CN117085689B - A copper-based catalyst for preparing methanol by hydrogenation of carbon dioxide and a preparation method thereof - Google Patents
A copper-based catalyst for preparing methanol by hydrogenation of carbon dioxide and a preparation method thereof Download PDFInfo
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Abstract
本发明公开了一种二氧化碳加氢制甲醇铜基催化剂及其制备方法，其制备方法为以铜源、锌源及锆源或铝源为原料、碳酸钠为沉淀剂、可溶性有机化合物为碳源，采用共沉淀‑原位炭化‑还原得到碳修饰铜基催化剂，该催化剂的组分包括Cu、ZnO、ZrO2或Al2O3和C，C在催化剂表面均匀分散，与活性组分铜紧密结合，促进铜分散，获得高CO2转化率和甲醇选择性；同时，对铜物种起限域作用，且增强催化剂表面的疏水性，有助于将反应生成的水及时脱附，维持铜价态稳定，获得高耐热稳定性，耐热前后CO2转化率和甲醇选择性几乎不变。该催化剂用于二氧化碳加氢合成甲醇反应，副产物只有CO，且液相产物中只含有甲醇和水，容易分离。
The invention discloses a copper-based catalyst for preparing methanol by hydrogenation of carbon dioxide and a preparation method thereof. The preparation method is to use a copper source, a zinc source and a zirconium source or an aluminum source as raw materials, sodium carbonate as a precipitant, and a soluble organic compound as a carbon source, and adopt coprecipitation-in-situ carbonization-reduction to obtain a carbon-modified copper-based catalyst. The components of the catalyst include Cu, ZnO, ZrO2 or Al2O3 and C. C is evenly dispersed on the catalyst surface, closely combined with the active component copper, promotes copper dispersion, and obtains high CO2 conversion rate and methanol selectivity; at the same time, it has a limiting effect on copper species, and enhances the hydrophobicity of the catalyst surface, which helps to desorb the water generated by the reaction in time, maintains the copper valence state stable, obtains high heat resistance stability, and the CO2 conversion rate and methanol selectivity before and after heat resistance are almost unchanged. The catalyst is used for the synthesis of methanol by hydrogenation of carbon dioxide, and the byproduct is only CO, and the liquid phase product contains only methanol and water, which is easy to separate.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a copper-based catalyst for preparing methanol by hydrogenation of carbon dioxide and a preparation method thereof.
Background
With the development and improvement of the civilization of the human industry, the use amount of fossil fuels is continuously increased, and the carbon dioxide emission amount is increased year by year. The high emission of carbon dioxide can accelerate global warming, acidification of seawater, desertification of land and the like. Therefore, carbon dioxide emission reduction and resource utilization become research hotspots in the current society.
The catalytic hydrogenation technology of CO 2 is used for converting CO 2 into a series of chemicals, such as methanol, dimethyl ether, methane, etc., and is an effective means for recycling CO 2. Among various hydrogenation products, the formation of methanol is preferred, because methanol is a clean energy source, can improve the crisis of energy exhaustion of a country to a great extent, is a good hydrogen energy carrier, and can improve the energy crisis of the oil-gas era and relieve the global warming pressure by using methanol fuel instead of fossil fuel as an energy storage medium, so that the methanol is one of the most promising research fields for reasonable utilization of CO 2 in recent years. Based on the advantages, the hydrogenation synthesis of the methanol by the carbon dioxide has important environmental protection potential and economic value.
The existing copper-based catalyst for preparing methanol by carbon dioxide hydrogenation mainly has the problems of low carbon dioxide conversion rate, low methanol selectivity, poor catalyst stability and the like. Researchers have achieved some effects by adding metal adjuvants such as Ga [ appl. Catalyst. B Environ,2013,142-143,241-248], in [ appl. Catalyst. A,2020,605,117805], etc., with some improvement In methanol selectivity, but no significant improvement In stability. And researchers also add carbon materials to improve the stability of the catalyst, because the carbon materials have hydrophobicity, the influence of water generated in the reaction process on active components can be effectively improved, and the growth and inactivation of ZnO are prevented, but the currently reported copper-based catalysts modified by the carbon materials are all prepared by directly adding carbon nano tubes [ catalyst, 2018,307,212-223], graphene [ chem. Eng. J,2018,334,1781-1791] and the like into the copper-based catalysts, and the method has the problems that the carbon is insoluble, the mixture of the carbon and other components in the copper-based catalysts is uneven, the repetition is difficult and the like.
Aiming at the problems, the invention adopts the soluble organic compound as a carbon source, prepares the carbon-modified copper-based catalyst which is uniformly mixed in an in-situ carbonization mode, and can improve the selectivity of methanol and the heat-resistant stability of the catalyst.
Disclosure of Invention
Based on the problems of the copper-based catalyst for preparing methanol by carbon dioxide hydrogenation at present, the invention aims to provide the copper-based catalyst for preparing methanol by carbon dioxide hydrogenation and the preparation method thereof, the invention takes copper salt, zinc salt, zirconium salt or aluminum salt as raw materials, the carbonate is used as a precipitator, and a carbon source is added as an auxiliary agent, and the prepared copper-based catalyst for preparing the methanol by hydrogenating the carbon dioxide has the characteristics of high CO 2 conversion rate, methanol selectivity, high stability and the like.
The invention discloses a copper-based catalyst for preparing methanol by hydrogenating carbon dioxide, which comprises Cu, znO, zrO 2 or Al 2O3 and an auxiliary agent C, wherein Cu, znO, zrO 2 or Al 2O3 in the catalyst is uniformly dispersed, the auxiliary agent C is uniformly dispersed on the surface of the catalyst and is tightly combined with an active component copper species to promote the copper species to be dispersed, and meanwhile, the catalyst plays a certain limiting domain role on the copper species, and enhances the hydrophobicity of the surface of the catalyst to ensure that the valence state of the copper species is kept stable.
Further, the invention also defines that each component in the catalyst comprises 20-70% of Cu, 10-60% of Zn, 1-20% of Zr or Al and 1-30% of C in mole percent.
The invention further provides a preparation method of the copper-based catalyst for preparing methanol by hydrogenation of carbon dioxide, which takes a copper source, a zinc source, a zirconium source or an aluminum source as raw materials, sodium carbonate as a precipitator, and a soluble organic compound as a carbon source, and adopts coprecipitation-in-situ carbonization-reduction to obtain the carbon-modified copper-based catalyst, and specifically comprises the following steps:
1) Dissolving a copper source, a zinc source, a zirconium source or an aluminum source in water according to a feeding ratio to prepare a metal salt solution;
2) Coprecipitating a metal salt solution and a sodium carbonate solution into a solution containing a carbon source under stirring, aging under stirring, and obtaining a catalyst precursor after suction filtration and washing of the precipitate;
3) Drying the catalyst precursor obtained in the step 2), roasting in inert atmosphere to perform in-situ carbonization, and reducing the catalyst by H 2/N2 to obtain the carbon-modified copper-based catalyst.
Further, the invention also defines that the carbon source is one or more of beta-cyclodextrin, polyethylene glycol (PEG), ethylene Glycol (EG), glucose or soluble starch.
The invention further defines that the copper source is copper nitrate or copper acetate, the zinc source is zinc nitrate or zinc acetate, the zirconium source is zirconium nitrate or zirconyl nitrate, and the aluminum source is aluminum nitrate or pseudo-boehmite.
Further, the invention also defines a molar ratio of total molar amount of copper source, zinc source, zirconium source or aluminum source to carbon of 1:0.01-0.3.
Further, the invention also defines the specific operation of the step 2), namely, under the temperature of 10-80 ℃, the metal salt solution and the sodium carbonate solution are titrated into the solution containing the carbon source in the step 1) in parallel flow, the pH=7-10 is maintained, the solution is stirred and aged for 0.5-24 hours under the temperature of 40-100 ℃ after precipitation, and the precipitate is washed by deionized water until no sodium ions are detected, so that the catalyst precursor is obtained.
Further, the invention also defines that the drying condition of the catalyst precursor in the step 3) is that the catalyst precursor is dried for 10 to 15 hours at 60 to 160 ℃, and the roasting condition is that the catalyst precursor is roasted for 3 to 6 hours at 300 to 500 ℃ under the atmosphere of nitrogen or argon.
When the copper-based catalyst for preparing methanol by hydrogenating carbon dioxide is used for preparing methanol, the composition of carbon dioxide raw material gas is 10-30vol.% CO 2、30％～90vol.％H2 and N 2 mixed gas which are used as balance gas, wherein the volume ratio of CO 2 to H 2 is about 1:3, and a fixed bed reactor is adopted to carry out CO 2 hydrogenation reaction under the conditions of 2-10 MPa of pressure, 180-280 ℃ of temperature and 6000-30000 mL g cat -1h-1 of airspeed.
By adopting the technology, compared with the prior art, the invention has the following beneficial effects:
1) According to the invention, copper salt, zinc salt, zirconium salt or aluminum salt is used as a raw material, carbonate is used as a precipitator, a soluble carbon source is used as an auxiliary agent, a coprecipitation-in-situ carbonization method is adopted to generate carbon on a copper-based catalyst in situ, a carbon-modified copper-based catalyst is synthesized, carbon generated by in-situ carbonization modifies the catalyst, so that the auxiliary agent and copper species can be fully mixed, and the interaction is stronger;
2) The carbon component in the catalyst plays a certain role in limiting copper species, enhances the hydrophobicity of the catalyst, improves the selectivity of the catalyst in synthesizing methanol by hydrogenating carbon dioxide and the heat-resistant stability of the catalyst, wherein the selectivity of the methanol is up to 95%, and the CO 2 conversion rate and the methanol selectivity are almost unchanged after the catalyst is heat-resistant at 350 ℃;
3) The catalyst is used in synthesizing methanol by hydrogenation of carbon dioxide, the reaction by-product is only CO, and the liquid-phase product only contains methanol and water, so that the separation is easy.
Drawings
FIG. 1 is an EDS-mapping graph of the copper-based catalyst β -CZZ prepared in example 1;
FIG. 2 is a graph showing contact angle measurements of copper-based catalysts prepared in example 1 and comparative example 1;
FIG. 3 is a schematic diagram of the structure of the copper-based catalyst prepared in example 1.
Detailed Description
The invention will be further illustrated with reference to specific examples, but the scope of the invention is not limited to the described scope.
Example 1
The preparation method comprises accurately weighing Cu(NO3)2·3H2O 14.50g、Zn(NO3)2·6H2O 8.93g、Zr(NO3)4·5H2O 4.29g to dissolve in 100mL deionized water according to a molar ratio of Cu, zn and Zr of 6:3:1 to prepare a metal salt solution 1 with total concentration of metal ions of 1mol L -1, accurately weighing Na 2CO3 15.90.90 g to dissolve in 150mL deionized water to prepare 1mol L -1 alkali liquor 2, accurately weighing beta-cyclodextrin of 0.14g to add into 100mL deionized water to prepare a carbon source solution 3, coprecipitating the metal salt solution 1 and the alkali liquor 2 into the carbon source solution 3 under 70 ℃ stirring, fully stirring in the precipitation process, keeping pH=7, aging at 70 ℃ for 2 hours, washing the precipitate with deionized water until no sodium ions are detected, drying at 110 ℃ for 12 hours, roasting at 400 ℃ for 4 hours under an atmosphere of N 2, and then introducing 20% H 2/N2 to reduce the catalyst (30 mL min -1) to obtain a carbon modified copper-based catalyst with total molar ratio of copper source, zinc source and zirconium source and carbon of 1:0.05, wherein the copper-CZ-based catalyst is shown in a schematic diagram of FIG. 3.
Example 2
The preparation method comprises accurately weighing Cu(NO3)2·3H2O 14.50g、Zn(NO3)2·6H2O 8.93g、Zr(NO3)4·5H2O 4.29g to dissolve in 100mL deionized water according to a molar ratio of Cu, zn and Zr of 6:3:1 to prepare a metal salt solution 1 with total concentration of metal ions of 1mol L -1, accurately weighing Na 2CO3 15.90.90 g to dissolve in 150mL deionized water to prepare 1mol L -1 alkali liquor 2, accurately weighing beta-cyclodextrin of 0.027g to add into 100mL deionized water to prepare a carbon source solution 3, coprecipitating the metal salt solution 1 and the alkali liquor 2 into the carbon source solution 3 under stirring at 70 ℃ to obtain a carbon-based copper-based catalyst with a total molar ratio of 1:0.01 of a copper source, a zinc source and a zirconium source, wherein the precipitation process needs to be fully stirred, pH=7 is kept, the precipitation is aged for 2h at 70 ℃, the precipitation is washed by deionized water until no sodium ions are detected, the precipitation is dried for 12h at 110 ℃, the temperature of 400 ℃ is baked for 4h under an atmosphere of N 2, and then the catalyst is subjected to reduction treatment (30 mL min -1) by introducing 20% H 2/N2 to obtain the carbon-based copper-modified catalyst with the beta-CZ 1.
Example 3
The method comprises accurately weighing Cu(NO3)2·3H2O 14.50g、Zn(NO3)2·6H2O 8.93g、Zr(NO3)4·5H2O 4.29g to dissolve in 100mL deionized water according to a molar ratio of Cu, zn and Zr of 6:3:1 to prepare a metal salt solution 1 with total concentration of metal ions of 1mol L -1, accurately weighing Na 2CO3 15.90.90 g to dissolve in 150mL deionized water to prepare 1mol L -1 alkali liquor 2, accurately weighing beta-cyclodextrin 0.27g to add into 100mL deionized water to prepare a carbon source solution 3, coprecipitating the metal salt solution 1 and the alkali liquor 2 into the carbon source solution 3 under 70 ℃ stirring, fully stirring in the precipitation process, keeping pH=7, aging at 70 ℃ for 2 hours, washing the precipitate with deionized water until no sodium ions are detected, drying at 110 ℃ for 12 hours, roasting at 400 ℃ for 4 hours under an atmosphere of N 2, introducing 20% H 2/N2, and carrying out reduction treatment (30 mL min -1) on the catalyst to obtain the beta-CZ-10 carbon modified copper-based catalyst with total molar ratio of 1:0.1.
Example 4
Accurately weighing Cu(NO3)2·3H2O 14.50g、Zn(NO3)2·6H2O 8.93g、Zr(NO3)4·5H2O 4.29g to be dissolved in 100mL of deionized water according to the molar ratio of Cu, zn and Zr of 6:3:1 to prepare a metal salt solution 1 with the total concentration of metal ions of 1mol L -1, accurately weighing 2CO3 15.90.90 g to be dissolved in 150mL of deionized water to prepare 1mol L -1 alkali liquor 2, accurately weighing 0.81g of beta-cyclodextrin to be added into 100mL of deionized water to prepare a carbon source solution 3, coprecipitating the metal salt solution 1 and the alkali liquor 2 into the carbon source solution 3 under 70 ℃ stirring, fully stirring the precipitation process, keeping the pH value of the solution=7 and the aging of the solution at 70 ℃ for 2 hours, washing the precipitate with deionized water until no sodium ions are detected, drying the precipitate at 110 ℃ for 12 hours, roasting at 400 ℃ under the atmosphere of N 2, introducing 20% H 2/N2, and carrying out reduction treatment (30 mL of min -1) on the catalyst to obtain the carbon modified copper-based catalyst with the total molar ratio of copper source, zinc source and zirconium source and carbon source of 1:0.3, namely beta-CZ-30.
Example 5
Cu(NO3)2·3H2O 14.50g、Zn(NO3)2·6H2O 8.93g、Al(NO3)3·9H2O 3.75g Is accurately weighed according to the molar ratio of Cu, zn and Al of 6:3:1 and is dissolved in 100mL of deionized water to prepare a metal salt solution 1 with the total concentration of metal ions of 1mol L -1, na 2CO3 15.90.90 g is accurately weighed and is dissolved in 150mL of deionized water to prepare an alkali solution 2 with the concentration of 1mol L -1, and 0.14g of beta-cyclodextrin is accurately weighed and is added into 100mL of deionized water to prepare a carbon source-containing solution 3. Coprecipitation of the metal salt solution 1 and the alkali liquor 2 into the carbon-containing source solution 3 under the stirring of 70 ℃, the precipitation process needs to be fully stirred, the pH=7 is kept, the aging is carried out for 2 hours at 70 ℃, the precipitate is washed by deionized water until no sodium ions are detected, the precipitate is dried for 12 hours at 110 ℃, baked for 4 hours at 400 ℃ under the atmosphere of N 2, then 20% H 2/N2 is introduced to carry out reduction treatment (30 mL min -1) on the catalyst, and the carbon-modified copper-based catalyst with the total molar ratio of copper source, zinc source and aluminum source to carbon of 1:0.05 is obtained and is named as beta-CZA.
Example 6
Cu(NO3)2·3H2O 14.50g、Zn(NO3)2·6H2O 8.93g、Zr(NO3)4·5H2O 4.29g Is accurately weighed according to the molar ratio of Cu, zn and Zr of 6:3:1 and dissolved in 100mL of deionized water to prepare solution 1 with total concentration of metal ions of 1mol L -1. Accurately weighing 15.90g of Na 2CO3 into 150mL of deionized water to prepare 1mol L -1 of alkali liquor 2. Accurately weighing PEG-40000.11g, adding the PEG-40000.11g into 100mL of deionized water, and preparing a carbon source-containing solution 3. Coprecipitation of the metal salt solution 1 and the alkali liquor 2 into the carbon-containing source solution 3 under the stirring of 70 ℃, the precipitation process needs to be fully stirred, the pH=7 is kept, the aging is carried out for 2 hours at 70 ℃, the precipitate is washed by deionized water until no sodium ions are detected, the precipitate is dried for 12 hours at 110 ℃, baked for 4 hours at 400 ℃ under the atmosphere of N 2, then 20% H 2/N2 is introduced to carry out reduction treatment (30 mL min -1) on the catalyst, and the carbon-modified copper-based catalyst with the total molar ratio of copper source, zinc source and zirconium source to carbon of 1:0.05 is obtained and is named PEG-CZZ.
Example 7
Cu(NO3)2·3H2O 14.50g、Zn(NO3)2·6H2O 8.93g、Zr(NO3)4·5H2O 4.29g Is accurately weighed according to the molar ratio of Cu, zn and Zr of 6:3:1 and dissolved in 100mL of deionized water to prepare solution 1 with total concentration of metal ions of 1mol L -1. Accurately weighing 15.90g of Na 2CO3 into 150mL of deionized water to prepare 1mol L -1 of alkali liquor 2. Accurately weighing 0.16g of ethylene glycol, and adding the ethylene glycol into 100mL of deionized water to prepare a carbon source-containing solution 3. Coprecipitation of the metal salt solution 1 and the alkali liquor 2 into the carbon-containing source solution 3 under the stirring of 70 ℃, the precipitation process needs to be fully stirred, the pH=7 is kept, the aging is carried out for 2 hours at 70 ℃, the precipitate is washed by deionized water until no sodium ions are detected, the precipitate is dried for 12 hours at 110 ℃, baked for 4 hours at 400 ℃ under the atmosphere of N 2, and then 20 percent H 2/N2 is introduced to carry out reduction treatment (30 mLmin -1) on the catalyst, so that the carbon-modified copper-based catalyst with the total molar ratio of copper source, zinc source and zirconium source to carbon of 1:0.05 is obtained, and the catalyst is named EG-CZZ.
Example 8
Cu(NO3)2·3H2O 14.50g、Zn(NO3)2·6H2O 8.93g、Zr(NO3)4·5H2O 4.29g Is accurately weighed according to the molar ratio of Cu, zn and Zr of 6:3:1 and dissolved in 100mL of deionized water to prepare solution 1 with total concentration of metal ions of 1mol L -1. Accurately weighing 15.90g of Na 2CO3 into 150mL of deionized water to prepare 1mol L -1 of alkali liquor 2. Accurately weighing 0.14g of soluble starch, and adding the soluble starch into 100mL of deionized water to prepare a carbon source-containing solution 3. Coprecipitation of the metal salt solution 1 and the alkali liquor 2 into the carbon-containing source solution 3 under the stirring of 70 ℃, the precipitation process needs to be fully stirred, the pH=7 is kept, the aging is carried out for 2 hours at 70 ℃, the precipitate is washed by deionized water until no sodium ions are detected, the precipitate is dried for 12 hours at 110 ℃, baked for 4 hours at 400 ℃ under the atmosphere of N 2, then 20% H 2/N2 is introduced to carry out reduction treatment (30 mL min -1) on the catalyst, and the carbon-modified copper-based catalyst with the total molar ratio of copper source, zinc source and zirconium source to carbon of 1:0.05 is obtained and is named as S-CZZ.
Example 9
Cu(NO3)2·3H2O 14.50g、Zn(NO3)2·6H2O 8.93g、Zr(NO3)4·5H2O 4.29g Is accurately weighed according to the molar ratio of Cu, zn and Zr of 6:3:1 and dissolved in 100mL of deionized water to prepare solution 1 with total concentration of metal ions of 1mol L -1. Accurately weighing 15.90g of Na 2CO3 into 150mL of deionized water to prepare 1mol L -1 of alkali liquor 2. Accurately weighing 0.15g of glucose, and adding the glucose into 100mL of deionized water to prepare a carbon source-containing solution 3. Coprecipitation of the metal salt solution 1 and the alkali liquor 2 into the carbon-containing source solution 3 under the stirring of 70 ℃, the precipitation process needs to be fully stirred, the pH=7 is kept, the aging is carried out for 2 hours at 70 ℃, the precipitate is washed by deionized water until no sodium ions are detected, the precipitate is dried for 12 hours at 110 ℃, baked for 4 hours at 400 ℃ under the atmosphere of N 2, and then 20% H 2/N2 is introduced to carry out reduction treatment (30 mLmin -1) on the catalyst, so that the carbon-modified copper-based catalyst with the total molar ratio of copper source, zinc source and zirconium source to carbon of 1:0.05 is obtained, and the catalyst is named GLC-CZZ.
Comparative example 1
The method comprises accurately weighing Cu(NO3)2·3H2O 14.50g、Zn(NO3)2·6H2O 8.93g、Zr(NO3)4·5H2O 4.29g according to the molar ratio of Cu, zn and Zr of 6:3:1, dissolving in 100mL of deionized water to prepare a metal salt solution 1 with the total concentration of metal ions of 1mol L -1, accurately weighing Na 2CO3 15.90.90 g, dissolving in 150mL of deionized water to prepare 1mol L -1 of alkali liquor 2, coprecipitating the metal salt solution 1 and the alkali liquor 2 in 100mL of deionized water under 70 ℃ stirring, fully stirring in the precipitation process, keeping pH=7 and aging at 70 ℃ for 2 hours, washing the precipitate by deionized water until no sodium ions are detected, drying at 110 ℃ for 12 hours, roasting at 400 ℃ for 4 hours under N 2 atmosphere, and introducing 20% H 2/N2 to perform reduction treatment (30 mLmin -1) on the catalyst, wherein the obtained catalyst is named as CZZ.
Comparative example 2
Cu(NO3)2·3H2O 14.50g、Zn(NO3)2·6H2O 8.93g、Zr(NO3)4·5H2O 4.29g Is accurately weighed according to the molar ratio of Cu, zn and Zr of 6:3:1 and dissolved in 100mL of deionized water to prepare solution 1 with total concentration of metal ions of 1mol L -1. Accurately weighing 15.90g of Na 2CO3 into 150mL of deionized water to prepare 1mol L -1 of alkali liquor 2. Accurately weighing CNTs0.06g, adding the CNTs0.06g into 100mL of deionized water, and preparing a carbon-containing suspension 3. Coprecipitation of the metal salt solution 1 and the alkali liquor 2 into the carbon-containing source suspension 3 under 70 ℃ stirring, the precipitation process needs to be fully stirred, the pH=7 is kept, the precipitation is aged for 2 hours under 70 ℃, the precipitation is washed by deionized water until no sodium ions are detected, the precipitation is dried for 12 hours under 110 ℃, the reaction is roasted for 4 hours under 400 ℃ in N 2 atmosphere, and then 20% H 2/N2 is introduced to carry out reduction treatment (30 mLmin -1) on the catalyst, so that the carbon-modified catalyst with the total molar ratio of copper source, zinc source and zirconium source to carbon of 1:0.05 is obtained, and the catalyst is named CNTs-CZZ.
Comparative example 3
Accurately weighing Cu(NO3)2·3H2O 14.50g、Zn(NO3)2·6H2O 8.93g、Zr(NO3)4·5H2O 4.29g to be dissolved in 100mL of deionized water according to the mol ratio of Cu to Zn to Zr of 6:3:1 to prepare a metal salt solution 1 with the total concentration of metal ions of 1mol L -1, accurately weighing 2CO3 15.90.90 g to be dissolved in 150mL of deionized water to prepare 1mol L -1 alkali liquor 2, accurately weighing GO of 0.06g to be added into 100mL of deionized water to prepare a carbon-containing suspension 3, coprecipitating the metal salt solution 1 and the alkali liquor 2 into the carbon-containing suspension 3 under 70 ℃ stirring, fully stirring the precipitation process, keeping the pH value of the solution=7 and the aging of the solution at 70 ℃ for 2 hours, washing the precipitate with deionized water until no sodium ions are detected, drying the precipitate for 12 hours under the atmosphere of N 2, roasting for 4 hours, and then introducing 20% H 2/N2 to perform reduction treatment (30 mL of min -1) on the catalyst to obtain the carbon-modified copper-based catalyst CZ with the total molar ratio of 1:0.05.
Comparative example 4
Industrial copper zinc aluminum methanol synthesis catalyst (industrial catalyst-1).
In order to evaluate the catalytic performance of the prepared catalyst, the performance test of synthesizing methanol by CO 2 hydrogenation is carried out on the catalyst by a micro-reverse evaluation device. The fixed bed reactor was used, each catalyst was added, and then a CO 2/H2/N2 (23:69:8) mixture was introduced at a flow rate of 50mL min -1, and CO 2 hydrogenation was performed at 220℃and 3MPa to synthesize methanol, the results of which are shown in Table 1.
Table 1 results of evaluation of reactivity in examples
Reaction conditions t=220 ℃, p=3.0 mpa, h 2/CO2＝3,WHSV＝6000mLgcat -1h-1
From the results listed in table 1, it can be found that the catalyst of the invention uses a soluble carbon source as an auxiliary agent, and modifies the catalyst in a manner of generating carbon by in-situ carbonization, thereby improving the activity of the copper-based catalyst and the selectivity of methanol, and remarkably improving the yield of methanol. The methanol selectivity of the catalyst can be improved when the carbon content is in a range of 1-30mol%, and the methanol selectivity of the catalyst shows a volcanic curve along with the increase of the carbon content, wherein the effect is optimal when the carbon content is 5mol%, the CO 2 conversion rate reaches 20.3%, and the methanol selectivity reaches 95.2%. Compared with a copper-based catalyst directly doped with a carbon material, the carbon-modified copper-based catalyst prepared by in-situ carbonization with a soluble compound as a carbon source can simultaneously improve the carbon dioxide conversion rate and the methanol selectivity under the condition of the same carbon content.
From the EDS-mapping graph of the copper-based catalyst β -CZZ prepared in example 1 of fig. 1, it can be found that C in the carbon-modified copper zinc zirconium catalyst prepared by in-situ carbonization using β -cyclodextrin as a carbon source is uniformly dispersed on the catalyst surface and tightly combined with the active component copper species.
From the contact angle measurement graph of the copper-based catalyst prepared in example 1 and comparative example 1 of fig. 2, it can be found that the copper-based catalyst β -CZZ prepared in example 1 has a larger contact angle, indicating that carbon modification of the catalyst surface can improve the hydrophobicity of the catalyst surface to some extent.
To evaluate the stability of the prepared catalyst, the performance of example 1, example 6 and comparative example 1 before and after heat resistance was compared, heat resistance condition was 350 ℃ heat resistance was carried out for 8 hours, and the results are shown in table 2.
Table 2 results of evaluation of heat stability in examples
Reaction conditions t=220 ℃, p=3.0 mpa, h 2/CO2＝3,WHSV＝6000mLgcat -1h-1
Heat-resistant condition of 350 ℃ for 8h
From the results listed in table 2, it can be found that, compared with comparative example 1, the CO 2 conversion rate and the methanol selectivity of the catalyst before and after heat resistance are hardly reduced, which indicates that the carbon-modified copper-based catalyst obtained by the preparation method of the invention has good structural stability, surface carbon plays a role in limiting the structure of copper species, the aggregation and inactivation of Cu active components in the heat resistance process are inhibited, and the modification of carbon enhances the hydrophobicity of the surface of the catalyst, so that H 2 O generated in the reaction process is desorbed in time, which is helpful for maintaining the valence state of copper species stable, therefore, after heat resistance, the catalyst still maintains high CO 2 conversion rate and methanol selectivity, and shows high heat resistance stability.
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