CN116764641A - Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof - Google Patents

Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof Download PDF

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CN116764641A
CN116764641A CN202310708036.4A CN202310708036A CN116764641A CN 116764641 A CN116764641 A CN 116764641A CN 202310708036 A CN202310708036 A CN 202310708036A CN 116764641 A CN116764641 A CN 116764641A
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catalyst
auxiliary agent
carbon dioxide
preparing
methanol
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李延鹏
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Zhejiang Green Zhixing Science And Technology Innovation Co ltd
Zhejiang Geely Holding Group Co Ltd
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Zhejiang Green Zhixing Science And Technology Innovation Co ltd
Zhejiang Geely Holding Group Co Ltd
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Abstract

The application discloses a catalyst for preparing methanol by carbon dioxide hydrogenation and a preparation method thereof, wherein the preparation method of the catalyst for preparing methanol by carbon dioxide hydrogenation comprises the following steps: coprecipitating copper salt, zinc salt, aluminum salt, a first auxiliary agent and a precipitator, and aging, washing and drying the coprecipitated product to obtain a catalyst precursor; introducing a second auxiliary agent onto the catalyst precursor, and roasting the product after the second auxiliary agent is introduced to obtain the catalyst for preparing methanol by hydrogenating carbon dioxide. The application solves the technical problems of lower carbon dioxide hydrogenation activity, lower methanol selectivity and lower stability of the catalyst for preparing methanol by carbon dioxide hydrogenation in the prior art.

Description

Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof
Technical Field
The application relates to the technical field of catalysts, in particular to a catalyst for preparing methanol by carbon dioxide hydrogenation and a preparation method thereof.
Background
Methanol is used as an important basic chemical raw material and can be used for synthesizing various chemicals such as dimethyl ether, light olefin, aromatic hydrocarbon, acetic acid and the like,and can be used as alternative fuel. The increase of the carbon dioxide concentration in the atmosphere is a main cause of global climate change at present, along with the rapid development of modern industry, the global carbon dioxide emission is gradually increased, and environmental pollution, extreme climate frequency and other phenomena cause great importance in various countries of the world, and the emission reduction of carbon dioxide is not sustained. The currently reported catalyst for preparing methanol by carbon dioxide hydrogenation mainly comprises the following components: copper-based catalyst, oxide catalyst, noble metal catalyst and MoS 2 (molybdenum sulfide) is a novel catalyst, wherein the copper-based catalyst has been industrially applied, however, the hydrogenation activity of carbon dioxide of the copper-based catalyst still has a large gap from the thermodynamic equilibrium conversion rate, and the selectivity and stability of methanol are still low.
Disclosure of Invention
The application mainly aims to provide a catalyst for preparing methanol by carbon dioxide hydrogenation and a preparation method thereof, and aims to solve the technical problems of low carbon dioxide hydrogenation activity, low methanol selectivity and low stability of the catalyst for preparing methanol by carbon dioxide hydrogenation in the prior art.
In order to achieve the above purpose, the application also provides a preparation method of the catalyst for preparing methanol by carbon dioxide hydrogenation, which comprises the following steps:
coprecipitating copper salt, zinc salt, aluminum salt, a first auxiliary agent and a precipitator, and aging, washing and drying the coprecipitated product to obtain a catalyst precursor;
introducing a second auxiliary agent onto the catalyst precursor, and roasting the product after the second auxiliary agent is introduced to obtain the catalyst for preparing methanol by hydrogenating carbon dioxide.
Optionally, the first auxiliary agent contains one or more of yttrium, molybdenum, niobium, gallium, indium, lanthanum, tungsten, magnesium and cadmium.
Optionally, the second auxiliary agent contains one or more of zirconium, gallium, indium and lanthanum.
Optionally, the mass fraction of the total amount of the first auxiliary agent and the second auxiliary agent in the catalyst is 2% -10%;
the mass fraction of the first auxiliary agent in the catalyst is 1% -6%;
the mass fraction of the second auxiliary agent in the catalyst is 1-6%.
Alternatively, the co-precipitation is co-current co-precipitation or counter-current co-precipitation.
Optionally, the pH of the coprecipitation is 6-11, the temperature is 40-90 ℃, and the aging time is 1-15 hours.
Optionally, the step of introducing the second auxiliary agent onto the catalyst precursor, and roasting the product after introducing the second auxiliary agent to obtain the catalyst for preparing methanol by hydrogenating carbon dioxide comprises the following steps:
preparing a second auxiliary agent into a second auxiliary agent solution, dripping the second auxiliary agent solution onto the catalyst precursor, dipping, drying and roasting a product after the second auxiliary agent is introduced, and obtaining the catalyst for preparing methanol by hydrogenating carbon dioxide.
Optionally, the step of introducing the second auxiliary agent onto the catalyst precursor, and roasting the product after introducing the second auxiliary agent to obtain the catalyst for preparing methanol by hydrogenating carbon dioxide comprises the following steps:
preparing a second auxiliary agent into a second auxiliary agent solution, mixing the second auxiliary agent solution, a precipitator and the catalyst precursor, and washing, drying and roasting a product after the second auxiliary agent is introduced to obtain the catalyst for preparing methanol by hydrogenating carbon dioxide.
Optionally, the step of introducing the second auxiliary agent onto the catalyst precursor, and roasting the product after introducing the second auxiliary agent to obtain the catalyst for preparing methanol by hydrogenating carbon dioxide comprises the following steps:
and mixing the second auxiliary agent and the catalyst precursor, performing ball milling, and roasting a product after the second auxiliary agent is introduced to obtain the catalyst.
Optionally, the roasting temperature of the roasting is 300-500 ℃ and the roasting time is 2-6 hours.
Optionally, the precipitant is one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, and potassium bicarbonate.
Optionally, the mass ratio of copper, zinc oxide and aluminum oxide in the catalyst is (3-7): (1-4): (1-3).
The application also provides a catalyst for preparing methanol by carbon dioxide hydrogenation, which is prepared by adopting the preparation method of the catalyst for preparing methanol by carbon dioxide hydrogenation.
The application provides a preparation method of a catalyst for preparing methanol by hydrogenation of carbon dioxide, which comprises the steps of coprecipitating a metal copper salt, a metal zinc salt, a metal aluminum salt, a first auxiliary agent and a precipitator, aging, washing and drying a coprecipitated product to obtain a catalyst precursor, wherein on one hand, the improvement of copper dispersity is realized, the enhancement of metal-oxide interface interaction is favorable for improving the hydrogenation activity of the catalyst, and on the other hand, part of auxiliary agents introduced in the coprecipitation process can promote oxygen vacancies and Cu + The generation of (cuprous ions) is beneficial to stabilizing formate and methoxy, inhibiting the decomposition of formate and methoxy to generate CO (carbon monoxide), and improving the selectivity of methanol, on the other hand, the addition of the auxiliary agent inhibits the sintering of an active center, and improves the heat resistance of the catalyst; furthermore, the second auxiliary agent is introduced onto the catalyst precursor, and the product after the second auxiliary agent is introduced is roasted to obtain the catalyst for preparing methanol by hydrogenating carbon dioxide, so that on one hand, the coverage of part of Cu (copper) sites is realized, the reverse water gas shift reaction active sites are reduced, the selectivity of methanol is improved, on the other hand, the oxide is covered on the Cu sites to form a high-activity oxide-Cu interface, the hydrogenation activity of the catalyst can be improved to a certain extent, on the other hand, the introduced part of the hydrophobic auxiliary agent can improve the hydrophobicity of the catalyst, and the sintering of active centers due to water is inhibited. Thus, by introducing the auxiliary agent twice, the technical defects that the carbon dioxide hydrogenation activity of the copper-based catalyst still has a larger gap from the thermodynamic equilibrium conversion rate and the selectivity and stability of the methanol are still lower are overcome, and meanwhile, the hydrogenation activity, selectivity and stability of the catalyst for preparing the methanol by hydrogenating the carbon dioxide are improved.
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The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and together with the description, serve to explain the principles of the application.
In order to more clearly illustrate the embodiments of the present application or the technical solutions of the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described, and it will be obvious to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a schematic flow chart of an embodiment of a method for preparing methanol by hydrogenating carbon dioxide according to the present application.
The achievement of the objects, functional features and advantages of the present application will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
In order to make the above objects, features and advantages of the present application more comprehensible, the following description will make the technical solutions of the embodiments of the present application clear and complete. It will be apparent that the described embodiments are only some, but not all, embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
The embodiment of the application provides a preparation method of a catalyst for preparing methanol by carbon dioxide hydrogenation, referring to fig. 1, the preparation method of the catalyst for preparing methanol by carbon dioxide hydrogenation is used for preparing the catalyst for preparing methanol by carbon dioxide hydrogenation, and comprises the following steps:
s10, coprecipitating a metal copper salt, a metal zinc salt, a metal aluminum salt, a first auxiliary agent and a precipitator, and aging, washing and drying the coprecipitated product to obtain a catalyst precursor;
in this embodiment, the copper-based catalyst formulation is controlled, for example, an auxiliary agent is introduced, so that the dispersibility of copper can be effectively improved, and the catalyst performance is improved. At present, there is a method for preparing an alloy catalyst by grinding and dispersing main components and auxiliary components of the catalyst, the method is simple to operate, but the interaction between metal and oxide of the catalyst prepared by the method is weak, so that the hydrogenation performance of carbon dioxide is low; the method also comprises the steps of preparing Cu-Zn-Zr (copper-zinc-zirconium) suspension by a countercurrent coprecipitation method, adding a metal auxiliary agent and a complexing agent into the suspension at the same time, stirring the mixture into gel, and obtaining a catalyst after the product is treated, dried, roasted and reduced, wherein the catalyst prepared by the method has high selectivity but lower carbon dioxide conversion rate; there is also a method for preparing a catalyst by a fractional coprecipitation method, which has a higher carbon dioxide conversion rate but a lower selectivity of the catalyst. That is, it is difficult to simultaneously improve the carbon dioxide hydrogenation activity, the methanol selectivity and the stability of the catalyst for preparing methanol by hydrogenating carbon dioxide in the prior art.
The catalyst for hydrogenation of carbon dioxide to methanol prepared in this example is a copper-based catalyst, and the copper-based catalyst is a catalyst having copper as an active site. In copper-based catalysts, the catalyst carrier used as an active center of the supported and dispersed catalyst plays a vital role, the carrier can be used as a dispersing agent and a stabilizing agent of an active component, the surface and a pore structure of the supported active component are provided, the active component of the catalyst is better dispersed and stabilized, znO (zinc oxide) can improve the specific surface area of the catalyst and prevent copper grains on the surface of the catalyst from sintering, and the catalyst carrier can be used as a carrier of the copper-based catalyst, and Al 2 O 3 The (alumina) not only plays a supporting role in the catalyst, but also can better disperse the active components of the catalyst, inhibit the reduction of copper oxide and improve the catalytic activity of the catalyst, and can also be used as a carrier of a copper-based catalyst. The auxiliary agent refers to an ingredient which can modify and modify the active ingredient and the carrier so as to influence the action of the active ingredient and the carrier in the catalyst and further influence the catalytic activity of the catalyst, and comprises rare earth element auxiliary agents, transition metal element auxiliary agents, alkaline earth element auxiliary agents, nonmetallic element auxiliary agents and the like.
The metal copper salt refers to a salt with cations of copper ions, and can be copper nitrate, copper sulfate, copper acetate and the like; the metal zinc saltThe cation is zinc ion salt, which can be zinc nitrate, zinc sulfate, zinc acetate and the like; the metal aluminum salt refers to a salt with positive ions of aluminum ions, such as aluminum nitrate, aluminum sulfate, aluminum acetate and the like; the first auxiliary agent can promote Cu + And oxygen vacancy, stable formate and intermediate products such as methoxy, etc., and inhibit its decomposition and produce metallic element auxiliary agent of CO, for example yttrium (Y), molybdenum (Mo), niobium (Nb), gallium (Ga), indium (In), lanthanum (La), tungsten (W), magnesium (Mg), salt of metals such as cadmium (Cd), in this way, can improve the selectivity of methanol, and said first auxiliary agent can improve the dispersion of the active center of metal, increase oxygen vacancy and interface effect of metal-oxide, help to improve hydrogenation activity of catalyst, in addition, can isolate copper as the spacer, in addition auxiliary agent can strengthen the interaction between copper and carrier, help to inhibit sintering of copper; the precipitant refers to an agent which can separate the mixed product of the metal copper salt, the metal zinc salt, the metal aluminum salt and the first auxiliary agent from the solution in a precipitated form without introducing impurities, and comprises carbonate, bicarbonate and the like.
As an example, the addition amounts of the metal copper salt, the metal zinc salt, the metal aluminum salt, the first auxiliary agent and the precipitant may be determined in advance according to data documents, experimental results and the like, the metal copper salt, the metal zinc salt, the metal aluminum salt, the first auxiliary agent and the precipitant may be respectively weighed according to the predetermined addition amounts, the metal copper salt, the metal zinc salt, the metal aluminum salt and the first auxiliary agent are configured into a first mixed solution, the precipitant is configured into a precipitant aqueous solution, the first mixed solution and the precipitant aqueous solution are added into a mixer to perform coprecipitation, and the coprecipitation product is aged, washed and dried to obtain a catalyst precursor, wherein the specific concentration of the first mixed solution and the precipitant aqueous solution may be determined according to the data documents, experimental results and the like, which is not limited; the coprecipitation can be a forward coprecipitation method, a reverse coprecipitation method, a parallel flow coprecipitation method, a countercurrent coprecipitation method, a uniform precipitation method and the like; the specific conditions of the coprecipitation, the aging, the washing, and the drying steps may be determined based on data documents, experimental results, and the like,the present embodiment is not limited thereto; the catalyst precursor may be expressed as CuO/ZnO/Al 2 O 3 X1, wherein X1 refers to an oxide of a metal element in the first auxiliary, the catalyst precursor may be expressed as CuO/ZnO/Al, for example 2 O 3 -Y 2 O 3 、CuO/ZnO/Al 2 O 3 -Ga 2 O 3 Etc.
In one embodiment, the concentration of the first mixed solution is 0.1 to 1mol/L, for example, 0.1mol/L, 0.3mol/L, 0.5mol/L, 0.8mol/L, 1mol/L, etc. Optionally, the first auxiliary agent contains one or more of yttrium, molybdenum, niobium, gallium, indium, lanthanum, tungsten, magnesium and cadmium.
In this embodiment, the first auxiliary agent may be one or more of yttrium salt, molybdenum salt, niobium salt, gallium salt, indium salt, lanthanum salt, tungsten salt, magnesium salt, and cadmium salt, and some alkaline auxiliary agent or other auxiliary agents introduced during coprecipitation process are beneficial to promoting Cu + And oxygen vacancy, can stabilize formate and methoxy intermediate products and inhibit decomposition thereof to produce CO, thereby improving methanol selectivity.
Alternatively, the co-precipitation is co-current co-precipitation or counter-current co-precipitation.
In the embodiment, the co-current co-precipitation or counter-current co-precipitation method is adopted, so that each component in the catalyst can be dispersed more uniformly, the particle size of the prepared catalyst is reduced, and the catalytic activity is improved.
Optionally, the pH of the coprecipitation is 6-11, the temperature is 40-90 ℃, and the aging time is 1-15 hours.
In this embodiment, the pH of the coprecipitation is 6 to 11, for example, 6, 8, 10, 11, etc.; the temperature is 40-90 ℃, such as 40 ℃, 60 ℃, 75 ℃, 90 ℃ and the like; the aging time is 1 to 15 hours, for example, 1h, 5h, 10h, 15h, etc.
And step S20, introducing a second auxiliary agent onto the catalyst precursor, and roasting a product after the second auxiliary agent is introduced to obtain the catalyst for preparing methanol by hydrogenating carbon dioxide.
In this embodiment, the second auxiliary agent is a metal element auxiliary agent that can cover a part of Cu sites and inhibit reverse water gas shift reaction, for example, salts of metals such as zirconium (Zr), gallium, indium, and lanthanum, so that the selectivity of methanol can be improved.
As an example, the addition amount of the second auxiliary agent may be determined in advance according to the data literature, experimental results, etc., the second auxiliary agent may be weighed according to the predetermined addition amount, the second auxiliary agent may be mixed with the catalyst precursor so as to introduce the metal element of the second auxiliary agent onto the catalyst precursor, the metal element of the second auxiliary agent introduced onto the catalyst precursor may cover the copper site having the reverse water gas activity, inhibit the reverse water gas shift reaction, improve the methanol selectivity, and then the product after the second auxiliary agent is introduced may be calcined to obtain the catalyst for preparing methanol by hydrogenation of carbon dioxide, wherein the method of introducing the second auxiliary agent into the catalyst precursor may be ball milling method, dipping method, deposition method, etc., the catalyst may be expressed as CuO/ZnO/Al 2 O 3 X2, wherein X2 refers to the oxide of the metal element in the first promoter and the oxide of the metal element in the second promoter, the catalyst precursor may be expressed as CuO/ZnO/Al, for example 2 O 3 -Y 2 O 3 -ZrO 2 、CuO/ZnO/Al 2 O 3 -Ga 2 O 3 -La 2 O 3 Etc.
Optionally, the mass ratio of copper, zinc oxide and aluminum oxide in the catalyst is (3-7): (1-4): (1-3).
In this embodiment, the mass ratio of copper, zinc oxide and aluminum oxide in the catalyst is (3-7): (1-4): (1-3), such as 3:1:1, 5:4:2, 6:3:1, 7:4:3, etc., according to the mass ratio of copper, zinc oxide and aluminum oxide in the final catalyst to be prepared, the addition amount of the metal copper salt, the metal zinc salt and the metal aluminum salt can be calculated.
Optionally, the second auxiliary agent contains one or more of zirconium, gallium, indium and lanthanum.
In this embodiment, the second auxiliary agent may be one or more of zirconium salt, gallium salt, indium salt and lanthanum salt, and the second auxiliary agent introduced for the second time covers a Cu site with reverse water gas activity, so as to inhibit reverse water gas shift reaction, improve methanol selectivity, and although covering a part of Cu active site, at the same time, introduce a high-activity oxide-Cu interface, so as to improve hydrogenation activity to a certain extent, and furthermore, the second auxiliary agent introduced for the second time has a certain hydrophobicity, so as to improve hydrophobicity of the catalyst, and inhibit sintering of active center of the catalyst due to water.
Optionally, the mass fraction of the total amount of the first auxiliary agent and the second auxiliary agent in the catalyst is 2% -10%;
the mass fraction of the first auxiliary agent in the catalyst is 1% -6%;
the mass fraction of the second auxiliary agent in the catalyst is 1-6%.
In this embodiment, the mass fraction of the total amount of the first auxiliary agent and the second auxiliary agent in the catalyst is 1% to 6%, for example, 1%, 3%, 5%, 6%, etc.; the mass fraction of the first auxiliary agent in the catalyst is 1% -6%, such as 1%, 3%, 5%, 6% and the like; the mass fraction of the second auxiliary agent in the catalyst is 2% -10%, such as 2%, 5%, 8%, 10% and the like.
Optionally, the step of introducing the second auxiliary agent onto the catalyst precursor, and roasting the product after introducing the second auxiliary agent to obtain the catalyst for preparing methanol by hydrogenating carbon dioxide comprises the following steps:
preparing a second auxiliary agent into a second auxiliary agent solution, dripping the second auxiliary agent solution onto the catalyst precursor, dipping, drying and roasting a product after the second auxiliary agent is introduced, and obtaining the catalyst for preparing methanol by hydrogenating carbon dioxide.
As an example, the addition amount of the second auxiliary agent may be determined in advance according to the data literature, experimental results, or the like, the second auxiliary agent is weighed according to the predetermined addition amount, the second auxiliary agent is prepared into a second auxiliary agent solution, the catalyst precursor is immersed in the second auxiliary agent solution after all of the second auxiliary agent solution is added dropwise, the metal element in the second auxiliary agent is introduced onto the catalyst precursor, part of Cu active sites are covered, and the product after the second auxiliary agent is introduced is dried and calcined to obtain the catalyst for preparing methanol by hydrogenation of carbon dioxide.
Optionally, the step of introducing the second auxiliary agent onto the catalyst precursor, and roasting the product after introducing the second auxiliary agent to obtain the catalyst for preparing methanol by hydrogenating carbon dioxide comprises the following steps:
preparing a second auxiliary agent into a second auxiliary agent solution, mixing the second auxiliary agent solution, a precipitator and the catalyst precursor, and washing, drying and roasting a product after the second auxiliary agent is introduced to obtain the catalyst for preparing methanol by hydrogenating carbon dioxide.
As an example, the addition amounts of the second auxiliary agent and the precipitant may be determined in advance according to the data literature, experimental results, and the like, the second auxiliary agent and the precipitant are weighed according to the predetermined addition amounts, the second auxiliary agent is prepared into a second auxiliary agent solution, the precipitant is prepared into a precipitant solution, the second auxiliary agent solution and the precipitant solution are simultaneously added into a mixer to which a catalyst precursor is added to be mixed, so that the metal element in the second auxiliary agent is introduced onto the catalyst precursor, part of Cu active sites are covered, and the product after the second auxiliary agent is introduced is washed, dried, and calcined to obtain the catalyst for preparing methanol by hydrogenation of carbon dioxide.
Optionally, the step of introducing the second auxiliary agent onto the catalyst precursor, and roasting the product after introducing the second auxiliary agent to obtain the catalyst for preparing methanol by hydrogenating carbon dioxide comprises the following steps:
and mixing the second auxiliary agent and the catalyst precursor, performing ball milling, and roasting a product after the second auxiliary agent is introduced to obtain the catalyst.
As an example, the addition amount of the second auxiliary agent may be determined in advance according to data literature, experimental results, etc., after the second auxiliary agent is uniformly mixed with the catalyst precursor, the mixture is added to a ball mill to perform ball milling, so that the metal element in the second auxiliary agent is introduced onto the catalyst precursor, part of Cu active sites are covered, and the product after the second auxiliary agent is introduced is calcined, thereby obtaining the catalyst for preparing methanol by hydrogenation of carbon dioxide.
Optionally, the roasting temperature of the roasting is 300-500 ℃ and the roasting time is 2-6 hours.
In this embodiment, the baking temperature of the baking is 300 to 500 ℃, for example 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, etc., and the baking time is 2 to 6 hours, for example 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, etc.
Optionally, the precipitant is one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, and potassium bicarbonate.
In this embodiment, the co-precipitation of copper salt, zinc salt, aluminum salt, first auxiliary agent and precipitant is performed to obtain a catalyst precursor, and the co-precipitation product is aged, washed and dried to realize the improvement of copper dispersity and the enhancement of metal-oxide interface interaction on the one hand, thereby being beneficial to improving the hydrogenation activity of the catalyst, and on the other hand, part of auxiliary agents introduced in the co-precipitation process can promote oxygen vacancies and Cu + The generation of the catalyst is favorable for stabilizing formate and methoxy, inhibiting the decomposition of the formate and methoxy to generate CO, and improving the selectivity of methanol, on the other hand, the addition of the auxiliary agent inhibits the sintering of an active center, and the heat resistance of the catalyst is improved; furthermore, the second auxiliary agent is introduced onto the catalyst precursor, and the product after the second auxiliary agent is introduced is roasted to obtain the catalyst for preparing methanol by hydrogenating carbon dioxide, so that on one hand, the coverage of part of Cu sites is realized, the reverse water gas shift reaction active sites are reduced, the selectivity of methanol is improved, on the other hand, the oxide is covered on the Cu sites to form a high-activity oxide-Cu interface, the hydrogenation activity of the catalyst can be improved to a certain extent, and on the other hand, the introduced part of hydrophobic auxiliary agent can improve the hydrophobicity of the catalyst, and the sintering of active centers due to water is inhibited. Thus, by introducing the auxiliary agent twice, the technical defects that the carbon dioxide hydrogenation activity of the copper-based catalyst still has a larger gap from the thermodynamic equilibrium conversion rate and the selectivity and stability of the methanol are still lower are overcome, and the preparation of the carbon dioxide hydrogenation is improvedHydrogenation activity, selectivity and stability of the methanol catalyst.
Further, the application also provides a catalyst for preparing methanol by carbon dioxide hydrogenation, which is prepared by adopting the preparation method of the catalyst for preparing methanol by carbon dioxide hydrogenation.
The catalyst for preparing methanol by carbon dioxide hydrogenation solves the technical problems of lower carbon dioxide hydrogenation activity, lower methanol selectivity and lower stability of the catalyst for preparing methanol by carbon dioxide hydrogenation in the prior art. Compared with the prior art, the catalyst for preparing methanol by carbon dioxide hydrogenation has the same beneficial effects as the preparation method of the catalyst for preparing methanol by carbon dioxide hydrogenation provided by the embodiment, and other technical characteristics of the catalyst for preparing methanol by carbon dioxide hydrogenation are the same as the characteristics disclosed by the method of the embodiment, and are not repeated herein.
Further, in order to further understand the present application, a method for preparing the catalyst for preparing methanol by hydrogenating carbon dioxide provided by the present application is specifically described below with reference to examples. Commercial raw materials are adopted in the embodiment of the application.
Example 1
The co-current coprecipitation method is adopted to prepare Cu: znO: al (Al) 2 O 3 The mass ratio is 6:3:1 catalyst, wherein Y 2 O 3 And ZrO(s) 2 The auxiliaries account for 3wt.% and 2wt.% of the total mass of the catalyst, respectively. The specific method comprises the following steps: 32.46g of copper nitrate hexahydrate, 14.91g of zinc nitrate hexahydrate, 5.24g of aluminum nitrate nonahydrate and 0.76g of yttrium nitrate hexahydrate are weighed, 205mL of deionized water is added, and the mixture is stirred and dissolved in a 500mL beaker to prepare a 1mol/L metal precursor solution, which is recorded as a solution A; 41.6g of anhydrous sodium carbonate is weighed, 400mL of deionized water is added, and stirring and dissolution are carried out to obtain 1mol/L precipitant solution, which is marked as solution B.
The solutions A and B are simultaneously dripped into a three-neck flask containing 100mL of deionized water, the pH value of the suspension in the three-neck flask is kept at 7 under the water bath condition of 70 ℃, and the three-neck flask is aged for 2 hours; and washing and drying the aged slurry to obtain a catalyst precursor, which is marked as p-Cat1.
0.74g of zirconium nitrate hexahydrate is dissolved in 10mL of deionized water, after complete dissolution, the zirconium nitrate solution is dropwise added onto p-Cat1, immersed for 12 hours, dried at 120 ℃ for 10 hours, and then baked in a muffle furnace at 350 ℃ for 4 hours to obtain a sample Cat1 catalyst.
Example 2
The co-current coprecipitation method is adopted to prepare Cu: znO: al (Al) 2 O 3 The mass ratio is 6:3:1 catalyst, wherein Y 2 O 3 And ZrO(s) 2 The auxiliaries account for 3wt.% and 2wt.% of the total mass of the catalyst, respectively. The specific method comprises the following steps: 21.64g of copper nitrate hexahydrate, 9.94g of zinc nitrate hexahydrate, 3.49g of aluminum nitrate nonahydrate and 0.51g of yttrium nitrate hexahydrate are weighed, 274mL of deionized water is added, and the mixture is stirred and dissolved in a 500mL beaker to prepare a metal precursor solution of 0.5mol/L, and the metal precursor solution is recorded as a solution A; 16.8g of anhydrous sodium bicarbonate was weighed, 400mL of deionized water was added, and the mixture was stirred and dissolved to form a 0.5mol/L precipitant solution, designated solution B.
The solution A and the solution B are simultaneously dripped into a three-neck flask, the pH value of the suspension in the three-neck flask is kept at 8 under the water bath condition of 70 ℃, and the three-neck flask is aged for 4 hours; and washing and drying the aged slurry for later use to obtain a sample p-Cat2.
0.74g of zirconium nitrate hexahydrate is dissolved in 10mL of deionized water, after complete dissolution, the zirconium nitrate solution is dropwise added to p-Cat2, immersed for 12 hours, dried at 120 ℃ for 10 hours, and then baked in a muffle furnace at 300 ℃ for 4 hours to obtain the Cat2 catalyst.
Example 3
Preparing Cu by adopting a countercurrent coprecipitation method: znO: al (Al) 2 O 3 The mass ratio is 5:4:2 catalyst, wherein MgO and CeO 2 The promoters constitute 5wt.% and 3wt.% of the total mass of the catalyst, respectively. The specific method comprises the following steps: 23.82g of copper nitrate hexahydrate, 17.50g of zinc nitrate hexahydrate, 9.22g of aluminum nitrate hexahydrate and 4.8g of magnesium nitrate hexahydrate are weighed, 207mL of deionized water is added, and the mixture is stirred and dissolved in a 500mL beaker to prepare a 1mol/L metal precursor solution, which is denoted as solution A; 41.6g of anhydrous sodium carbonate is weighed, 400mL of deionized water is added, and stirring and dissolution are carried out to form 1mol/L precipitatorThe solution was designated as solution B.
Pouring the solution B into a three-neck flask, gradually dropwise adding the solution A, controlling the pH of the suspension to 8 under the water bath condition of 80 ℃, continuously stirring and aging for 4 hours, washing and drying the aged slurry, and marking the sample as p-Cat.3.
1.14g of cerium nitrate hexahydrate is dissolved in 10mL of deionized water, after complete dissolution, zirconium nitrate solution is dropwise added onto p-Cat.3, after 12 hours of impregnation, the solution is dried at 120 ℃ for 10 hours, and then baked in a muffle furnace at 300 ℃ for 4 hours to obtain the Cat.3 catalyst.
Example 4
Cu：ZnO：Al 2 O 3 The mass ratio is 7:4:3 preparation of catalyst wherein CdO and In 2 O 3 The auxiliaries account for 6wt.% and 4wt.% of the total mass of the catalyst, respectively. The specific method comprises the following steps: 25.63g of copper nitrate hexahydrate, 13.45g of zinc nitrate hexahydrate, 7.09g of aluminum nitrate nonahydrate and 2.17g of cadmium nitrate tetrahydrate are weighed, 363mL of deionized water is added, and the mixture is stirred and dissolved in a 500mL beaker to prepare a metal precursor solution with the concentration of 0.5mol/L, and the metal precursor solution is marked as a solution A; 16.8g of anhydrous sodium bicarbonate was weighed, 400mL of deionized water was added, and the mixture was stirred and dissolved to form a 0.5mol/L precipitant solution, designated solution B.
Pouring the solution B into a three-neck flask, gradually dropwise adding the solution A, controlling the pH of the suspension to 8 under the water bath condition of 80 ℃, continuously stirring and aging for 4 hours, washing and drying for later use, and marking the sample as p-Cat.4.
0.69g of indium nitrate hexahydrate was dissolved in 10mL of deionized water and designated solution C;2.08g of anhydrous sodium carbonate, 20mL of deionized water was added and dissolved with stirring to form a precipitant solution, designated solution D.
And (3) simultaneously dropwise adding the solution C and the solution D into a three-neck flask containing p-Cat.4, regulating the pH to 7, drying the product after precipitation is completed, and roasting the product in a muffle furnace at 300 ℃ for 6 hours to obtain the Cat.4 catalyst.
Example 5
Cu：ZnO：Al 2 O 3 The mass ratio is 5:4:2 preparation of catalyst wherein MgO and CeO 2 The promoters constitute 5wt.% and 3wt.% of the total mass of the catalyst, respectively. The specific method comprises the following steps: weighing 23.82g of copper nitrate hexahydrate, 17.50g of zinc nitrate hexahydrate, 9.22g of aluminum nitrate hexahydrate and 4.8g of magnesium nitrate hexahydrate are added with 207mL of deionized water, and are stirred and dissolved in a 500mL beaker to prepare a 1mol/L metal precursor solution, which is recorded as a solution A; 41.6g of anhydrous sodium carbonate is weighed, 400mL of deionized water is added, and the mixture is stirred and dissolved to form 1mol/L precipitant solution, which is marked as solution B.
The solution A and the solution B are simultaneously dripped into a three-mouth flask, the pH value of the suspension in the three-mouth flask is kept at 8 under the water bath condition of 80 ℃, and the stirring and aging are continued for 4 hours; and washing and drying the aged slurry for later use, and marking the slurry as p-Cat.5.
1.14g cerium nitrate hexahydrate was dissolved in 10mL deionized water and designated solution C;2.08g of anhydrous sodium bicarbonate, 20mL of deionized water was added and dissolved with stirring to form a precipitant solution, designated solution D.
And (3) simultaneously dropwise adding the solution C and the solution D into a three-neck flask containing p-Cat.4, regulating the pH to 8, drying the product after precipitation is completed, and roasting the product in a muffle furnace at 350 ℃ for 4 hours to obtain the Cat.5 catalyst.
Example 6
Cu：ZnO：Al 2 O 3 The mass ratio is 5:3:3 preparation of the catalyst wherein Ga 2 O 3 And La (La) 2 O 3 The auxiliaries account for 4wt.% and 6wt.% of the total mass of the catalyst, respectively. The specific method comprises the following steps: 23.30g of copper nitrate hexahydrate, 12.84g of zinc nitrate hexahydrate, 13.54g of aluminum nitrate hexahydrate and 1.20g of lanthanum nitrate hexahydrate are weighed, 202mL of deionized water is added, and the mixture is stirred and dissolved in a 500mL beaker to prepare a 1mol/L metal precursor solution, which is denoted as solution A; 41.6g of anhydrous sodium carbonate is weighed, 400mL of deionized water is added, and the mixture is stirred and dissolved to form 1mol/L precipitant solution, which is marked as solution B.
The solutions A and B are simultaneously dripped into a three-neck flask, the pH value of the suspension in the three-neck flask is kept at 7, and the solution is kept at 80 ℃ for continuous stirring and ageing for 2 hours; and washing and drying the aged slurry for later use, and marking the slurry as p-Cat.6.
Mixing and ball milling 0.82g of gallium nitrate hydrate and 15g of p-Cat.6, wherein the ball-to-material ratio is 7 at the rotating speed of 100 r/min: under the condition 1, ball milling is carried out for 1 hour, and the product is dried and then baked in a muffle furnace at 400 ℃ for 3 hours to obtain the Cat.6 catalyst.
Example 7
Cu：ZnO：Al 2 O 3 The mass ratio is 7:4:2 preparation of the catalyst wherein Ga 2 O 3 And La (La) 2 O 3 The auxiliaries account for 4wt.% and 6wt.% of the total mass of the catalyst, respectively. The specific method comprises the following steps: 27.60g of copper nitrate hexahydrate, 14.49g of zinc nitrate hexahydrate, 7.64g of aluminum nitrate nonahydrate and 1.20g of lanthanum nitrate hexahydrate are weighed, 192mL of deionized water is added, and the mixture is stirred and dissolved in a 500mL beaker to prepare a 1mol/L metal precursor solution, which is denoted as solution A; 41.6g of anhydrous sodium carbonate is weighed, 400mL of deionized water is added, and the mixture is stirred and dissolved to form 1mol/L precipitant solution, which is marked as solution B.
Pouring the solution B into a three-neck flask, gradually dropwise adding the solution A, controlling the pH of the suspension to 8, aging, washing and drying for later use, and marking the sample as p-Cat.7.
Mixing and ball milling 0.82g of gallium nitrate hydrate and 15g of p-Cat.7, wherein the rotation speed is 150r/min, and the ball-to-material ratio is 5: ball milling for 2 hours under the condition 1, drying the product, and roasting in a muffle furnace at 450 ℃ for 2 hours to obtain the Cat.7 catalyst.
Example 8
Cu：ZnO：Al 2 O 3 The mass ratio is 3:1:1 preparation of a catalyst wherein Ga 2 O 3 And La (La) 2 O 3 The auxiliaries account for 1wt.% and 1wt.% of the total mass of the catalyst, respectively. The specific method comprises the following steps: 30.44g of copper nitrate hexahydrate, 9.32g of zinc nitrate hexahydrate, 9.83g of aluminum nitrate nonahydrate and 0.20g of lanthanum nitrate hexahydrate are weighed, 186mL of deionized water is added, and the mixture is stirred and dissolved in a 500mL beaker to prepare a 1mol/L metal precursor solution which is recorded as a solution A; 41.6g of anhydrous sodium carbonate is weighed, 400mL of deionized water is added, and the mixture is stirred and dissolved to form 1mol/L precipitant solution, which is marked as solution B.
The solutions A and B are simultaneously dripped into a three-neck flask, the pH value of the suspension in the three-neck flask is kept at 7, and the solution is kept at 80 ℃ for continuous stirring and aging for 15 hours; and washing and drying the aged slurry for later use, and marking the slurry as p-Cat.8.
Mixing and ball milling 0.20g of gallium nitrate hydrate and 15g of p-Cat.7, wherein the rotation speed is X r/min, and the ball-to-material ratio is 3: under the condition 1, ball milling is carried out for 1 hour, and the product is dried and then baked in a muffle furnace at 500 ℃ for 2 hours to obtain the Cat.8 catalyst.
Comparative example 1
Cu：ZnO：Al 2 O 3 The mass ratio is 6:3:1 preparing a catalyst, wherein the specific method is as follows: 34.17g of copper nitrate trihydrate, 15.69g of zinc nitrate hexahydrate and 5.51g of aluminum nitrate nonahydrate are weighed, 211mL of deionized water is added, and stirred and dissolved in a 500mL beaker to prepare a 1mol/L metal precursor solution, which is recorded as solution A; 41.6g of anhydrous sodium carbonate is weighed, 400mL of deionized water is added, and the mixture is stirred and dissolved to form 1mol/L precipitant solution, which is marked as solution B.
The solutions A and B are simultaneously dripped into a three-neck flask, the pH value of the suspension in the three-neck flask is kept at 7, and the solution is kept at 70 ℃ for continuous stirring and aging for 2 hours; and washing and drying the aged slurry, and roasting in a muffle furnace at 350 ℃ for 4 hours to obtain the Cat.9 catalyst.
Comparative example 2
Cu：ZnO：Al 2 O 3 The mass ratio is 6:3:1 preparation of the catalyst wherein Y 2 O 3 The promoter accounts for 3wt.% of the total mass of the catalyst. The specific method comprises the following steps: 32.46g of copper nitrate hexahydrate, 14.91g of zinc nitrate hexahydrate, 5.24g of aluminum nitrate nonahydrate and 0.76g of yttrium nitrate hexahydrate are weighed, 205mL of deionized water is added, and the mixture is stirred and dissolved in a 500mL beaker to prepare a 1mol/L metal precursor solution, which is recorded as a solution A; 41.6g of anhydrous sodium carbonate is weighed, 400mL of deionized water is added, and the mixture is stirred and dissolved to form 1mol/L precipitant solution, which is marked as solution B.
The solution A and the solution B are simultaneously dripped into a three-mouth flask, the pH value of the suspension in the three-mouth flask is kept at 7 under the water bath condition of 70 ℃, and the stirring and aging are continued for 2 hours; the aged slurry was washed, dried and calcined in a muffle furnace at 350 ℃ for 4 hours to give a catalyst, labeled cat.10.
Comparative example 3
Cu：ZnO：Al 2 O 3 The mass ratio is 6:3:1 preparation of the catalyst wherein ZrO 2 The promoter accounts for 2wt.% of the total mass of the catalyst. The specific method comprises the following steps: weighing 32.46g of copper nitrate trihydrate, 14.91g of zinc nitrate hexahydrate and 5.24g of aluminum nitrate nonahydrateAdding 205mL of deionized water, stirring and dissolving in a 500mL beaker to prepare 1mol/L metal precursor solution, and marking the solution as solution A; 41.6g of anhydrous sodium carbonate is weighed, 400mL of deionized water is added, and the mixture is stirred and dissolved to form 1mol/L precipitant solution, which is marked as solution B.
The solutions A and B are simultaneously dripped into a three-neck flask, the pH value of the suspension in the three-neck flask is kept at 7, and the solution is kept at 70 ℃ for continuous stirring and aging for 2 hours; the aged slurry was washed and dried for use, and labeled p-Cat.11.
0.74g of zirconium nitrate hexahydrate is dissolved in 10mL of deionized water and added dropwise to CuO/ZnO/Al 2 O 3 And (3) drying and roasting in a muffle furnace at 350 ℃ for 4 hours to obtain the Cat.10 catalyst.
Further, the catalysts prepared in examples 1 to 7 and comparative examples 1 to 3 were used for the reaction performance test of preparing methanol by hydrogenating carbon dioxide, and the reaction performance test conditions were: the reaction temperature is 250 ℃, the reaction pressure is 5MPa, and the reaction space velocity is 10000 mL.h -1 ·g cat -1 ，H 2 And CO 2 The flow ratio is 3:1. the test results are shown in table 1:
TABLE 1
As can be seen from table 1, compared with comparative example 1 (sample name cat.9) without introducing the auxiliary agent and comparative example 2 (sample name cat.10) and comparative example 3 (sample name cat.11) with one-time introducing the auxiliary agent, the catalyst of the present application can simultaneously improve the carbon dioxide hydrogenation activity, the methanol selectivity and the stability of the catalyst for preparing methanol by hydrogenating carbon dioxide by introducing the auxiliary agent twice.
The foregoing description is only of the preferred embodiments of the present application and is not intended to limit the scope of the application, and all equivalent structures or equivalent processes using the teachings of this application or direct or indirect application in other related arts are included in the scope of this application.

Claims (13)

1. The preparation method of the catalyst for preparing methanol by carbon dioxide hydrogenation is characterized by comprising the following steps of:
coprecipitating copper salt, zinc salt, aluminum salt, a first auxiliary agent and a precipitator, and aging, washing and drying the coprecipitated product to obtain a catalyst precursor;
introducing a second auxiliary agent onto the catalyst precursor, and roasting the product after the second auxiliary agent is introduced to obtain the catalyst for preparing methanol by hydrogenating carbon dioxide.
2. The method for preparing a catalyst for preparing methanol by hydrogenating carbon dioxide according to claim 1, wherein the first auxiliary agent comprises one or more of yttrium, molybdenum, niobium, gallium, indium, lanthanum, tungsten, magnesium and cadmium.
3. The method for preparing a catalyst for preparing methanol by hydrogenating carbon dioxide as claimed in claim 1, wherein the second auxiliary agent contains one or more of zirconium, gallium, indium and lanthanum.
4. The method for preparing a catalyst for preparing methanol by hydrogenating carbon dioxide according to claim 1, wherein the mass fraction of the total amount of the first auxiliary agent and the second auxiliary agent in the catalyst is 2% -10%;
the mass fraction of the first auxiliary agent in the catalyst is 1% -6%;
the mass fraction of the second auxiliary agent in the catalyst is 1-6%.
5. The method for preparing a catalyst for preparing methanol by hydrogenating carbon dioxide according to claim 1, wherein the coprecipitation is co-current coprecipitation or counter current coprecipitation.
6. The method for preparing a catalyst for hydrogenation of carbon dioxide to methanol according to claim 1, wherein the pH of the coprecipitation is 6 to 11, the temperature is 40 to 90 ℃, and the aging time is 1 to 15 hours.
7. The method for preparing the catalyst for preparing methanol by hydrogenating carbon dioxide according to claim 1, wherein the step of introducing the second auxiliary agent onto the catalyst precursor and roasting the product after the introduction of the second auxiliary agent to obtain the catalyst for preparing methanol by hydrogenating carbon dioxide comprises the following steps:
preparing a second auxiliary agent into a second auxiliary agent solution, dripping the second auxiliary agent solution onto the catalyst precursor, dipping, drying and roasting a product after the second auxiliary agent is introduced, and obtaining the catalyst for preparing methanol by hydrogenating carbon dioxide.
8. The method for preparing the catalyst for preparing methanol by hydrogenating carbon dioxide according to claim 1, wherein the step of introducing the second auxiliary agent onto the catalyst precursor and roasting the product after the introduction of the second auxiliary agent to obtain the catalyst for preparing methanol by hydrogenating carbon dioxide comprises the following steps:
preparing a second auxiliary agent into a second auxiliary agent solution, mixing the second auxiliary agent solution, a precipitator and the catalyst precursor, and washing, drying and roasting a product after the second auxiliary agent is introduced to obtain the catalyst for preparing methanol by hydrogenating carbon dioxide.
9. The method for preparing the catalyst for preparing methanol by hydrogenating carbon dioxide according to claim 1, wherein the step of introducing the second auxiliary agent onto the catalyst precursor and roasting the product after the introduction of the second auxiliary agent to obtain the catalyst for preparing methanol by hydrogenating carbon dioxide comprises the following steps:
and mixing the second auxiliary agent and the catalyst precursor, performing ball milling, and roasting a product after the second auxiliary agent is introduced to obtain the catalyst.
10. The method for preparing a catalyst for hydrogenation of carbon dioxide to methanol according to any one of claims 1 to 9, wherein the calcination temperature is 300 to 500 ℃ and the calcination time is 2 to 6 hours.
11. The method for preparing the catalyst for preparing methanol by hydrogenating carbon dioxide according to any one of claims 1 to 9, wherein the precipitant is one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate and potassium bicarbonate.
12. The method for preparing a catalyst for preparing methanol by hydrogenating carbon dioxide according to any one of claims 1 to 9, wherein the mass ratio of copper, zinc oxide and aluminum oxide in the catalyst is (3 to 7): (1-4): (1-3).
13. A catalyst for preparing methanol by hydrogenation of carbon dioxide, which is characterized in that the catalyst for preparing methanol by hydrogenation of carbon dioxide is prepared by the preparation method of the catalyst for preparing methanol by hydrogenation of carbon dioxide according to any one of claims 1-12.
CN202310708036.4A 2023-06-14 2023-06-14 Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof Pending CN116764641A (en)

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