A method and system for treating sulfur-containing hydrocarbon oils

Abstract

The present application relates to a kind of method and system for processing sulfur-containing hydrocarbon oil, the method includes that sulfur-containing hydrocarbon oil is contacted with catalyst in desulfurization reactor and carries out selective desulfurization reaction under the condition of hydrogen, and the sulfur-containing hydrocarbon oil after desulfurization and spent catalyst are obtained;Then the spent catalyst is directly contacted with hydrogen donor and carries out sulfur transfer reaction, and the sulfur transfered catalyst is obtained, and at least one of the sulfur transfered catalyst is returned to desulfurization reactor and carries out selective desulfurization reaction.The present application can realize the deep conversion and transfer of sulfide on catalyst by controlling the hydrogen partial pressure when spent catalyst is contacted with hydrogen donor and carries out sulfur transfer reaction higher than desulfurization reactor, restores the partial activity of spent catalyst, so that it can continue to participate in desulfurization reaction;At the same time, since the catalyst after sulfur transfer reaction is loaded with part of sulfur and carbon, the desulfurization selectivity increases, and the octane loss of desulfurization refined product is less.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of petrochemical industry, and particularly relates to a method and system for treating sulfur-containing hydrocarbon oil. BACKGROUND

[0002] With the increasingly serious environmental problems, the limitation on the sulfur content in fuel is also becoming more and more stringent. For example, the national standard VI A (GB-17930-2016) implemented in China on January 1, 2019 stipulates that the sulfur content in gasoline is not more than 10 μg / g, and the volume fraction of olefins is not more than 18%; the national standard VI B (GB-17930-2016) implemented in China on January 1, 2023 stipulates that the sulfur content in gasoline is not more than 10 μg / g, and the volume fraction of olefins is not more than 15%.

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

[0004] However, there is still a problem of high loss of octane value of hydrocarbon oil in the prior art when catalytic cracking gasoline is desulfurized. SUMMARY

[0005] The purpose of the present application is to further reduce the loss of octane value of hydrocarbon oil in the desulfurization reaction.

[0006] To achieve the above purpose, the first aspect of the present application provides a method for treating sulfur-containing hydrocarbon oil, which comprises 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 a hydrogen condition to obtain desulfurized hydrocarbon oil and spent catalyst;

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

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

[0010] Preferably, in the desulfurization reactor, the conditions of the desulfurization reaction 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, and 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 30-100%, preferably 50-100%, and further preferably 70-100%.

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

[0014] Optionally, the mass fraction of sulfur in the spent catalyst is 1-12%, preferably 3-9%, based on the weight of the spent catalyst. The catalyst includes a carrier and a metal active component supported on the carrier, the carrier contains 15-85 wt% of zinc oxide, 10-80 wt% of aluminum oxide, and 5-75 wt% of silica, based on the total weight of the carrier; the weight of the metal active component accounts for 2-30% of the total weight of the catalyst; and 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 a narrow fraction of gasoline; and the sulfur content in the sulfur-containing hydrocarbon oil is 30-5000 μg / g, preferably 50-3000 μg / g.

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

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

[0018] Optionally, the sulfur-transferred catalyst is subjected to oxygen-containing coking in an oxygen-containing gas atmosphere, and the oxygen-containing coking conditions 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 mixture of oxygen and nitrogen, and a mixture of air and nitrogen; the volume fraction of oxygen in the oxygen-containing gas is 5-50 vol%; and the gas replacement is performed in a hydrogen-containing gas atmosphere.

[0019] The second aspect of the present application provides a system for processing sulfur-containing hydrocarbon oil, which comprises a desulfurization reactor, a lock hopper, and a regenerator; the desulfurization reactor is connected with a reactor receiver and a reactor feed tank; the regenerator is connected with a regenerator feed tank and a regenerator receiver;

[0020] The bottom of the desulfurization reactor is provided with a material inlet for premixed material, the lower part is provided with a catalyst inlet, the upper part is provided with a hydrogen-containing gas inlet and a spent catalyst outlet, and the top is provided with an oil gas outlet;

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

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

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

[0024] The spent catalyst outlet of the desulfurization reactor is in communication with the spent catalyst inlet of the reactor receiver, and the hydrogen-containing gas outlet of the reactor receiver is in communication with the hydrogen-containing gas inlet of the desulfurization reactor;

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

[0026] The first material outlet of the closed hopper can be switchingly communicated with the catalyst inlet of the regenerator feed tank, the catalyst outlet of the regenerator feed tank is communicated with the catalyst inlet of the regenerator, the regenerated catalyst outlet of the regenerator is communicated with the regenerated catalyst inlet of the regenerator receiver, the regenerated catalyst outlet of the regenerator receiver is communicated with the second material inlet of the closed hopper, and the second material outlet of the closed hopper is communicated with the catalyst inlet of the reactor feed tank.

[0027] By the technical scheme, the deep conversion and transfer of sulfides on the catalyst can be realized, the partial activity of the spent catalyst is recovered, and the spent catalyst can continue to participate in the desulfurization reaction; at the same time, the desulfurization selectivity of the catalyst after the sulfur transfer reaction is increased, and the octane loss of the desulfurization refined product is less.

[0028] Other features and advantages of the present application will be described in detail in the following specific embodiments. BRIEF DESCRIPTION OF DRAWINGS

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

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

[0031] EXPLANATION 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 closed 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 application are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0039] The first aspect of the present application provides a method for treating sulfur-containing hydrocarbon oil, which comprises 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 a hydrogen condition to obtain a desulfurized hydrocarbon oil and a spent catalyst;

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

[0042] The present application can achieve deep conversion and transfer of sulfides on the catalyst, release metal active centers, and restore part of the activity of the spent catalyst by controlling the hydrogen partial pressure of the sulfur transfer reaction of the spent catalyst with the hydrogen donor to be higher than that of the desulfurization reactor, so that the spent catalyst can continue to participate in the desulfurization reaction. Due to the loading of part of the sulfur and carbon on the catalyst after the sulfur transfer reaction, the desulfurization selectivity is increased, and the octane loss of the desulfurization refined product is less. In addition, the catalyst with part of the activity restored continues to return to the desulfurization reactor for reaction, which can reduce the frequency of catalyst oxidation regeneration, reduce catalyst regeneration loss, and prolong the service life of the catalyst.

[0043] In the present application, "at least one stream" means part or all. For example, in one specific embodiment of the present application, all of the sulfur-transferred catalyst is returned to the desulfurization reactor of step (1) for selective desulfurization reaction. In another specific embodiment of the present application, part of the sulfur-transferred catalyst is returned to the desulfurization reactor, and the remaining sulfur-transferred catalyst is subjected to oxygen-containing coke burning regeneration and reduction before being returned to the desulfurization reactor. The way in which the sulfur-transferred catalyst is returned to the desulfurization reactor depends on the sulfur content and carbon content in the sulfur-transferred catalyst.

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

[0045] The conditions of the desulfurization reaction in the desulfurization reactor include: a temperature of 350-500 ℃, 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, and a weight hourly space velocity (WHSV) of the sulfur-containing hydrocarbon oil of 1-10 h -1The sulfur content in the refined product is reduced to less than 10 ppm, and the loss of olefins is less after the sulfur-containing hydrocarbon oil is reacted under the above desulfurization conditions.

[0046] Preferably, the hydrogen gas has a hydrogen volume fraction of 30-100%, preferably 50-100%, and further preferably 70-100%.

[0047] Preferably, the hydrogen 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 application, the desulfurization reactor can be a fluidized bed, a moving bed, and a fixed bed, and the specific form of the reaction bed is adjusted according to the desulfurization depth and reaction economy.

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

[0050] The mass fraction of sulfur in the spent catalyst is 1-12%, preferably 3-9%, based on the weight of the spent catalyst. The catalyst includes a carrier and a metal active component loaded on the carrier. The carrier contains 15-85 wt% of zinc oxide, 10-80 wt% of aluminum oxide, and 5-75 wt% of silica, based on the total weight of the carrier. 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 application, when the desulfurization reactor is a fluidized bed reactor, the catalyst is preferably microspherical to facilitate catalyst fluidization. For example, in one specific embodiment of the present application, the catalyst is microspherical, and the average particle size of the catalyst is 20-200 μm, preferably 40-100 μm.

[0052] 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 in the sulfur-containing hydrocarbon oil is 30-5000 μg / g, preferably 50-3000 μg / g.

[0053] The mass fraction of sulfur in the sulfur-transferred catalyst is 1-12%, preferably 3-9%, based on the weight of the sulfur-transferred catalyst.

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

[0055] The sulfur-transferred catalyst is subjected to oxygen-containing coking in an oxygen-containing gas atmosphere, and the oxygen-containing coking conditions 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 mixture of oxygen and nitrogen, and a mixture of air and nitrogen; the volume fraction of oxygen in the oxygen-containing gas is 5-50 vol%; and the gas replacement is performed in a hydrogen-containing gas atmosphere.

[0056] The second aspect of the present application provides a system for treating sulfur-containing hydrocarbon oil, Figure 1 The device of the system for treating sulfur-containing hydrocarbon oil in one embodiment of the present application is schematically shown. It should be noted that, Figure 1 The device shown is only an example of the device that can be used in the method of one embodiment of the present application, and does not mean that the method of the embodiment of the present application cannot use other devices or equipment.

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

[0058] The desulfurization reactor 2 is provided with a material inlet for premixed material at the bottom, a catalyst inlet at the lower part, a hydrogen-containing gas inlet and a spent catalyst outlet at the upper part, and an oil gas outlet at the top;

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

[0060] The lock 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 spent catalyst outlet of the desulfurization reactor 2 is in communication with the spent catalyst inlet of the reactor receiver 5, and the hydrogen-containing gas outlet of the reactor receiver 5 is in communication with the hydrogen-containing gas inlet of the desulfurization reactor 2;

[0063] The first material inlet of the closed hopper 9 is communicated with the catalyst outlet of the reactor receiver 5, the first material outlet of the closed hopper 9 is switchably communicated with the catalyst inlet of the reactor feed tank 21, the catalyst outlet of the reactor feed tank 21 is communicated with the catalyst inlet of the desulfurization reactor 2;

[0064] The first material outlet of the closed hopper 9 is also switchably communicated with the catalyst inlet of the regenerator feed tank 12, the catalyst outlet of the regenerator feed tank 12 is communicated with the catalyst inlet of the regenerator 15, the regenerated catalyst outlet of the regenerator 15 is communicated with the regenerated catalyst inlet of the regenerator receiver 18, the regenerated catalyst outlet of the regenerator receiver 18 is communicated with the second material inlet of the closed hopper 9, and the second material outlet of the closed hopper 9 is communicated with the catalyst inlet of the reactor feed tank 21.

[0065] In one specific embodiment of the present application, the preheated sulfur-containing hydrocarbon oil feedstock and hydrogen enter from the bottom of the desulfurization reactor 2 through pipeline 1, and are in contact with the catalyst in the desulfurization reactor 2 from bottom to top to perform selective desulfurization reaction, and the reacted oil gas and sulfur-laden catalyst enter the oil-catalyst separation section at the top of the desulfurization reactor to perform oil-catalyst separation, and the desulfurized oil gas mixture is sent to the subsequent stabilization system through pipeline 3. The sulfur-laden catalyst is sent to the reactor receiver 5 through pipeline 4, and is in contact with the hydrogen donor sent to the reactor receiver 5 through pipeline 6 to perform sulfur transfer reaction, and the reacted gas is sent to the desulfurization reactor 2 through pipeline 7. Part of the catalyst after sulfur transfer reaction enters the closed hopper through pipeline 8, is transported to the reactor feed tank 21 through pipeline 20 after pressure reduction, and then is returned to the desulfurization reactor 2 through pipeline 22.

[0066] The catalyst after sulfur transfer reaction can also enter the closed hopper 9 through pipeline 8, and the hydrogen atmosphere of the spent catalyst is changed to a nitrogen atmosphere, and then is sent to the regenerator feed tank 12 through pipeline 11, and then is sent to the regenerator 15 through pipeline 13, and is in contact with the oxygen-containing gas coming from pipeline 14 to perform oxygen-containing coking to burn off the sulfur and carbon loaded on the catalyst, and the regenerated flue gas is sent to a sulfur production unit or a flue gas treatment unit through pipeline 16. The coked catalyst enters the regenerator receiver 18 through pipeline 17, and then enters the closed hopper to perform gas replacement to change 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 is sent to the desulfurization reactor 2 through pipeline 22 to continue to participate in selective desulfurization reaction.

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

[0068] The present application is further illustrated in detail by the following examples. The raw materials used in the examples can be obtained by commercial channels. Among them, the catalytic cracking gasoline raw material used in the examples and comparative examples of the present application comes from SINOPEC Cangzhou Branch Company, and its properties are shown in Table 1.

[0069] Table 1 Properties of catalytic cracking gasoline raw material

[0070] Feed type Cat. cracked gasoline Sulfur content, ppmw 992 n-alkanes, m% 5.67 iso-alkanes, m% 37.06 olefins, m% 13.97 naphthenes, m% 7.46 aromatics, m% 34.91 RON 91.8

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

[0072] Example 1

[0073] This example prepares a sulfur-containing catalyst with low sulfur content and partial activity, which is used to simulate the catalyst after sulfur transfer, and specifically includes 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℃, the pressure is 1.5 MPa, the time is 1 h, and the volume ratio of hydrogen to catalyst is 900;

[0075] (2) The reduced FCAS catalyst and the pre-sulfur reagent are subjected to desulfurization reaction with dimethyl disulfide (DMDS) and cyclohexane with a sulfur content of 3wt% as the pre-sulfur reagent. The temperature during the desulfurization reaction is 400℃, the pressure is 1.5 MPa, the volume ratio of hydrogen to pre-sulfur reagent is 1600, the reaction is stopped after 32 min of pre-sulfur reagent feeding, then hydrogen stripping is carried out under normal pressure for 30 min and nitrogen blowing is carried out under normal pressure for 15 min in sequence; after cooling to room temperature, the catalyst is unloaded for standby, and is marked as FCAS-S1. The properties of catalyst FCAS-S1 are shown in Table 2.

[0076] Example 2

[0077] This example prepares a sulfur-containing catalyst with high sulfur content and partial activity, which is used to simulate the catalyst after sulfur transfer, and specifically includes 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℃, the pressure is 1.5 MPa, the time is 1 h, and the volume ratio of hydrogen to catalyst is 900;

[0079] (2) The reduced FCAS catalyst and the pre-sulfur reagent were subjected to desulfurization reaction with dimethyl disulfide (DMDS) and cyclohexane as the pre-sulfur reagent containing 3wt% sulfur, the temperature of the desulfurization reaction was 400°C, the pressure was 1.5 MPa, the volume ratio of hydrogen to the pre-sulfur reagent was 1600, the pre-sulfur reagent feeding was stopped after 64 min of reaction, then the catalyst was stripped with hydrogen for 30 min under normal pressure and purged with nitrogen for 15 min under normal pressure in sequence; after cooling to room temperature, the catalyst was unloaded for standby, and was 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] 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 example, the gasoline feedstock was subjected to desulfurization treatment under the condition of hydrogen, which specifically included the following steps:

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

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

[0086] (3) After the desulfurization reaction was completed, the catalyst gasoline feedstock was stopped, the temperature, pressure and hydrogen feed amount in the reactor were maintained unchanged, and the time was 1 h, then the gasoline feedstock was resumed under the condition that other conditions were unchanged, and the reaction was performed for 6 h, and sampling analysis was performed every 2 hours. The properties of the reaction product are shown in Table 3.

[0087] Example 4

[0088] In this example, the gasoline feedstock was subjected to desulfurization treatment under the condition of hydrogen, which specifically included the following steps:

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

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

[0091] (3) After the desulfurization reaction was completed, the feed of catalytic gasoline was stopped, the temperature, the pressure and the hydrogen feed amount in the reactor were maintained, and the time was 1 h. Then, the feed of the gasoline feedstock was resumed under the condition that other conditions were unchanged, and the reaction was performed for 6 h. The sampling analysis was performed every 2 hours. The properties of the reaction products were shown in Table 3.

[0092] Comparative Example 1

[0093] In this comparative example, the gasoline feedstock was subjected to desulfurization treatment under the condition of hydrogen, and the specific steps included the following:

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

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

[0096] (3) After the desulfurization reaction was completed, the feed of catalytic gasoline was stopped, the temperature, the pressure and the hydrogen feed amount in the reactor were maintained, and the time was 1 h. Then, the feed of the gasoline feedstock was resumed under the condition that other conditions were unchanged, and the reaction was performed for 6 h. The sampling analysis was performed every 2 hours. The properties of the reaction products were shown in Table 3.

[0097] Comparative Example 2

[0098] In this comparative example, the gasoline feedstock was subjected to desulfurization treatment under the condition of hydrogen, and the specific steps included the following:

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

[0100] (2) the gasoline feedstock and hydrogen are contacted with the reduced FCAS-S2 catalyst to perform a desulfurization reaction, and the reaction conditions include: a temperature of 400℃, a pressure of 1.38 MPa, a hydrogen-oil molar ratio of 0.35, and a weight hourly space velocity of the gasoline feedstock of 5h -1 Sampling analysis is performed every 2 hours, and the reaction time is 12 hours. The properties of the reaction products are shown in Table 3.

[0101] Table 3 Properties of the reaction products

[0102]

[0103] As shown in Table 3, after the spent catalyst is contacted with hydrogen to perform a sulfur transfer reaction, the sulfides on the desulfurization catalyst are deeply converted and transferred, the desulfurization selectivity of the catalyst with restored partial activity is better, and the octane number loss of the refined gasoline prepared by the method for treating sulfur-containing hydrocarbon oil is less.

[0104] The above describes the preferred embodiments of the present application in detail, but the present application is not limited to the specific details in the above embodiments, and within the technical concept range of the present application, the technical solutions of the present application can be variously and simply modified, and these simple modifications all belong to the protection range of the present application.

[0105] In addition, it should be noted that each specific technical feature described in the above specific embodiments can be combined in any appropriate manner without contradiction. In order to avoid unnecessary repetition, the present application will not further describe various possible combinations.

[0106] In addition, various different embodiments of the present application can also be combined in any manner, as long as it does not deviate from the technical concept of the present application, and it should also be considered as disclosed content of the present application.

Claims

1. A method for processing sulfur-containing hydrocarbon oils, characterized in that, The method includes the following steps: (1) Sulfur-containing hydrocarbon oil is contacted with a catalyst in a desulfurization reactor and subjected to selective desulfurization under hydrogen conditions to obtain desulfurized hydrocarbon oil and a catalyst to be produced; the catalyst includes a support and a metal active component supported on the support, and based on the total weight of the support, the support contains 15-85 wt% zinc oxide, 10-80 wt% alumina and 5-75 wt% silica; the metal active component is selected from one or more of cobalt, nickel, iron, manganese, copper, molybdenum, tungsten, silver, tin and vanadium; (2) The catalyst to be produced is directly contacted with a hydrogen donor to carry out a sulfur transfer reaction to obtain a sulfur-transferred catalyst. Then, at least one of the sulfur-transferred catalysts is returned 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 0.1~3 MPa higher than the hydrogen partial pressure of the desulfurization reaction. Based on the weight of the sulfur-transferred catalyst, the mass fraction of sulfur in the sulfur-transferred catalyst is 1~12%. The conditions for the sulfur transfer reaction include: a temperature of 350~550 ℃ and a hydrogen partial pressure of 1.0~6 MPa during the sulfur transfer. The contact time between the catalyst to be generated and the hydrogen donor is 0.1~20 h; The hydrogen donor is selected from one or more of hydrogen and dry gas; the volume fraction of hydrogen in the hydrogen donor is 70-100%.

2. The method according to claim 1, wherein, The desulfurization reaction is carried out in a hydrogen-containing gas atmosphere. The conditions for the desulfurization reaction include: a temperature of 300~550 °C, a pressure of 0.5~5 MPa, a molar ratio of hydrogen to sulfur-containing hydrocarbon oil of 0.1~5.0, and a weight hourly space velocity (WHSV) of 0.1~100 h⁻¹ for the sulfur-containing hydrocarbon oil. -1 ; The volume fraction of hydrogen in the hydrogen-containing gas is 30-100%. 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 2, wherein, 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, and a weight hourly space velocity (WHSV) of 1–10 h⁻¹ for the sulfur-containing hydrocarbon oil. -1 ; The volume fraction of hydrogen in the hydrogen-containing gas is 50-100%.

4. The method according to claim 3, wherein, The volume fraction of hydrogen in the hydrogen-containing gas is 70-100%.

5. The method according to claim 1, wherein, The conditions for the sulfur transfer reaction include: the hydrogen partial pressure during sulfur transfer is 1.5~4.5 MPa; The contact time between the catalyst to be generated and the hydrogen donor is 0.5~10 h; The hydrogen donor contains 80-100% hydrogen by volume.

6. The method according to claim 1, wherein, Based on the weight of the catalyst to be generated, the mass fraction of sulfur in the catalyst is 1-12%.

7. The method according to claim 6, wherein, Based on the weight of the catalyst to be generated, the mass fraction of sulfur in the catalyst is 3-9%.

8. The method according to claim 1, wherein, The weight of the metal active component accounts for 2 to 30% of the total weight of the catalyst.

9. The method according to claim 1, wherein, The sulfur-containing hydrocarbon oil is selected from one or more of liquefied petroleum gas, gasoline, diesel, and narrow fractions of gasoline; The sulfur content in the sulfur-containing hydrocarbon oil is 30~5000 μg / g.

10. The method according to claim 9, wherein, The sulfur content in the sulfur-containing hydrocarbon oil is 50~3000 μg / g.

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

12. The method according to claim 1, wherein, The method further includes: regenerating the other catalyst after sulfur transfer by oxygen-containing coking and gas replacement, and then returning it to the desulfurization reactor in step (1) to participate in the selective desulfurization reaction.

13. The method according to claim 12, wherein, The catalyst after sulfur transfer is subjected to oxygen-containing coking in an oxygen-containing gas atmosphere. The conditions for oxygen-containing coking include: a temperature of 300~800 °C; a pressure of 0.1~3.0 MPa; the oxygen-containing gas is one of air, a mixture of oxygen and nitrogen, or a mixture of air and nitrogen; and the volume fraction of oxygen in the oxygen-containing gas is 5~50% by volume. The gas replacement is carried out in a gas atmosphere containing hydrogen.

14. The method according to claim 13, wherein, The conditions for oxygen-containing coking include: a temperature of 350~600 ℃ and a pressure of 0.1~1.0 MPa.

15. A system for processing sulfur-containing hydrocarbon oils, characterized in that, The system includes a desulfurization reactor (2), a closed 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 at the bottom for premixed materials to enter, a catalyst inlet at the bottom, a hydrogen gas inlet and a catalyst outlet at the top, and an oil and gas outlet at the top. The reactor receiver (5) is provided with a catalyst inlet, a catalyst outlet and a hydrogen-containing gas outlet; The locked 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) has a flue gas outlet at the top, a catalyst inlet at the top, an oxygen-containing gas inlet at the bottom, and a regenerated catalyst outlet at the bottom. The outlet of the desulfurization reactor (2) is connected to the inlet of the desulfurization reactor receiver (5), and the outlet of the reactor receiver (5) is connected to the inlet of the desulfurization reactor (2). The first material inlet of the closed hopper (9) is connected to the catalyst outlet of the reactor receiver (5), and the first material outlet of the closed 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 closed hopper (9) can also be switched to be 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 regeneration catalyst outlet of the regenerator (15) is connected to the regeneration catalyst inlet of the regenerator receiver (18), the regeneration catalyst outlet of the regenerator receiver (18) is connected to the second material inlet of the closed hopper (9), and the second material outlet of the closed hopper (9) is connected to the catalyst inlet of the reactor feed tank (21).

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