CN116408094A - Adsorption desulfurization catalyst and preparation method and application thereof - Google Patents
Adsorption desulfurization catalyst and preparation method and application thereof Download PDFInfo
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- CN116408094A CN116408094A CN202111642357.6A CN202111642357A CN116408094A CN 116408094 A CN116408094 A CN 116408094A CN 202111642357 A CN202111642357 A CN 202111642357A CN 116408094 A CN116408094 A CN 116408094A
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 186
- 230000023556 desulfurization Effects 0.000 title claims abstract description 186
- 239000003054 catalyst Substances 0.000 title claims abstract description 170
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
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- 238000011282 treatment Methods 0.000 claims abstract description 91
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 58
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- 230000003009 desulfurizing effect Effects 0.000 claims description 24
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- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 claims description 8
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims description 8
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- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 3
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- 229910052984 zinc sulfide Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/825—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with gallium, indium or thallium
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8953—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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Abstract
The invention provides an adsorption desulfurization catalyst and a preparation method and application thereof, wherein the adsorption desulfurization catalyst comprises a carrier, a first metal component and a second metal component, the carrier is compounded by raw materials comprising small-pore pseudo-boehmite, zirconia and modified large-pore pseudo-boehmite, wherein the pore volume of the small-pore pseudo-boehmite is not more than 0.6mL/g, the pore volume of the modified large-pore pseudo-boehmite is not less than 1.5mL/g, and the modified large-pore pseudo-boehmite is obtained by modifying the pseudo-boehmite raw materials by water vapor at 550-650 ℃; the first metal component comprises zinc and nickel and the second metal component comprises silver and/or gallium. The adsorption desulfurization catalyst has the advantages of high strength, good stability, high desulfurization efficiency and the like, and is particularly suitable for desulfurization treatment of heavy oil.
Description
Technical Field
The invention relates to an adsorption desulfurization catalyst, a preparation method and application thereof, and belongs to the field of sulfur-containing oil product desulfurization.
Background
With the increasing environmental protection requirements, low-sulfur clean oil products are becoming a focus of attention, taking marine fuel oil as an example, and pollutants such as sulfides are generated in the combustion process, and in order to control pollution, international Maritime Organization (IMO) announces that new regulations for sulfur emission limitation are enforced from 1 month 1 day 2020, so that it is highly demanded to reduce the sulfur content in the fuel oil products and develop low-sulfur clean oil products. In addition, the desulfurization treatment is carried out on heavy oil such as residual oil, and the heavy oil is converted into low-sulfur clean oil, so that the low-sulfur clean oil is used as a blending component of oil products such as fuel oil, and is an important way for realizing the efficient utilization of the heavy oil.
Hydrodesulfurization and adsorption desulfurization are common means for achieving the purposes of oil product desulfurization and the like, for example, patent document CN101439288A discloses a combined alumina-based selective hydrodesulfurization catalyst and a preparation method thereof, which are used for selective hydrodesulfurization of gasoline; CN112745905a discloses a method for selectively removing mercaptans, which comprises the steps of carrying out hydrodesulphurization on oil products by adopting a first catalyst, wherein the first catalyst comprises a supported zinc-containing catalyst, a supported sulfidic metal hydrogenation catalyst and/or a supported nickel-based catalyst; CN101766984a discloses a phosphorus-containing desulfurization adsorbent for desulfurization treatment of cracked-gasoline and diesel fuel; CN104056632a discloses a fuel oil deep adsorption desulfurization catalyst, a preparation method and application thereof, and has better desulfurization effect on catalytically cracked gasoline; CN101327419a discloses a method for preparing adsorption desulfurizing agent for catalytic cracking gasoline, the prepared adsorption desulfurizing agent is used for desulfurizing catalytic cracking gasoline; CN105688801a discloses a gasoline adsorption desulfurizing agent and a preparation method thereof, which are used for adsorption desulfurizing of gasoline, and can reduce octane number loss while improving desulfurizing rate; CN102463100a discloses an adsorption desulfurization adsorbent and a preparation method thereof, which are used for desulfurizing the cracked gasoline and diesel, improving the octane number of the cracked gasoline and improving the low-temperature flow property of the diesel; CN104511282a discloses a desulfurization catalyst for desulfurization treatment of cracked-gasoline and diesel fuel.
The desulfurizing agent is an important factor affecting the desulfurizing effect, and optimizing the structure and performance of the desulfurizing agent is an effective means for improving the desulfurizing effect, while researches and reports on desulfurizing agents such as a hydrodesulfurizing agent, an adsorption desulfurizing agent and the like are currently available, on the one hand, the strength, desulfurizing activity, stability and other performances of the desulfurizing agent at the present stage and the desulfurizing efficiency are required to be further improved, on the other hand, the desulfurizing agent at the present stage is mostly used for desulfurizing treatment of light oil such as gasoline, kerosene, diesel oil and the like, and the desulfurizing effect on heavy oil is limited, and on the other hand, development of an effective desulfurizing agent suitable for desulfurizing heavy oil is required to be urgently developed.
Disclosure of Invention
The invention provides an adsorption desulfurization catalyst, a preparation method and application thereof, which have the advantages of high catalyst strength, good stability, high desulfurization efficiency and the like, are particularly suitable for desulfurization treatment of heavy oil, and effectively overcome the defects existing in the prior art.
In one aspect of the invention, an adsorption desulfurization catalyst is provided, comprising a carrier, a first metal component and a second metal component, wherein the carrier is compounded by raw materials comprising small-pore pseudo-boehmite, zirconia and modified large-pore pseudo-boehmite, wherein the pore volume of the small-pore pseudo-boehmite is not more than 0.6mL/g, the pore volume of the modified large-pore pseudo-boehmite is not less than 1.5mL/g, and the modified large-pore pseudo-boehmite is obtained by modifying the pseudo-boehmite raw materials by water vapor at 550-650 ℃; the first metal component comprises zinc and nickel and the second metal component comprises silver and/or gallium.
According to an embodiment of the present invention, the oxide of the first metal component and the oxide of the second metal component satisfy the following conditions: the mass of the first metal component accounts for 55% -85% of the sum of the mass of the carrier and the mass of the first metal component; and/or the mass of nickel in the first metal component accounts for 4% -15% of the sum of the mass of the carrier and the mass of the first metal component; and/or, the mass of the second metal component accounts for 0.1-0.8% of the sum of the mass of the carrier and the mass of the first metal component.
According to one embodiment of the invention, the pore volume of the small pore pseudo-boehmite is 0.4 mL/g-0.6 mL/g, and the specific surface area is 180m 2 /g～260m 2 G, peptization index greater than 95%; and/or the pore volume of the modified macroporous pseudo-boehmite is 1.5 mL/g-2.2 mL/g; and/or the mass ratio of the small-pore pseudo-boehmite to the modified large-pore pseudo-boehmite is 1 (1-3); and/or the ratio of the mass of the zirconia to the sum of the mass of the modified macroporous pseudo-boehmite and the mass of the small pore pseudo-boehmite is (0.05-0.25): 1.
According to one embodiment of the invention, the pore volume of the pseudo-boehmite raw material is 1.0 mL/g-1.2 mL/g, and the specific surface area is 280-360 m 2 /g; and/or the modified macroporous pseudo-boehmite is prepared according to the process comprising the following steps: the pseudo-boehmite raw material is contacted and modified with steam at 550-650 ℃ to prepare the modified macroporous pseudo-boehmite; wherein the modification time is 2-5 h, and the mass airspeed of the water vapor is 0.5-1 h -1 。
In still another aspect of the present invention, there is provided a method for preparing the adsorption desulfurization catalyst described above, comprising: (I) Adding inorganic acid and water into a mixture containing modified macroporous pseudo-boehmite, small pore pseudo-boehmite, zirconia, a binder, zinc oxide and a nickel compound, and then sequentially forming, drying and roasting to obtain a first intermediate; (II) impregnating the first intermediate with a first impregnating solution containing a compound of a second metal component, and drying and roasting the impregnated product to obtain a second intermediate; (III) modifying the second intermediate by adopting diamine hydrogen phosphate, and drying and roasting to obtain a catalyst precursor; (IV) subjecting the catalyst precursor to a first reduction treatment in an atmosphere containing hydrogen to obtain the adsorption desulfurization catalyst.
According to an embodiment of the present invention, the binder includes at least one of methylcellulose, sodium carboxymethyl starch, sesbania powder; and/or the mass of the binder accounts for 3-8% of the sum of the mass of the modified macroporous pseudo-boehmite, the small pore pseudo-boehmite, the zirconia, the zinc oxide and the nickel compound in terms of nickel oxide; and/or, the zinc oxide comprises nano zinc oxide powder with the particle size not more than 100 nm; and/or the ratio of the mass of the inorganic acid to the sum of the mass of the modified macroporous pseudo-boehmite and the mass of the small pore pseudo-boehmite is (0.05-0.5): 1; and/or, the roasting conditions in the step (I) are as follows: the roasting temperature is 400-700 ℃ and the roasting time is 1-10 h; and/or the roasting conditions in step (II) are: the roasting temperature is 400-700 ℃ and the roasting time is 1-10 h; and/or, the roasting conditions in the step (III) are: the roasting temperature is 400-700 ℃ and the roasting time is 1-10 h; and/or, in the step (IV), the volume space velocity of the hydrogen is 500h -1 ～4000h -1 The temperature of the first reduction treatment process is 300-550 ℃, the pressure of the first reduction treatment process is 0-3 MPa, and the time of the first reduction treatment process is 1-6 h.
In still another aspect, the present invention provides a method for adsorption desulfurization of sulfur-containing oils, comprising: desulfurizing the sulfur-containing oil product by adopting the adsorption desulfurization catalyst; or, the adsorption desulfurization catalyst is prepared according to the preparation method, and sulfur-containing oil products are subjected to desulfurization treatment by adopting the prepared adsorption desulfurization catalyst.
According to one embodiment of the invention, the temperature of the desulfurization treatment is 300-550 ℃; and/or the pressure of the desulfurization treatment is 0.5 MPa-10 MPa; and/or the feeding airspeed of the sulfur-containing oil product is 0.1h -1 ～1.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the And/or the desulfurization treatment is carried out under the atmosphere of hydrogen, and the volume ratio of the hydrogen to the sulfur-containing oil product is (100-800): 1.
According to an embodiment of the present invention, further comprising: after the desulfurization treatment, respectively obtaining a desulfurized oil product and a spent catalyst; regenerating the spent catalyst to obtain a regenerated catalyst; returning the regenerated catalyst to the desulfurization treatment; wherein the regeneration process includes: oxidizing and regenerating the spent catalyst in the presence of oxygen-containing gas to obtain a regenerated catalyst precursor; wherein the volume fraction of oxygen in the oxygen-containing gas is 1-10%, and the volume airspeed of the oxygen-containing gas is 1000h -1 ～3000h -1 The temperature of the oxidation regeneration is 300-500 ℃, the pressure of the oxidation regeneration is 0-0.5 MPa, and the time of the oxidation regeneration is 20-100 h; subjecting the regenerated catalyst precursor to a second reduction treatment in an atmosphere containing hydrogen to obtain the regenerated catalyst; wherein the volume space velocity of the hydrogen is 500h -1 ～4000h -1 The temperature of the second reduction treatment is 300-500 ℃, the pressure of the second reduction treatment is 0-3 MPa, and the time of the second reduction treatment is 1-6 h.
According to an embodiment of the present invention, the sulfur component in the sulfur-containing oil product includes at least one of carbonyl sulfide, carbon disulfide, mercaptan, hydrogen sulfide, and thiophene compounds, and the thiophene compounds include at least one of benzothiophene, dibenzothiophene, benzonaphthothiophene, alkylbenzothiophene, alkyldibenzothiophene, and alkylbenzonaphthothiophene; and/or the sulfur-containing oil product comprises a heavy oil, wherein the heavy oil comprises at least one of wax oil, atmospheric residuum and vacuum residuum.
The adsorption desulfurization catalyst provided by the invention has the advantages of good mechanical property, long service life, good desulfurization activity and the like, can obviously improve the desulfurization rate, has a wide application range, is especially suitable for desulfurization treatment of heavy oil, effectively removes sulfides such as thiophenes and the like, realizes deep desulfurization of sulfur-containing oil products such as heavy oil and the like, improves the quality of the desulfurized oil products, and can be used as a clean gasoline blending component or other purposes. Researches show that the adsorption desulfurization catalyst has the fracture strength of more than 35N, good mechanical property and structural stability, meets the requirements of processes such as a moving bed and the like, and has wide application range; the desulfurization rate of heavy oil is up to more than 85%, and after the adsorption desulfurization catalyst is regenerated for 1-35 times or more, the catalyst can still achieve good desulfurization rate, shows good activity stability and has long service life. In addition, the adsorption desulfurization catalyst has the advantages of low cost, simple preparation process, simple desulfurization process, mild condition, high efficiency and the like, and has important significance for practical industrial application.
Drawings
FIG. 1 is an XRD spectrum (abscissa 2. Theta. Angle (Theta.) and ordinate peak intensity) of a catalyst precursor during the preparation of fresh adsorption desulfurization catalysts S1, S2, D4, and D5;
fig. 2 is an XRD spectrum of a regenerated catalyst precursor in the regeneration process of a spent catalyst produced after desulfurization treatment of S1, S2, D4, D5.
Detailed Description
The present invention will be described in further detail below for the purpose of better understanding of the aspects of the present invention by those skilled in the art. The following detailed description is merely illustrative of the principles and features of the present invention, and examples are set forth for the purpose of illustration only and are not intended to limit the scope of the invention. All other embodiments, which can be made by those skilled in the art based on the examples of the invention without making any inventive effort, are intended to be within the scope of the invention. In the description of the present invention, the terms "first", "second", etc. are used for descriptive purposes only, for example to distinguish between components, in order to more clearly illustrate/explain the technical solution, but are not to be understood as indicating or implying a quantity of technical features indicated or an order of substantial significance, etc.
The adsorption desulfurization catalyst comprises a carrier, a first metal component and a second metal component, wherein the carrier is compounded by raw materials comprising small-pore pseudo-boehmite, zirconia and modified macroporous pseudo-boehmite, the pore volume of the small-pore pseudo-boehmite is not more than 0.6mL/g, the pore volume of the modified macroporous pseudo-boehmite is not less than 1.5mL/g, and the modified macroporous pseudo-boehmite is obtained by modifying the pseudo-boehmite raw materials by steam at 550-650 ℃; the first metal component comprises zinc and nickel and the second metal component comprises silver and/or gallium.
According to research and analysis, the inventor considers that under the adsorption desulfurization catalyst composition system, the first metal component is used as a main active component for sulfur adsorption/absorption, in the desulfurization treatment process of an oil product, sulfur element in the oil product is grabbed by nickel component in the catalyst to form nickel sulfide, the nickel sulfide acts with zinc component to form zinc sulfide, the second metal component is used as active metal, and the sulfur transfer and other processes can be promoted, so that sulfur component in the oil product is adsorbed in the adsorption desulfurization catalyst in the form of metal sulfide such as zinc sulfide through multi-step synergistic reaction, and the desulfurization purpose is achieved.
In general, when the adsorption desulfurization catalyst using a conventional alumina-based carrier and using zinc oxide and nickel as main adsorption active components is used for adsorption desulfurization of heavy oil, there are at least the following problems: firstly, the strength of the catalyst is poor due to the self-properties of ZnO as a main adsorption component, and secondly, active components (such as ZnO) and carrier Al are adsorbed 2 O 3 The catalyst has strong interaction, zinc-aluminum spinel is easy to form in the cycle processes of adsorption desulfurization reaction, catalyst regeneration and the like, so that part of adsorption active components such as ZnO lose the desulfurization and sulfur storage capacity, the catalyst is gradually deactivated, the strength of the catalyst is reduced, the desulfurization performance, the service life and other qualities of the catalyst are influenced, and sulfide in heavy oil is mainly benzothiophene, dibenzothiophene and benzo And the asphaltene and colloid particles in heavy oil teach that the catalyst pore canal is easy to be blocked, so that the catalyst is deactivated.
According to the research of the invention, the carrier compounded by the small-pore pseudo-boehmite, the modified large-pore pseudo-boehmite and the zirconia is adopted, and the first metal component and the second metal component are matched to form the adsorption desulfurization catalyst, so that the problems can be effectively solved; the addition of zirconia can improve the dispersity of active components in the catalyst, further weaken the interaction of alumina and zinc oxide, inhibit the generation of zinc-aluminum spinel, thereby ensuring the performances of the catalyst such as strength, desulfurization activity, stability and the like, being beneficial to the cyclic regeneration and use of the catalyst and prolonging the service life.
In the invention, the modified macroporous pseudo-boehmite can be prepared according to the following steps: the pseudo-boehmite raw material is contacted and modified with steam at 550-650 ℃ to prepare modified macroporous pseudo-boehmite; wherein the modification time is 2 h-5 h, such as 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h or the range of any two of them, and the mass airspeed of the water vapor is 0.5-1 h -1 The temperature in the modification process is, for example, 550 ℃, 580 ℃, 600 ℃, 620 ℃, 650 ℃ or a range composed of any two of them. Typically, the pseudo-boehmite material used in the modification process is a macroporous pseudo-boehmite material having a relatively large pore volume, and in some embodiments, the pores of the pseudo-boehmite materialThe volume is 1.0 mL/g-1.2 mL/g, and the specific surface area is 280m 2 /g～360m 2 /g, e.g. 280m 2 /g、290m 2 /g、300m 2 /g、310m 2 /g、320m 2 /g、330m 2 /g、340m 2 /g、350m 2 /g、360m 2 /g or any two thereof.
In some embodiments, the pore volume of the modified macroporous pseudo-boehmite is in the range of 1.5mL/g to 2.2mL/g, e.g., 0.8mL/g, 0.9mL/g, 1mL/g, 1.1mL/g, 1.2mL/g, or any two of these.
To further optimize the catalyst performance, the pore volume of the pore pseudo-boehmite may be 0.4mL/g to 0.6mL/g, for example, 0.4mL/g, 0.5mL/g, 0.6mL/g, etc., and the specific surface area may be 180m 2 /g～260m 2 /g, e.g. 180m 2 /g、190m 2 /g、200m 2 /g、210m 2 /g、220m 2 /g、230m 2 /g、240m 2 /g、250m 2 /g、260m 2 /g or any two thereof, and the peptization index is greater than 95%.
In some embodiments, the mass ratio of small pore pseudo-boehmite to modified large pore pseudo-boehmite may be in the range of 1 (1-3), such as 1:1, 1:1.5, 1:2, 1:2.5, 1:3, or any two of these.
In some embodiments, the ratio of the mass of zirconia to the sum of the mass of modified macroporous pseudo-boehmite and the mass of small pore pseudo-boehmite is (0.05 to 0.25): 1, e.g., a range of 0.05:1, 0.1:1, 0.15:1, 0.2:1, 0.25:1, or any two thereof.
In the above-described adsorptive desulfurization catalyst, the mass percent of the first metal component as the sulfur absorbing unit is generally not less than (i.e., equal to or greater than) the mass percent of the support, and in some preferred embodiments, the mass of the first metal component is in the range of 55% to 85%, such as 55%, 60%, 65%, 70%, 80%, 85%, or any two thereof, of the sum of the mass of the support and the first metal component, and the mass of the support is in the range of 15% to 45%, such as 15%, 20%, 25%, 30%, 35%, 40%, 45%, or any two thereof, of the sum of the mass of the support and the first metal component, based on the oxide of the first metal component.
In general, it is preferable that the mass percentage of zinc in the first metal component is higher than the mass percentage of nickel, based on the oxide of the first metal component. In some embodiments, the mass of nickel in the first metal component is in the range of 4% to 15%, e.g., 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, or any two of these, based on the mass of the first metal component oxide.
In some embodiments, the mass of the second metal component is from 0.1% to 0.8%, such as from 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, or a range of any two of the compositions, calculated as the oxide of the first metal component and the oxide of the second metal component, of the sum of the mass of the support and the mass of the first metal component.
In the adsorption desulfurization catalyst, the first metal component and the second metal component are supported on a carrier, and in general, most of the metal components exist in the form of oxides (such as zinc exists in the form of zinc oxide), wherein at least part of nickel can exist in a reduced state (namely, in the form of a nickel simple substance), and when the adsorption desulfurization catalyst is concretely implemented, the compounds (such as metal oxides and/or metal salts and the like) of the metal components can be adopted, the metal components are supported on the carrier through an impregnation method, and after the supporting of the metal components is completed, the obtained catalyst precursor is subjected to first reduction treatment in an atmosphere containing hydrogen so that the nickel component in the catalyst precursor is at least partially reduced into the nickel simple substance, thereby preparing the adsorption desulfurization catalyst, and improving the desulfurization activity of the adsorption desulfurization catalyst.
The carrier can be specifically formed by compounding raw materials containing modified macroporous pseudo-boehmite, small pore pseudo-boehmite, zirconia and a binder, and the preparation process can comprise the following steps: mixing modified macroporous pseudo-boehmite, small pore pseudo-boehmite, zirconia, a binder, inorganic acid and water, drying and roasting to form the carrier. The metal component may be introduced during the preparation of the support, or may be impregnated after the support is prepared.
In a preferred embodiment of the present invention, the method for preparing the adsorption desulfurization catalyst includes: (I) Adding inorganic acid and water into a mixture containing modified macroporous pseudo-boehmite, small pore pseudo-boehmite, zirconia, a binder, zinc oxide and a nickel compound, and then sequentially forming, drying and roasting to obtain a first intermediate; (II) impregnating the first intermediate with a first impregnating solution containing a compound of a second metal component, and drying and roasting the impregnated product to obtain a second intermediate; (III) modifying the second intermediate by adopting diamine hydrogen phosphate, and drying and roasting to obtain a catalyst precursor; (IV) subjecting the catalyst precursor to a first reduction treatment in an atmosphere containing hydrogen to obtain the adsorption desulfurization catalyst.
In the preparation process, the raw materials (zinc oxide and nickel compounds) of the first metal component and the carrier raw materials (modified macroporous pseudo-boehmite, small pore pseudo-boehmite, zirconia and binder) are mixed and molded, and then the second metal component is impregnated, so that the strength, the desulfurization activity and other performances of the prepared adsorption desulfurization catalyst can be improved. The inventor considers that in the preparation process, after the treatments of drying, roasting and the like in the steps (I) - (II), modified macroporous pseudo-boehmite, small pore pseudo-boehmite and zirconia are compounded to form a carrier, and the binder is gradually volatilized in the roasting process, so that a pore structure is formed in the prepared catalyst, and the nickel compound and the compound of the second metal component are basically converted into metal oxides; after the first reduction treatment in the step (IV), nickel in the catalyst can basically exist in a reduced state, and other metal components (such as zinc and a second metal component) usually still exist in a metal oxide form, so that the adsorption desulfurization catalyst with proper composition and structure can be prepared, is suitable for desulfurization treatment of heavy oil, can show good adsorption desulfurization activity, stability, mechanical property and the like, and improves desulfurization rate and service life.
In addition, according to the study of the invention, the performance such as desulfurization activity of the catalyst can be further improved by modifying the hydrogen diamine phosphate in the step (III), and the reason is presumedIn that, during the diamine hydrogen phosphate modification process, phosphorus therein can interact with alumina to produce AlPO on the alumina surface 4 Improving carrier acidity, enhancing cracking capability of catalyst, improving C-S reactivity in sulfur-containing oil products in desulfurization treatment process, and simultaneously enabling octahedral Ni 2+ And Co 2+ The number of the desulfurization active centers is increased, and more desulfurization active centers are generated on the surface of the carrier, so that the desulfurization activity of the catalyst is further improved.
Specifically, in the above preparation process, the first metal component compound includes zinc oxide and nickel compound, and the second metal component compound includes silver compound and/or gallium compound. In general, the content of each metal component in the prepared adsorption desulfurization catalyst can be regulated by the amount of each metal component compound and other raw materials, and the amount of each raw material is specifically as follows: the mass ratio of the small pore pseudo-boehmite to the modified macroporous pseudo-boehmite is 1, calculated by the oxide of each metal component (for example, nickel compound is calculated by nickel oxide, silver compound is calculated by silver oxide, gallium compound is calculated by gallium oxide), the mass of the first metal component compound accounts for 55% -85% of the sum of the mass of the carrier and the mass of the first metal component compound, the mass of the nickel compound accounts for 4% -15% of the sum of the mass of the carrier and the mass of the first metal component compound, the mass of the second metal component compound accounts for 0.1% -0.8% of the sum of the mass of the carrier and the mass of the first metal component compound: (1-3), wherein the ratio of the mass of zirconia to the sum of the mass of the modified macroporous pseudo-boehmite and the mass of the modified microporous pseudo-boehmite is (0.05-0.25): 1.
In the step (I), the mixture may be a wet mixture, a paste mixture, a dough, a slurry, or the like, and the molding process may be oil-ammonia column molding, oil-water column molding, oil column molding, ball molding, or ball extrusion molding, or the like, preferably ball extrusion molding, wherein the amount of water may be sufficient for molding, for example, ball extrusion molding is not particularly limited. The first intermediate formed by the above-mentioned molding treatment may be spherical and/or toothed, and the particle diameter of the first intermediate is preferably in the range of 1.5mm to 3mm, for example, 1.5mm, 2mm, 2.5mm, 3mm, or any two thereof.
In step (I), the nickel compound may particularly comprise a soluble compound of nickel (e.g. a water-soluble nickel compound), for example comprising a soluble nickel salt, preferably comprising nickel nitrate and/or nickel acetate, which may be in the form of a hydrate without or with water of crystallization, which is not particularly limited in the present invention.
In step (I), the zinc oxide may comprise nano-sized particulate zinc oxide, preferably nano-zinc oxide powder having a particle size of no more than 100 nm. In particular, the purity of the zinc oxide used is greater than 96%.
In the step (I), the binder may include at least one of methylcellulose, sodium carboxymethyl starch, sesbania powder. In addition, the amount of binder can be generally controlled as follows: the mass of the binder accounts for 3% -8%, such as 3%, 4%, 5%, 6%, 7%, 8% or any two of the mass of the sum of the mass of the modified pseudo-boehmite, the small-pore pseudo-boehmite, the zirconia, the zinc oxide and the nickel compound calculated by nickel oxide.
In some embodiments, the ratio of the mass of the inorganic acid to the sum of the mass of the modified macroporous pseudo-boehmite and the mass of the small pore pseudo-boehmite in step (I) is (0.05-0.5): 1, e.g., 0.05:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, or a range of any two of these. The ratio of the mass of the inorganic acid to the sum of the mass of the modified macroporous pseudo-boehmite and the mass of the small pore pseudo-boehmite is calculated by the inorganic acid without solvent such as water, and when the method is specifically implemented, inorganic acid solutions with different concentration specifications can be adopted, and the ratio of the mass of the inorganic acid (non-solution) to the sum of the mass of the modified macroporous pseudo-boehmite and the mass of the small pore pseudo-boehmite can be controlled to be (0.05-0.5): 1 according to the mass of the inorganic acid in the inorganic acid solution converted according to the concentration. Preferably, the inorganic acid comprises nitric acid.
In step (II), the first impregnation liquid may be a solution or suspension, preferably the compound of the second metal component comprises a soluble compound of the second metal component (typically a water-soluble compound), and the first impregnation liquid is a solution made of a soluble compound of the second metal component dissolved in water, which may in particular comprise a soluble salt of the second metal component (i.e. comprising a soluble salt of silver and/or a soluble salt of gallium), preferably comprises a nitrate of the second metal component (i.e. comprising silver nitrate and/or gallium nitrate).
In the specific embodiment, in the step (II), the impregnation may be performed by an isovolumetric impregnation method. In some embodiments, in step (II), the impregnation temperature is in the range of 20 ℃ to 90 ℃, e.g. 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 65 ℃, 70 ℃, 80 ℃, 90 ℃ or any two thereof, preferably 40 to 65 ℃, the impregnation time is in the range of 1h to 24h, e.g. 1h, 5h, 10h, 15h, 20h, 24h or any two thereof, preferably 6h to 12h; the mass ratio of the first impregnating solution to the first intermediate is (1-4): 1, for example, 1:1, 2:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1 or any two of them.
In the step (III), the second intermediate may be modified by an impregnation method, and in particular, the second intermediate may be impregnated with a solution containing a diamine hydrogen phosphate to achieve modification of the second intermediate; the mass ratio of the diamine hydrogen phosphate to the second intermediate may be (0.05 to 0.2): 1, for example, a range of 0.05:1, 0.1:1, 0.15:1, 0.2:1, or any two thereof, and the mass ratio of the diamine hydrogen phosphate-containing solution to the second intermediate may be (1 to 3): 1, for example, a range of 1:1, 1.5:1, 2:1, 2.5:1, 3:1, or any two thereof, and the diamine hydrogen phosphate-containing solution may be an aqueous solution of diamine hydrogen phosphate.
Optionally, the drying process in step (I), step (II), step (III) each independently comprises: drying at 20-30 deg.c (e.g. normal temperature) for 12-48 hr, drying at 60-120 deg.c (preferably 80-110 deg.c) for 3-24 hr, e.g. 6-12 hr or 6-10 hr, and roasting the obtained dried product. Wherein, the conditions of the drying temperature, the drying time and the like in the step (I), the step (II) and the step (III) can be the same or different.
In addition, the firing conditions in step (I), step (II), step (III) may each be, independently: the firing temperature is 400 to 700 ℃, for example 400 to 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃ or any two of them, preferably 450 to 650 ℃, and the firing time is 1 to 10 hours, for example 1 to 3 hours, 5 hours, 7 hours, 10 hours or any two of them, preferably 3 to 5 hours. Wherein, the conditions of the roasting temperature, the roasting time and the like in the step (I), the step (II) and the step (III) can be the same or different.
In step (IV), hydrogen is specifically introduced into the system to make the catalyst precursor contact with the hydrogen for the first reduction treatment, and the volume space velocity of the hydrogen is 500h -1 ～4000h -1 For example 500h -1 、1000h -1 、1500h -1 、2000h -1 、2500h -1 、3000h -1 、3500h -1 、4000h -1 Or any two thereof, preferably 1500h -1 ～3000h -1 . In general, in the atmosphere containing hydrogen in the step (IV), the volume fraction of hydrogen is 50% to 100%, for example, 50%, 60%, 70%, 80%, 90%, 100% or a range of any two of these, and the balance is, for example, an inert gas or the like.
In the step (IV), the temperature of the first reduction treatment process may be 300 to 550 ℃, such as 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, or any two thereof, the pressure of the first reduction treatment process is 0 to 3MPa, such as 0MPa, 0.5MPa, 1MPa, 1.5MPa, 2MPa, 2.5MPa, 3MPa, or any two thereof, preferably 0.5 to 1.5MPa, and the time of the first reduction treatment is 1 to 6 hours, such as 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, or any two thereof, preferably 2 hours to 4 hours.
In the invention, unless otherwise specified, the mass of the modified macroporous pseudo-boehmite and the small pore pseudo-boehmite are calculated by the dry mass of alumina, and the mass of the raw materials such as zirconia, zinc oxide and the like are calculated by the dry mass.
In one embodiment of the present invention, a sulfur-containing oil adsorption desulfurization method is provided, comprising: desulfurizing the sulfur-containing oil product by adopting the adsorption desulfurization catalyst; or, the adsorption desulfurization catalyst is prepared according to the preparation method, and sulfur-containing oil products are subjected to desulfurization treatment by adopting the prepared adsorption desulfurization catalyst.
In some embodiments, the temperature of the desulfurization treatment may be in the range of 300 ℃ to 550 ℃, such as 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, or any two of these, preferably 400 to 450 ℃; the pressure of the desulfurization treatment is 0.5 to 10MPa, for example, 0.5MPa, 1MPa, 2MPa, 3MPa, 4MPa, 5MPa, 6MPa, 7MPa, 8MPa, 9MPa, 10MPa or a range composed of any two of them, preferably 3 to 7MPa; the feeding airspeed of the sulfur-containing oil product is 0.1h -1 ～1.0h -1 For example 0.1h -1 、0.3h -1 、0.5h -1 、0.8h -1 、1h -1 Or a range of any two of these.
In some embodiments, the desulfurization treatment is performed under a hydrogen atmosphere, even though the sulfur-containing oil product is contacted with the adsorption desulfurization catalyst under a hydrogen atmosphere to perform the desulfurization treatment. Wherein the volume ratio of hydrogen to sulfur-containing oil (hydrogen oil volume ratio) is (100-800): 1, such as 100:1, 200:1, 300:1, 400:1, 500:1, 600:1, 700:1, 800:1 or any two of them.
In some embodiments, the desulfurization process further comprises: after desulfurization treatment, respectively obtaining a desulfurization oil product and a spent catalyst; regenerating the catalyst to be regenerated to obtain a regenerated catalyst; returning the regenerated catalyst to carry out desulfurization treatment.
Wherein the regeneration process comprises: oxidizing and regenerating the spent catalyst in the presence of oxygen-containing gas to obtain a regenerated catalyst precursor; wherein the volume fraction of oxygen in the oxygen-containing gas is 1% -10%, such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% or any two thereof, and the volume space velocity of the oxygen-containing gas is 1000h -1 ～3000h -1 For example 1000h -1 、1300h -1 、1500h -1 、1800h -1 、2000h -1 、2300h -1 、2500h -1 、2800h -1 、3000h -1 Or a range of any two thereof; the temperature of the oxidative regeneration is 300-500 ℃, such as 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 DEG COr a range of any two thereof; the pressure of the oxidation regeneration is 0-0.5 MPa; the time of oxidation regeneration is 20-100 h; subjecting the regenerated catalyst precursor to a second reduction treatment in an atmosphere containing hydrogen to obtain a regenerated catalyst; wherein the temperature of the second reduction treatment is 300 ℃ to 500 ℃, such as 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃ or a range consisting of any two thereof, preferably 350 ℃ to 450 ℃, and the pressure of the second reduction treatment is 0 to 3MPa, such as 0MPa, 0.5MPa, 1MPa, 1.5MPa, 2MPa, 2.5MPa, 3MPa or a range consisting of any two thereof, preferably 0.5 to 1.5MPa, and the time of the second reduction treatment is 1h to 6h, such as 1h, 2h, 3h, 4h, 5h, 6h or a range consisting of any two thereof, preferably 2h to 4h. In the present invention, unless otherwise specified, the pressures are gauge pressures.
In specific implementation, hydrogen can be introduced into the system to make the regenerated catalyst precursor contact with the hydrogen for the second reduction treatment, and the volume space velocity of the hydrogen can be 500h -1 ～4000h -1 For example 500h -1 、1000h -1 、1500h -1 、2000h -1 、2500h -1 、3000h -1 、3500h -1 、4000h -1 Or any two thereof, preferably 1500h -1 ～3000h -1 . In general, in the second reduction treatment, the volume fraction of hydrogen in the hydrogen-containing atmosphere is 10% to 100%, for example, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100% or any two thereof, preferably 60% to 100%, and the balance may be an inert gas or an oil gas such as methane.
In particular, the desulfurization treatment described above is carried out in a reactor, which may comprise a fixed bed reactor and/or a moving bed reactor. Taking a reactor as a fixed bed reactor as an example, in the specific implementation, an adsorption desulfurization catalyst can be filled in the fixed bed reactor, and then sulfur-containing oil products enter the fixed bed reactor to be in contact reaction with the adsorption desulfurization catalyst in the fixed bed reactor, so that the desulfurization oil products and spent catalyst are respectively obtained; after the regeneration treatment, the catalyst to be regenerated is returned to the fixed bed reactor to form circulation.
In the invention, the adsorption desulfurization catalyst can be used for removing small molecular sulfides and macromolecular sulfides in sulfur-containing oil products, has a wide application range, generally comprises at least one of carbonyl sulfide, carbon disulfide, mercaptan, hydrogen sulfide and thiophene compounds, but is not limited to the carbonyl sulfide, the mercaptan compounds comprise at least one of benzothiophene, dibenzothiophene, benzonaphthothiophene, alkylbenzothiophene, alkyldibenzothiophene and alkylbenzothiophene. In some embodiments, the sulfur-containing oil comprises a heavy oil comprising at least one of a wax oil, an atmospheric residue, and a vacuum residue.
In general, the sulfide in heavy oil has an equivalent double bond value (DBE) ranging from 9 to 16, and has a carbon number of C 22 -C 46 The adsorption desulfurization catalyst disclosed by the invention can be used for efficiently removing sulfides in heavy oil, has good activity stability, can be regenerated and used for multiple times, and keeps good desulfurization efficiency.
In the invention, the sulfur-containing oil product is desulfurized by adopting the desulfurization adsorbent, and the high-efficiency desulfurization can be realized for the sulfur-containing oil product with high sulfur content (such as the heavy oil), and the desulfurization rate can reach more than 85 percent by taking the heavy oil with the sulfur content of about 2.3 weight percent (such as vacuum residue) as an example.
For the purpose of promoting an understanding of the principles of the invention, reference will now be made in detail to specific examples, some but not all of which are illustrated in the accompanying drawings. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following examples, the relevant performance test procedure is as follows:
(1) The total sulfur content of the liquid oil sample was determined by ultraviolet fluorescence/chemiluminescence using a United states photonLAB total sulfur total nitrogen analyzer at 1000℃under argon at 30psi and oxygen at 10psi, reference standard SH/T0689-2000. According to the method, the mass percentage x of the total sulfur in the heavy oil raw material is respectively measured 0 And the mass percentage x of total sulfur in the desulfurized oil product 1 According to w= (x 0 -x 1 )/x 0 Calculating the desulfurization rate w;
(2) The mechanical strength of the molded body particles (S1 to S6, D1 to D6, as described below) was measured by a universal automatic strength tester, the measuring range of the tester was 0 to 500N, the accuracy was 0.1N, and the measurement process was as follows: placing a single sample between two rigid platforms, one of which remains stationary and the other of which moves axially downward at an extremely low rate, creating crush friction on the particles, the breaking strength (or crushing strength) being determined as the maximum load measured before the particles break; according to the process, 50 regular particles are selected for each sample to carry out a crushing strength test, so that representative mechanical properties are obtained;
(3) Carrying out crystal structure characterization on each catalyst sample by X-Ray Diffraction (XRD) analysis, specifically carrying out XRD analysis by adopting a Japanese science D/max 2200 PCX-Ray powder diffractometer, and measuring under the conditions of a Cu target, a graphite monochromator, a scanning speed of 10 degrees/min, a scanning step of 0.02 degree, a voltage of 40kv and a current of 20 mA; the catalyst composition (including the species, structure, crystalline state, state of existence of elements, etc.) is judged by qualitative analysis of the intensity and position of diffraction peaks in the measured XRD spectrum.
In the following examples and comparative examples, orificial boehmite, available from petrochemical technology Co., ltd., product model P-D-03, had a pore volume of0.52mL/g, and a specific surface area of 213m 2 G, peptization index greater than 95%; the macroporous pseudo-boehmite raw material is purchased from the Bo Ying chemical Co Ltd, model YH-2, the pore volume of the macroporous pseudo-boehmite raw material is 1.08mL/g, and the specific surface area is 341m 2 /g; other reagents were purchased from the aara Ding Shiji mesh; the zinc oxide is nano zinc oxide powder with the particle size not more than 100 nm.
In the following examples, the modified macroporous pseudo-boehmite used was prepared as follows:
1. the macroporous pseudo-boehmite raw material is modified by water vapor for 3 hours at 550 ℃ and the mass space velocity of the water vapor is 1.0 hour -1 The modified macroporous pseudo-boehmite I is prepared, and the pore volume of the modified macroporous pseudo-boehmite I is 1.96m through test 2 /g；
2. The macroporous pseudo-boehmite raw material is modified by water vapor for 3 hours at 600 ℃ and the water vapor mass airspeed is 1.0 hour -1 The modified macroporous pseudo-boehmite II is prepared, and the pore volume of the modified macroporous pseudo-boehmite II is 2.13m 2 /g；
3. The macroporous pseudo-boehmite raw material is modified by water vapor for 3 hours at 650 ℃ and the mass space velocity of the water vapor is 1.0 hour -1 The modified macroporous pseudo-boehmite III is prepared, and the pore volume of the modified macroporous pseudo-boehmite I II is 1.89m through test 2 /g。
Example 1
(1) Uniformly mixing 60g of small-pore pseudo-boehmite, 60g of modified large-pore pseudo-boehmite I, 30g of zirconia, 30g of sesbania powder, 700g of zinc oxide powder and 583g of nickel nitrate hexahydrate, adding 480g of water and 60g of nitric acid, uniformly mixing, and extruding into pellets with the particle diameter of 2 mm; naturally drying the pellets at normal temperature for 24 hours, then drying at 100 ℃ for 8 hours, and roasting at 550 ℃ for 4 hours to obtain a first pellet intermediate;
(2) Weighing 2.73g of gallium nitrate, adding 1500g of water to prepare a first impregnating solution, placing the catalyst pellets prepared in the step (2) into the first impregnating solution, and impregnating for 6 hours at 60 ℃; naturally drying the obtained impregnation product at normal temperature for 12 hours, then drying at 110 ℃ for 6 hours, and roasting at 600 ℃ for 3 hours to obtain a globular second intermediate;
(3) Weighing 100g of monoammonium phosphate, adding 2900g of water to prepare a solution, placing a second intermediate in the solution, and soaking for 6 hours at 60 ℃; naturally drying the obtained impregnated product at normal temperature for 12 hours, then drying at 110 ℃ for 6 hours, and roasting at 600 ℃ for 3 hours to obtain a small spherical catalyst precursor;
(4) Carrying out reduction treatment on the catalyst precursor in an atmosphere containing hydrogen to obtain a small spherical adsorption desulfurization catalyst S1; wherein, the conditions of the reduction treatment are as follows: the pressure is 1MPa, the temperature is 400 ℃, the reduction treatment time is 3h, and the volume space velocity of hydrogen is 2000h -1 The volume fraction of hydrogen in the atmosphere containing hydrogen was 80%;
wherein the first metal component (zinc+nickel) and the second metal component (gallium) are calculated by oxide, the mass of the first metal component accounts for 85% of the sum of the mass of the carrier and the first metal component, the mass of nickel in the first metal component accounts for 15% of the sum of the mass of the carrier and the first metal component, and the mass of the second metal component (gallium oxide) accounts for 0.2% of the sum of the mass of the carrier and the first metal component.
Example 2
(1) Uniformly mixing 107g of small-pore pseudo-boehmite, 321g of modified large-pore pseudo-boehmite II, 33g of zirconia, 80g of sesbania powder, 550g of zinc oxide powder and 167g of nickel acetate tetrahydrate, adding 510g of water and 43g of nitric acid, uniformly mixing, and extruding into pellets with the particle diameter of 2 mm; naturally drying the pellets at normal temperature for 12 hours, then drying at 110 ℃ for 6 hours, and roasting at 450 ℃ for 5 hours to obtain a first pellet intermediate;
(2) Weighing 5.86g of silver nitrate, adding 3900g of water to prepare a first impregnating solution, placing the catalyst pellets prepared in the step (2) into the first impregnating solution, and impregnating for 10 hours at 50 ℃; naturally drying the obtained impregnation product at normal temperature for 24 hours, then drying at 100 ℃ for 9 hours, and roasting at 500 ℃ for 5 hours to obtain a globular second intermediate;
(3) Weighing 120g of monoammonium phosphate, adding 880g of water to prepare a solution, placing a second intermediate in the solution, and soaking for 12 hours at 65 ℃; naturally drying the obtained impregnated product at normal temperature for 24 hours, then drying the impregnated product at 80 ℃ for 10 hours, and roasting the impregnated product at 650 ℃ for 4 hours to obtain a small spherical catalyst precursor;
(4) Carrying out reduction treatment on the catalyst precursor in an atmosphere containing hydrogen to obtain a small spherical adsorption desulfurization catalyst S2; wherein, the conditions of the reduction treatment are as follows: the pressure is 0.5MPa, the temperature is 350 ℃, the reduction treatment time is 4h, and the volume space velocity of hydrogen is 1500h -1 The volume fraction of hydrogen in the atmosphere containing hydrogen was 90%;
wherein the first metal component (zinc+nickel) and the second metal component (silver) are calculated by oxide, the mass of the first metal component accounts for 56.6% of the sum of the mass of the carrier and the first metal component, the mass of nickel in the first metal component accounts for 4.71% of the sum of the mass of the carrier and the first metal component, and the mass of the second metal component (silver oxide) accounts for 0.75% of the sum of the mass of the carrier and the first metal component.
Example 3
(1) Uniformly mixing 91g of small-pore pseudo-boehmite, 136g of modified large-pore pseudo-boehmite III, 23g of zirconia, 50g of sesbania powder, 650g of zinc oxide powder and 389g of nickel nitrate hexahydrate, adding 460g of water and 91g of nitric acid, uniformly mixing, and extruding into pellets with the particle diameter of 2 mm; naturally drying the pellets at normal temperature for 36 hours, then drying the pellets at 90 ℃ for 9 hours, and roasting the pellets at 500 ℃ for 3 hours to obtain a first pellet intermediate;
(2) Weighing 5.46g of gallium nitrate, adding 2000g of water to prepare a first impregnating solution, placing the catalyst pellets prepared in the step (1) into the first impregnating solution, and impregnating for 9 hours at 60 ℃; naturally drying the obtained impregnated product at normal temperature for 20 hours, then drying at 80 ℃ for 12 hours, and roasting at 450 ℃ for 4 hours to obtain a globular second intermediate;
(3) Weighing 150g of monoammonium phosphate, adding 2350g of water to prepare a solution, placing a second intermediate in the solution, and soaking for 9h at 55 ℃; naturally drying the obtained impregnated product at normal temperature for 18 hours, then drying the impregnated product at 100 ℃ for 6 hours, and roasting the impregnated product at 650 ℃ for 4 hours to obtain a small spherical catalyst precursor;
(4) Carrying out reduction treatment on the catalyst precursor in an atmosphere containing hydrogen to obtain a small spherical adsorption desulfurization catalyst S3; wherein, the conditions of the reduction treatment are as follows: pressure 1.5MPa, temperature 450 ℃, reduction treatmentThe time is 2h, the volume space velocity of hydrogen is 2500h -1 The volume fraction of hydrogen in the atmosphere containing hydrogen was 70%;
wherein the first metal component (zinc+nickel) and the second metal component (gallium) are calculated by oxide, the mass of the first metal component accounts for 75% of the sum of the mass of the carrier and the first metal component, the mass of nickel in the first metal component accounts for 10% of the sum of the mass of the carrier and the first metal component, and the mass of the second metal component (gallium oxide) accounts for 0.4% of the sum of the mass of the carrier and the first metal component.
Example 4
(1) Mixing 87g of small-pore pseudo-boehmite, 174g of modified large-pore pseudo-boehmite I, 39g of zirconia, 40g of sesbania powder, 620g of zinc oxide powder and 266g of nickel acetate tetrahydrate uniformly, adding 530g of water and 52g of nitric acid, uniformly mixing and extruding into pellets with the particle diameter of 2 mm; naturally drying the pellets at normal temperature for 18 hours, then drying at 100 ℃ for 7 hours, and roasting at 550 ℃ for 3 hours to obtain a first pellet intermediate;
(2) Weighing 4.4g of silver nitrate, adding 2900g of water to prepare a first impregnating solution, placing the catalyst pellets prepared in the step (1) into the first impregnating solution, and impregnating for 8 hours at 60 ℃; naturally drying the obtained impregnated product at normal temperature for 24 hours, then drying the impregnated product at 80 ℃ for 10 hours, and roasting the impregnated product at 600 ℃ for 3 hours to obtain a globular second intermediate;
(3) 130g of monoammonium phosphate is weighed, 1400g of water is added to prepare a solution, and the second intermediate is placed in the solution and immersed for 10 hours at 45 ℃; naturally drying the obtained impregnated product at normal temperature for 18 hours, then drying the impregnated product at 100 ℃ for 9 hours, and roasting the impregnated product at 550 ℃ for 4 hours to obtain a small spherical catalyst precursor;
(4) Carrying out reduction treatment on the catalyst precursor in an atmosphere containing hydrogen to obtain a small spherical adsorption desulfurization catalyst S4; wherein, the conditions of the reduction treatment are as follows: the pressure is 0.75MPa, the temperature is 400 ℃, the reduction treatment time is 3h, and the volume space velocity of hydrogen is 3000h -1 The volume fraction of hydrogen in the atmosphere containing hydrogen was 60%;
wherein the first metal component (zinc+nickel) and the second metal component (silver) are calculated by oxide, the mass of the first metal component accounts for 70% of the sum of the mass of the carrier and the first metal component, the mass of nickel in the first metal component accounts for 8% of the sum of the mass of the carrier and the first metal component, and the mass of the second metal component (silver oxide) accounts for 0.6% of the sum of the mass of the carrier and the first metal component.
Example 5
(1) Mixing 83g of small-pore pseudo-boehmite, 209g of modified large-pore pseudo-boehmite II, 58g of zirconia, 60g of sesbania powder, 630g of zinc oxide powder and 467g of nickel nitrate hexahydrate uniformly, adding 420g of water and 88g of nitric acid, uniformly mixing and extruding into pellets with the particle diameter of 2 mm; naturally drying the pellets at normal temperature for 24 hours, then drying the pellets at 80 ℃ for 10 hours, and roasting the pellets at 450 ℃ for 5 hours to obtain a first pellet intermediate;
(2) Weighing 2.93g of silver nitrate, adding 2500g of water to prepare a first impregnating solution, placing the catalyst pellets prepared in the step (1) into the first impregnating solution, and impregnating for 10 hours at 50 ℃; naturally drying the obtained impregnated product at normal temperature for 20 hours, then drying at 110 ℃ for 6 hours, and roasting at 550 ℃ for 5 hours to obtain a globular second intermediate;
(3) Weighing 150g of monoammonium phosphate, adding 1850g of water to prepare a solution, placing a second intermediate in the solution, and soaking for 6h at 65 ℃; naturally drying the obtained impregnated product at normal temperature for 24 hours, then drying the impregnated product at 90 ℃ for 9 hours, and roasting the impregnated product at 500 ℃ for 5 hours to obtain a small spherical catalyst precursor;
(4) Carrying out reduction treatment on the catalyst precursor in an atmosphere containing hydrogen to obtain a small spherical adsorption desulfurization catalyst S5; wherein, the conditions of the reduction treatment are as follows: the pressure is 1.5MPa, the temperature is 550 ℃, the reduction treatment time is 3h, and the volume space velocity of hydrogen is 1500h -1 The volume fraction of hydrogen in the atmosphere containing hydrogen was 80%;
wherein the first metal component (zinc+nickel) and the second metal component (silver) are calculated by oxide, the mass of the first metal component accounts for 68% of the sum of the mass of the carrier and the first metal component, the mass of nickel in the first metal component accounts for 10.9% of the sum of the mass of the carrier and the first metal component, and the mass of the second metal component (silver oxide) accounts for 0.36% of the sum of the mass of the carrier and the first metal component.
Example 6
(1) Uniformly mixing 104g of small-pore pseudo-boehmite, 157g of modified large-pore pseudo-boehmite III, 39g of zirconia, 50g of sesbania powder, 600g of zinc oxide powder and 333g of nickel acetate tetrahydrate, adding 530g of water and 78g of nitric acid, uniformly mixing, and extruding into pellets with the particle diameter of 2 mm; naturally drying the pellets at normal temperature for 12 hours, then drying the pellets at 90 ℃ for 10 hours, and roasting the pellets at 600 ℃ for 4 hours to obtain a first pellet intermediate;
(2) Weighing 8.19g of gallium nitrate, adding 1500g of water to prepare a first impregnating solution, placing the catalyst pellets prepared in the step (1) into the first impregnating solution, and impregnating for 10 hours at 55 ℃; naturally drying the obtained impregnation product at normal temperature for 18 hours, then drying at 100 ℃ for 6 hours, and roasting at 500 ℃ for 4 hours to obtain a globular second intermediate;
(3) Weighing 110g of monoammonium phosphate, adding 1900g of water to prepare a solution, placing a second intermediate in the solution, and soaking for 8 hours at 65 ℃; naturally drying the obtained impregnated product at normal temperature for 24 hours, then drying the impregnated product at 110 ℃ for 6 hours, and roasting the impregnated product at 650 ℃ for 3 hours to obtain a small spherical catalyst precursor;
(4) Carrying out reduction treatment on the catalyst precursor in an atmosphere containing hydrogen to obtain a small spherical adsorption desulfurization catalyst S6; wherein, the conditions of the reduction treatment are as follows: the pressure is 0.5MPa, the temperature is 450 ℃, the reduction treatment time is 2h, and the volume space velocity of hydrogen is 2500h -1 The volume fraction of hydrogen in the atmosphere containing hydrogen was 100%;
wherein the first metal component (zinc+nickel) and the second metal component (gallium) are calculated by oxide, the mass of the first metal component accounts for 70% of the sum of the mass of the carrier and the first metal component, the mass of nickel in the first metal component accounts for 10% of the sum of the mass of the carrier and the first metal component, and the mass of the second metal component (gallium oxide) accounts for 0.6% of the sum of the mass of the carrier and the first metal component.
Comparative example 1 differs from example 3 in that the ammonium dihydrogen phosphate modification process of step (3) was omitted, i.e., the second intermediate was directly subjected to the reduction treatment of step (4) as a catalyst precursor, to obtain the adsorption desulfurization catalyst D1.
Comparative example 2 is different from example 3 in that the small pore pseudo-boehmite in step (1) is replaced with a modified large pore pseudo-boehmite to obtain the adsorption desulfurization catalyst D2.
Comparative example 3 is different from example 3 in that the modified macroporous pseudo-boehmite in step (1) is replaced with small pore pseudo-boehmite to obtain the adsorption desulfurization catalyst D3.
Comparative example 4 differs from example 4 in that the zirconia in step (1) was replaced with modified macroporous pseudo-boehmite to obtain an adsorption desulfurization catalyst D4.
Comparative example 5 differs from example 5 in that zirconia in step (1) was replaced with small pore pseudo-boehmite to obtain an adsorption desulfurization catalyst D5.
Comparative example 6 differs from example 6 in that the modified macroporous pseudo-boehmite in step (1) was replaced with a macroporous pseudo-boehmite raw material to obtain an adsorptive desulfurization catalyst D6.
Application examples
The desulfurization process of this application example is as follows: 200g of catalyst is filled in a fixed bed reactor, then heavy oil raw materials enter the fixed bed reactor and are contacted with an adsorption desulfurization catalyst for reaction (namely, desulfurization reaction is carried out) under the hydrogen atmosphere, so that desulfurization oil products and spent catalyst are respectively obtained; wherein, the heavy oil raw material is vacuum residuum with 2.3wt% sulfur content, and the conditions of the desulfurization treatment process are as follows: the temperature was 420℃and the pressure was 4MPa, the feed rate of the heavy oil feedstock was 100g/h (the space velocity of the feed of the heavy oil feedstock was 0.5 h) -1 ) The hydrogen flow rate was 35L/h (the volume ratio of hydrogen to heavy oil feedstock was 400: 1).
The desulfurization process was performed using S1 to S6 and D1 to D6 as adsorption desulfurization catalysts, respectively, to evaluate the performances of S1 to S6 and D1 to D6. The crush strengths of catalysts S1 to S6 and D1 to D6, and the desulfurization rates achieved by the respective catalysts are shown in tables 1 and 2, respectively.
TABLE 1 evaluation results of adsorption desulfurization catalyst Performance
| Adsorption desulfurization catalyst | S1 | S2 | S3 | S4 | S5 | S6 |
| Crush strength/N | 35 | 39 | 37 | 38 | 36 | 39 |
| Desulfurization rate/% | 88 | 85 | 87 | 86 | 87 | 89 |
TABLE 2 evaluation results of adsorption desulfurization catalyst Performance
| Adsorption desulfurization catalyst | D1 | D2 | D3 | D4 | D5 | D6 |
| Crush strength/N | 35 | 15 | 23 | 33 | 32 | 33 |
| Desulfurization rate/% | 76 | 83 | 67 | 82 | 83 | 72 |
As can be seen from tables 1 and 2, S1 to S6 have both good mechanical properties and desulfurization activity relative to D1 to D6.
In addition, the stability of the catalyst is evaluated on S1-S6 and D1-D6, and the desulfurization activity of the catalyst after different regeneration times is measured, so that the stability of the desulfurization activity of the S1-S6 is far better than that of the D1-D6. Specifically, the desulfurization rate of the catalyst after various times of regeneration was measured according to the following desulfurization-regeneration process:
the desulfurization process is carried out by adopting fresh unused catalyst to obtain desulfurized oil products and primary spent catalyst respectively, and the desulfurization rate of the fresh catalyst is measured;
The regeneration treatment of the spent catalyst is carried out according to the following regeneration process: oxidizing and regenerating the primary spent catalyst in the presence of oxygen-containing gas to obtain a regenerated catalyst precursor; wherein the volume fraction of oxygen in the oxygen-containing gas is 7%, and the volume space velocity of the oxygen-containing gas is 2000h -1 The temperature of the oxidation regeneration is 350 ℃, the pressure of the oxidation regeneration is 0.5MPa, and the time of the oxidation regeneration is 60 hours; subjecting the regenerated catalyst precursor to a second reduction treatment in an atmosphere containing hydrogen to obtain a primary regenerated catalyst (i.e., 1 regeneration); wherein the volume fraction of hydrogen in the atmosphere containing hydrogen is 75%, and the volume space velocity of hydrogen is 2000h -1 The temperature of the second reduction treatment is 400 ℃, the pressure of the second reduction treatment is 1.0MPa, and the time of the second reduction treatment is 4 hours;
the desulfurization process is carried out by adopting a primary regenerated catalyst to obtain a desulfurized oil product and a secondary spent catalyst respectively, and the desulfurization rate of the primary regenerated catalyst is measured; then the secondary spent catalyst is regenerated according to the regeneration process to obtain a secondary regenerated catalyst (i.e. regenerated 2 times); and then the secondary regenerated catalyst is adopted to carry out the desulfurization process to respectively obtain a desulfurized oil product and a secondary spent catalyst, the desulfurization rate … … of the secondary regenerated catalyst is measured, and the desulfurization rates after the catalyst is regenerated for 1 time, 4 times, 7 times, 10 times, 13 times, 16 times, 19 times, 22 times, 25 times, 28 times, 32 times and 35 times are respectively measured by analogy according to the process.
The desulfurization rates corresponding to the number of regenerations measured in the above-described manner are shown in table 3, taking S4, S5, D4, and D5 as examples.
TABLE 3 evaluation results of catalyst stability
Note that: after the regeneration of D4 and D5 for 16 times, the desulfurization rate was greatly reduced, which is not shown in table 3.
As can be seen from Table 3, after the regeneration of S4 and S5 for 35 times, the desulfurization rate can still be kept high, which is basically equivalent to that of the fresh adsorption desulfurization catalyst, and the desulfurization activity stability is good.
In addition, to further illustrate the difference in performance between the adsorption desulfurization catalyst prepared in the examples and the adsorption desulfurization catalyst prepared in the comparative examples, XRD analysis was performed on the catalyst precursor during the preparation thereof (i.e., the product before the first reduction treatment) and the regenerated catalyst precursor during the 5 th regeneration according to the above desulfurization-regeneration process (i.e., the product before the second reduction treatment), respectively, as shown in fig. 1 and 2, wherein the fresh catalyst S1 in fig. 1 is the catalyst precursor during the preparation of the fresh adsorption desulfurization catalyst S1, the fresh catalyst S2 is the catalyst precursor during the preparation of the fresh adsorption desulfurization catalyst S2, and the fresh catalyst D4 is the catalyst precursor during the preparation of the fresh adsorption desulfurization catalyst D4, and the fresh catalyst D5 is the catalyst precursor during the preparation of the fresh adsorption desulfurization catalyst D5; in fig. 2, the regenerant S1 is a regenerated catalyst precursor in the case of the 5 th regeneration of the desulfurization-regeneration process using the fresh adsorption desulfurization catalyst S1, the regenerant S2 is a regenerated catalyst precursor in the case of the 5 th regeneration of the desulfurization-regeneration process using the fresh adsorption desulfurization catalyst S2, the regenerant D4 is a regenerated catalyst precursor in the case of the 5 th regeneration of the desulfurization-regeneration process using the fresh adsorption desulfurization catalyst D4, and the regenerant D5 is a regenerated catalyst precursor in the case of the 5 th regeneration of the desulfurization-regeneration process using the fresh adsorption desulfurization catalyst D5.
As can be seen from fig. 1 and 2, the main characteristic diffraction peaks in the fresh agent S1, the fresh agent S2, the fresh agent D4 and the fresh agent D5 are zinc oxide crystal phase peaks (31.5 °, 34.4 °, 36.2 °) and nickel oxide crystal phase peaks (36.9 ° and 43.0 °) respectively, and the characteristic diffraction peak of ZnO is sharp in peak shape and high in intensity, and is a main active component; the regenerants (i.e., regenerants S1, S2, D4, and regeneration)The agent D5) has obviously increased complexity of XRD spectrum (figure 2), wherein besides the regenerated products such as ZnO and NiO, the desulfurized products such as ZnS and ZnAl are also used 2 O 4 The intensities of diffraction peaks characteristic of the zinc aluminate spinel are remarkably enhanced in XRD patterns of the regenerants D4 and D5 relative to those of the regenerants S1 and S2.
The active ZnO in the adsorption desulfurization catalyst continuously reacts with an aluminum source in the carrier to generate inactive zinc aluminate spinel, and the zinc aluminate spinel cannot be converted into active ZnO in the regeneration process, which means that the active ZnO is difficult to regenerate, so that inactive components are formed, the content of the active component ZnO in the adsorption desulfurization catalyst is greatly reduced due to the higher content of the active component ZnO, so that the problems of difficult sulfur transfer and the like in the adsorption desulfurization process are caused, and the performances of the adsorption desulfurization catalyst such as desulfurization activity and the like are influenced; meanwhile, the carrier structure is damaged due to the generation of zinc-aluminum spinel, so that the strength of the adsorption desulfurization catalyst is reduced, the adsorption desulfurization catalyst is easier to break, and the service performance is poor. Thus, it is further demonstrated by the XRD analysis that the adsorption desulfurization catalyst prepared by the examples has better desulfurization activity stability and mechanical strength, etc., than the adsorption desulfurization catalyst prepared by the comparative examples.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The adsorption desulfurization catalyst is characterized by comprising a carrier, a first metal component and a second metal component, wherein the carrier is formed by compounding raw materials comprising small-pore pseudo-boehmite, zirconia and modified macroporous pseudo-boehmite, wherein the pore volume of the small-pore pseudo-boehmite is not more than 0.6mL/g, the pore volume of the modified macroporous pseudo-boehmite is not less than 1.5mL/g, and the modified macroporous pseudo-boehmite is obtained by modifying the pseudo-boehmite raw materials by water vapor at 550-650 ℃; the first metal component comprises zinc and nickel and the second metal component comprises silver and/or gallium.
2. The adsorptive desulfurization catalyst of claim 1, characterized in that, based on the oxide of the first metal component, the oxide of the second metal component, it satisfies:
the mass of the first metal component accounts for 55% -85% of the sum of the mass of the carrier and the mass of the first metal component; and/or the number of the groups of groups,
The mass of nickel in the first metal component accounts for 4-15% of the sum of the mass of the carrier and the mass of the first metal component; and/or the number of the groups of groups,
the mass of the second metal component accounts for 0.1-0.8% of the sum of the mass of the carrier and the mass of the first metal component.
3. The adsorption desulfurization catalyst according to claim 1, characterized in that,
the pore volume of the small-pore pseudo-boehmite is 0.4 mL/g-0.6 mL/g, and the specific surface area is 180m 2 /g～260m 2 G, peptization index greater than 95%; and/or the number of the groups of groups,
the pore volume of the modified macroporous pseudo-boehmite is 1.5 mL/g-2.2 mL/g; and/or the number of the groups of groups,
the mass ratio of the small-pore pseudo-boehmite to the modified large-pore pseudo-boehmite is 1 (1-3); and/or the number of the groups of groups,
the ratio of the mass of the zirconia to the sum of the mass of the modified macroporous pseudo-boehmite and the mass of the small pore pseudo-boehmite is (0.05-0.25): 1.
4. The adsorption desulfurization catalyst according to claim 1 or 3, characterized in that,
the pore volume of the pseudo-boehmite raw material is 1.0 mL/g-1.2 mL/g, and the specific surface area is 280-360 m 2 /g; and/or the number of the groups of groups,
the modified macroporous pseudo-boehmite is prepared according to the process comprising the following steps: the pseudo-boehmite raw material is contacted and modified with steam at 550-650 ℃ to prepare the modified macroporous pseudo-boehmite; wherein the modification time is 2-5 h, and the quality of the water vapor is empty The speed is 0.5 to 1h -1 。
5. The method for producing an adsorptive desulfurization catalyst according to any one of claims 1 to 4, characterized by comprising:
(I) Adding inorganic acid and water into a mixture containing modified macroporous pseudo-boehmite, small pore pseudo-boehmite, zirconia, a binder, zinc oxide and a nickel compound, and then sequentially forming, drying and roasting to obtain a first intermediate;
(II) impregnating the first intermediate with a first impregnating solution containing a compound of a second metal component, and drying and roasting the impregnated product to obtain a second intermediate;
(III) modifying the second intermediate by adopting diamine hydrogen phosphate, and drying and roasting to obtain a catalyst precursor;
(IV) subjecting the catalyst precursor to a first reduction treatment in an atmosphere containing hydrogen to obtain the adsorption desulfurization catalyst.
6. The method according to claim 5, wherein,
the binder comprises at least one of methylcellulose, sodium carboxymethyl starch and sesbania powder; and/or the number of the groups of groups,
the mass of the binder accounts for 3% -8% of the sum of the mass of the modified macroporous pseudo-boehmite, the small pore pseudo-boehmite, the zirconia, the zinc oxide and the nickel compound in terms of nickel oxide; and/or the number of the groups of groups,
The zinc oxide comprises nano zinc oxide powder with the particle size not more than 100 nm; and/or the number of the groups of groups,
the ratio of the mass of the inorganic acid to the sum of the mass of the modified macroporous pseudo-boehmite and the mass of the modified microporous pseudo-boehmite is (0.05-0.5): 1; and/or the number of the groups of groups,
the roasting conditions in the step (I) are as follows: the roasting temperature is 400-700 ℃ and the roasting time is 1-10 h; and/or the number of the groups of groups,
the roasting conditions in the step (II) are as follows: the roasting temperature is 400-700 ℃ and the roasting time is 1-10 h; and/or the number of the groups of groups,
the roasting conditions in step (III) are: the roasting temperature is 400-700 ℃ and the roasting time is 1-10 h; and/or the number of the groups of groups,
in the step (IV), the volume space velocity of the hydrogen is 500h -1 ～4000h -1 The temperature of the first reduction treatment process is 300-550 ℃, the pressure of the first reduction treatment process is 0-3 MPa, and the time of the first reduction treatment process is 1-6 h.
7. The adsorption desulfurization method for the sulfur-containing oil product is characterized by comprising the following steps of:
desulfurizing sulfur-containing oil products by using the adsorption desulfurization catalyst according to any one of claims 1 to 4; or alternatively, the process may be performed,
the adsorption desulfurization catalyst prepared by the preparation method according to claim 5 or 6, and sulfur-containing oil products are subjected to desulfurization treatment by using the prepared adsorption desulfurization catalyst.
8. The sulfur-containing oil adsorption desulfurization method according to claim 7, characterized in that,
the temperature of the desulfurization treatment is 300-550 ℃; and/or the number of the groups of groups,
the pressure of the desulfurization treatment is 0.5 MPa-10 MPa; and/or the number of the groups of groups,
the feeding airspeed of the sulfur-containing oil product is 0.1h -1 ～1.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the And/or the number of the groups of groups,
the desulfurization treatment is carried out in a hydrogen atmosphere, and the volume ratio of the hydrogen to the sulfur-containing oil product is (100-800): 1.
9. The sulfur-containing oil adsorption desulfurization method according to claim 7, further comprising: after the desulfurization treatment, respectively obtaining a desulfurized oil product and a spent catalyst; regenerating the spent catalyst to obtain a regenerated catalyst; returning the regenerated catalyst to the desulfurization treatment; wherein the regeneration process includes:
the spent catalyst is subjected to oxidative regeneration in the presence of oxygen-containing gas to obtain a regenerated catalystA body; wherein the volume fraction of oxygen in the oxygen-containing gas is 1-10%, and the volume airspeed of the oxygen-containing gas is 1000h -1 ～3000h -1 The temperature of the oxidation regeneration is 300-500 ℃, the pressure of the oxidation regeneration is 0-0.5 MPa, and the time of the oxidation regeneration is 20-100 h;
Subjecting the regenerated catalyst precursor to a second reduction treatment in an atmosphere containing hydrogen to obtain the regenerated catalyst; wherein the volume space velocity of the hydrogen is 500h -1 ～4000h -1 The temperature of the second reduction treatment is 300-500 ℃, the pressure of the second reduction treatment is 0-3 MPa, and the time of the second reduction treatment is 1-6 h.
10. The sulfur-containing oil adsorption desulfurization method according to claim 7, wherein the sulfur component in the sulfur-containing oil comprises at least one of carbonyl sulfide, carbon disulfide, mercaptan, hydrogen sulfide, and thiophenic compounds, and the thiophenic compounds comprise at least one of benzothiophene, dibenzothiophene, benzothiophene, alkylbenzothiophene, alkyldibenzothiophene, and alkylbenzothiophene; and/or the sulfur-containing oil product comprises a heavy oil, wherein the heavy oil comprises at least one of wax oil, atmospheric residuum and vacuum residuum.
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