor receiver 5 through pipeline 4, and contacts with the hydrogen donor sent to the reactor receiver 5 through pipeline 6 for sulfur transfer reaction, and the reacted gas is sent to the desulfurization reactor 2 through pipeline 7. Part of the catalyst after the sulfur transfer reaction enters the lock hopper through pipeline 8, and after reducing the pressure, it is transported to the reactor feed tank 21 through pipeline 20, and then returns to the desulfurization reactor 2 through pipeline 22.

[0066] The catalyst after the sulfur transfer reaction can also enter the lock hopper 9 through pipeline 8, and the hydrogen atmosphere of the catalyst to be regenerated is converted into a nitrogen atmosphere, and then enter the regenerator feed tank 12 through pipeline 11, and then enter the regenerator 15 through pipeline 13, and contact with the oxygen-containing gas from pipeline 14 for oxygen-containing charring to burn off the sulfur and carbon loaded on the catalyst, and the regenerated flue gas is sent to the sulfur production unit or flue gas treatment unit through pipeline 16. The charred catalyst enters the regenerator receiver 18 through pipeline 17, and then enters the lock hopper through pipeline 19 for gas replacement, and changes from a low-pressure nitrogen environment to a high-pressure hydrogen environment, and then is sent to the reactor feed tank 21 through pipeline 20, and enters the desulfurization reactor 2 through pipeline 22 to continue to participate in the selective desulfurization reaction.

[0067] The present invention realizes the transfer circulation of catalyst between different atmospheres, different pressures and reaction vessels by adopting a lock hopper system.

[0068] The present invention is further described in detail by way of examples. The raw materials used in the examples can be obtained through commercial sources. Among them, the catalytic cracking gasoline raw materials used in the examples and comparative examples of the present invention are from Sinopec Cangzhou Branch, and their properties are shown in Table 1.

[0069] Table 1 Catalytic gasoline raw material properties

[0070] Raw material type Catalytic cracking gasoline Sulfur content, ppmw 992 Normal alkanes, m% 5.67 Isoalkanes, m% 37.06 Olefins, m% 13.97 Cycloalkanes, m% 7.46 Aromatics, m% 34.91 RON 91.8

[0071] The desulfurization catalyst used in the examples and comparative examples of the present invention is FCAS catalyst, which is produced by Sinopec Catalyst Company Nanjing Branch. The properties of the catalyst FCAS are shown in Table 2.

[0072] Example 1

[0073] This example prepares a sulfur-carrying catalyst with a low sulfur content and partially restored activity to simulate a catalyst after sulfur transfer, specifically comprising the following steps:

[0074] (1) The FCAS desulfurization catalyst is loaded into a small fixed fluidized bed reactor and contacted with hydrogen for reduction treatment. The temperature during the reduction treatment is 400° C., the pressure is 1.5 MPa, the time is 1 hour, and the volume ratio of hydrogen to catalyst is 900;

[0075] (2) Using dimethyl disulfide (DMDS) with a sulfur content of 3 wt% and cyclohexane as preloaded sulfur reagents, the reduced FCAS catalyst and the preloaded sulfur reagents were subjected to a desulfurization reaction. The temperature during the desulfurization reaction was 400°C, the pressure was 1.5 MPa, the volume ratio of hydrogen to the preloaded sulfur reagent was 1600, and the preloaded sulfur reagent feeding was stopped after the reaction for 32 minutes. Then, the catalyst was stripped with hydrogen for 30 minutes at normal pressure and purged with nitrogen for 15 minutes at normal pressure. After cooling to room temperature, the catalyst was unloaded for standby use and marked as FCAS-S1. The properties of the catalyst FCAS-S1 are shown in Table 2.

[0076] Example 2

[0077] This example prepares a sulfur-loaded catalyst with a high sulfur content and partially restored activity to simulate a catalyst after sulfur transfer, specifically comprising the following steps:

[0078] (1) The FCAS desulfurization catalyst is loaded into a small fixed fluidized bed reactor and contacted with hydrogen for reduction treatment. The temperature during the reduction treatment is 400° C., the pressure is 1.5 MPa, the time is 1 hour, and the volume ratio of hydrogen to catalyst is 900;

[0079] (2) Using dimethyl disulfide (DMDS) with a sulfur content of 3 wt% and cyclohexane as preloaded sulfur reagents, the reduced FCAS catalyst and the preloaded sulfur reagents were subjected to a desulfurization reaction. The temperature during the desulfurization reaction was 400°C, the pressure was 1.5 MPa, the volume ratio of hydrogen to the preloaded sulfur reagent was 1600, and the preloaded sulfur reagent feeding was stopped after 64 minutes of reaction. Then, the catalyst was stripped with hydrogen for 30 minutes at normal pressure and purged with nitrogen for 15 minutes at normal pressure in turn; after cooling to room temperature, the catalyst was unloaded for standby use and marked as FCAS-S2. The properties of the catalyst FCAS-S2 are shown in Table 2.

[0080] Table 2 Properties of FCAS fresh agent and sulfur-loaded catalysts FCAS-S1 and FCAS-S2

[0081] Physical property analysis FCAS FCAS-S1 FCAS-S2 C,％ 0.0335 0.0327 0.098 S,％ 0.195 1.78 3.7 ZnO, % 40.4 39.3 36.5 ZnS, % 0 3.3 8.1 ZnAl2O4,% 14.9 15 17.8 Specific surface area, m2 / g 35.27 36.88 36.12 Specific pore volume, m3 / g 0.078 0.093 0.089

[0082] Example 3

[0083] In this embodiment, the gasoline raw material is subjected to desulfurization treatment under hydrogen conditions, which specifically includes the following steps:

[0084] (1) The sulfur-carrying catalyst FCAS-S1 is loaded on a small fixed bed as a catalyst after sulfur transfer, and FCAS-S1 is contacted with hydrogen for reduction. The temperature during reduction is 400° C., the pressure is 1.38 MPa, the volume ratio of hydrogen to catalyst is 1000, and the reduction time is 1 hour;

[0085] (2) The gasoline feedstock and hydrogen are contacted with the reduced FCAS-S1 catalyst for desulfurization reaction. The reaction conditions include: temperature of 400°C, pressure of 1.38 MPa, hydrogen-to-oil molar ratio of 0.35, and weight hourly space velocity of the gasoline feedstock of 5 h -1 , sampling and analysis were carried out every 2 hours, and the reaction time was 6 hours;

[0086] (3) After the desulfurization reaction was completed, the catalytic gasoline feed was stopped, and the temperature, pressure and hydrogen feed amount in the reactor were maintained unchanged for 1 hour. Then, the gasoline feed was resumed while other conditions remained unchanged, and the reaction was continued for 6 hours. Samples were taken and analyzed every 2 hours. The properties of the reaction products are shown in Table 3.

[0087] Example 4

[0088] In this embodiment, the gasoline raw material is subjected to desulfurization treatment under hydrogen conditions, which specifically includes the following steps:

[0089] (1) The sulfur-carrying catalyst FCAS-S2 is loaded on a small fixed bed as a catalyst after sulfur transfer, and FCAS-S2 is contacted with hydrogen for reduction. The temperature during reduction is 400° C., the pressure is 1.38 MPa, the volume ratio of hydrogen to catalyst is 1000, and the reduction time is 1 hour;

[0090] (2) The gasoline feedstock and hydrogen are contacted with the reduced FCAS-S2 catalyst for desulfurization reaction. The reaction conditions include: temperature of 400°C, pressure of 1.38 MPa, hydrogen-to-oil molar ratio of 0.35, and weight hourly space velocity of the gasoline feedstock of 5 h -1 , sampling and analysis were carried out every 2 hours, and the reaction time was 6 hours;

[0091] (3) After the desulfurization reaction was completed, the catalytic gasoline feed was stopped, and the temperature, pressure and hydrogen feed amount in the reactor were maintained unchanged for 1 hour. Then, the gasoline feed was resumed while other conditions remained unchanged, and the reaction was continued for 6 hours. Samples were taken and analyzed every 2 hours. The properties of the reaction products are shown in Table 3.

[0092] Comparative Example 1

[0093] In this comparative example, gasoline raw material is subjected to desulfurization treatment under hydrogen conditions, which specifically includes the following steps:

[0094] (1) FCAS catalyst is loaded as a fresh catalyst on a small fixed bed, and FCAS is contacted with hydrogen for reduction. The temperature during reduction is 400° C., the pressure is 1.38 MPa, the volume ratio of hydrogen to catalyst is 1000, and the reduction time is 1 h;

[0095] (2) contacting the gasoline feedstock and hydrogen with the reduced FCAS catalyst for desulfurization reaction, the reaction conditions including: temperature of 400°C, pressure of 1.38 MPa, hydrogen-to-oil molar ratio of 0.35, and weight hourly space velocity of the gasoline feedstock of 5 h -1 , sampling and analysis were carried out every 2 hours, and the reaction time was 6 hours;

[0096] (3) After the desulfurization reaction was completed, the catalytic gasoline feed was stopped, and the temperature, pressure and hydrogen feed amount in the reactor were maintained unchanged for 1 hour. Then, the gasoline feed was resumed while other conditions remained unchanged, and the reaction was continued for 6 hours. Samples were taken and analyzed every 2 hours. The properties of the reaction products are shown in Table 3.

[0097] Comparative Example 2

[0098] In this comparative example, gasoline raw material is subjected to desulfurization treatment under hydrogen conditions, which specifically includes the following steps:

[0099] (1) FCAS-S2 catalyst is loaded as a sulfur-supported catalyst with a high sulfur content on a small fixed bed, and FCAS-S2 is contacted with hydrogen for reduction. The temperature during reduction is 400° C., the pressure is 1.38 MPa, the volume ratio of hydrogen to catalyst is 1000, and the reduction time is 1 h;

[0100] (2) The gasoline feedstock and hydrogen are contacted with the reduced FCAS-S2 catalyst for desulfurization reaction. The reaction conditions include: temperature of 400°C, pressure of 1.38 MPa, hydrogen-to-oil molar ratio of 0.35, and weight hourly space velocity of the gasoline feedstock of 5 h -1 The reaction time was 12 hours, and the samples were taken and analyzed every 2 hours. The properties of the reaction products are shown in Table 3.

[0101] Table 3 Properties of reaction products

[0102]

[0103] As can be seen from Table 3, after the spent catalyst is contacted with hydrogen to carry out sulfur transfer reaction, the sulfide on the desulfurization catalyst is deeply converted and transferred, the desulfurization selectivity of the catalyst with partially restored activity is better, and the octane number loss of the refined gasoline prepared by the method for treating sulfur-containing hydrocarbon oil of the present invention is small.

[0104] The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0105] 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 invention will not further describe various possible combinations.

[0106] In addition, various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.

Claims

1. A method for treating sulfur-containing hydrocarbon oil, characterized in that: The method comprises the following steps: (1) contacting the sulfur-containing hydrocarbon oil with a catalyst in a desulfurization reactor and performing a selective desulfurization reaction under hydrogen conditions to obtain desulfurized hydrocarbon oil and a spent catalyst; (2) directly contacting the spent catalyst with a hydrogen donor to carry out a sulfur transfer reaction to obtain a catalyst after sulfur transfer, and then returning at least one stream of the catalyst after sulfur transfer to step (1) to contact the sulfur-containing hydrocarbon oil and hydrogen to carry out a selective desulfurization reaction; the hydrogen partial pressure of the sulfur transfer is 0.1 to 3 MPa higher than the hydrogen partial pressure of the desulfurization reaction.

2. The method according to claim 1, wherein: The desulfurization reaction is carried out in a gas atmosphere containing hydrogen. The conditions of the desulfurization reaction include: a temperature of 300 to 550° C., a pressure of 0.5 to 5 MPa, a molar ratio of hydrogen in the hydrogen-containing gas to the sulfur-containing hydrocarbon oil of 0.1 to 5.0, and a weight hourly space velocity of the sulfur-containing hydrocarbon oil of 0.1 to 100 h -1 ; Preferably, in the desulfurization reactor, the desulfurization reaction conditions include: a temperature of 350-500°C, a pressure of 1.0-3.5 MPa, a molar ratio of hydrogen in the hydrogen-containing gas to the sulfur-containing hydrocarbon oil of 0.3-2.5, a weight hourly space velocity of the sulfur-containing hydrocarbon oil of 1-10 h -1 ; Preferably, the volume fraction of hydrogen in the hydrogen-containing gas is 30 to 100%, preferably 50 to 100%, and more preferably 70 to 100%; Preferably, the hydrogen-containing gas is one or more of hydrogen, dry gas, catalytic cracking dry gas, coking dry gas and thermal cracking dry gas.

3. The method according to claim 1, wherein: The conditions of the sulfur transfer reaction include: a temperature of 350 to 550° C., a hydrogen partial pressure of 1.0 to 6 MPa, preferably 1.5 to 4.5 MPa; The time for the catalyst to be generated to contact with the hydrogen donor is 0.1 to 20 hours, preferably 0.5 to 10 hours; The volume fraction of hydrogen in the hydrogen donor is 70-100%, preferably 80-100%; The hydrogen donor is selected from one or more of hydrogen and dry gas.

4. The method according to claim 1, wherein: Based on the weight of the spent catalyst, the mass fraction of sulfur in the spent catalyst is 1 to 12%, preferably 3 to 9%.

5. The method according to claim 1, wherein: The catalyst comprises a carrier and a metal active component supported on the carrier, and based on the total weight of the carrier, the carrier contains 15 to 85 wt% of zinc oxide, 10 to 80 wt% of aluminum oxide and 5 to 75 wt% of silica; The weight of the metal active component accounts for 2 to 30% of the total weight of the catalyst; The metal active component is selected from one or more of cobalt, nickel, iron, manganese, copper, molybdenum, tungsten, silver, tin and vanadium.

6. The method according to claim 1, wherein: The sulfur-containing hydrocarbon oil is selected from one or more of liquefied gas, gasoline, diesel and a narrow fraction of gasoline; The sulfur content of the sulfur-containing hydrocarbon oil is 30 to 5000 μg / g, preferably 50 to 3000 μg / g.

7. The method according to claim 1, wherein: Based on the weight of the catalyst after the sulfur transfer, the mass fraction of sulfur in the catalyst after the sulfur transfer is 1 to 12%, preferably 3 to 9%.

8. The method according to claim 1, wherein: The method further comprises: subjecting the other stream of the catalyst after the sulfur transfer to oxygen-containing coke regeneration and gas replacement and then returning it to the desulfurization reactor of step (1) to participate in the selective desulfurization reaction.

9. The method according to claim 8, wherein: The catalyst after sulfur transfer is subjected to oxygen-containing charring in an oxygen-containing gas atmosphere, and the conditions of the oxygen-containing charring include: a temperature of 300 to 800° C., preferably 350 to 600° C.; a pressure of 0.1 to 3.0 MPa, preferably 0.1 to 1.0 MPa; the oxygen-containing gas is one of air, a mixed gas of oxygen and nitrogen, and a mixed gas of air and nitrogen; the volume fraction of oxygen in the oxygen-containing gas is 5 to 50% by volume; The gas replacement is performed in a gas atmosphere containing hydrogen.

10. A system for treating sulfur-containing hydrocarbon oil, characterized in that: The system comprises a desulfurization reactor (2), a lock hopper (9) and a regenerator (15); the desulfurization reactor (2) is connected to a reactor receiver (5) and a reactor feed tank (21); the regenerator (15) is connected to a regenerator feed tank (12) and a regenerator receiver (18); The desulfurization reactor (2) is provided with a material inlet for the premixed material to enter at the bottom, a catalyst inlet at the bottom, a hydrogen-containing gas inlet and a catalyst outlet to be produced at the top, and an oil and gas outlet at the top; The reactor receiver (5) is provided with an inlet for the catalyst to be produced, an outlet for the catalyst and an outlet for the hydrogen-containing gas; The lock hopper (9) is provided with a first material inlet, a first material outlet, a second material inlet, and a second material outlet; The regenerator (15) is provided with a flue gas outlet at the top, a catalyst inlet at the upper part, an oxygen-containing gas inlet at the lower part, and a regenerated catalyst outlet at the bottom; The outlet of the catalyst to be regenerated of the desulfurization reactor (2) is connected to the inlet of the catalyst to be regenerated of the reactor receiver (5), and the outlet of the hydrogen-containing gas of the reactor receiver (5) is connected to the inlet of the hydrogen-containing gas of the desulfurization reactor (2); The first material inlet of the lock hopper (9) is connected to the catalyst outlet of the reactor receiver (5), the first material outlet of the lock hopper (9) is switchably connected to the catalyst inlet of the reactor feed tank (21), and the catalyst outlet of the reactor feed tank (21) is connected to the catalyst inlet of the desulfurization reactor (2); The first material outlet of the lock hopper (9) of the feed tank can also be switchably connected to the catalyst inlet of the regenerator feed tank (12), the catalyst outlet of the regenerator feed tank (12) is connected to the catalyst inlet of the regenerator (15), the regenerated catalyst outlet of the regenerator (15) is connected to the regenerated catalyst inlet of the regenerator receiver (18), the regenerated catalyst outlet of the regenerator receiver (18) is connected to the second material inlet of the lock hopper (9), and the second material outlet of the lock hopper (9) is connected to the catalyst inlet of the reactor feed tank (21).

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