CN115178276B - Preparation and application of nickel-based catalyst for reverse water gas shift reaction - Google Patents

Preparation and application of nickel-based catalyst for reverse water gas shift reaction Download PDF

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CN115178276B
CN115178276B CN202210818897.3A CN202210818897A CN115178276B CN 115178276 B CN115178276 B CN 115178276B CN 202210818897 A CN202210818897 A CN 202210818897A CN 115178276 B CN115178276 B CN 115178276B
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CN115178276A (en
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臧云浩
张子仪
高峰
曲江英
顾建峰
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Dongguan University of Technology
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention discloses a nickel-based catalyst (Ni/M-S) for reverse water gas shift reaction, a preparation method and application thereof. The prepared nickel-based catalyst (Ni/M-S) is used for reverse water gas shift reaction, and the selectivity of carbon monoxide (CO) is close to 100%.

Description

Preparation and application of nickel-based catalyst for reverse water gas shift reaction
Technical Field
The invention relates to a catalyst for reverse water gas shift reaction, in particular to a preparation and application of a nickel-based catalyst which takes sulfur as an auxiliary agent and is loaded by oxide.
Background
Slowing down the adverse effects of greenhouse effects on climate is a significant proposition commonly faced by global scientists. Carbon dioxide (CO) 2 ) Is the most dominant greenhouse gas, however, from a resource perspective, CO 2 Also a large amount of carbon source compounds in nature, if CO can be added 2 The method is converted into useful chemicals or fuels, so that not only can the environmental problem caused by carbon emission be solved, but also the method becomes a very ideal energy supplementing form. CO is an excellent platform compound in C1 chemistry by means of reverse water gas shift reaction (RWGS, CO 2 +H 2 →CO+H 2 O ΔH 298K ＝41.3KJ·mol -1 ) CO is firstly processed 2 Reducing into more active CO, and then further hydrogenating and converting the CO into high-added value chemicals such as olefin, aromatic hydrocarbon, gasoline and the like. Thus, the RWGS reaction is CO 2 The important ring of resource utilization is essential, and has important theoretical and practical significance for deep research.
The reverse water gas shift reaction is an endothermic reaction, and the high temperature is favorable for the rapid generation of CO. However, at near atmospheric pressure CO 2 CH is prepared in hydrogenation catalytic system 4 And CO-production reactions tend to coexist and compete with each other, resulting in a decrease in selectivity of the target product. The nickel-based catalyst has stronger hydrogenation capacity according toAs a result of the study by et al (Applied Catalysis B: environmental,2021,295,120319), the CO desorption energy (345 kJ. Mol-1) on the Ni (111) crystal face was slightly higher than the critical value (318 kJ. Mol-1), and the hydrogenation product was represented by CH 4 Is mainly and therefore often used for the catalysis of CO 2 CH generation 4 (Catalysis Today,2016, 273,234-243；Applied Catalysis B:Environmental,2014,147,359-368.)。
From earlier stage CO 2 In-situ spectroscopy characterization and theoretical calculation research of hydrogenation show that CO 2 First chemisorbed and activated to CO2 at the catalyst surface, then undergo two possible reaction pathways: 1) Generating an intermediate formate (hcoox) and dissociating into adsorbed CO; 2) Direct reduction to adsorbed CO. CO with weaker adsorption can be quickly desorbed and converted into gas-phase CO, and the CO 2 The hydrogenation product is mainly CO; conversely, CO with higher adsorption tends to continue deep hydrogenation and produce the product CH 4 . It can be seen that the adsorption strength of the adsorbed CO determines the CO under near atmospheric reaction conditions 2 The selectivity of the hydrogenated product.
At present, CO is realized 2 Hydrogenation product from CH 4 Three methods of selective control to CO are mainly used, one is to construct a bi/multi-metal catalyst (CN 109499577B, iScience,2019,17,315-324); second, the nickel metal particle size is reduced (Catalysis Science&Technology,2015,5, 4154-4163); thirdly, by means of nickel-goldStrong interaction between the genus-vectors (Applied Catalysis B: environmental,2018,224,442-450). The essence is to weaken the adsorption strength of CO by changing the electron density/chemical state of the active Ni surface. However, the above Ni-based catalysts all suffer from some drawbacks, such as too complicated strategy for constructing bi/multi-metal catalysts and lack of versatility and versatility; catalyst CO prepared by method for reducing nickel metal particle size and regulating and controlling strong interaction between nickel metal and carrier 2 The conversion was too low (less than 10%). Therefore, the design of a novel high-efficiency Ni-based catalyst with low CO adsorption strength is a key problem to be solved urgently by breaking through the regulatory framework of the conventional Ni-based catalyst.
Disclosure of Invention
The invention aims to provide a preparation and application method of a nickel-based catalyst for reverse water gas shift reaction. The catalyst has the characteristics of high conversion rate, nearly 100% CO selectivity and good stability in the reverse water gas shift reaction.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the synthesis method of the nickel-based catalyst (Ni/M-S) comprises the following steps:
1) Dispersing a nickel precursor, a sulfur precursor and a carrier M into a mixed solution of deionized water and an organic solvent, and magnetically stirring for 0.5-3h;
2) Placing the mixed solution in the step 1) into an oven at 30-150 ℃ to be dried for more than 12 hours to obtain a solid catalyst precursor;
3) Roasting the catalyst precursor obtained in the step 2) for 1-5 hours in an air atmosphere at 400-900 ℃ to obtain NiO/M-S;
4) And 3) placing the NiO/M-S obtained in the step 3) in a hydrogen atmosphere at 400-900 ℃ for reduction for 1-5h to obtain the Ni/M-S catalyst.
In the step 1), the mass content of the active component nickel is 0.1% -40%, and the nickel precursor comprises one or a mixture of more of nickel nitrate, nickel chloride, nickel sulfate, nickel acetate and nickel acetylacetonate; the mass content of the auxiliary sulfur is 0.1% -5%, and the sulfur precursor comprises one or a mixture of more of elemental sulfur, sodium sulfide, ammonium sulfide, nickel sulfate, ammonium sulfate, sodium thiosulfate, thioacetamide, thiocarbamide, hydrogen sulfide, sulfur dioxide and sulfuric acid; the carrier M is one or a mixture of more of zirconium oxide, aluminum oxide, silicon oxide, titanium oxide and cerium oxide; the organic solvent is one or a mixture of several of methanol, ethanol and glycol.
In the step 3), the temperature rising rate in the roasting process is 5 ℃/min-20 ℃/min.
In the step 4), the hydrogen atmosphere is a mixed gas of hydrogen and nitrogen or argon, and the volume ratio of the hydrogen in the mixed gas is 2% -30%.
The catalyst obtained in the step 4) is used for the reverse water gas shift reaction, and the reaction evaluation conditions are as follows: the catalyst is filled in a fixed bed reactor, reaction gas is introduced, and the molar ratio of hydrogen to carbon dioxide in the reaction gas is 1-9; the flow rate of the reaction gas is 3000-50000 mL/(g.h), the reaction pressure is normal pressure or near normal pressure (0.1 Mpa-1 Mpa), and the reaction temperature is 250-800 ℃; after the reaction, the selectivity of carbon monoxide (CO) in the obtained reaction product is close to 100%.
The invention also claims a nickel-based catalyst (Ni/M-S) for reverse water gas shift reaction, which consists of an active component, an auxiliary agent and a carrier, wherein the active component is nickel, the auxiliary agent is sulfur, and the carrier is oxide M. The mass content of active component nickel in the catalyst is 0.1% -40%, and the nickel precursor comprises one or a mixture of several of nickel nitrate, nickel chloride, nickel sulfate, nickel acetate and nickel acetylacetonate. The mass content of the auxiliary sulfur in the catalyst is 0.1% -5%, and the sulfur precursor comprises one or a mixture of more of elemental sulfur, sodium sulfide, ammonium sulfide, nickel sulfate, ammonium sulfate, sodium thiosulfate, thioacetamide, thiosemicarbazide, hydrogen sulfide, sulfur dioxide and sulfuric acid.
The invention further claims the use of a nickel-based catalyst (Ni/M-S) for reverse water gas shift reactions. The selectivity of carbon monoxide (CO) is close to 100%, and the conversion rate is 10% -50%.
Drawings
Fig. 1 is an XRD pattern of inventive example 1 and comparative example 1.
Fig. 2 is a TEM image of example 1 of the present invention.
FIG. 3 is a graph showing the catalytic performance of the catalyst prepared according to the present invention.
Fig. 4 is an in-situ infrared spectrum of example 1 of the present invention.
Fig. 5 is a graph of catalytic stability test of inventive example 1 and comparative example 1.
Detailed Description
Example 1:
1) And (3) preparing a catalyst: 1.877g of zirconyl nitrate and 0.584g of nickel nitrate nonahydrate are weighed and dissolved in 20mL of deionized water, and stirred for 30min to be completely dissolved; adding 0.03g of ammonium sulfate into the solution, and stirring for 30min to completely dissolve; drying the mixed solution in an oven at 60 ℃ for 12 hours to obtain a solid catalyst precursor; the obtained catalyst precursor was placed in a muffle furnace (air atmosphere), the muffle furnace temperature was raised from room temperature to 500℃at a heating rate of 5℃per minute and calcined for 2 hours, and the obtained sample was named NiO/ZrO 2 -S 0.03 . Table 1 shows NiO/ZrO obtained by X-ray fluorescence spectroscopy (XRF) testing 2 -S 0.03 The actual content of elemental sulfur in the catalyst was found to be 0.56wt.%. NiO/ZrO 2 -S 0.03 Reducing for 2h in 500 ℃ hydrogen atmosphere (mixed gas of hydrogen and nitrogen, volume ratio of hydrogen in the mixed gas is 10%), and obtaining final catalyst named as Ni/ZrO 2 -S 0.03 . FIG. 1 is Ni/ZrO 2 -S 0.03 XRD pattern of the catalyst revealed that ZrO with tetragonal phase structure was successfully synthesized 2 And simple substance Ni. FIG. 2 is Ni/ZrO 2 -S 0.03 TEM image of catalyst.
TABLE 1 sample NiO/ZrO 2 -S 0.03 XRF test results of (2)
2)Catalyst application: the Ni/ZrO obtained by the preparation method 2 -S 0.03 The method is applied to the reverse water gas shift reaction. Tabletting and crushing the catalyst into 40-80 mesh size, and filling 0.2g into a quartz tube reactor; introducing reaction gas under the condition of near normal pressure (0.1 Mpa), wherein the molar ratio of the gas is hydrogen: carbon dioxide: nitrogen = 4:1:5, a step of; the reaction temperature is 300-500 ℃ and the space velocity is 15000 mL/(g h). CO at a reaction temperature of 500 DEG C 2 The conversion of (2) was 25.2% and the CO selectivity was 100%. FIG. 3 is a graph showing the catalytic performance of the catalyst produced. FIG. 4 is Ni/ZrO 2 -S 0.03 The in-situ infrared spectrogram of the catalyst shows that the essence of the catalyst with the CO selectivity of 100% can still be attributed to the fact that the addition of sulfur can promote adsorption-state CO to desorb, so that the CO selectivity is improved. FIG. 5 is Ni/ZrO 2 -S 0.03 The catalyst stability test chart of the catalyst can be seen in Ni/ZrO 2 -S 0.03 Excellent stability can be maintained in the 50 hour test.
Example 2:
1) And (3) preparing a catalyst: 1.877g of zirconyl nitrate and 0.584g of nickel nitrate nonahydrate are weighed and dissolved in 20mL of deionized water, and stirred for 30min to be completely dissolved; adding 0.5g of ammonium sulfate into the solution, and stirring for 30min to completely dissolve; drying the mixed solution in an oven at 60 ℃ for 12 hours to obtain a solid catalyst precursor; the obtained catalyst precursor was placed in a muffle furnace (air atmosphere), the muffle furnace temperature was raised from room temperature to 500℃at a heating rate of 5℃per minute and calcined for 2 hours, and the obtained sample was named NiO/ZrO 2 -S 0.5 The method comprises the steps of carrying out a first treatment on the surface of the NiO/ZrO 2 -S 0.5 Reducing for 2h in 500 ℃ hydrogen atmosphere (mixed gas of hydrogen and nitrogen, volume ratio of hydrogen in the mixed gas is 10%), and obtaining final catalyst named as Ni/ZrO 2 -S 0.5 。
2) Catalyst application: the Ni/ZrO obtained by the preparation method 2 -S 0.5 The method is applied to the reverse water gas shift reaction. Tabletting and crushing the catalyst into 40-80 mesh size, and filling 0.2g into a quartz tube reactor; introducing reaction gas under the condition of near normal pressure (0.1 Mpa), wherein the molar ratio of the gas is hydrogen: carbon dioxide: nitrogen = 4:1:5, a step of; the reaction temperature is 300-5 DEG C00℃and space velocity of 15000 mL/(g h). CO at a reaction temperature of 500 DEG C 2 The conversion of (2) was 39.2% and the CO selectivity was 100%. FIG. 3 is a graph showing the catalytic performance of the catalyst produced.
Example 3:
1) And (3) preparing a catalyst: 3.525g of cerium nitrate hexahydrate and 0.584g of nickel nitrate nonahydrate are weighed and dissolved in 20mL of deionized water, and stirred for 30min to be completely dissolved; adding 0.03g of ammonium sulfate into the solution, and stirring for 30min to completely dissolve; drying the mixed solution in an oven at 60 ℃ for 12 hours to obtain a solid catalyst precursor; the obtained catalyst precursor was placed in a muffle furnace (air atmosphere), the muffle furnace temperature was raised from room temperature to 500℃at a heating rate of 5℃per minute and calcined for 2 hours, and the obtained sample was named NiO/CeO 2 -S 0.03 The method comprises the steps of carrying out a first treatment on the surface of the NiO/CeO 2 -S 0.03 Reducing for 2h in 500 ℃ hydrogen atmosphere (the volume ratio of hydrogen to nitrogen is 10 percent in the mixed gas), and obtaining the final catalyst named Ni/CeO 2 -S 0.03 。
2) Catalyst application: the prepared Ni/CeO 2 -S 0.03 The method is applied to the reverse water gas shift reaction. Tabletting and crushing the catalyst into 40-80 mesh size, and filling 0.2g into a quartz tube reactor; introducing reaction gas under the condition of near normal pressure (0.1 Mpa), wherein the molar ratio of the gas is hydrogen: carbon dioxide: nitrogen = 4:1:5, a step of; the reaction temperature is 300-500 ℃ and the space velocity is 15000 mL/(g h). CO at a reaction temperature of 500 DEG C 2 The conversion of (2) was 29.7% and the CO selectivity was 100%. FIG. 3 is a graph showing the catalytic performance of the catalyst produced.
Example 4:
1) And (3) preparing a catalyst: 3.045g of aluminum nitrate nonahydrate and 0.584g of nickel nitrate nonahydrate are weighed and dissolved in 20mL of deionized water, and stirred for 30min to be completely dissolved; adding 0.03g of ammonium sulfate into the solution, and stirring for 30min to completely dissolve; drying the mixed solution in an oven at 60 ℃ for 12 hours to obtain a solid catalyst precursor; the obtained catalyst precursor is placed in a muffle furnace (air atmosphere), the temperature of the muffle furnace is raised to 500 ℃ from room temperature at a heating rate of 5 ℃/min and baked for 2 hours,the resulting sample was designated NiO/Al 2 O 3 -S 0.03 The method comprises the steps of carrying out a first treatment on the surface of the NiO/Al 2 O 3 -S 0.03 Reducing for 2h in 500 ℃ hydrogen atmosphere (the volume ratio of hydrogen to nitrogen is 10 percent in the mixed gas), and obtaining the final catalyst which is named as Ni/Al 2 O 3 -S 0.03 。
2) Catalyst application: the Ni/Al prepared is 2 O 3 -S 0.03 The method is applied to the reverse water gas shift reaction. Tabletting and crushing the catalyst into 40-80 mesh size, and filling 0.2g into a quartz tube reactor; introducing reaction gas under the condition of near normal pressure (0.1 Mpa), wherein the molar ratio of the gas is hydrogen: carbon dioxide: nitrogen = 4:1:5, a step of; the reaction temperature is 300-500 ℃ and the space velocity is 15000 mL/(g h). CO at a reaction temperature of 500 DEG C 2 The conversion of (2) was 18.6% and the CO selectivity was 100%. FIG. 3 is a graph showing the catalytic performance of the catalyst produced.
Comparative example 1:
as a comparative experimental group, a synthesis method similar to that of examples 1 and 2 above was employed, except that no sulfur precursor was added.
1) And (3) preparing a catalyst: 1.877g of zirconyl nitrate and 0.584g of nickel nitrate nonahydrate are weighed and dissolved in 20mL of deionized water, and stirred for 30min to be completely dissolved; drying the mixed solution in an oven at 60 ℃ for 12 hours to obtain a solid catalyst precursor; the obtained catalyst precursor was placed in a muffle furnace (air atmosphere), the muffle furnace temperature was raised from room temperature to 500℃at a heating rate of 5℃per minute and calcined for 2 hours, and the obtained sample was named NiO/ZrO 2 The method comprises the steps of carrying out a first treatment on the surface of the NiO/ZrO 2 Reducing for 2h in 500 ℃ hydrogen atmosphere (mixed gas of hydrogen and nitrogen, volume ratio of hydrogen in the mixed gas is 10%), and obtaining final catalyst named as Ni/ZrO 2 。
2) Catalyst application: the Ni/ZrO obtained by the preparation method 2 The method is applied to the reverse water gas shift reaction. Tabletting and crushing the catalyst into 40-80 mesh size, and filling 0.2g into a quartz tube reactor; introducing reaction gas under the condition of near normal pressure (0.1 Mpa), wherein the molar ratio of the gas is hydrogen: carbon dioxide: nitrogen = 4:1:5, a step of; the reaction temperature was 3The air speed is 15000 mL/(g h) at 00-500 ℃. CO at a reaction temperature of 500 DEG C 2 The conversion of (2) was 39.2% and the CO selectivity was 10.0%. FIG. 3 is a graph showing the catalytic performance of the catalyst produced.
Comparative example 2:
as a comparative experimental group, a synthesis method similar to that of example 3 above was employed, except that no sulfur precursor was added.
1) And (3) preparing a catalyst: 3.525g of cerium nitrate hexahydrate and 0.584g of nickel nitrate nonahydrate are weighed and dissolved in 20mL of deionized water, and stirred for 30min to be completely dissolved; drying the mixed solution in an oven at 60 ℃ for 12 hours to obtain a solid catalyst precursor; the obtained catalyst precursor was placed in a muffle furnace (air atmosphere), the muffle furnace temperature was raised from room temperature to 500℃at a heating rate of 5℃per minute and calcined for 2 hours, and the obtained sample was named NiO/CeO 2 The method comprises the steps of carrying out a first treatment on the surface of the NiO/CeO 2 Reducing for 2h in 500 ℃ hydrogen atmosphere (the volume ratio of hydrogen to nitrogen is 10 percent in the mixed gas), and obtaining the final catalyst named Ni/CeO 2 。
2) Catalyst application: the prepared Ni/CeO 2 The method is applied to the reverse water gas shift reaction. Tabletting and crushing the catalyst into 40-80 mesh size, and filling 0.2g into a quartz tube reactor; introducing reaction gas under the condition of near normal pressure (0.1 Mpa), wherein the molar ratio of the gas is hydrogen: carbon dioxide: nitrogen = 4:1:5, a step of; the reaction temperature is 300-500 ℃ and the space velocity is 15000 mL/(g h). CO at a reaction temperature of 500 DEG C 2 The conversion of (2) was 48.7% and the CO selectivity was 12.2%. FIG. 3 is a graph showing the catalytic performance of the catalyst produced.
Comparative example 3:
as a comparative experimental group, a synthesis method similar to that of example 4 above was employed, except that no sulfur precursor was added.
1) And (3) preparing a catalyst: 3.045g of aluminum nitrate nonahydrate and 0.584g of nickel nitrate nonahydrate are weighed and dissolved in 20mL of deionized water, and stirred for 30min to be completely dissolved; drying the mixed solution in an oven at 60 ℃ for 12 hours to obtain a solid catalyst precursor; the resulting catalyst precursor was placed in a muffle furnace (air gasAtmosphere), the muffle furnace temperature was raised from room temperature to 500 ℃ at a heating rate of 5 ℃/min and baked for 2 hours, and the obtained sample was named NiO/Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the NiO/Al 2 O 3 Reducing for 2h in 500 ℃ hydrogen atmosphere (the volume ratio of hydrogen to nitrogen is 10 percent in the mixed gas), and obtaining the final catalyst which is named as Ni/Al 2 O 3 。
2) Catalyst application: the Ni/Al prepared is 2 O 3 The method is applied to the reverse water gas shift reaction. Tabletting and crushing the catalyst into 40-80 mesh size, and filling 0.2g into a quartz tube reactor; introducing reaction gas under the condition of near normal pressure (0.1 Mpa), wherein the molar ratio of the gas is hydrogen: carbon dioxide: nitrogen = 4:1:5, a step of; the reaction temperature is 300-500 ℃ and the space velocity is 15000 mL/(g h). CO at a reaction temperature of 500 DEG C 2 The conversion of (2) was 38.4% and the CO selectivity was 10.2%. FIG. 3 is a graph showing the catalytic performance of the catalyst produced.
It should be apparent that the above experimental examples are given for clarity of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.

Claims (5)

1. The application of the nickel-based catalyst for the reverse water gas shift reaction comprises an active component, an auxiliary agent and a carrier, wherein the active component is nickel, the auxiliary agent is sulfur, the carrier is oxide M, and the preparation process comprises the following steps:
1) Dispersing or filling nickel precursor, sulfur precursor and carrier M into the mixed solution of deionized water and organic solvent, and magnetically stirring for 0.5-3h;
2) Placing the mixed solution in an oven at 30-150 ℃ for drying for more than 12 hours to obtain a solid catalyst precursor;
3) Roasting the catalyst precursor in an air atmosphere at 400-900 ℃ for 1-5h to obtain NiO/M-S;
4) Placing the NiO/M-S in a hydrogen atmosphere at 400-900 ℃ for reduction for 1-5h to obtain a Ni/M-S catalyst;
the mass content of active component nickel in the catalyst is 0.1% -40%, the nickel precursor comprises one or a mixture of several of nickel nitrate, nickel chloride, nickel sulfate, nickel acetate and nickel acetylacetonate, the mass content of auxiliary sulfur in the catalyst is 0.1% -5%, the sulfur precursor comprises one or a mixture of several of elemental sulfur, sodium sulfide, ammonium sulfide, nickel sulfate, ammonium sulfate, sodium thiosulfate, thioacetamide, thiosemicarbazide, hydrogen sulfide, sulfur dioxide and sulfuric acid, and the carrier M in the catalyst is one or a mixture of several of zirconium oxide, aluminum oxide, silicon oxide, titanium oxide and cerium oxide.
2. The use according to claim 1, characterized in that: in the step 1), the organic solvent is one or a mixture of a plurality of methanol, ethanol and glycol.
3. The use according to claim 1, characterized in that: in the step 3), the heating rate of the roasting process is 5 ℃/min-20 ℃/min.
4. The use according to claim 1, characterized in that: in the step 4), the hydrogen atmosphere is a mixed gas of hydrogen and inert gas, the inert gas is nitrogen or argon, and the volume ratio of the hydrogen in the mixed gas is 2% -30%.
5. The use according to claim 1, characterized in that: the reaction evaluation conditions were: the catalyst is filled in a fixed bed reactor, reaction gas is introduced, the molar ratio of hydrogen to carbon dioxide in the reaction gas is 1-9, and nitrogen is used as diluent gas; the flow rate of the reaction gas is 3000-50000 mL/(g.h), the reaction pressure is 0.1Mpa-1Mpa, and the reaction temperature is 250-800 ℃.
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