CN114160143A - CO (carbon monoxide)2Catalyst for preparing methanol by hydrogenation, preparation method and application thereof - Google Patents

CO (carbon monoxide)2Catalyst for preparing methanol by hydrogenation, preparation method and application thereof Download PDF

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CN114160143A
CN114160143A CN202111492089.4A CN202111492089A CN114160143A CN 114160143 A CN114160143 A CN 114160143A CN 202111492089 A CN202111492089 A CN 202111492089A CN 114160143 A CN114160143 A CN 114160143A
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copper
catalyst
source
reaction
hydrogenation
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CN114160143B (en
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孙予罕
王慧
吴兆萱
王浩渺
黄超杰
夏林
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Shanghai Cluster Rui Low Carbon Energy Technology Co ltd
Shanghai Advanced Research Institute of CAS
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Shanghai Cluster Rui Low Carbon Energy Technology Co ltd
Shanghai Advanced Research Institute of CAS
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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
    • B01J23/80—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 zinc, cadmium or mercury
    • 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
    • C07C29/154—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 copper, silver, gold, 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 provides CO2A catalyst for preparing methanol by hydrogenation, a preparation method and application thereof. The catalyst comprises zinc oxide and a copper nanotube, wherein the copper nanotube is coated by the zinc oxide, and the general formula of the copper nanotube is Cu2Si2O5(OH)2. The preparation method comprises the following steps: and (2) dipping the copper nanotube in a dipping solution containing zinc ions, and then roasting to obtain the catalyst. The application of the catalyst in preparing methanol by hydrogenating carbon dioxide. CO 22And H2The reaction is carried out in the presence of the catalyst to obtain methanol. The catalyst of the invention has excellent catalytic performance, CO2The conversion rate and the methanol selectivity are excellent, and a wide prospect is provided for subsequent industrial application.

Description

CO (carbon monoxide)2Catalyst for preparing methanol by hydrogenation, preparation method and application thereof
Technical Field
The invention relates to CO2The technical field of hydrogenation catalytic conversion, in particular to CO2A catalyst for preparing methanol by hydrogenation, a preparation method and application thereof.
Background
Methanol is an important chemical intermediate raw material and can be used as a fuel for internal combustion engines and fuel cells, and along with the gradual reduction of non-renewable energy sources, methanol as a replaceable chemical raw material can be used for synthesizing various chemicals, gasoline and other fuels. In recent years, with the development of technologies such as a molecular sieve catalyst, Methanol To Olefin (MTO), Methanol to aromatic (MTG), and the like, the Demand of a fuel obtained from Methanol in the international market has been rapidly increasing (Johnson, d.global Methanol Demand Growth; IHS inc., 2016). The traditional industrial preparation of methanol adopts a synthesis gas conversion method, but mainly faces to a catalyst (Cu/ZnO/Al)2O3) The active sites are easy to sinter under the reaction conditions, which causes poor stability, and moreover, the raw material synthesis gas output of the process is often accompanied with the consumption of fossil resources such as coal, natural gas and the like and CO caused by the conversion process2Discharge and environmental pollution.
CO2Are the main components of greenhouse gases in the atmosphere, which result from the combustion of large quantities of fossil fuels and lead to increasingly deeper global climate change over the past decades. Human activity emits CO to the atmosphere every year2Nearly 400 hundred million tons of atmospheric CO in 20192The content is as high as 407ppm, and the growth is 20 percent in the last 40 years. Reduction of CO2The amount of discharge is certainly a pressing issue. If mixing CO with2By converting renewable energy into chemical raw materials, not only can CO be solved2Excess emission problem, and CO generation2Becomes a novel carbon source for replacing the traditional fossil fuel. CO 22The molecules being chemically inert but incorporating H having a high free energy2The molecule as a reactant makes the reaction thermodynamically easy, while H2If the water is obtained by a renewable mode such as electrolytic water or photolytic water, the whole process has wide prospects in environment and economy. Thus, using CO2Catalytic hydrogenation to methanol is an attractive means of reducing CO2Discharge and create a new carbon cycle process scenario.
At present, CO2The preparation of methanol by hydrogenation mainly adopts a supported metal or metal oxide catalyst, and a plurality of research teams aim to disclose factors influencing the activity, selectivity and stability of the catalyst, wherein ZnO is an important carrier in the preparation of Cu-based catalyst, is used for regulating the shape of the carrier and stabilizing copper species, and can also utilize ZrO2，Al2O3，La2O3And SiO2As an additional aid to better disperse the copper species. CO based on Cu-based catalysts in recent years2The reaction for preparing methanol by hydrogenation is often limited to the surface interface characteristic of the catalyst, and has a breakthrough in catalytic performance.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, it is an object of the present invention to provide a CO2A catalyst for preparing methanol by hydrogenation, a preparation method and application thereof solve the problems of low methanol selectivity and reaction activity of the traditional catalyst and the like.
To achieve the above and other related objects, the first aspect of the present invention provides a CO2The catalyst for preparing the methanol by hydrogenation comprises zinc oxide and a copper nano tube, wherein the zinc oxide coats the copper nano tube, and the general formula of the copper nano tube is Cu2Si2O5(OH)2。
Preferably, the zinc oxide accounts for 2.5-20% of the catalyst by mass, such as 2.5-5%, 5-10%, 10-15% or 15-20%.
In a second aspect of the present invention, the catalyst is prepared by immersing the copper nanotubes in an immersion solution containing zinc ions, drying, and calcining.
Preferably, at least one of the following technical features is also included:
1) the dipping solution containing zinc ions is a zinc nitrate aqueous solution;
2) the drying temperature is 20-30 ℃, such as 20-25 ℃ or 25-30 ℃;
3) the roasting temperature is 450-550 ℃, such as 450-500 ℃ or 500-550 ℃;
4) the copper nanotube is obtained by a preparation method comprising the following steps: carrying out hydrothermal reaction on a copper source and a silicon source, and then filtering, washing, drying and roasting.
More preferably, in the feature 4), at least one of the following technical features is further included:
41) the copper source is copper nitrate;
42) the silicon source is silica gel;
43) the hydrothermal reaction specifically comprises the following steps: carrying out hydrothermal reaction on an aqueous solution containing a copper source and an ammonium source, an aqueous solution containing a silicon source and an alkali solution;
44) the temperature of the hydrothermal reaction is 180-200 ℃, such as 180 ℃, 185 ℃, 190 ℃, 195 ℃ or 200 ℃;
45) the drying temperature is 50-80 ℃, such as 50-60 ℃ or 60-80 ℃;
41) the roasting temperature is 450-550 ℃, such as 450-500 ℃ or 500-550 ℃.
Even more preferably, feature 43) further comprises at least one of the following technical features:
431) the ammonium source is selected from at least one of ammonium chloride and ammonium nitrate; the pH value of the solution is adjusted by utilizing the weak acidity of the ammonium source, the hydrolysis of the copper source is inhibited, a buffer solution is formed, and the precipitate formed after later addition of an alkali solution has a more regular shape and a higher specific surface. Moreover, the ammonium source provides free ammonium ions, so that Cu ions form Cu ammonium complex ions to help the Cu ammonium complex ions coordinate with the silicon-oxygen tetrahedron;
432) the concentration of copper ions in the aqueous solution containing the copper source and the ammonium source is 0.12-0.16 mol/L, such as 0.12-0.14 mol/L or 0.14-0.16 mol/L;
433) the concentration of ammonium ions in the aqueous solution containing the copper source and the ammonium source is 0.39-0.47 mol/L, such as 0.39-0.43 mol/L or 0.43-0.47 mol/L;
434) the molar ratio of copper ions to ammonium ions in the aqueous solution containing the copper source and the ammonium source is 1: 2.5-1: 3.5, as shown in 1: 2.5-1: 3 or 1: 3-1: 3.5;
435) the alkali solution is ammonia water;
436) the concentration of the alkali solution is 17.5-19 mol/L, such as 17.5-18.5 mol/L or 18.5-19 mol/L;
437) the molar ratio of copper ions to alkali in the aqueous solution containing the copper source and the ammonium source is 1: 10-1: 13, as shown in 1: 10-1: 11.5 or 1: 11.5-1: 13.
in a third aspect, the present invention provides the use of the above catalyst in the hydrogenation of carbon dioxide to produce methanol.
Preferably, the catalyst is subjected to hydrogenation reduction prior to use in the hydrogenation of carbon dioxide to produce methanol.
More preferably, at least one of the following technical characteristics is also included:
1) the temperature of the hydrogenation reduction is 200-300 ℃, such as 200-250 ℃ or 250-300 ℃, and can be 200 ℃, 250 ℃ or 300 ℃.
2) The time of the hydrogenation reduction is 6-16 h, such as 6-12 h or 12-16 h, and can be 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h or 16 h.
3) The hydrogenation reduction pressure is 0.01-0.5 MPa, such as 0.01-0.1 MPa or 0.1-0.5 MPa, and may be 0.05MPa, 0.1MPa, 0.15MPa, 0.2MPa, 0.25MPa, 0.3MPa, 0.35MPa, 0.4MPa, 0.45MPa or 0.5 MPa.
4) The space velocity of hydrogen for hydrogenation reduction is 2500-3500 ml/g/h, such as 2500-3000 ml/g/h or 3000-3500 ml/g/h.
In a fourth aspect, the present invention provides a CO2Method for preparing methanol by hydrogenation, CO2And H2The reaction is carried out in the presence of the above catalyst to obtain methanol.
Preferably, at least one of the following technical features is also included:
1)CO2and H2Is 1: 2-1: 7, as shown in 1: 2-1: 3 or 1: 3-1: 7; more preferably, CO2And H2The volume ratio of (A) to (B) is 1: 3;
2) the reaction temperature is 240-300 ℃, such as 240-250 ℃, 250-260 ℃, 260-270 ℃, 270-280 ℃ or 280-300 ℃; more preferably, the reaction temperature is 240 ℃;
3) the reaction pressure is 2-7 MPa, such as 2-5 MPa or 5-7 MPa; more preferably, the reaction pressure is 5 MPa;
4) the reaction space velocity is 5000-24000 ml/g/h, such as 5000-8000 ml/g/h, 8000-12000 ml/g/h, 12000-16000 ml/g/h, 16000-20000 ml/g/h or 20000-24000 ml/g/h.
Compared with the prior art, the invention has at least one of the following beneficial effects:
1) the catalyst is a nanotube material based on copper silicate, so that metal Cu is spatially uniformly distributed along the surface of the nanotube, Cu particle growth is effectively inhibited, the defect that an active phase of a traditional Cu-based catalyst is easy to aggregate is overcome, and long-range stability of the catalyst under reaction conditions is favorably realized.
2) The catalyst of the invention has excellent catalytic performance, CO2The conversion rate and the methanol selectivity are excellent.
3) Compared with the traditional Cu-based catalyst, the catalyst provided by the invention has higher specific surface area and active site, and the Zn-Cu interface is changed by regulating and controlling the ZnO loading, so that the methanol selectivity is changed. The existence of Cu-O-SiOx interface can effectively stabilize Cu0/Cu+Active site, the stable activity of the catalyst is favorable for large-scale industrial application.
4) The invention provides a novel preparation method of a ZnO coated Cu nanotube catalyst, and the ZnO coated Cu nanotube catalyst is used for evaluating the reaction performance in a fixed bed reactor, has the characteristics of high methanol selectivity and long-time stable operation at higher temperature and pressure, and provides wide prospects for subsequent industrial application.
5) The catalyst of the invention has simple preparation process, is easy to repeat, and can be prepared in large scale.
Drawings
FIG. 1 is an XRD spectrum of copper nanotubes before and after firing in example 1 of the present invention.
Detailed Description
The invention is further illustrated by the following examples. It should be understood that these examples are only for illustrating the present invention, and are not to be construed as limiting the scope of the present invention. The experimental methods and reagents of the formulations not specified in the following examples were carried out or configured according to the conventional conditions or the conditions recommended by the manufacturers.
Example 1
Preparation of copper nanotubes (Cu) by hydrothermal method2Si2O5(OH)2). Copper nitrate and ammonium chloride (1.57 g and 1.39g in mass) were dissolved in 60mL of deionized water to form a salt solution A, and then stirred at 30 ℃ for 2 hours while dropwise adding 5mL of an alkali solution (18.5 mol/L saturated ammonia water) to form a blue solution B. 1g of silica gel was dissolved in the blue solution B and stirred well. Transferring the solution B into a 100mL stainless steel hydrothermal kettle, heating at 200 ℃ for 48 hours, filtering precipitates, fully washing with deionized water, drying at 60 ℃ in vacuum, cooling the solid to room temperature (the XRD spectrogram is shown as Cu-NPST in figure 1), and roasting at 500 ℃ in air for 2 hours to obtain the copper nanotube catalyst, wherein the XRD spectrogram is shown as Cu-NPST-clacination in figure 1. 0.072g of zinc nitrate is dissolved in 5mL of deionized water to form a solution C, then the copper nanotube catalyst is fully mixed with the solution C, and the mixture is dried at room temperature and then is roasted in the air at 500 ℃ for 2 hours to obtain the zinc oxide coated copper nanotube catalyst (the content of ZnO is 2.5%).
Placing the obtained zinc oxide coated copper nanotube catalyst in a fixed bed high-pressure microreactor, introducing hydrogen to reduce at normal pressure, wherein the reduction space velocity is 3000ml/g/H, the reduction temperature is 250 ℃, the reduction time is 12H, cooling the reaction furnace to room temperature after the reduction process is finished, and introducing H2/CO2The reaction is carried out by the reaction gas with the ratio of 3, the reaction pressure is 5MPa, and the reaction space velocity is 5000ml g-1·h-1The reaction temperature was 240 ℃ and the results of activity evaluation are shown in Table 1.
Example 2
Preparation of copper nanotubes (Cu) by hydrothermal method2Si2O5(OH)2). Copper nitrate and ammonium chloride (1.57 g and 1.39g in mass) were dissolved in 60mL of deionized water to form a salt solution A, and then stirred at 30 ℃ for 2 hours while dropwise adding 5mL of an alkali solution (18.5 mol/L saturated ammonia water) to form a blue solution B. 1g of silica gel was dissolved in the blue solution B and stirred well. Transferring the solution B into a 100mL stainless steel hydrothermal kettle, heating at 200 ℃ for 48 hours, filtering the precipitate, fully washing with deionized water, drying at 60 ℃ in vacuum, cooling the solid to room temperature, and roasting at 500 ℃ in air for 2 hours to obtain the copper nanotube catalyst. Dissolving 0.145g of zinc nitrate in 5mL of deionized water to form a solution C, then fully mixing the copper nanotube catalyst with the solution C, drying at room temperature, and roasting at 500 ℃ in the air for 2 hours to obtain the zinc oxide coated copper nanotube catalyst (with 5% of ZnO).
Placing the obtained zinc oxide coated copper nanotube catalyst in a fixed bed high-pressure microreactor, introducing hydrogen to reduce at normal pressure, wherein the reduction space velocity is 3000ml/g/H, the reduction temperature is 250 ℃, the reduction time is 12H, cooling the reaction furnace to room temperature after the reduction process is finished, and introducing H2/CO2The reaction is carried out by the reaction gas with the ratio of 3, the reaction pressure is 5MPa, and the reaction space velocity is 5000ml g-1·h-1The reaction temperature was 240 ℃ and the results of activity evaluation are shown in Table 1.
Example 3
Preparation of copper nanotubes (Cu) by hydrothermal method2Si2O5(OH)2). Copper nitrate and ammonium chloride (1.57 g and 1.39g in mass) were dissolved in 60mL of deionized water to form a salt solution A, and then stirred at 30 ℃ for 2 hours while dropwise adding 5mL of an alkali solution (18.5 mol/L saturated ammonia water) to form a blue solution B. 1g of silica gel was dissolved in the blue solution B and stirred well. The solution B was transferred to a 100mL stainless steel hydrothermal kettle and heated at 200 ℃ for 48 hours, then the precipitate was filtered and washed thoroughly with deionized water, then dried under vacuum at 60 ℃ and the solid cooled to room temperature, then left to stand emptyRoasting for 2 hours at 500 ℃ in gas to obtain the copper nanotube catalyst. 0.29g of zinc nitrate is dissolved in 5mL of deionized water to form a solution C, then the copper nanotube catalyst and the solution C are fully mixed, dried at room temperature and roasted at 500 ℃ for 2 hours in the air, and the zinc oxide coated copper nanotube catalyst (with the ZnO content of 10%) is obtained.
Placing the obtained zinc oxide coated copper nanotube catalyst in a fixed bed high-pressure microreactor, introducing hydrogen to reduce at normal pressure, wherein the reduction space velocity is 3000ml/g/H, the reduction temperature is 250 ℃, the reduction time is 12H, cooling the reaction furnace to room temperature after the reduction process is finished, and introducing H2/CO2The reaction is carried out by the reaction gas with the ratio of 3, the reaction pressure is 5MPa, and the reaction space velocity is 5000ml g-1·h-1The reaction temperature was 240 ℃ and the results of activity evaluation are shown in Table 1.
Example 4
Preparation of copper nanotubes (Cu) by hydrothermal method2Si2O5(OH)2). Copper nitrate and ammonium chloride (1.57 g and 1.39g in mass) are dissolved in 60mL of deionized water to form a salt solution A, and then the solution A is stirred for 2 hours at 30 ℃ while 5mL of alkali solution (saturated ammonia water is 18.5mol/L) is added dropwise to form a blue solution B. 1g of silica gel was dissolved in the blue solution B and stirred well. Transferring the solution B into a 100mL stainless steel hydrothermal kettle, heating at 200 ℃ for 48 hours, filtering the precipitate, fully washing with deionized water, drying at 60 ℃ in vacuum, cooling the solid to room temperature, and roasting at 500 ℃ in air for 2 hours to obtain the copper nanotube catalyst. 0.435g of zinc nitrate is dissolved in 5mL of deionized water to form a solution C, then the copper nanotube catalyst and the solution C are fully mixed, dried at room temperature and roasted at 500 ℃ for 2 hours in the air, and the zinc oxide coated copper nanotube catalyst (ZnO content is 15%) is obtained.
Placing the obtained zinc oxide coated copper nanotube catalyst in a fixed bed high-pressure microreactor, introducing hydrogen to reduce at normal pressure, wherein the reduction space velocity is 3000ml/g/H, the reduction temperature is 250 ℃, the reduction time is 12H, cooling the reaction furnace to room temperature after the reduction process is finished, and introducing H2/CO2Ratio of3, the reaction pressure is 5MPa, and the reaction space velocity is 5000ml g-1·h-1The reaction temperature was 240 ℃ and the results of activity evaluation are shown in Table 1.
Example 5
Preparation of copper nanotubes (Cu) by hydrothermal method2Si2O5(OH)2). Copper nitrate and ammonium chloride (1.57 g and 1.39g in mass) were dissolved in 60mL of deionized water to form a salt solution A, and then stirred at 30 ℃ for 2 hours while dropwise adding 5mL of an alkali solution (18.5 mol/L saturated ammonia water) to form a blue solution B. 1g of silica gel was dissolved in the blue solution B and stirred well. Transferring the solution B into a 100mL stainless steel hydrothermal kettle, heating at 200 ℃ for 48 hours, filtering the precipitate, fully washing with deionized water, drying at 60 ℃ in vacuum, cooling the solid to room temperature, and roasting at 500 ℃ in air for 2 hours to obtain the copper nanotube catalyst. Dissolving 0.58g of zinc nitrate in 5mL of deionized water to form a solution C, then fully mixing the copper nanotube catalyst with the solution C, drying at room temperature, and roasting at 500 ℃ in the air for 2 hours to obtain the zinc oxide coated copper nanotube catalyst (with the ZnO content of 20%).
Placing the obtained zinc oxide coated copper nanotube catalyst in a fixed bed high-pressure microreactor, introducing hydrogen to reduce at normal pressure, wherein the reduction space velocity is 3000ml/g/H, the reduction temperature is 250 ℃, the reduction time is 12H, cooling the reaction furnace to room temperature after the reduction process is finished, and introducing H2/CO2The reaction is carried out by the reaction gas with the ratio of 3, the reaction pressure is 5MPa, and the reaction space velocity is 5000ml g-1·h-1The reaction temperature was 240 ℃ and the results of activity evaluation are shown in Table 1.
Example 6
Preparation of copper nanotubes (Cu) by hydrothermal method2Si2O5(OH)2). Copper nitrate and ammonium chloride (1.57 g and 1.39g in mass) were dissolved in 60mL of deionized water to form a salt solution A, and then stirred at 30 ℃ for 2 hours while dropwise adding 5mL of an alkali solution (18.5 mol/L saturated ammonia water) to form a blue solution B. 1g of silica gel was dissolved in the blue solution B and stirred well. Transfer B solution to 100mLHeating in a stainless steel hydrothermal kettle at 200 ℃ for 48 hours, filtering the precipitate, fully washing with deionized water, vacuum-drying at 60 ℃, cooling the solid to room temperature, and roasting in air at 500 ℃ for 2 hours to obtain the copper nanotube catalyst. 0.29g of zinc nitrate is dissolved in 5mL of deionized water to form a solution C, then the copper nanotube catalyst and the solution C are fully mixed, dried at room temperature and roasted at 500 ℃ for 2 hours in the air, and the zinc oxide coated copper nanotube catalyst (with the ZnO content of 10%) is obtained.
Placing the obtained zinc oxide coated copper nanotube catalyst in a fixed bed high-pressure microreactor, introducing hydrogen to reduce at normal pressure, wherein the reduction space velocity is 3000ml/g/H, the reduction temperature is 250 ℃, the reduction time is 12H, cooling the reaction furnace to room temperature after the reduction process is finished, and introducing H2/CO2The reaction is carried out by the reaction gas with the ratio of 3, the reaction pressure is 5MPa, and the reaction space velocity is 8000ml/g-1·h-1The reaction temperature was 250 ℃ and the results of activity evaluation are shown in Table 1.
Example 7
Preparation of copper nanotubes (Cu) by hydrothermal method2Si2O5(OH)2). Copper nitrate and ammonium chloride (1.57 g and 1.39g in mass) were dissolved in 60mL of deionized water to form a salt solution A, and then stirred at 30 ℃ for 2 hours while dropwise adding 5mL of an alkali solution (18.5 mol/L saturated ammonia water) to form a blue solution B. 1g of silica gel was dissolved in the blue solution B and stirred well. Transferring the solution B into a 100mL stainless steel hydrothermal kettle, heating at 200 ℃ for 48 hours, filtering the precipitate, fully washing with deionized water, drying at 60 ℃ in vacuum, cooling the solid to room temperature, and roasting at 500 ℃ in air for 2 hours to obtain the copper nanotube catalyst. 0.29g of zinc nitrate is dissolved in 5mL of deionized water to form a solution C, then the copper nanotube catalyst and the solution C are fully mixed, dried at room temperature and roasted at 500 ℃ for 2 hours in the air, and the zinc oxide coated copper nanotube catalyst (with the ZnO content of 10%) is obtained.
Putting the obtained zinc oxide coated copper nanotube catalyst into a fixed bed high-pressure microreactor, and introducing hydrogen at normal pressureReducing at a reduction space velocity of 3000ml/g/H, a reduction temperature of 250 ℃ for 12H, cooling the reaction furnace to room temperature after the reduction process is finished, and introducing H2/CO2The reaction is carried out by the reaction gas with the ratio of 3, the reaction pressure is 5MPa, and the reaction space velocity is 12000ml g-1·h-1The reaction temperature was 260 ℃ and the results of activity evaluation are shown in Table 1.
Example 8
Preparation of copper nanotubes (Cu) by hydrothermal method2Si2O5(OH)2). Copper nitrate and ammonium chloride (1.57 g and 1.39g in mass) were dissolved in 60mL of deionized water to form a salt solution A, and then stirred at 30 ℃ for 2 hours while dropwise adding 5mL of an alkali solution (18.5 mol/L saturated ammonia water) to form a blue solution B. 1g of silica gel was dissolved in the blue solution B and stirred well. Transferring the solution B into a 100mL stainless steel hydrothermal kettle, heating at 200 ℃ for 48 hours, filtering the precipitate, fully washing with deionized water, drying at 60 ℃ in vacuum, cooling the solid to room temperature, and roasting at 500 ℃ in air for 2 hours to obtain the copper nanotube catalyst. 0.29g of zinc nitrate is dissolved in 5mL of deionized water to form a solution C, then the copper nanotube catalyst and the solution C are fully mixed, dried at room temperature and roasted at 500 ℃ for 2 hours in the air, and the zinc oxide coated copper nanotube catalyst (with the ZnO content of 10%) is obtained.
Placing the obtained zinc oxide coated copper nanotube catalyst in a fixed bed high-pressure microreactor, introducing hydrogen to reduce at normal pressure, wherein the reduction space velocity is 3000ml/g/H, the reduction temperature is 250 ℃, the reduction time is 12H, cooling the reaction furnace to room temperature after the reduction process is finished, and introducing H2/CO2Reacting with 3 of reaction gas, the reaction pressure is 5MPa, and the reaction space velocity is 16000ml g-1·h-1The reaction temperature was 270 ℃ and the results of activity evaluation are shown in Table 1.
Example 9
Preparation of copper nanotubes (Cu) by hydrothermal method2Si2O5(OH)2). Copper nitrate and ammonium chloride (1.57 g and 1.39g in mass) were dissolved in 60mL of deionized water to form a salt solution A, and the solution was addedStirring was carried out at 30 ℃ for 2h while dropwise adding 5mL of an alkali solution (saturated aqueous ammonia: 18.5mol/L) to form a blue solution B. 1g of silica gel was dissolved in the blue solution B and stirred well. Transferring the solution B into a 100mL stainless steel hydrothermal kettle, heating at 200 ℃ for 48 hours, filtering the precipitate, fully washing with deionized water, drying at 60 ℃ in vacuum, cooling the solid to room temperature, and roasting at 500 ℃ in air for 2 hours to obtain the copper nanotube catalyst. 0.29g of zinc nitrate is dissolved in 5mL of deionized water to form a solution C, then the copper nanotube catalyst and the solution C are fully mixed, dried at room temperature and roasted at 500 ℃ for 2 hours in the air, and the zinc oxide coated copper nanotube catalyst (with the ZnO content of 10%) is obtained.
Placing the obtained zinc oxide coated copper nanotube catalyst in a fixed bed high-pressure microreactor, introducing hydrogen to reduce at normal pressure, wherein the reduction space velocity is 3000ml/g/H, the reduction temperature is 250 ℃, the reduction time is 12H, cooling the reaction furnace to room temperature after the reduction process is finished, and introducing H2/CO2The reaction is carried out by the reaction gas with the ratio of 3, the reaction pressure is 5MPa, and the reaction space velocity is 20000ml g-1·h-1The reaction temperature was 280 ℃ and the results of activity evaluation are shown in Table 1.
Example 10
Preparation of copper nanotubes (Cu) by hydrothermal method2Si2O5(OH)2). Copper nitrate and ammonium chloride (1.57 g and 1.39g in mass) were dissolved in 60mL of deionized water to form a salt solution A, and then stirred at 30 ℃ for 2 hours while dropwise adding 5mL of an alkali solution (18.5 mol/L saturated ammonia water) to form a blue solution B. 1g of silica gel was dissolved in the blue solution B and stirred well. Transferring the solution B into a 100mL stainless steel hydrothermal kettle, heating at 200 ℃ for 48 hours, filtering the precipitate, fully washing with deionized water, drying at 60 ℃ in vacuum, cooling the solid to room temperature, and roasting at 500 ℃ in air for 2 hours to obtain the copper nanotube catalyst. Dissolving 0.29g of zinc nitrate in 5mL of deionized water to form a solution C, then fully mixing the copper nanotube catalyst with the solution C, drying at room temperature, and roasting at 500 ℃ in air for 2 hours to obtain zinc oxide coated copper nanoparticlesRice-tube catalyst (ZnO content 10%).
Placing the obtained zinc oxide coated copper nanotube catalyst in a fixed bed high-pressure microreactor, introducing hydrogen to reduce at normal pressure, wherein the reduction space velocity is 3000ml/g/H, the reduction temperature is 250 ℃, the reduction time is 12H, cooling the reaction furnace to room temperature after the reduction process is finished, and introducing H2/CO2Reacting with 3 of reaction gas, the reaction pressure is 5MPa, and the reaction space velocity is 24000ml/g-1·h-1The reaction temperature was 300 ℃ and the results of activity evaluation are shown in Table 1.
Catalytic Performance data in the examples of Table 1
Figure BDA0003399741260000091
The above examples are intended to illustrate the disclosed embodiments of the invention and are not to be construed as limiting the invention. In addition, various modifications of the methods and compositions set forth herein, as well as variations of the methods and compositions of the present invention, will be apparent to those skilled in the art without departing from the scope and spirit of the invention. While the invention has been specifically described in connection with various specific preferred embodiments thereof, it should be understood that the invention should not be unduly limited to such specific embodiments. Indeed, various modifications of the above-described embodiments which are obvious to those skilled in the art to which the invention pertains are intended to be covered by the scope of the present invention.

Claims (11)

1. CO (carbon monoxide)2The catalyst for preparing methanol by hydrogenation is characterized by comprising zinc oxide and a copper nano tube, wherein the zinc oxide coats the copper nano tube, and the general formula of the copper nano tube is Cu2Si2O5(OH)2。
2. The catalyst according to claim 1, wherein the zinc oxide accounts for 2.5-20% by mass of the catalyst.
3. The method for preparing a catalyst according to claim 1 or 2, wherein the catalyst is obtained by impregnating the copper nanotubes in an impregnation solution containing zinc ions, drying, and calcining.
4. The method of claim 3, further comprising at least one of the following technical features:
1) the dipping solution containing zinc ions is a zinc nitrate aqueous solution;
2) the drying temperature is 20-30 ℃;
3) the roasting temperature is 450-550 ℃;
4) the copper nanotube is obtained by a preparation method comprising the following steps: carrying out hydrothermal reaction on a copper source and a silicon source, and then filtering, washing, drying and roasting.
5. The method for preparing a catalyst according to claim 4, wherein the characteristic 4) further comprises at least one of the following technical characteristics:
41) the copper source is copper nitrate;
42) the silicon source is silica gel;
43) the hydrothermal reaction specifically comprises the following steps: carrying out hydrothermal reaction on an aqueous solution containing a copper source and an ammonium source, an aqueous solution containing a silicon source and an alkali solution;
44) the temperature of the hydrothermal reaction is 180-200 ℃;
45) the drying temperature is 50-80 ℃;
41) the roasting temperature is 450-550 ℃.
6. The method for preparing a catalyst according to claim 5, wherein the characteristic 43) further comprises at least one of the following technical characteristics:
431) the ammonium source is selected from at least one of ammonium chloride and ammonium nitrate;
432) the concentration of copper ions in the aqueous solution containing the copper source and the ammonium source is 0.12-0.16 mol/L;
433) the concentration of ammonium ions in the aqueous solution containing the copper source and the ammonium source is 0.39-0.47 mol/L;
434) the molar ratio of copper ions to ammonium ions in the aqueous solution containing the copper source and the ammonium source is 1: 2.5-1: 3.5;
435) the alkali solution is ammonia water;
436) the concentration of the alkali solution is 17.5-19 mol/L;
437) the molar ratio of copper ions to alkali in the aqueous solution containing the copper source and the ammonium source is 1: 10-1: 13.
7. use of a catalyst according to claim 1 or 2 for the hydrogenation of carbon dioxide to methanol.
8. Use of a catalyst according to claim 7, wherein the catalyst is subjected to hydrogenation reduction prior to use in the hydrogenation of carbon dioxide to produce methanol.
9. Use of a catalyst according to claim 8, characterised in that it further comprises at least one of the following technical features:
1) the temperature of hydrogenation reduction is 200-300 ℃;
2) the hydrogenation reduction time is 6-16 h;
3) the pressure of hydrogenation reduction is 0.01-0.5 MPa;
4) the space velocity of hydrogen for hydrogenation reduction is 2500-3500 ml/g/h.
10. CO (carbon monoxide)2The method for preparing the methanol by hydrogenation is characterized in that CO2And H2The reaction is carried out in the presence of the catalyst of claim 1 or 2 to obtain methanol.
11. The CO of claim 102The method for preparing the methanol by hydrogenation is characterized by also comprising at least one of the following technical characteristics:
1)CO2and H2Is 1: 2-1: 7;
2) the reaction temperature is 240-300 ℃;
3) the reaction pressure is 2-7 Mpa;
4) the reaction space velocity is 5000-24000 ml/g/h.
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