Preparation method and application of indium-based catalyst for synthesizing low-carbon alcohol by hydrogenation of carbon dioxide

Abstract

The invention discloses a catalyst for converting carbon dioxide to prepare low-carbon alcohols, and a preparation method and application thereof, which belongs to the technical field of carbon dioxide resource utilization. The preparation method is as follows: dissolving an indium precursor and adding a precipitant to obtain a precipitate and stirring and aging, filtering and washing to obtain an indium oxide precursor, drying and roasting, adding the indium oxide obtained after roasting to an alkali metal auxiliary agent and a transition metal auxiliary agent precursor solution and stirring, drying and roasting the obtained complex, and activating it in a hydrogen and argon mixed atmosphere or a carbon monoxide atmosphere to obtain a catalyst product. This product provides a preparation method for a catalyst for converting carbon dioxide to prepare low-carbon alcohols. After heat treatment, the indium precursor and the alkali metal and transition metal auxiliary agent precursor raw materials form triple sites of indium oxide, transition metal and alkali metal, which can respectively promote the generation of carbon monoxide intermediates, catalyze the growth of carbon chains and regulate the adsorption strength of hydrogen, significantly promoting the selectivity of low-carbon alcohols, and the selectivity of low-carbon alcohols is as high as 95.5%; wherein the selectivity of ethanol and C3+ alcohols reaches 70.2% and 13.2%, respectively. The preparation method has the characteristics of less pollution, lower raw material cost and simple process, and has good application prospect.

Description

Technical Field

[0001] The technical field of carbon dioxide resource utilization, specifically, relates to a preparation method and application of a catalyst for preparing low-carbon alcohols by hydrogenating carbon dioxide. Background Art

[0002] With the rapid consumption of fossil fuels in recent years, the concentration of carbon dioxide in the atmosphere has risen to an unprecedented level. The greenhouse effect and ocean acidification seriously threaten the sustainable development of human society. Capturing and utilizing carbon dioxide is an important means to reduce the concentration of carbon dioxide in the atmosphere. On the other hand, carbon dioxide is also a non-toxic, cheap, and easily accessible renewable carbon resource. If carbon dioxide is converted into high-value-added chemicals such as alkanes, alkenes, and alcohols, carbon emissions can be reduced, carbon resources can be recycled, and economic value can be created. Low-carbon mixed alcohols (C 1-4 OH) is an important basic chemical raw material, which can be used as fuel and solvent, so it has a wide market demand. However, due to the high chemical inertness of carbon dioxide and the difficulty in accurately controlling the reaction process, the conversion of carbon dioxide to prepare low-carbon mixed alcohols has not yet been applied on a large scale in industry.

[0003] CN115228491A uses molybdate, potassium salt and rhodium salt as raw materials to prepare a highly dispersed supported rhodium-based catalyst; a rhodium salt, a molybdate solution and an aromatic amine compound are subjected to an organic-inorganic hybridization reaction to obtain a composite; the potassium salt solution and the composite are mixed to prepare a supported rhodium-based catalyst; a second active component rhodium with a carbonyl insertion function is introduced into a molybdenum carbide catalyst having a carbonyl insertion function for hydrogenating carbon dioxide to generate methanol to form a composite catalyst with dual active centers. Under the modification of an alkali metal auxiliary agent, the catalyst has good activity and a high carbon dioxide conversion rate. However, due to the high price of rhodium salt, the catalyst cost is significantly increased, which is not conducive to large-scale industrial application.

[0004] CN110947356A uses a mixed solution of ethanol and butyl titanate as a solvent, directly adds copper nitrate, iron nitrate and cobalt nitrate, uses ethylene glycol as a complexing agent, and then drips a potassium hydroxide aqueous solution, and finally uses a water bath magnetic stirring to hydrolyze butyl titanate to form a colloid, and then ages, dries and roasts the colloid to obtain a catalyst. The catalyst can directly obtain high-value-added alcohol fuels such as ethanol, propanol, and butanol by hydrogenating carbon dioxide, and the distribution of low-carbon alcohols can be controlled by adjusting the proportion of metals, but C 2+ The selectivity of alcohol only reached 18.35%, which has a large room for improvement.

[0005] CN109908960A effectively improves the effect of preparing n-butanol by hydrogenating carbon dioxide through the synergistic effect of a compound containing a transition metal element, an organic ligand and an iodide co-catalyst; the catalyst reacts in 1,3-dimethyl-2-imidazolidinone, tetrahydrofuran, isotridecane, N-methylpyrrolidone, 1,4-dioxane, dimethyl sulfoxide, ethanol, benzene, water, [OMIm]HSO4, [OMIm]H2PO4, [Emim]HSO4, [Hmim]H2PO4, [Bmim]Cl, [C6mim]Br, [Bmim]BF4 solvents. Although homogeneous catalysis can improve the reaction efficiency, catalyst recovery and product separation are difficult, which increases the cost.

[0006] In summary, the current hydrogenation of carbon dioxide to produce low-carbon alcohols still has disadvantages such as low selectivity, high cost and complex preparation process. Summary of the invention

[0007] In view of the deficiencies in the prior art, the object of the present invention is to provide a catalyst for preparing low-carbon alcohols by converting carbon dioxide, and a preparation method and application thereof. The preparation method is simple and low-cost, and the catalyst has high selectivity for low-carbon alcohols in the reaction of preparing low-carbon alcohols by catalytic hydrogenation of carbon dioxide.

[0008] In order to achieve the above object, the present invention adopts the following technical solution:

[0009] A method for preparing a catalyst for converting carbon dioxide to low-carbon alcohols, characterized in that an indium precursor is dissolved and a precipitant is added to obtain a precipitate, which is stirred and aged, filtered and washed to obtain an indium oxide precursor, which is then dried and calcined, the indium oxide obtained after calcination is mixed with an alkali metal auxiliary agent and a transition metal auxiliary agent precursor in a solution and dried to obtain a composite, the obtained composite is dried and calcined, and the catalyst product is obtained after activation in a hydrogen and argon mixed atmosphere or a carbon monoxide atmosphere.

[0010] As a further preferred embodiment of the technical solution of the present invention, the indium precursor is selected from one or more mixtures of indium nitrate, indium chloride and indium sulfate.

[0011] As a further preferred embodiment of the technical solution of the present invention, the precipitant is selected from a mixture of one or more of monohydrated ammonia, sodium hydroxide, and potassium hydroxide; the precipitation process temperature is 20 to 80° C., the pH value is 8.5 to 11, the aging temperature is 20 to 80° C., and the aging time is 1 to 48 hours.

[0012] As a further preferred embodiment of the technical solution of the present invention, the alkali metal auxiliary agent precursor is selected from a mixture of one or more of sodium nitrate and potassium nitrate.

[0013] As a further preferred embodiment of the technical solution of the present invention, the metal additive precursor is selected from a mixture of one or more of ferric nitrate, ferric chloride, ferric sulfate, nickel nitrate, nickel chloride, magnesium nitrate, magnesium chloride, cobalt nitrate, cobalt chloride, cobalt sulfate, nickel sulfate, copper nitrate, copper chloride, zinc sulfate, and copper sulfate.

[0014] As a further preferred embodiment of the technical solution of the present invention, the mass ratio of indium oxide precursor: alkali metal auxiliary agent precursor: metal auxiliary agent precursor is 53-96: 1-10: 2-14.

[0015] As a further preferred embodiment of the technical solution of the present invention, the drying temperature of the indium oxide precursor is 60-150° C., the drying time is 1-12 hours, the calcination temperature is 400-900° C., and the calcination time is 1-3 hours.

[0016] As a further preferred embodiment of the technical solution of the present invention, the drying temperature of the impregnated composite is 60-150° C., the drying time is 2-24 hours, the calcination temperature is 300-900° C., and the calcination time is 1-6 hours.

[0017] As a further preferred embodiment of the technical solution of the present invention, the catalyst activation process is carried out in an atmosphere containing hydrogen and argon or carbon monoxide at 400-800°C.

[0018] At the same time, the present invention also claims protection for the catalyst prepared by the above method.

[0019] At the same time, the present invention also claims the use of the above catalyst in the preparation of low-carbon alcohols by catalytic hydrogenation of carbon dioxide. Compared with the prior art, the present invention has the following beneficial effects:

[0020] (1) The present invention uses indium oxide rich in oxygen vacancies as a carrier to promote the reverse water gas shift reaction between carbon dioxide and hydrogen to generate the key intermediate CO. Further, a transition metal additive is introduced into indium oxide to form M 0 The introduction of alkali metal additives can effectively control the hydrogen adsorption strength on the catalyst surface and inhibit the rapid hydrogenation of alkanes at the metal sites. x H y Coupling with non-dissociated CO forms lower alcohols.

[0021] (2) The catalyst prepared by the present invention has three sites of indium oxide, transition metal and alkali metal, each of which has a different function. The synergistic effect of the three ultimately significantly improves the selectivity of low-carbon alcohols. DETAILED DESCRIPTION

[0022] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0023] Unless otherwise specified, all commodities or reagents in the present invention were purchased through market channels.

[0024] Example 1

[0025] A method for preparing a catalyst for converting carbon dioxide to low-carbon alcohols, comprising the following steps:

[0026] (1) weighing 5.5 g of indium sulfate and dissolving it in 20 mL of deionized water, adding 0.2 M sodium hydroxide methanol solution dropwise to the indium sulfate solution in a 20° C. water bath, stirring continuously until the pH value is 8.5, aging in a 20° C. water bath for 48 hours, filtering, and washing to obtain an indium oxide precursor, placing the indium oxide precursor in a 60° C. oven to dry for 12 hours, and placing the dried indium oxide precursor in a 400° C. muffle furnace to roast for 1 hour to obtain indium oxide;

[0027] (2) Weigh 0.3 g of sodium nitrate, 0.3 g of ferric nitrate, and 0.2 g of nickel nitrate and dissolve them in 10 mL of deionized water to obtain an additive solution;

[0028] (3) adding 0.8 g of indium oxide obtained in step (1) to the auxiliary agent solution obtained in step (2) and continuously stirring, placing the obtained slurry in an oven at 150° C. and drying for 2 hours, placing the dried mixture in a muffle furnace at 300° C. and calcining for 6 hours to obtain a catalyst precursor;

[0029] (4) placing the mixture obtained in step (3) in 90% hydrogen / 10% argon at 400° C. for heat treatment for 3 hours, and taking out the mixture after the heat treatment;

[0030] The catalyst performance was tested in a slurry bed reactor.

[0031] Example 2

[0032] A method for preparing a catalyst for converting carbon dioxide to low-carbon alcohols, comprising the following steps:

[0033] (1) 6.5 g of indium chloride was weighed and dissolved in 20 mL of deionized water, 0.1 M ammonia water was added dropwise to the indium chloride solution in a 45° C. water bath, and the mixture was stirred continuously until the pH value was 9.0, aged in a 45° C. water bath for 24 hours, filtered, and washed to obtain an indium oxide precursor, the indium oxide precursor was placed in a 150° C. oven to dry for 1 hour, and the dried indium oxide precursor was placed in a 550° C. muffle furnace to roast for 2 hours to obtain indium oxide;

[0034] (2) Weigh 0.5 g potassium nitrate, 0.4 g ferric sulfate, and 0.3 g nickel chloride and dissolve them in 10 mL deionized water to obtain an additive solution;

[0035] (3) adding 1 g of indium oxide obtained in step (1) to the auxiliary agent solution obtained in step (2) and continuously stirring, placing the obtained slurry in a 60° C. oven and drying it for 12 hours, and placing the dried mixture in a muffle furnace at 800° C. and calcining it for 1 hour to obtain a catalyst precursor;

[0036] (4) placing the mixture after the heat treatment in step (3) in 25% hydrogen / 75% argon at 800° C. for 1 hour, and taking out the mixture after the heat treatment;

[0037] The catalyst performance was tested in a fixed bed reactor.

[0038] Example 3

[0039] A method for preparing a catalyst for converting carbon dioxide to low-carbon alcohols, comprising the following steps:

[0040] (1) 6.0 g of indium nitrate was weighed and dissolved in 50 mL of deionized water, and a 0.2 M sodium hydroxide ethanol solution was added dropwise to the indium nitrate solution under a 65° C. water bath condition, and the mixture was stirred continuously until the pH value was 10.0, and the mixture was aged under a 65° C. water bath condition for 6 hours, filtered, and washed to obtain an indium oxide precursor, and the indium oxide precursor was placed in a 75° C. oven for drying for 11 hours, and the dried indium oxide precursor was placed in a 700° C. muffle furnace for calcining for 3 hours to obtain indium oxide;

[0041] (2) Weigh 0.8 g of sodium nitrate, 0.1 g of ferric chloride, 0.2 g of nickel sulfate, and 0.3 g of magnesium nitrate and dissolve them in 15 mL of deionized water to obtain an additive solution;

[0042] (3) adding 3 g of indium oxide obtained in step (1) to the auxiliary agent solution obtained in step (2) and continuously stirring, placing the obtained slurry in a 90° C. oven to dry for 18 hours, and placing the dried mixture in a 600° C. muffle furnace to calcine for 4.5 hours to obtain a catalyst precursor;

[0043] (4) placing the mixture obtained in step (3) in 10% hydrogen / 90% argon at 600° C. for 4 hours, and taking out the mixture after the heat treatment;

[0044] The catalyst performance was tested in a slurry bed reactor.

[0045] Example 4

[0046] A method for preparing a catalyst for converting carbon dioxide to low-carbon alcohols, comprising the following steps:

[0047] (1) 7.0 g of indium chloride was weighed and dissolved in 20 mL of deionized water, and 0.1 M potassium hydroxide ethanol solution was added dropwise to the indium chloride solution under a 75° C. water bath condition, and the mixture was stirred continuously until the pH value was 10.0, and the mixture was aged under a 75° C. water bath condition for 36 hours, filtered, and washed to obtain an indium oxide precursor, and the indium oxide precursor was placed in an oven at 80° C. to dry for 12 hours, and the dried indium oxide precursor was placed in a muffle furnace at 750° C. to calcine for 2.5 hours to obtain indium oxide;

[0048] (2) Weigh 0.2 g potassium nitrate, 0.05 g magnesium nitrate, 0.1 g cobalt nitrate, 0.05 g copper nitrate, and 0.15 g zinc sulfate and dissolve them in 25 mL deionized water to obtain an additive solution;

[0049] (3) adding 0.5 g of indium oxide obtained in step (1) to the auxiliary agent solution obtained in step (2) and continuously stirring, placing the obtained slurry in an oven at 100° C. and drying for 16 hours, placing the dried mixture in a muffle furnace at 600° C. and calcining for 5 hours to obtain a catalyst precursor;

[0050] (4) placing the mixture after the heat treatment in step (3) in a mixed atmosphere of hydrogen and argon at 500° C. for 3 hours, and taking out the mixture after the heat treatment;

[0051] The catalyst performance was tested in a fixed bed reactor.

[0052] Example 5

[0053] A method for preparing a catalyst for converting carbon dioxide to low-carbon alcohols, comprising the following steps:

[0054] (1) 5.3 g of indium nitrate was weighed and dissolved in 35 mL of deionized water, and a 0.15 M potassium hydroxide ethanol solution was added dropwise to the indium nitrate solution under 80° C. water bath conditions, and the mixture was stirred continuously until the pH value was 11.0, and the mixture was aged under 80° C. water bath conditions for 1 hour, filtered, and washed to obtain an indium oxide precursor, and the indium oxide precursor was placed in an 80° C. oven for drying for 9 hours, and the dried indium oxide precursor was placed in an 800° C. muffle furnace for calcination for 3 hours to obtain indium oxide;

[0055] (2) Weigh 1.0 g of sodium nitrate, 0.5 g of nickel nitrate, 0.5 g of cobalt sulfate, and 0.25 g of copper chloride and dissolve them in 30 mL of deionized water to obtain an additive solution;

[0056] (3) adding 3 g of indium oxide obtained in step (1) to the auxiliary agent solution obtained in step (2) and continuously stirring, placing the obtained slurry in an oven at 150° C. and drying for 24 hours, placing the dried mixture in a muffle furnace at 750° C. and calcining for 4.5 hours to obtain a catalyst precursor;

[0057] (4) placing the mixture after the heat treatment in step (3) in a carbon monoxide atmosphere at 600° C. for 5 hours, and taking out the mixture after the heat treatment;

[0058] The catalyst performance was tested in a fixed bed reactor.

[0059] Example 6

[0060] A method for preparing a catalyst for converting carbon dioxide to low-carbon alcohols, comprising the following steps:

[0061] (1) 5.5 g of indium chloride was weighed and dissolved in 40 mL of deionized water, 0.15 M ammonia solution was added dropwise to the indium chloride solution under 80° C. water bath conditions, and the mixture was stirred continuously until the pH value was 9.5, aged under 80° C. water bath conditions for 48 hours, filtered, and washed to obtain an indium oxide precursor, the indium oxide precursor was placed in a 120° C. oven for 18 hours, and the dried indium oxide precursor was placed in a 900° C. muffle furnace for calcination for 3 hours to obtain indium oxide;

[0062] (2) Weigh 0.5 g potassium nitrate, 0.5 g cobalt sulfate, 0.6 g copper chloride, and 0.05 g zinc sulfate and dissolve them in 25 mL deionized water to obtain an additive solution;

[0063] (3) adding 3 g of indium oxide obtained in step (1) to the auxiliary agent solution obtained in step (2) and continuously stirring, placing the obtained slurry in an oven at 120° C. and drying for 24 hours, placing the dried mixture in a muffle furnace at 800° C. and calcining for 2 hours to obtain a catalyst precursor;

[0064] (4) placing the mixture obtained in step (3) in a carbon monoxide atmosphere at 400° C. for 3 hours, and taking out the mixture after the heat treatment;

[0065] The catalyst performance was tested in a slurry bed reactor.

[0066] Example 7

[0067] A method for preparing a catalyst for converting carbon dioxide to low-carbon alcohols, comprising the following steps:

[0068] (1) 9.6 g of indium nitrate was weighed and dissolved in 60 mL of deionized water, and a 0.2 M sodium hydroxide ethanol solution was added dropwise to the indium nitrate solution under a 50° C. water bath condition, and the mixture was stirred continuously until the pH value was 9.0, and the mixture was aged under a 50° C. water bath condition for 48 hours, filtered, and washed to obtain an indium oxide precursor, and the indium oxide precursor was placed in a 65° C. oven to dry for 8 hours, and the dried indium oxide precursor was placed in a 400° C. muffle furnace to roast for 3 hours to obtain indium oxide;

[0069] (2) Weigh 1.0 g potassium nitrate, 0.05 g copper sulfate, 0.1 g nickel chloride, and 0.05 g cobalt nitrate and dissolve them in 30 mL deionized water to obtain an additive solution;

[0070] (3) adding 5 g of indium oxide obtained in step (1) to the auxiliary agent solution obtained in step (2) and continuously stirring, placing the obtained slurry in an oven at 120° C. and drying for 24 hours, placing the dried mixture in a muffle furnace at 900° C. and calcining for 1 hour to obtain a catalyst precursor;

[0071] (4) placing the mixture after the heat treatment in step (3) in a mixed atmosphere of hydrogen and argon at 400° C. for 1 hour, and taking out the mixture after the heat treatment;

[0072] The catalyst performance was tested in a fixed bed reactor.

[0073] Example 8

[0074] (1) Weighing 6.5 g of indium sulfate and dissolving it in 50 mL of deionized water, adding 0.3 M sodium hydroxide ethanol solution dropwise to the indium sulfate solution in a 60° C. water bath, stirring continuously until pH=11, aging in a 60° C. water bath for 28 hours, filtering, and washing to obtain an indium oxide precursor, placing the indium oxide precursor in a 90° C. oven to dry for 12 hours, and placing the dried indium oxide precursor in an 800° C. muffle furnace to calcine for 2 hours to obtain indium oxide;

[0075] (2) Weigh 0.8 g of sodium nitrate, 0.05 g of cobalt chloride, 0.02 g of nickel nitrate, 0.05 g of ferric nitrate, 0.15 g of ferric chloride, and 0.5 g of magnesium chloride and dissolve them in 50 mL of deionized water to obtain an additive solution;

[0076] (3) adding 2 g of indium oxide obtained in step (1) to the auxiliary agent solution obtained in step (2) and continuously stirring, placing the obtained slurry in an oven at 110° C. and drying for 12 hours, placing the dried mixture in a muffle furnace at 850° C. and calcining for 5 hours to obtain a catalyst precursor;

[0077] (4) placing the mixture after the heat treatment in step (3) in 5% hydrogen / 95% argon at 700° C. for 5 hours, and taking out the mixture after the heat treatment;

[0078] The catalyst performance was tested in a fixed bed reactor.

[0079] Comparative Example 1

[0080] A method for preparing a catalyst for converting carbon dioxide to low-carbon alcohols, comprising the following steps:

[0081] (1) 3.0 g of indium nitrate was weighed and dissolved in 40 mL of deionized water, and a 0.2 M sodium hydroxide ethanol solution was added dropwise to the indium nitrate solution under a 50° C. water bath condition, and the mixture was stirred continuously until the pH value was 9.5, and the mixture was aged under a 50° C. water bath condition for 30 hours, filtered, and washed to obtain an indium oxide precursor, and the indium oxide precursor was placed in an oven at 70° C. and dried for 12 hours, and the dried indium oxide precursor was placed in a muffle furnace and calcined at 650° C. for 2.5 hours to obtain indium oxide;

[0082] (2) calcining 3 g of indium oxide obtained in step (1) in a muffle furnace at 800° C. for 5 hours to obtain a catalyst precursor;

[0083] (3) heat treating the catalyst precursor obtained in step (2) in 15% hydrogen / 85% argon at 400° C. for 2 hours to obtain a catalyst;

[0084] The catalyst performance was tested in a slurry bed reactor.

[0085] Test Case

[0086] Fixed bed reactor: 0.3 g of the prepared catalyst was mixed with 2.5 g of SiC and placed in a reactor. The raw gas (a mixture of 25 v% carbon dioxide, 65 v% hydrogen, and 10 v% nitrogen) flowed through the catalyst bed at a certain flow rate. The space velocity adopted was 3.5 liters / gram catalyst / hour. The reaction pressure was gradually increased to 7.0 MPa, and the reaction temperature was gradually increased to 330°C to start the reaction. A performance test lasting 100 hours was carried out. The product at the reactor outlet was kept warm at 160°C and passed into the chromatograph for online analysis.

[0087] Slurry bed reactor: 2.5 g of the prepared catalyst was mixed with 120 mL of high boiling wax oil at room temperature, and then the mixture was transferred to a 0.9 L continuous stirring reactor. The feed gas (a mixture of 25 v% carbon dioxide, 65 v% hydrogen, and 10 v% nitrogen) was introduced into the reactor at a certain flow rate, and the space velocity adopted was 3.5 L / g catalyst / hour. The reaction pressure was gradually increased to 7.0 MPa, and the reaction temperature was gradually increased to 330°C to start the reaction. The product at the reactor outlet was kept at 160°C and introduced into a chromatogram for online analysis.

[0088] The carbon dioxide conversion rate and product selectivity were calculated according to the following formula:

[0089] Carbon dioxide conversion rate = (imported carbon dioxide moles - exported carbon dioxide moles) / imported carbon dioxide moles * 100%;

[0090] Product selectivity = number of moles of outlet product * number of carbon atoms in the product / (number of moles of inlet carbon dioxide - number of moles of outlet carbon dioxide) * 100%.

[0091] The test results are shown in Table 1.

[0092] Table 1 Catalytic performance test results of catalysts

[0093]

[0094] It can be seen from Table 1 that the catalyst prepared by the present invention can achieve a good technical effect of preparing low-carbon alcohols by hydrogenation of carbon dioxide. Taking Example 4 as an example, the conversion rate of carbon dioxide is 13.7%, and the total alcohol selectivity is as high as 95.5%; among which ethanol and C 3+ The selectivities of alcohols reached 70.2% and 13.2%, respectively.

[0095] The present invention illustrates the technical concept of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of individual raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. Catalyst for the preparation of C by hydrogenation of carbon dioxide 3+ The use of alcohol, characterized in that The preparation method of the catalyst comprises the following steps: (1) 6.0 g of indium nitrate was weighed and dissolved in 50 mL of deionized water, and a 0.2 M sodium hydroxide ethanol solution was added dropwise to the indium nitrate solution under a 65° C. water bath condition, and the mixture was stirred continuously until the pH value was 10.0, and the mixture was aged under a 65° C. water bath condition for 6 hours, filtered, and washed to obtain an indium oxide precursor, and the indium oxide precursor was placed in a 75° C. oven for drying for 11 hours, and the dried indium oxide precursor was placed in a 700° C. muffle furnace for calcining for 3 hours to obtain indium oxide; (2) Weigh 0.8 g of sodium nitrate, 0.1 g of ferric chloride, 0.2 g of nickel sulfate, and 0.3 g of magnesium nitrate and dissolve them in 15 mL of deionized water to obtain an additive solution; (3) adding 3 g of indium oxide obtained in step (1) to the auxiliary agent solution obtained in step (2) and continuously stirring, placing the obtained slurry in a 90° C. oven to dry for 18 hours, and placing the dried mixture in a 600° C. muffle furnace to calcine for 4.5 hours to obtain a catalyst precursor; (4) The catalyst precursor obtained in step (3) was placed in 10% hydrogen / 90% argon at 600° C. for heat treatment for 4 hours. After the heat treatment, the product was taken out, 2.5 g of the prepared catalyst was mixed with 120 mL of high-boiling point wax oil at room temperature, and then the mixture was transferred to a 0.9 L continuous stirring reactor. The raw gas was introduced into the reactor at a certain flow rate, wherein the raw gas contained 25 v% carbon dioxide, 65 v% hydrogen, and 10 v% nitrogen. The space velocity used was 3.5 L / g catalyst / hour. The reaction pressure was gradually increased to 7.0 MPa, and the reaction temperature was gradually increased to 330° C. to start the reaction. The product at the reactor outlet was kept warm at 160° C. and introduced into a chromatogram for online analysis. The preparation C 3+ In the process of alcohol, the selectivity of carbon monoxide is 8.8%, C 3+ The selectivity to alcohol was 15.9%.

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