CN112371132A - Low-temperature sulfur-tolerant shift catalyst for inhibiting mercaptan, and preparation method and application thereof - Google Patents

Low-temperature sulfur-tolerant shift catalyst for inhibiting mercaptan, and preparation method and application thereof Download PDF

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CN112371132A
CN112371132A CN202011370217.3A CN202011370217A CN112371132A CN 112371132 A CN112371132 A CN 112371132A CN 202011370217 A CN202011370217 A CN 202011370217A CN 112371132 A CN112371132 A CN 112371132A
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active metal
precursor
mercaptan
gamma
cobalt
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李博
郑全利
孙海燕
胡爱众
李友祝
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Qingdao Zhongruiteda Catalytic New Material Co ltd
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Qingdao Zhongruiteda Catalytic New Material Co ltd
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Abstract

The invention belongs to the technical field of shift catalysts, and particularly relates to a low-temperature sulfur-tolerant shift catalyst for inhibiting mercaptan, and a preparation method and application thereof. The catalyst provided by the invention takes gamma-alumina with a porous structure as a carrier, and a metal oxide auxiliary agent and an active metal compound are loaded on the surface and in pores of the carrier, wherein the metal oxide auxiliary agent comprises zirconia, and the metal oxide auxiliary agent not only can effectively inhibit the generation of mercaptan during the hydrogen production by CO transformation, but also has the effects of enhancing the stability of a carrier skeleton structure and prolonging the service life of the catalyst; and when the active metal compound comprises cobalt oxide, molybdenum oxide and potassium carbonate, high conversion rate of CO can be realized.

Description

Low-temperature sulfur-tolerant shift catalyst for inhibiting mercaptan, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of shift catalysts, and particularly relates to a low-temperature sulfur-tolerant shift catalyst for inhibiting mercaptan, and a preparation method and application thereof.
Background
At present, the process route for coal utilization is implemented mainly through two important directions of coal-to-liquid and coal-to-gas, wherein the process route for coal-to-gas is gas-to-methanol or gas-to-synthetic ammonia, and the determination of the process route for gas-to-methanol or gas-to-synthetic ammonia is required to depend on the hydrogen-carbon ratio obtained by the shift reaction in the process of producing hydrogen through CO shift.
In the prior art for preparing hydrogen by CO conversion, catalysts are changed into alumina-supported cobalt oxide and molybdenum oxide; the conversion rate of the first-stage CO can only reach 90 percent, and the mercaptan content in the product is high.
Disclosure of Invention
In view of the above, the invention aims to provide a mercaptan-inhibiting low-temperature sulfur-tolerant shift catalyst, and a preparation method and an application thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides a low-temperature sulfur-tolerant shift catalyst for inhibiting mercaptan, which comprises a gamma-alumina carrier, and a metal oxide auxiliary agent and an active metal compound which are loaded on the surface and in pores of the gamma-alumina carrier;
the metal oxide additive comprises zirconium oxide;
the active metal compound includes cobalt oxide, molybdenum oxide, and potassium carbonate.
Preferably, the mass ratio of the gamma-alumina carrier to the metal oxide auxiliary agent is 500: (8-13); the mass ratio of the gamma-alumina carrier to the active metal compound is 100 (14.5-25).
Preferably, the mass ratio of the cobalt element in the cobalt oxide, the molybdenum element in the molybdenum oxide and the potassium element in the potassium carbonate is (1.5-3): (5-10): (8-12).
The invention provides a preparation method of a low-temperature sulfur-tolerant shift catalyst for inhibiting mercaptan, which comprises the following steps:
carrying out first mixing on gamma-alumina, soluble zirconium salt, a binder and water to obtain mixed slurry;
performing first roasting on the mixed slurry to obtain a first precursor;
secondly, mixing a cobalt-containing compound, a molybdenum-containing compound, a potassium-containing compound and water to obtain an active metal impregnation liquid;
dipping the first precursor in an active metal dipping solution to obtain a second precursor;
and carrying out second roasting on the second precursor to obtain the mercaptan-inhibiting low-temperature sulfur-tolerant shift catalyst.
Preferably, the binder comprises cement and/or sodium carboxymethyl cellulose; the mass ratio of the gamma-alumina to the soluble zirconium salt to the binder is 500 (15-25): (30-100).
Preferably, the mass concentration of the cobalt element in the active metal impregnation liquid is 1.5-3%, the mass concentration of the molybdenum element is 5-10%, and the mass concentration of the potassium element is 8-12%.
Preferably, the mixed slurry further comprises a pore-forming agent, and the pore-forming agent comprises a carbon simple substance and/or attapulgite; the mass ratio of the gamma-alumina to the binder to the pore-forming agent is 500 (30-100) to 20-50.
Preferably, the active metal impregnation liquid also comprises an impregnation penetrating agent, and the impregnation penetrating agent comprises one or more of sodium alkyl sulfate, glycol, EDTA and citric acid; the mass ratio of the impregnating penetrating agent to the cobalt element in the cobalt-containing compound is (2-4): (1.5-3).
Preferably, the temperature of the first roasting is 450 ℃, and the time is 3-6 h; the temperature of the second roasting is 550 ℃, and the time is 2-4 hours.
The invention also provides the application of the mercaptan-inhibiting low-temperature sulfur-tolerant shift catalyst in the technical scheme or the mercaptan-inhibiting low-temperature sulfur-tolerant shift catalyst obtained by the preparation method in the technical scheme in hydrogen production through CO shift.
In order to achieve the purpose, the low-temperature sulfur-tolerant shift catalyst for inhibiting mercaptan provided by the invention comprises a gamma-alumina carrier, and a metal oxide auxiliary agent and an active metal compound which are loaded on the surface and in pores of the gamma-alumina carrier; the metal oxide additive comprises zirconium oxide; the active metal compound includes cobalt oxide, molybdenum oxide, and potassium carbonate. The low-temperature sulfur-tolerant shift catalyst for inhibiting mercaptan provided by the invention takes gamma-alumina with a porous structure as a carrier, and a metal oxide auxiliary agent and an active metal compound are loaded on the surface and in pores, wherein the metal oxide auxiliary agent comprises zirconia, the metal oxide auxiliary agent can improve the hydrogenation capacity of the catalyst, reduce the energy threshold of hydrogenation reaction and improve the hydrogenation conversion rate, and the existing or generated COS and mercaptan in reaction raw materials are subjected to hydrogenation reaction on the surface of the catalyst to generate H2S, therefore, the generation of mercaptan during the hydrogen production by CO conversion can be effectively inhibited, and the catalyst also has the effects of enhancing the stability of the carrier skeleton structure and prolonging the service life of the catalyst; and the active metal compounds including cobalt oxide, molybdenum oxide and potassium carbonate can realize high conversion rate of CO. The results of the embodiment show that when the catalyst for inhibiting the mercaptan low-temperature sulfur-tolerant shift conversion is used for catalyzing CO shift to produce hydrogen, the conversion rate of CO is 92.6-98.2%, the mass content of alcohol in the product is 0.08-0.37 ppm, and the service life of the catalyst is 82-98 h when the CO conversion rate is kept to be more than 92%.
Drawings
FIG. 1 is a flow chart of a process for producing hydrogen by catalyzing CO shift with a low-temperature sulfur-tolerant shift catalyst for inhibiting mercaptan prepared by an example.
Detailed Description
The invention provides a low-temperature sulfur-tolerant shift catalyst for inhibiting mercaptan, which comprises a gamma-alumina carrier, and a metal oxide auxiliary agent and an active metal compound which are loaded on the surface and in pores of the gamma-alumina carrier;
the metal oxide additive comprises zirconium oxide;
the active metal compound includes cobalt oxide, molybdenum oxide, and potassium carbonate.
In the invention, the particle size of the gamma-alumina carrier is preferably 48-75 μm, and the pore volume is preferably 0.25-0.50 cm3The specific surface area is preferably 250-400 m2(ii) in terms of/g. In the invention, the gamma-alumina carrier has the characteristic of a porous structure, and can realize the loading of the metal oxide auxiliary agent and the active metal compound.
In the present invention, the metal oxide assistant comprises zirconia. In the invention, the metal oxide auxiliary agent is loaded on the surface and in pores of the gamma-alumina carrier, and the metal oxide auxiliary agent not only can inhibit the generation of mercaptan during the hydrogen production by CO conversion, but also has the effects of enhancing the stability of a carrier skeleton structure and prolonging the service life of the catalyst.
In the present invention, the mass ratio of the γ -alumina support to the metal oxide auxiliary is preferably 500: (8-13), more preferably 500: (9.5-12.5).
In the invention, the active metal compound comprises cobalt oxide, molybdenum oxide and potassium carbonate, the mass ratio of cobalt element in the cobalt oxide, molybdenum element in the molybdenum oxide and potassium element in the potassium carbonate is preferably (1.5-3): (5-10): (8-12), more preferably 2.5:7:10, and in the invention, the mass ratio of the gamma-alumina carrier and the active metal compound is preferably 100 (14.5-25), more preferably 100 (15.5-20). In the present invention, the active metal compound is supported on the surface and in the pores of the γ -alumina carrier, and the active metal compound can realize high conversion of CO.
In the invention, the metal oxide auxiliary agent is loaded on the surface and in the pores of the gamma-alumina carrier, metal oxide auxiliary agent particles are uniformly covered on the surface and in the pores of the gamma-alumina carrier, compact films are formed on the surface and in the pores of the gamma-alumina carrier, active metal oxide particles are uniformly covered on the surface of the metal oxide auxiliary agent particles and are combined with the metal oxide auxiliary agent through van der Waals force, namely, the metal oxide auxiliary agent and the active metal compound form two layers of compact films on the surface and in the pores of the gamma-alumina carrier.
The invention provides a preparation method of a low-temperature sulfur-tolerant shift catalyst for inhibiting mercaptan, which comprises the following steps:
carrying out first mixing on gamma-alumina, soluble zirconium salt, a binder and water to obtain mixed slurry;
performing first roasting on the mixed slurry to obtain a first precursor;
secondly, mixing a cobalt-containing compound, a molybdenum-containing compound and a potassium-containing compound with water to obtain an active metal impregnation liquid;
dipping the first precursor in an active metal dipping solution to obtain a second precursor;
and carrying out second roasting on the second precursor to obtain the mercaptan-inhibiting low-temperature sulfur-tolerant shift catalyst.
In the present invention, all the raw materials are commercially available products unless otherwise specified.
The method comprises the steps of mixing gamma-alumina, soluble zirconium salt, a binder and water for the first time to obtain mixed slurry.
In the present invention, the first mixing preferably includes the steps of:
carrying out dry mixing on the gamma-alumina and a binder to obtain a dry mixture;
wet mixing the soluble zirconium salt and water to obtain a soluble zirconium salt solution;
and finally mixing the dry mixture and the soluble zirconium salt solution to obtain mixed slurry.
The method comprises the steps of dry mixing gamma-alumina and a binder to obtain a dry mixture; in the invention, the particle size of the gamma-alumina is preferably 48-75 μm, and the pore volume is preferably 0.2-0.45 cm3The specific surface area is preferably 200 to 350 m/g2(ii)/g; in the invention, the binder preferably comprises cement and/or sodium carboxymethyl cellulose (CMC), more preferably comprises cement or sodium carboxymethyl cellulose, and in the invention, when the binder preferably comprises cement and sodium carboxymethyl cellulose, the mass ratio of the cement to the sodium carboxymethyl cellulose is preferably (1-2): 1. in the present invention, the gamma-alumina and the binderThe mass ratio of the agent is preferably 500 (30-100).
In the present invention, the mixed slurry preferably further includes a pore-forming agent. In the invention, when the mixed slurry preferably further comprises a pore-forming agent, the dry mixing preferably comprises dry mixing of gamma-alumina, a binder and the pore-forming agent to obtain a dry mixture; in the invention, the pore-forming agent preferably comprises a carbon simple substance and/or attapulgite, more preferably comprises a carbon simple substance or attapulgite, and the diameters of the carbon simple substance and the attapulgite are independent, preferably 48-75 μm, more preferably 55-65 μm; in the present invention, when the pore-forming agent preferably includes a simple substance carbon and attapulgite, the mass ratio of the simple substance carbon to the attapulgite is preferably 1: (1-2). In the invention, the mass ratio of the gamma-alumina to the binder to the pore-forming agent is preferably 500 (30-100) to 20-50. In the present invention, the elemental carbon preferably includes graphite.
The purpose of adding the pore-forming agent is to improve the porous structure of the gamma-alumina to obtain the gamma-alumina carrier with larger pore volume and specific surface area.
The time and the temperature of the dry mixing are not particularly required by the invention to ensure that the raw materials are uniformly mixed, and in the specific embodiment of the invention, the dry mixing time is 20 min. The present invention is not particularly limited to the particular embodiment of the dry blending, and may be carried out in a manner well known to those skilled in the art.
The method comprises the following steps of wet mixing the soluble zirconium salt and water to obtain a soluble zirconium salt solution; in the present invention, the soluble zirconium salt preferably comprises zirconium chloride; in the present invention, the water is preferably pure water, and in the present invention, the mass ratio of the soluble zirconium salt to the water is preferably (15-25): 150. The present invention does not require any particular embodiment of the wet mixing, which is the addition of the soluble zirconium salt to water for dissolution, and can be performed by procedures well known to those skilled in the art.
After the dry mixture and the soluble zirconium salt solution are obtained, the dry mixture and the soluble zirconium salt solution are finally mixed to obtain the mixed slurry. In the present invention, the mass ratio of the γ -alumina to the soluble zirconium salt is preferably 500: (15-25), in the present invention, the final mixing is preferably performed under stirring conditions, and the present invention has no special requirements for the specific embodiment of the stirring; in the present invention, the specific embodiment of the final mixing is preferably to add the soluble zirconium salt solution into the dry mixture, and in the present invention, the addition is preferably to add in batches, and the number of the batches added in the present invention has no special requirement, and the dry mixture and the soluble zirconium salt solution can be uniformly mixed.
In the present invention, the mixed slurry obtained after the final mixing is in a muddy state.
After mixed slurry is obtained, carrying out first roasting on the mixed slurry to obtain a first precursor; in the invention, before the first roasting, the mixed slurry is preferably subjected to extrusion forming, in the invention, the extrusion forming is preferably carried out in an extruder provided with an extrusion grinding tool, and the extrusion mould is preferably phi 4mm, in the invention, the shape of the extruded blank is preferably a cylinder, and the invention has no special requirement on the length-diameter ratio of the blank and is determined according to the actual production requirement.
After the blank is obtained, the blank is preferably dried at the temperature of 120 ℃ for 2-4 h.
Preferably, performing first roasting on the dried blank to obtain a first precursor; the first roasting temperature is preferably 450 ℃, and the time is preferably 3-6 h.
In the invention, after the first roasting, the binder forms a framework of the catalyst, the gamma-alumina carrier is distributed in the framework, and the soluble zirconium salt is roasted to generate zirconium oxide which is uniformly dispersed on the surface and in the gaps of the gamma-alumina carrier. The zirconium oxide is used as a metal oxide auxiliary agent, and can inhibit the generation of mercaptan in the hydrogen production by CO transformation.
Secondly mixing a cobalt-containing compound, a molybdenum-containing compound, a potassium-containing compound and water to obtain an active metal impregnation liquid; in the present invention, the cobalt-containing compound preferably comprises basic cobalt carbonate and/or cobalt nitrate, more preferably comprises basic cobalt carbonate or cobalt nitrate; the molybdenum-containing compound preferably comprises ammonium tetramolybdate; the potassium-containing compound is preferably potassium carbonate and/or potassium hydroxide, more preferably comprises potassium carbonate or potassium hydroxide; in the invention, the mass concentration of the cobalt element in the active metal impregnation liquid is preferably 1.5-3%, the mass concentration of the molybdenum element is preferably 5-10%, and the mass concentration of the potassium element is preferably 8-12%.
In the present invention, the active metal impregnation solution preferably further includes an impregnation penetrant, and in the present invention, when the active metal impregnation solution preferably further includes an impregnation penetrant, the second mixing preferably includes the steps of: primarily mixing a cobalt-containing compound, a molybdenum-containing compound, a potassium-containing compound and water to obtain an active metal mixed solution; and remixing the active metal mixed solution and the impregnation penetrating agent to obtain the active metal impregnation solution. In the invention, the impregnation penetrating agent preferably comprises one or more of sodium alkyl sulfate, glycol, EDTA and citric acid, and more preferably comprises sodium alkyl sulfate, glycol or EDTA. In the invention, the mass ratio of the mass of the impregnation penetrating agent to the mass of the cobalt element in the cobalt-containing compound is preferably (2-4): (1.5-3), and more preferably 2: 2.5.
The purpose of adding the impregnation penetrating agent is to ensure that the active metal compound can be impregnated into the first precursor more fully, so that the active metal compound can enter the porous structure of the gamma-alumina carrier fully.
After a first precursor and an active metal impregnation liquid are obtained, the first precursor is impregnated in the active metal impregnation liquid to obtain a second precursor; in the invention, the impregnation is preferably carried out in a double cone, the first precursor is preferably added into the double cone, the double cone is vacuumized, the active metal impregnation liquid is sucked into the double cone through pressure difference, the first precursor is impregnated, the impregnation time is preferably 2-6 h, the vacuum degree of the double cone vacuumizing is not specially required, and the active metal impregnation liquid can smoothly enter the double cone.
After the impregnation is finished, the impregnated first precursor is preferably dried to obtain a second precursor; in the present invention, the drying temperature is preferably 100 ℃ and the drying time is preferably 4 hours.
After a second precursor is obtained, carrying out second roasting on the second precursor to obtain the mercaptan-inhibiting low-temperature sulfur-tolerant shift catalyst; in the invention, the second roasting temperature is preferably 550 ℃, and the time is preferably 2-4 h.
In the invention, cobalt-containing compounds, molybdenum-containing compounds and potassium-containing compounds which are soaked in the surface of the gamma-alumina and can be in the pore diameter are subjected to chemical reaction to generate cobalt oxide, molybdenum oxide and potassium carbonate through second roasting, so that high conversion rate of CO can be realized.
The invention also provides the application of the mercaptan-inhibiting low-temperature sulfur-tolerant shift catalyst in the technical scheme or the mercaptan-inhibiting low-temperature sulfur-tolerant shift catalyst obtained by the preparation method in the technical scheme in hydrogen production through CO shift.
In the invention, the inlet temperature of the reactor for producing hydrogen by CO conversion is preferably 190-220 ℃, the reaction pressure is preferably 3MPa, the water gas is preferably 40%, and the equipment for producing hydrogen by CO conversion is preferably an isothermal conversion reactor.
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
Weighing 500g of gamma-alumina (particle size is 48-75 mu m, pore volume is 0.2-0.45 cm)3A specific surface area of 200 to 350 m/g2Dry mixing 20g of carbon simple substance (with the particle size of 48-75 mu m) and 30g of cement for 20min to obtain a dry mixture;
adding 20g of zirconium chloride into 150g of pure water for dissolution to obtain a zirconium chloride solution, adding the zirconium chloride solution into the dry mixture in multiple batches, stirring in the adding process until the mixture becomes mud, extruding the mixture by using an extruder to obtain a cylindrical blank with phi 4mm, drying the blank at 120 ℃ for 2 hours, and then performing first roasting at 450 ℃ for 4 hours to obtain a first precursor;
preparing basic cobalt carbonate, ammonium tetramolybdate, potassium carbonate and water into an active metal compound solution, wherein the mass content of cobalt element is 2.5%, the mass content of molybdenum element is 7% and the mass content of potassium element is 10%, and then adding 2% of sodium alkyl sulfate into the active metal compound solution to be fully mixed to obtain an active metal compound impregnation solution;
adding the first precursor into a double cone for vacuumizing, sucking an active metal compound impregnation liquid into the double cone by means of negative pressure, soaking for 2 hours to remove the impregnated first precursor, and drying for 4 hours at 100 ℃ to obtain a second precursor;
and roasting the second precursor at 550 ℃ for 2 hours to obtain the mercaptan-inhibiting low-temperature sulfur-tolerant shift catalyst.
Example 2
Weighing 500g of gamma-alumina (particle size is 48-75 mu m, pore volume is 0.2-0.45 cm)3A specific surface area of 200 to 350 m/g2Dry mixing 20g of attapulgite (the particle size is 48-75 mu m) and 30g of cement for 20min to obtain a dry mixture;
adding 15g of zirconium chloride into 150g of pure water for dissolution to obtain a zirconium chloride solution, adding the zirconium chloride solution into the dry mixture in multiple batches, stirring in the adding process until the mixture becomes mud, extruding the mixture by using an extruder to obtain a cylindrical blank with phi 4mm, drying the blank at 120 ℃ for 2 hours, and then performing first roasting at 450 ℃ for 4 hours to obtain a first precursor;
preparing basic cobalt carbonate, ammonium tetramolybdate, potassium carbonate and water into an active metal compound solution, wherein the mass content of cobalt element is 2.5%, the mass content of molybdenum element is 7% and the mass content of potassium element is 10%, and then adding 2% of glycol into the active metal compound solution for fully mixing to obtain an active metal compound impregnation solution;
adding the first precursor into a double cone for vacuumizing, sucking an active metal compound impregnation liquid into the double cone by means of negative pressure, soaking for 2 hours to remove the impregnated first precursor, and drying for 4 hours at 100 ℃ to obtain a second precursor;
and roasting the second precursor at 550 ℃ for 2 hours to obtain the mercaptan-inhibiting low-temperature sulfur-tolerant shift catalyst.
Example 3
Weighing 500g of gamma-alumina (particle size is 48-75 mu m, pore volume is 0.2-0.45 cm)3A specific surface area of 200 to 350 m/g2Dry mixing 20g of attapulgite (the particle size is 48-75 mu m) and 30g of CMC for 20min to obtain a dry mixture;
adding 25g of zirconium chloride into 150g of pure water for dissolution to obtain a zirconium chloride solution, adding the zirconium chloride solution into the dry mixture in multiple batches, stirring in the adding process until the mixture becomes mud, extruding the mixture by using an extruder to obtain a cylindrical blank with phi 4mm, drying the blank at 120 ℃ for 2 hours, and then performing first roasting at 450 ℃ for 4 hours to obtain a first precursor;
preparing basic cobalt carbonate, ammonium tetramolybdate, potassium carbonate and water into an active metal compound solution, wherein the mass content of cobalt element is 2.5%, the mass content of molybdenum element is 7% and the mass content of potassium element is 10%, and then adding 2% of EDTA into the active metal compound solution to be fully mixed to obtain an active metal compound impregnation solution;
adding the first precursor into a double cone for vacuumizing, sucking an active metal compound impregnation liquid into the double cone by means of negative pressure, soaking for 2 hours to remove the impregnated first precursor, and drying for 4 hours at 100 ℃ to obtain a second precursor;
and roasting the second precursor at 550 ℃ for 2 hours to obtain the mercaptan-inhibiting low-temperature sulfur-tolerant shift catalyst.
Example 4
Weighing 500g of gamma-alumina (particle size is 48-75 mu m, pore volume is 0.2-0.45 cm)3A specific surface area of 200 to 350 m/g2/g) and 30g of cement are dry-mixed and driedMixing for 20min to obtain dry mixture;
adding 20g of zirconium chloride into 150g of pure water for dissolution to obtain a zirconium chloride solution, adding the zirconium chloride solution into the dry mixture in multiple batches, stirring in the adding process until the mixture becomes mud, extruding the mixture by using an extruder to obtain a cylindrical blank with phi 4mm, drying the blank at 120 ℃ for 2 hours, and then performing first roasting at 450 ℃ for 4 hours to obtain a first precursor;
preparing basic cobalt carbonate, ammonium tetramolybdate, potassium carbonate and water into an active metal compound solution, wherein the mass content of cobalt element is 2.5%, the mass content of molybdenum element is 7% and the mass content of potassium element is 10%, and then adding 2% of sodium alkyl sulfate into the active metal compound solution to be fully mixed to obtain an active metal compound impregnation solution;
adding the first precursor into a double cone for vacuumizing, sucking an active metal compound impregnation liquid into the double cone by means of negative pressure, soaking for 2 hours to remove the impregnated first precursor, and drying for 4 hours at 100 ℃ to obtain a second precursor;
and roasting the second precursor at 550 ℃ for 2 hours to obtain the mercaptan-inhibiting low-temperature sulfur-tolerant shift catalyst.
Example 5
Weighing 500g of gamma-alumina (particle size is 48-75 mu m, pore volume is 0.2-0.45 cm)3A specific surface area of 200 to 350 m/g2Dry mixing 20g of carbon simple substance (with the particle size of 48-75 mu m) and 30g of cement for 20min to obtain a dry mixture;
adding 20g of zirconium chloride into 150g of pure water for dissolution to obtain a zirconium chloride solution, adding the zirconium chloride solution into the dry mixture in multiple batches, stirring in the adding process until the mixture becomes mud, extruding the mixture by using an extruder to obtain a cylindrical blank with phi 4mm, drying the blank at 120 ℃ for 2 hours, and then performing first roasting at 450 ℃ for 4 hours to obtain a first precursor;
preparing active metal compound solution from basic cobalt carbonate, ammonium tetramolybdate, potassium carbonate and water, wherein the mass content of cobalt element is 2.5%, the mass content of molybdenum element is 7% and the mass content of potassium element is 10%, so as to obtain active metal compound impregnation liquid;
adding the first precursor into a double cone for vacuumizing, sucking an active metal compound impregnation liquid into the double cone by means of negative pressure, soaking for 2 hours to remove the impregnated first precursor, and drying for 4 hours at 100 ℃ to obtain a second precursor;
and roasting the second precursor at 550 ℃ for 2 hours to obtain the mercaptan-inhibiting low-temperature sulfur-tolerant shift catalyst.
Comparative example 1
Weighing 500g of gamma-alumina (particle size is 48-75 mu m, pore volume is 0.2-0.45 cm)3A specific surface area of 200 to 350 m/g2Dry mixing 20g of carbon simple substance (with the particle size of 48-75 mu m) and 30g of cement for 20min to obtain a dry mixture;
adding 150g of pure water into the dry mixture, adding the pure water in multiple batches, stirring in the adding process until the mixture becomes mud, extruding the mixture by using an extruder to obtain a cylindrical blank with the diameter of 4mm, drying the blank at 120 ℃ for 2 hours, and then performing first roasting at 450 ℃ for 4 hours to obtain a first precursor;
preparing basic cobalt carbonate, ammonium tetramolybdate, potassium carbonate and water into an active metal compound solution, wherein the mass content of cobalt element is 2.5%, the mass content of molybdenum element is 7% and the mass content of potassium element is 10%, and then adding 2% of sodium alkyl sulfate into the active metal compound solution to be fully mixed to obtain an active metal compound impregnation solution;
adding the first precursor into a double cone for vacuumizing, sucking an active metal compound impregnation liquid into the double cone by means of negative pressure, soaking for 2 hours to remove the impregnated first precursor, and drying for 4 hours at 100 ℃ to obtain a second precursor;
and roasting the second precursor at 550 ℃ for 2 hours to obtain the mercaptan-inhibiting low-temperature sulfur-tolerant shift catalyst.
Comparative example 2
Weighing 500g of gamma-alumina (particle size is 48-75 mu m, pore volume is 0.2-0.45 cm)3A specific surface area of 200 to 350 m/g2Per gram), 20 grams of carbon simple substance (particle size is 48-75 mu m) and 3Carrying out dry mixing on 0g of cement for 20min to obtain a dry mixture;
adding 20g of zirconium chloride into 150g of pure water for dissolution to obtain a metal oxide auxiliary agent salt solution, adding the metal oxide auxiliary agent salt solution into the dry mixture, adding the mixture in multiple batches, stirring in the adding process until the mixture becomes mud, extruding the mixture by using an extruder by mounting a grinding tool to obtain a cylindrical blank with phi 4mm, drying the blank at 120 ℃ for 2 hours, and then performing first roasting at 450 ℃ for 4 hours to obtain a first precursor;
preparing basic cobalt carbonate, ammonium tetramolybdate and water into an active metal compound solution, wherein the mass content of cobalt element is 2.5%, the mass content of molybdenum element is 7% and the mass content of potassium element is 10%, and then adding 2% of sodium alkyl sulfate into the active metal compound solution to be fully mixed to obtain an active metal compound impregnation solution;
adding the first precursor into a double cone for vacuumizing, sucking an active metal compound impregnation liquid into the double cone by means of negative pressure, soaking for 2 hours to remove the impregnated first precursor, and drying for 4 hours at 100 ℃ to obtain a second precursor;
and roasting the second precursor at 550 ℃ for 2 hours to obtain the mercaptan-inhibiting low-temperature sulfur-tolerant shift catalyst.
Comparative example 3
Weighing 500g of gamma-alumina (particle size is 48-75 mu m, pore volume is 0.2-0.45 cm)3A specific surface area of 200 to 350 m/g2Dry mixing 20g of carbon simple substance (with the particle size of 48-75 mu m) and 30g of cement for 20min to obtain a dry mixture;
adding 20g of cerium chloride into 150g of pure water for dissolution to obtain a metal compound auxiliary salt solution, adding the metal compound auxiliary salt solution into the dry mixture, adding the mixture in multiple batches, stirring in the adding process until the mixture becomes mud, extruding the mixture by using an extruder by mounting a grinding tool to obtain a cylindrical blank with phi 4mm, drying the blank at 120 ℃ for 2 hours, and then performing first roasting at 450 ℃ for 4 hours to obtain a first precursor;
preparing basic cobalt carbonate, ammonium tetramolybdate, potassium carbonate and water into an active metal compound solution, wherein the mass content of cobalt element is 2.5%, the mass content of molybdenum element is 7% and the mass content of potassium element is 10%, and then adding 2% of sodium alkyl sulfate into the active metal compound solution to be fully mixed to obtain an active metal compound impregnation solution;
adding the first precursor into a double cone for vacuumizing, sucking an active metal compound impregnation liquid into the double cone by means of negative pressure, soaking for 2 hours to remove the impregnated first precursor, and drying for 4 hours at 100 ℃ to obtain a second precursor;
and roasting the second precursor at 500 ℃ for 2 hours to obtain the mercaptan-inhibiting low-temperature sulfur-tolerant shift catalyst.
Comparative example 4
Weighing 500g of gamma-alumina (particle size is 48-75 mu m, pore volume is 0.2-0.45 cm)3A specific surface area of 200 to 350 m/g2Dry mixing 20g of carbon simple substance (with the particle size of 48-75 mu m) and 30g of cement for 20min to obtain a dry mixture;
adding 150g of pure water into the dry mixture, adding the pure water in multiple batches, stirring in the adding process until the mixture becomes mud, extruding the mixture by using an extruder to obtain a cylindrical blank with the diameter of 4mm, drying the blank at 120 ℃ for 2 hours, and then performing first roasting at 450 ℃ for 4 hours to obtain a first precursor;
preparing active metal compound solution from basic cobalt carbonate, ammonium tetramolybdate and water, wherein the mass content of cobalt element is 2.5%, and the mass content of molybdenum element is 7%, and fully mixing to obtain active metal compound impregnation liquid;
adding the first precursor into a double cone for vacuumizing, sucking an active metal compound impregnation liquid into the double cone by means of negative pressure, soaking for 2 hours to remove the impregnated first precursor, and drying for 4 hours at 100 ℃ to obtain a second precursor;
and roasting the second precursor at 550 ℃ for 2 hours to obtain the mercaptan-inhibiting low-temperature sulfur-tolerant shift catalyst.
Comparative example 5
Weighing 500g of gamma-alumina (particle size is 48-75 mu m, pore volume is 0.2-0.45 cm)3A specific surface area of 200 to 350 m/g2Dry mixing 20g of carbon simple substance (with the particle size of 48-75 mu m) and 30g of cement for 20min to obtain a dry mixture;
adding 20g of zirconium chloride into 150g of pure water for dissolution to obtain a zirconium chloride solution, adding the zirconium chloride solution into the dry mixture in multiple batches, stirring in the adding process until the mixture becomes mud, extruding the mixture by using an extruder to obtain a cylindrical blank with phi 4mm, drying the blank at 120 ℃ for 2 hours, and then performing first roasting at 450 ℃ for 4 hours to obtain a first precursor;
preparing basic cobalt carbonate, ammonium tetramolybdate, potassium carbonate and water into an active metal compound solution, wherein the mass content of cobalt element is 2.5%, the mass content of molybdenum element is 7% and the mass content of potassium element is 10%, and then adding 2% of sodium alkyl sulfate into the active metal compound solution to be fully mixed to obtain an active metal compound impregnation solution;
adding the first precursor into a double cone for vacuumizing, sucking an active metal compound impregnation liquid into the double cone by means of negative pressure, soaking for 2 hours to remove the impregnated first precursor, and drying for 4 hours at 100 ℃ to obtain a second precursor;
and roasting the second precursor at 600 ℃ for 2 hours to obtain the mercaptan-inhibiting low-temperature sulfur-tolerant shift catalyst.
Comparative example 6
Weighing 500g of gamma-alumina (particle size is 48-75 mu m, pore volume is 0.2-0.45 cm)3A specific surface area of 200 to 350 m/g2Dry mixing 20g of attapulgite (the particle size is 48-75 mu m) and 30g of cement for 20min to obtain a dry mixture;
adding 15g of zirconium chloride into 150g of pure water for dissolution to obtain a zirconium chloride solution, adding the zirconium chloride solution into the dry mixture in multiple batches, stirring in the adding process until the mixture becomes mud, extruding the mixture by using an extruder to obtain a cylindrical blank with phi 4mm, drying the blank at 120 ℃ for 2 hours, and then performing first roasting at 450 ℃ for 4 hours to obtain a first precursor;
preparing basic cobalt carbonate, ammonium tetramolybdate, potassium carbonate and water into an active metal compound solution, wherein the mass content of cobalt element is 2.5%, the mass content of molybdenum element is 7% and the mass content of potassium element is 10%, and then adding 2% of glycol into the active metal compound solution for fully mixing to obtain an active metal compound impregnation solution;
adding the first precursor into a double cone for vacuumizing, sucking an active metal compound impregnation liquid into the double cone by means of negative pressure, soaking for 2 hours to remove the impregnated first precursor, and drying for 4 hours at 100 ℃ to obtain a second precursor;
and roasting the second precursor at 500 ℃ for 2 hours to obtain the mercaptan-inhibiting low-temperature sulfur-tolerant shift catalyst.
Comparative example 7
Weighing 500g of gamma-alumina (particle size is 48-75 mu m, pore volume is 0.2-0.45 cm)3A specific surface area of 200 to 350 m/g2Dry mixing 20g of carbon simple substance (with the particle size of 48-75 mu m) and 30g of cement for 20min to obtain a dry mixture;
adding 150g of pure water into the dry mixture, adding the pure water in multiple batches, stirring in the adding process until the mixture becomes mud, extruding the mixture by using an extruder to obtain a cylindrical blank with the diameter of 4mm, drying the blank at 120 ℃ for 2 hours, and then performing first roasting at 400 ℃ for 4 hours to obtain a first precursor;
preparing active metal compound solution from basic cobalt carbonate, ammonium tetramolybdate and water, wherein the mass content of cobalt element is 2.5%, and the mass content of molybdenum element is 7%, and fully mixing to obtain active metal compound impregnation liquid;
adding the first precursor into a double cone for vacuumizing, sucking an active metal compound impregnation liquid into the double cone by means of negative pressure, soaking for 2 hours to remove the impregnated first precursor, and drying for 4 hours at 100 ℃ to obtain a second precursor;
and roasting the second precursor at 550 ℃ for 2 hours to obtain the mercaptan-inhibiting low-temperature sulfur-tolerant shift catalyst.
Comparative example 8
Weighing 500g of gamma-alumina (particle size is 48-75 mu m, pore volume is 0.2-0.45 cm)3A specific surface area of 200 to 350 m/g2/g)、Carrying out dry mixing on 20g of carbon simple substance (with the particle size of 48-75 mu m) and 30g of cement for 20min, and fully mixing to obtain a dry mixture;
adding 150g of pure water into the dry mixture, adding the pure water in multiple batches, stirring in the adding process until the mixture becomes mud, extruding the mixture by using an extruder to obtain a cylindrical blank with the diameter of 4mm, drying the blank at 120 ℃ for 2 hours, and then performing first roasting at 500 ℃ for 4 hours to obtain a first precursor;
preparing active metal compound solution from basic cobalt carbonate, ammonium tetramolybdate and water, wherein the mass content of cobalt element is 2.5%, and the mass content of molybdenum element is 7%, and fully mixing to obtain active metal compound impregnation liquid;
adding the first precursor into a double cone for vacuumizing, sucking an active metal compound impregnation liquid into the double cone by means of negative pressure, soaking for 2 hours to remove the impregnated first precursor, and drying for 4 hours at 100 ℃ to obtain a second precursor;
and roasting the second precursor at 550 ℃ for 2 hours to obtain the mercaptan-inhibiting low-temperature sulfur-tolerant shift catalyst.
Test example
The mercaptan-inhibiting low-temperature sulfur-tolerant shift catalyst prepared in the examples 1-5 and the comparative examples 1-8 is used at 200 ℃, 200MPa of pressure, 40% of water-gas ratio and 2000h of reaction gas space velocity-1And under the condition that the content of CO is 45%, hydrogen is produced by CO conversion in an isothermal conversion reactor, and the using amount of the catalyst is 30 g. The performance of the catalysts obtained in the examples and comparative examples was evaluated by the CO conversion and the mercaptan content in the product. The specific results are shown in Table 1, and the results in Table 1 show that the mercaptan-inhibiting low-temperature sulfur-tolerant shift catalyst provided by the invention can realize high CO conversion rate and low mercaptan content, the CO conversion rate is 92.6-98.2%, the mass content of mercaptan in the product is 0.08-0.37 ppm, the service life of the catalyst is 82-98H when the CO conversion rate is kept to be more than 92%, and the catalyst provided by the invention can be used in the process of converting H2The catalyst has high catalytic activity when the S content is more than 200ppm, wherein the catalyst prepared in the comparative example 1 does not contain metal oxide auxiliary agent, and the mercaptan content in the product is 0.68ppmThe catalyst is obviously higher than the catalyst products prepared in the embodiments 1-5 of the invention; the active metal compound in the catalyst prepared in the comparative document 2 does not contain potassium carbonate, and the conversion rate of CO is 84.4%, which is obviously lower than that of the catalyst products prepared in the embodiments 1-5 of the invention; in the comparative example 3, cerium chloride is used as a metal oxide assistant, and compared with the comparative example 1, the content of mercaptan is reduced, so that the cerium chloride can play a certain role in inhibiting the generation of mercaptan when being used as the metal oxide assistant, but compared with the catalysts provided in the examples 1-5 of the invention, the catalyst prepared in the invention is superior to the catalyst obtained in the comparative example 3; comparative example 4 is a catalyst in the prior art, and both the CO conversion rate and the ability to suppress mercaptans are lower than the catalysts prepared in examples 1-5 of the present invention.
TABLE 1 Performance of catalysts obtained in examples 1 to 5 and comparative examples 1 to 8
Figure BDA0002805892350000151
Figure BDA0002805892350000161
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.

Claims (10)

1. The low-temperature sulfur-tolerant shift catalyst for inhibiting mercaptan comprises a gamma-alumina carrier, and a metal oxide auxiliary agent and an active metal compound which are loaded on the surface and in pores of the gamma-alumina carrier;
the metal oxide additive comprises zirconium oxide;
the active metal compound includes cobalt oxide, molybdenum oxide, and potassium carbonate.
2. The thiol-inhibited low-temperature sulfur-tolerant shift catalyst according to claim 1, wherein the mass ratio of the γ -alumina support to the metal oxide promoter is 500: (8-13); the mass ratio of the gamma-alumina carrier to the active metal compound is 100 (14.5-25).
3. The catalyst of claim 1, wherein the mass ratio of cobalt element in the cobalt oxide, molybdenum element in the molybdenum oxide and potassium element in the potassium carbonate is (1.5-3): 5-10): 8-12.
4. The method for preparing the mercaptan-inhibited low-temperature sulfur-tolerant shift catalyst according to any one of claims 1 to 3, comprising the steps of:
carrying out first mixing on gamma-alumina, soluble zirconium salt, a binder and water to obtain mixed slurry;
performing first roasting on the mixed slurry to obtain a first precursor;
secondly, mixing a cobalt-containing compound, a molybdenum-containing compound, a potassium-containing compound and water to obtain an active metal impregnation liquid;
dipping the first precursor in an active metal dipping solution to obtain a second precursor;
and carrying out second roasting on the second precursor to obtain the mercaptan-inhibiting low-temperature sulfur-tolerant shift catalyst.
5. The method of claim 4, wherein the binder comprises cement and/or sodium carboxymethyl cellulose; the mass ratio of the gamma-alumina to the soluble zirconium salt to the binder is 500 (15-25): (30-100).
6. The production method according to claim 4, wherein the active metal impregnation liquid contains 1.5 to 3% by mass of cobalt, 5 to 10% by mass of molybdenum, and 8 to 12% by mass of potassium.
7. The preparation method according to claim 4, wherein the mixed slurry further comprises a pore-forming agent, and the pore-forming agent comprises elemental carbon and/or attapulgite; the mass ratio of the gamma-alumina to the binder to the pore-forming agent is 500 (30-100) to 20-50.
8. The preparation method according to claim 4, wherein the active metal impregnation liquid further comprises an impregnation penetrant, and the impregnation penetrant comprises one or more of sodium alkyl sulfate, ethylene glycol, EDTA and citric acid; the mass ratio of the impregnating penetrating agent to the cobalt element in the cobalt-containing compound is (2-4): (1.5-3).
9. The preparation method according to claim 4, wherein the temperature of the first roasting is 450 ℃ and the time is 3-6 h; the temperature of the second roasting is 550 ℃, and the time is 2-4 hours.
10. Use of the mercaptan-inhibiting low-temperature sulfur-tolerant shift catalyst according to any one of claims 1 to 3 or the mercaptan-inhibiting low-temperature sulfur-tolerant shift catalyst obtained by the preparation method according to any one of claims 4 to 9 in hydrogen production through CO shift.
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