CN116099540A - Preparation method and application of low-carbon indium alkoxide based catalyst synthesized by carbon dioxide hydrogenation - Google Patents

Preparation method and application of low-carbon indium alkoxide based catalyst synthesized by carbon dioxide hydrogenation Download PDF

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CN116099540A
CN116099540A CN202310251287.4A CN202310251287A CN116099540A CN 116099540 A CN116099540 A CN 116099540A CN 202310251287 A CN202310251287 A CN 202310251287A CN 116099540 A CN116099540 A CN 116099540A
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catalyst
preparing
carbon dioxide
precursor
carbon
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曾丰
何一鸣
付伟杰
刘水莲
陈建
唐振辰
谭兴
钟奇彤
杜瑞兴
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Nanjing Tech University
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    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/825—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with gallium, indium or thallium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • 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 catalyst for preparing low-carbon alcohol by converting carbon dioxide, and a preparation method and application thereof, and belongs to the technical field of carbon dioxide resource utilization. The preparation method comprises the following steps: dissolving indium precursor, adding precipitant to obtain precipitate, stirring for ageing, filtering, washing to obtain indium oxide precursor, drying, roasting, adding the roasted indium oxide into alkali metal assistant and transition metal assistant precursor solution, stirring, drying and roasting the obtained compound, and activating by using mixed atmosphere of hydrogen and argon or carbon monoxide to obtain the catalyst product. According to the preparation method of the catalyst for preparing the low-carbon alcohol through carbon dioxide conversion, three sites of indium oxide, transition metal and alkali metal are formed after the indium precursor, the alkali metal and the transition metal auxiliary precursor raw materials are subjected to heat treatment, and can be used for respectively promoting the generation of a carbon monoxide intermediate, the growth of a catalytic carbon chain and regulating and controlling the adsorption strength of hydrogen, so that the selectivity of the low-carbon alcohol is obviously promoted, and the selectivity of the low-carbon alcohol 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, simple process and the like, and has good application prospect.

Description

Preparation method and application of low-carbon indium alkoxide based catalyst synthesized by carbon dioxide hydrogenation
Technical Field
The technical field of carbon dioxide resource utilization, in particular to a preparation method and application of a catalyst for preparing low-carbon alcohol by hydrogenation of carbon dioxide.
Background
With the rapid consumption of fossil fuels in recent years, the concentration of carbon dioxide in the atmosphere has risen to an unprecedented level, and the greenhouse effect and the acidification of the ocean have severely threatened the sustainable development of human society. Capturing and utilizing carbon dioxide is an important means of reducing the concentration of carbon dioxide in the atmosphere. Carbon dioxide, on the other hand, is a non-toxic, inexpensive, readily available renewable carbon resource. If the carbon dioxide is converted into chemicals with high added value such as alkane, alkene, alcohol and the like, the carbon emission can be reduced, the recycling of carbon resources can be realized, and the economic value is created. Lower alcohol (C) 1-4 OH) is an important basic chemical raw material, and can be used as fuel and solvent, thus having wide market demands. However, due to high chemical inertness of carbon dioxide and difficult precise regulation and control of the reaction process, the preparation of low-carbon mixed alcohol by converting carbon dioxide has not been applied in large-scale industry at present.
CN115228491a uses molybdate, potassium salt, rhodium salt as raw materials to prepare a high-dispersion supported rhodium-based catalyst; rhodium salt, molybdate solution and aromatic amine compound are subjected to organic-inorganic hybridization reaction to obtain a compound; mixing potassium salt solution with the compound to prepare a supported rhodium-based catalyst; the second active component rhodium with carbonyl insertion function is introduced into the molybdenum carbide catalyst for generating methanol by hydrogenating carbon dioxide to form a double active center synergistic composite catalyst, and the catalyst has good activity and higher carbon dioxide conversion rate under the modification of alkali metal auxiliary agent, but the cost of the catalyst is obviously increased due to the high price of rhodium salt, so that the catalyst is unfavorable for large-scale industrial application.
CN110947356A is prepared by directly adding copper nitrate, ferric nitrate and cobalt nitrate into a mixed solution of ethanol and butyl titanate serving as a solvent, using ethylene glycol as a complexing agent, then dropwise adding an aqueous solution of potassium hydroxide, finally magnetically stirring in a water bath, hydrolyzing the butyl titanate to form colloid, aging the colloid, drying and roasting to obtain the catalyst. The catalyst can directly obtain alcohol fuels with high added value such as ethanol, propanol, butanol and the like through carbon dioxide hydrogenation, and the distribution of low-carbon alcohol can be controlled by regulating and controlling the proportion of metal, but C 2+ The selectivity of the alcohol only reaches 18.35 percent, and the method has larger lifting space.
CN109908960a effectively improves the effect of preparing n-butanol by hydrogenation of carbon dioxide by the synergistic effect of a compound containing a transition metal element, an organic ligand and an iodide promoter; the catalyst is prepared in 1, 3-dimethyl-2-imidazolidinone, tetrahydrofuran, isotridecyl, N-methylpyrrolidone, 1, 4-dioxane, dimethyl sulfoxide, ethanol, benzene, water, [ OMIm ]]HSO 4 、[OMIm]H 2 PO 4 、[Emim]HSO 4 、[Hmim]H 2 PO 4 、[Bmim]Cl、[C 6 mim]Br、[Bmim]BF 4 The reaction in the solvent can promote the reaction efficiency by homogeneous catalysis, but the catalyst recovery and the product separation are difficult, and the cost is increased.
In summary, the existing method for preparing the low-carbon alcohol by hydrogenation of carbon dioxide still has the defects of low selectivity, high cost, complex preparation process and the like.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a catalyst for preparing low-carbon alcohol by converting carbon dioxide, and a preparation method and application thereof.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the catalyst for preparing the low-carbon alcohol by converting carbon dioxide is characterized by dissolving an indium precursor, adding a precipitator to obtain a precipitation solution, stirring and aging, filtering and washing to obtain an indium oxide precursor, drying and roasting, mixing and drying indium oxide obtained after roasting, an alkali metal auxiliary agent and a transition metal auxiliary agent precursor in a solution to obtain a compound, drying and roasting the obtained compound, and activating the obtained compound in a mixed atmosphere of hydrogen and argon or in a carbon monoxide atmosphere to obtain the catalyst product.
As a further preferred aspect of the present invention, the indium precursor is selected from one or more of indium nitrate, indium chloride, and indium sulfate.
As a further preferred aspect of the present invention, the precipitating agent is selected from one or more of ammonia monohydrate, sodium hydroxide, potassium hydroxide; the temperature of the precipitation process is 20-80 ℃, the pH value is 8.5-11, the aging temperature is 20-80 ℃ and the aging time is 1-48 hours.
As a further preferred aspect of the present invention, the alkali metal promoter precursor is selected from one or more of sodium nitrate and potassium nitrate.
As a further preferred aspect of the present invention, the metal auxiliary precursor is selected from 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, copper sulfate.
As a further preferred aspect of the present invention, the indium oxide precursor: alkali metal promoter precursor: the mass ratio of the metal auxiliary precursor is 53-96:1-10:2-14.
As a further preferred aspect of the present invention, the indium oxide precursor is dried at 60 to 150 ℃ for 1 to 12 hours, calcined at 400 to 900 ℃ for 1 to 3 hours.
As a further preferred aspect of the present invention, the drying temperature of the impregnated composite is 60-150 ℃, the drying time is 2-24 hours, the roasting temperature is 300-900 ℃, and the roasting time is 1-6 hours.
As a further preferred embodiment of the present invention, the catalyst activation process is carried out in an atmosphere containing hydrogen and argon or carbon monoxide at 400 to 800 ℃.
Meanwhile, the invention also claims the catalyst prepared by the method.
Meanwhile, the invention also claims the application of the catalyst in preparing low-carbon alcohol by carbon dioxide hydrogenation catalysis. Compared with the prior art, the invention has the following beneficial effects:
(1) The invention adopts indium oxide rich in oxygen vacancy as a carrier, which can promote carbon dioxide and hydrogen to generate reverse water gas shift reaction to generate a key intermediate CO. Further incorporating a transition metal promoter into the indium oxide, M can be formed 0 Sites, which facilitate the dissociative adsorption of CO and promote the growth of carbon chains. The introduction of the alkali metal auxiliary agent can effectively control the hydrogen adsorption strength on the surface of the catalyst, and inhibit the rapid hydrogenation on metal sites to produce alkane. Dissociation of CO-generated C x H y Coupling with non-dissociated CO forms lower alcohols.
(2) The catalyst prepared by the invention has three sites of indium oxide, transition metal and alkali metal, respectively has different functions, and the synergistic effect of the three sites finally and obviously improves the selectivity of the low-carbon alcohol.
Detailed Description
The following description of the embodiments of the present invention will clearly and fully describe the technical aspects of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
All commercial products or reagents of the invention are purchased through market channels unless otherwise specified.
Example 1
The preparation method of the catalyst for preparing the low-carbon alcohol by converting the carbon dioxide comprises the following steps:
(1) Weighing 5.5g of indium sulfate, dissolving in 20mL of deionized water, dropwise adding 0.2M sodium hydroxide methanol solution into the indium sulfate solution under the water bath condition of 20 ℃, continuously stirring until the pH=8.5, aging for 48 hours under the water bath condition of 20 ℃, filtering, washing to obtain an indium oxide precursor, drying the indium oxide precursor in a baking oven of 60 ℃ for 12 hours, and roasting the dried indium oxide precursor in a muffle furnace of 400 ℃ for 1 hour to obtain indium oxide;
(2) Weighing 0.3g of sodium nitrate, 0.3g of ferric nitrate and 0.2g of nickel nitrate, and dissolving in 10mL of deionized water to obtain an auxiliary agent solution;
(3) Adding 0.8g of indium oxide obtained in the step (1) into the auxiliary agent solution obtained in the step (2), continuously stirring, putting the obtained slurry into a baking oven at 150 ℃ for drying for 2 hours, and putting the dried mixture into a muffle furnace at 300 ℃ for roasting for 6 hours to obtain a catalyst precursor;
(4) Placing the mixture obtained in the step (3) in 90% hydrogen/10% argon at 400 ℃ for heat treatment for 3 hours, and taking out the mixture after the heat treatment is finished;
catalyst performance testing was performed in a slurry bed reactor.
Example 2
The preparation method of the catalyst for preparing the low-carbon alcohol by converting the carbon dioxide comprises the following steps:
(1) Weighing 6.5g of indium chloride, dissolving in 20mL of deionized water, dropwise adding 0.1M ammonia water into the indium chloride solution under the water bath condition of 45 ℃, continuously stirring until the pH=9.0, aging for 24 hours under the water bath condition of 45 ℃, filtering, washing to obtain an indium oxide precursor, drying the indium oxide precursor in a baking oven of 150 ℃ for 1 hour, and roasting the dried indium oxide precursor in a muffle furnace of 550 ℃ for 2 hours to obtain indium oxide;
(2) Weighing 0.5g of potassium nitrate, 0.4g of ferric sulfate and 0.3g of nickel chloride, and dissolving in 10mL of deionized water to obtain an auxiliary agent solution;
(3) Adding 1g of indium oxide obtained in the step (1) into the auxiliary agent solution obtained in the step (2), continuously stirring, putting the obtained slurry into a 60 ℃ oven for drying for 12 hours, and putting the dried mixture into a 800 ℃ muffle furnace for roasting for 1 hour to obtain a catalyst precursor;
(4) Placing the mixture subjected to the heat treatment in the step (3) in 25% hydrogen/75% argon at 800 ℃ for heat treatment for 1 hour, and taking out the mixture after the heat treatment is finished;
catalyst performance testing was performed in a fixed bed reactor.
Example 3
The preparation method of the catalyst for preparing the low-carbon alcohol by converting the carbon dioxide comprises the following steps:
(1) Weighing 6.0g of indium nitrate, dissolving in 50mL of deionized water, dropwise adding a 0.2M sodium hydroxide ethanol solution into the indium nitrate solution under the water bath condition of 65 ℃, continuously stirring until the pH=10.0, aging for 6 hours under the water bath condition of 65 ℃, filtering, washing to obtain an indium oxide precursor, drying the indium oxide precursor in a baking oven of 75 ℃ for 11 hours, and roasting the dried indium oxide precursor in a muffle furnace of 700 ℃ for 3 hours to obtain indium oxide;
(2) Weighing 0.8g of sodium nitrate, 0.1g of ferric chloride, 0.2g of nickel sulfate and 0.3g of magnesium nitrate, and dissolving in 15mL of deionized water to obtain an auxiliary agent solution;
(3) Adding 3g of indium oxide obtained in the step (1) into the auxiliary agent solution obtained in the step (2), continuously stirring, putting the obtained slurry into a 90 ℃ oven for drying for 18 hours, and putting the dried mixture into a 600 ℃ muffle furnace for roasting for 4.5 hours to obtain a catalyst precursor;
(4) Placing the mixture obtained in the step (3) in 10% hydrogen/90% argon at 600 ℃ for heat treatment for 4 hours, and taking out the mixture after the heat treatment is finished;
catalyst performance testing was performed in a slurry bed reactor.
Example 4
The preparation method of the catalyst for preparing the low-carbon alcohol by converting the carbon dioxide comprises the following steps:
(1) 7.0g of indium chloride is weighed and dissolved in 20mL of deionized water, 0.1M potassium hydroxide ethanol solution is dripped into the indium chloride solution under the water bath condition of 75 ℃, the solution is continuously stirred until the pH=10.0, the solution is aged for 36 hours under the water bath condition of 75 ℃, the solution is filtered and washed to obtain an indium oxide precursor, the indium oxide precursor is put into an oven of 80 ℃ for drying for 12 hours, and the dried indium oxide precursor is put into a muffle furnace of 750 ℃ for roasting for 2.5 hours to obtain indium oxide;
(2) Weighing 0.2g of potassium nitrate, 0.05g of magnesium nitrate, 0.1g of cobalt nitrate, 0.05g of copper nitrate and 0.15g of zinc sulfate, and dissolving in 25mL of deionized water to obtain an auxiliary agent solution;
(3) Adding 0.5g of indium oxide obtained in the step (1) into the auxiliary agent solution obtained in the step (2), continuously stirring, putting the obtained slurry into a 100 ℃ oven for drying for 16 hours, and putting the dried mixture into a 600 ℃ muffle furnace for roasting for 5 hours to obtain a catalyst precursor;
(4) Placing the mixture subjected to the heat treatment in the step (3) in a mixed atmosphere of hydrogen and argon at 500 ℃ for heat treatment for 3 hours, and taking out the mixture after the heat treatment is finished;
catalyst performance testing was performed in a fixed bed reactor.
Example 5
The preparation method of the catalyst for preparing the low-carbon alcohol by converting the carbon dioxide comprises the following steps:
(1) Weighing 5.3g of indium nitrate, dissolving in 35mL of deionized water, dropwise adding 0.15M potassium hydroxide ethanol solution into the indium nitrate solution under the water bath condition of 80 ℃, continuously stirring until the pH=11.0, aging for 1 hour under the water bath condition of 80 ℃, filtering, washing to obtain an indium oxide precursor, drying the indium oxide precursor in an oven of 80 ℃ for 9 hours, and roasting the dried indium oxide precursor in a muffle furnace of 800 ℃ for 3 hours to obtain indium oxide;
(2) 1.0g of sodium nitrate, 0.5g of nickel nitrate, 0.5g of cobalt sulfate and 0.25g of copper chloride are weighed and dissolved in 30mL of deionized water to obtain an auxiliary agent solution;
(3) Adding 3g of indium oxide obtained in the step (1) into the auxiliary agent solution obtained in the step (2), continuously stirring, putting the obtained slurry into a baking oven at 150 ℃ for drying for 24 hours, and putting the dried mixture into a muffle furnace at 750 ℃ for roasting for 4.5 hours to obtain a catalyst precursor;
(4) Placing the mixture subjected to the heat treatment in the step (3) in a carbon monoxide atmosphere at 600 ℃ for heat treatment for 5 hours, and taking out the mixture after the heat treatment is finished;
catalyst performance testing was performed in a fixed bed reactor.
Example 6
The preparation method of the catalyst for preparing the low-carbon alcohol by converting the carbon dioxide comprises the following steps:
(1) Weighing 5.5g of indium chloride, dissolving in 40mL of deionized water, dropwise adding 0.15M ammonia water solution into the indium chloride solution under the water bath condition of 80 ℃, continuously stirring until the pH=9.5, aging for 48 hours under the water bath condition of 80 ℃, filtering, washing to obtain an indium oxide precursor, drying the indium oxide precursor in a baking oven of 120 ℃ for 18 hours, and roasting the dried indium oxide precursor in a muffle furnace of 900 ℃ for 3 hours to obtain indium oxide;
(2) Weighing 0.5g of potassium nitrate, 0.5g of cobalt sulfate, 0.6g of copper chloride and 0.05g of zinc sulfate, and dissolving in 25mL of deionized water to obtain an auxiliary agent solution;
(3) Adding 3g of indium oxide obtained in the step (1) into the auxiliary agent solution obtained in the step (2), continuously stirring, putting the obtained slurry into a baking oven at 120 ℃ for drying for 24 hours, and putting the dried mixture into a muffle furnace at 800 ℃ for roasting for 2 hours to obtain a catalyst precursor;
(4) Placing the mixture obtained in the step (3) in a carbon monoxide atmosphere at 400 ℃ for heat treatment for 3 hours, and taking out the mixture after the heat treatment is finished;
catalyst performance testing was performed in a slurry bed reactor.
Example 7
The preparation method of the catalyst for preparing the low-carbon alcohol by converting the carbon dioxide comprises the following steps:
(1) 9.6g of indium nitrate is weighed and dissolved in 60mL of deionized water, 0.2M sodium hydroxide ethanol solution is dripped into the indium nitrate solution under the water bath condition of 50 ℃, the solution is continuously stirred until the pH=9.0, the solution is aged for 48 hours under the water bath condition of 50 ℃, the solution is filtered and washed to obtain an indium oxide precursor, the indium oxide precursor is put into a 65 ℃ oven for drying for 8 hours, and the dried indium oxide precursor is put into a 400 ℃ muffle furnace for roasting for 3 hours to obtain indium oxide;
(2) 1.0g of potassium nitrate, 0.05g of copper sulfate, 0.1g of nickel chloride and 0.05g of cobalt nitrate are weighed and dissolved in 30mL of deionized water to obtain an auxiliary agent solution;
(3) Adding 5g of indium oxide obtained in the step (1) into the auxiliary agent solution obtained in the step (2), continuously stirring, putting the obtained slurry into a baking oven at 120 ℃ for drying for 24 hours, and putting the dried mixture into a muffle furnace at 900 ℃ for roasting for 1 hour to obtain a catalyst precursor;
(4) Placing the mixture subjected to the heat treatment in the step (3) in a mixed atmosphere containing hydrogen and argon at 400 ℃ for treatment for 1 hour, and taking out the mixture after the heat treatment is finished;
catalyst performance testing was performed in a fixed bed reactor.
Example 8
(1) Weighing 6.5g of indium sulfate, dissolving in 50mL of deionized water, dropwise adding a 0.3M sodium hydroxide ethanol solution into the indium sulfate solution under the water bath condition of 60 ℃, continuously stirring until the pH value is=11, aging for 28 hours under the water bath condition of 60 ℃, filtering and washing to obtain an indium oxide precursor, drying the indium oxide precursor in a 90 ℃ oven for 12 hours, and roasting the dried indium oxide precursor in a 800 ℃ muffle furnace for 2 hours to obtain indium oxide;
(2) Weighing 0.8g of sodium nitrate, 0.05g of cobalt chloride, 0.02g of nickel nitrate, 0.05g of ferric nitrate, 0.15g of ferric chloride and 0.5g of magnesium chloride, and dissolving in 50mL of deionized water to obtain an auxiliary agent solution;
(3) Adding 2g of indium oxide obtained in the step (1) into the auxiliary agent solution obtained in the step (2), continuously stirring, putting the obtained slurry into a 110 ℃ oven for drying for 12 hours, and putting the dried mixture into a 850 ℃ muffle furnace for roasting for 5 hours to obtain a catalyst precursor;
(4) Placing the mixture subjected to the heat treatment in the step (3) in 5% hydrogen/95% argon at 700 ℃ for heat treatment for 5 hours, and taking out the mixture after the heat treatment is finished;
catalyst performance testing was performed in a fixed bed reactor.
Comparative example 1
The preparation method of the catalyst for preparing the low-carbon alcohol by converting the carbon dioxide comprises the following steps:
(1) 3.0g of indium nitrate is weighed and dissolved in 40mL of deionized water, 0.2M sodium hydroxide ethanol solution is dripped into the indium nitrate solution under the water bath condition of 50 ℃, the solution is continuously stirred until the pH=9.5, the solution is aged for 30 hours under the water bath condition of 50 ℃, the solution is filtered and washed to obtain an indium oxide precursor, the indium oxide precursor is put into a baking oven for drying for 12 hours at 70 ℃, and the dried indium oxide precursor is put into a muffle furnace for roasting for 2.5 hours at 650 ℃ to obtain indium oxide;
(2) Roasting 3g of indium oxide obtained in the step (1) in a muffle furnace at 800 ℃ for 5 hours to obtain a catalyst precursor;
(3) Placing the catalyst precursor obtained in the step (2) in 15% hydrogen/85% argon at 400 ℃ for heat treatment for 2 hours to obtain a catalyst;
catalyst performance testing was performed in a slurry bed reactor.
Test case
A fixed bed reactor: mixing 0.3g of the prepared catalyst with 2.5g of SiC, placing the mixture in a reactor, allowing raw material gas (25 v% carbon dioxide, 65v% hydrogen and 10v% nitrogen mixture) to flow through a catalyst bed layer at a certain flow rate, adopting a space velocity of 3.5 liters/g catalyst/h, gradually increasing the reaction pressure to 7.0MPa, gradually increasing the reaction temperature to 330 ℃ to start the reaction, performing performance test for 100h, keeping the temperature of a reactor outlet product at 160 ℃, and introducing chromatograph for online analysis.
Slurry bed reactor: 2.5g of the catalyst prepared were mixed with 120mL of high-boiling wax oil at room temperature, and the mixture was subsequently transferred to a 0.9L continuously stirred reactor. The raw material gas (25 v% carbon dioxide, 65v% hydrogen and 10v% nitrogen mixture) is introduced into the reactor at a certain flow rate, the space velocity adopted is 3.5 liters/gram catalyst/hour, the reaction pressure is gradually increased to 7.0MPa, the reaction temperature is gradually increased to 330 ℃ to start the reaction, the outlet product of the reactor is kept at 160 ℃, and the reactor is introduced into the chromatograph for online analysis.
The carbon dioxide conversion and product selectivity were calculated according to the following formulas:
carbon dioxide conversion= (moles of carbon dioxide inlet-moles of carbon dioxide outlet)/moles of carbon dioxide inlet 100%;
product selectivity = moles of product exiting/(moles of carbon dioxide inlet-moles of carbon dioxide outlet) 100% of carbon atoms in the product.
The test results are shown in Table 1.
TABLE 1 results of catalyst performance test
Figure BSA0000296720430000071
As can be seen from table 1, the catalyst prepared by the invention can better realize the technical effect of preparing low-carbon alcohol by hydrogenating 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%; wherein ethanol and C 3+ The selectivity of the alcohol reaches 70.2% and 13.2%, respectively.
The technical idea of the present invention is described by the above embodiments, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must be implemented depending on the above embodiments. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of individual raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims (10)

1. The preparation method of the catalyst for preparing the low-carbon alcohol by converting carbon dioxide is characterized by dissolving an indium precursor, adding a precipitator to obtain a precipitation solution, stirring and aging, filtering and washing to obtain an indium oxide precursor, drying and roasting, mixing and drying indium oxide obtained after roasting, an alkali metal auxiliary agent and a transition metal auxiliary agent precursor in a solution to obtain a compound, drying and roasting the obtained compound, and activating the obtained compound in a mixed atmosphere of hydrogen and argon or in a carbon monoxide atmosphere to obtain the catalyst product.
2. The method for preparing a catalyst for preparing low-carbon alcohol by converting carbon dioxide according to claim 1, wherein the indium precursor is one or more of indium nitrate, indium chloride and indium sulfate.
3. The method for preparing a catalyst for preparing lower alcohols by converting carbon dioxide according to claim 1, wherein the precipitant is selected from one or more of ammonia monohydrate, sodium hydroxide, potassium hydroxide; the temperature of the precipitation process is 20-80 ℃, the pH value is 8.5-11, the aging temperature is 20-80 ℃ and the aging time is 1-48 hours.
4. The method for preparing a catalyst for preparing lower alcohols by converting carbon dioxide according to claim 1, wherein the alkali metal auxiliary precursor is selected from one or more of sodium nitrate and potassium nitrate.
5. The method for preparing a catalyst for preparing low-carbon alcohol by converting carbon dioxide according to claim 1, wherein the metal auxiliary precursor is selected from 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.
6. The method for preparing a catalyst for preparing low-carbon alcohol by converting carbon dioxide according to claim 1, wherein the mass ratio of indium oxide precursor to alkali metal auxiliary precursor to metal auxiliary precursor is 53-96:1-10:2-14.
7. The method for preparing a catalyst for preparing low-carbon alcohol by converting carbon dioxide according to claim 1, wherein the drying temperature of the indium oxide precursor is 60-150 ℃, the drying time is 1-12 hours, the roasting temperature is 400-900 ℃ and the roasting time is 1-3 hours; the drying temperature of the impregnated compound is 60-150 ℃, the drying time is 2-24 hours, the roasting temperature is 300-900 ℃, and the roasting time is 1-6 hours.
8. The method for preparing a catalyst for preparing low-carbon alcohol by converting carbon dioxide according to claim 1, wherein the catalyst activation process comprises hydrogen and argon or carbon monoxide at 400-800 ℃.
9. A catalyst prepared by the method of any one of claims 1 to 8.
10. Use of the catalyst of claim 9 in the preparation of lower alcohols by hydrogenation of carbon dioxide.
CN202310251287.4A 2023-03-15 2023-03-15 Preparation method and application of low-carbon indium alkoxide based catalyst synthesized by carbon dioxide hydrogenation Pending CN116099540A (en)

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