CN112755996A - Catalyst for synthesizing methanol by carbon dioxide hydrogenation, preparation method and application - Google Patents

Catalyst for synthesizing methanol by carbon dioxide hydrogenation, preparation method and application Download PDF

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CN112755996A
CN112755996A CN202011437598.2A CN202011437598A CN112755996A CN 112755996 A CN112755996 A CN 112755996A CN 202011437598 A CN202011437598 A CN 202011437598A CN 112755996 A CN112755996 A CN 112755996A
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catalyst
methanol
carbon dioxide
temperature
preparation
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孙予罕
王慧
张然清
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Shanghai Cluster Rui Low Carbon Energy Technology Co ltd
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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
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble metals
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8953—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
    • C07C29/157—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention belongs to the field of chemistry, and relates to a catalyst for catalyzing carbon dioxide hydrogenation to prepare methanol, and a preparation method and application thereof. More particularly relates to a catalyst for catalyzing the reaction of preparing methanol by carbon dioxide hydrogenation, a preparation method and application thereof. The catalyst is obtained by reducing and post-treating a catalyst precursor. The catalyst precursor at least comprises: cu, a metal assistant M1 and a noble metal assistant M2, wherein the molar ratio of Co to M1 is 1: 1-20: 1, and the mass percent of M2 is 0.05-5 wt%. The catalyst provided by the invention has high activity, high selectivity and good stability in the reaction operation of preparing methanol by carbon dioxide hydrogenation under mild conditions, can be operated at a lower temperature such as 170-250 ℃, and is low in cost, simple and convenient to prepare and easy for industrial amplification.

Description

Catalyst for synthesizing methanol by carbon dioxide hydrogenation, preparation method and application
Technical Field
The invention relates to a catalyst for synthesizing methanol by carbon dioxide hydrogenation, a preparation method and application, belonging to the technical field of preparation of chemical materials.
Background
Methanol is an important liquid fuel and has high economic value. Compared with traditional fuels such as coal, petroleum and the like, the methanol fuel has the advantages of clean combustion, less greenhouse gas emission and the like, and has considerable economic and environmental benefits. Meanwhile, with the increasing energy demand, the consumption of fossil fuel and CO2The total amount of emissions rises rapidly. Thus, CO is converted2Directly converted into methanol, not only can realize CO2The resource is recycled, an environment-friendly alternative energy is provided, the storage problem of renewable energy sources and atmospheric CO can be simultaneously solved2Environmental problems resulting from increased concentrations and energy safety issues that are overly dependent on fossil fuels.
At present, the commonly used traditional methanol preparation catalyst is generally a plurality of supported metal catalysts, such as Cu/ZnO/Al2O3、Cu/ZrO2And Pd/ZnO, etc., wherein Cu/ZnO/Al2O3The catalyst exhibits excellent reaction properties. For example, a Cu/Mn/Al system catalyst is prepared by adopting a cocurrent coprecipitation method in the catalytic research institute of Zhejiang university, CO2The total conversion rate is 15.8%, the methanol selectivity is 20.8%, and the once-through yield of methanol is 4.3%; the courage of the university of east China is in Cu/ZnO/Al2O3CO on catalyst2Study of methanol Synthesis by hydrogenation, CO2The conversion rate reaches 26.38 percent, and the selectivity of the methanol is 12.57 percent. However, the catalyst is easy to generate reverse water gas shift reaction, so that the selectivity of methanol is low, and carbon deposition inactivation of Cu active sites is accelerated at high temperature.
From a thermodynamic point of view, CO2The hydrogenation synthesis of methanol is an exothermic reaction, and the endothermic reverse water gas shift reaction can be inhibited under the low temperature condition, thereby being beneficial to improving the yield of methanol and simultaneously avoiding the sintering inactivation of the active metal of the catalyst at high temperature. Utilization of CO under relatively mild reaction conditions2The hydrogenation synthesis of methanol not only can realize the high-efficiency utilization of carbon-containing resources in the nature, but also saves the resource cost, and becomes the inevitable trend of future developmentAnd (4) potential.
The noble metal auxiliary agents such as Pd, Au, Pt and the like have good hydrogen overflow effect, can effectively activate hydrogen gas, generate active hydrogen atoms and show methanol synthesis activity similar to that of the Cu-based catalyst. The methanol preparation catalyst doped with the noble metal can effectively moderate reaction conditions, and has good stability and sintering resistance. For example, Chen et al reported in JACS that CeO was supported on an oxygen-rich vacancy carrierx/TiO2The XPS shows that the carrier CeO is used for preparing the catalyst loaded with Au nano particlesxCan activate noble metal Au to generate CO by charge transfer2The activated interface central site is adsorbed, so that the methanol can be easily synthesized by hydrogenation under low pressure. Tsang et al report that a Pd @ Zn core-shell structure catalyst can effectively inhibit CO and H generated in the methanol synthesis process2The selectivity of methanol of the catalyst can reach 70% under the pressure of 2MPa or below, and is nearly 10% higher than the industrial level. Therefore, it is important to develop a catalyst for preparing methanol by hydrogenation of carbon dioxide under mild conditions with high efficiency, high selectivity and stability.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the existing catalyst for catalyzing the reaction of preparing methanol by carbon dioxide hydrogenation has low selectivity.
In order to solve the technical problem, the invention provides a catalyst for synthesizing methanol by hydrogenating carbon dioxide, which is characterized in that the catalyst is obtained by carrying out reduction post-treatment on a corresponding catalyst precursor, the catalyst precursor comprises Cu and a metal auxiliary M1, and the metal auxiliary M1 adopts transition metal.
Preferably, the molar ratio of the Cu to the metal auxiliary M1 is (1-20):1, preferably (2-10): 1; the transition metal is any one or more of zinc (Zn), molybdenum (Mo), zirconium (Zr), cerium (Ce), titanium (Ti) and cobalt (Co).
Preferably, the catalyst precursor further comprises a noble metal promoter M2.
More preferably, the mass percent of the noble metal assistant M2 is 0.05-5%, preferably 0.05-2%; the noble metal assistant M2 is any one or more of gold (Au), platinum (Pt), palladium (Pd), ruthenium (Ru) and silver (Ag).
Preferably, the catalyst precursor further comprises an alkali metal promoter M3.
More preferably, the alkali metal assistant M3 is any one or more of lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs).
The invention also provides a preparation method of the catalyst for synthesizing methanol by hydrogenating carbon dioxide, which is characterized by comprising the following steps of:
step 1): dripping a mixed solution containing a copper source, a metal assistant M1 and a noble metal assistant M2 and a precipitator containing an alkali metal assistant M3 into water to react to form a coprecipitation solution;
step 2): aging, washing, drying and roasting the coprecipitation solution to obtain a catalyst precursor;
step 3): and (3) placing the catalyst precursor in a reducing gas atmosphere for heating and reducing.
Preferably, the molar concentration of the copper source in the mixed solution in the step 1) is not more than 5 mol/L; the molar concentration of the precipitant in the coprecipitation solution is not more than 3 mol/L.
Preferably, in the mixed solution in the step 1), the source of the metal promoter M1 is at least one of nitrate, chloride and sulfate of M1, the source of the noble metal promoter M2 is at least one of nitrate, chloride and sulfate of M2, and the copper source is at least one of nitrate, chloride and sulfate containing copper; the precipitant is LiOH or Na2CO3、NaHCO3、NaOH、KOH、Rb2CO3And Cs2CO3At least one of (1).
Preferably, the volume ratio of the mixed solution to the precipitant in the step 1) is 1: 2-5: 1; the reaction temperature is 10-80 ℃, and the pH is 6-12.
More preferably, the reaction temperature is 20-60 ℃ and the pH value is 8-11.
Preferably, the aging temperature in the step 2) is 10-90 ℃, and the time is 1-50 h; drying at the temperature of 40-100 ℃ for 12-48 h, roasting at the temperature of 200-600 ℃ for 1-24 h; the atmosphere for drying and baking is air atmosphere, nitrogen atmosphere or argon atmosphere.
More preferably, the aging temperature is 50-90 ℃ and the aging time is 10-30 h; the drying temperature is 60-80 ℃, the drying time is 12-15 hours, the roasting temperature is 250-500 ℃, and the roasting time is 2-5 hours.
Preferably, the reducing atmosphere in the step 3) is H2The space velocity of the synthetic gas and CO or the mixed gas of the synthetic gas and inert gas is 1000-20000 mL/(gcat.h); reducing and heating to 200-600 ℃, wherein the reduction time is 2-15 h.
More preferably, the reduction is heated to 250-400 ℃ for 5-10 h.
The invention also provides application of the catalyst for synthesizing methanol by hydrogenating carbon dioxide, which is characterized in that a fixed bed reactor is used as a reaction device to react CO2And H2The formed raw material gas is synthesized into methanol under the action of the catalyst; the reaction conditions are as follows: the temperature is 170-250 ℃, the pressure is 2-7 MPa, and the space velocity is 500-20000 mL/(gcat. h).
More preferably, the reaction conditions are: the temperature is 180-220 ℃, the pressure is 4-6 MPa, and the space velocity is 2000-10000 mL/(gcat. h).
Preferably, the raw material gas contains CO2And H2The volume ratio of (A) to (B) is 1 (1-10), preferably 1:1 to 1: 5.
The catalyst provided by the invention has high activity, high selectivity and good stability in the reaction operation of preparing methanol by carbon dioxide hydrogenation under mild conditions, can be operated at a lower temperature such as 170-250 ℃, and is low in cost, simple and convenient to prepare and easy for industrial amplification.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below.
Example 1
Adding Cu (NO)3)2And Zn (NO)3)2The solution was prepared as a 1mol/L metal mixed salt solution in a Cu/Zn ratio of 2 (molar ratio)Liquid, mixing NaOH and Na2CO3Dissolving the mixture in a certain deionized water according to a molar ratio of 1:0.4 to prepare a 2mol/L precipitator solution.
100mL of deionized water was added to the beaker, and the mixed metal salt and precipitant solution were added dropwise to the beaker simultaneously, and stirred and mixed. The temperature of coprecipitation was 25 ℃ and the pH of coprecipitation was 9.5. After titration, the mixture is aged at 65 ℃ for 20h, the aged product is centrifugally washed by deionized water until the pH value is 7, then the dried product is placed in an oven at 65 ℃ for drying for 12h, and finally the dried product is roasted in a muffle furnace at 500 ℃ for 4 h.
The above catalyst was evaluated for catalytic performance in a fixed bed. 1.5g of the catalyst and 4.5g of quartz sand particles are weighed and mixed, and the catalyst and the quartz sand are 40-60 meshes. High purity H2Reducing at GSHV 4000 mL/(g)catH), the reduction temperature is 300 ℃ and is maintained for 5 h. After reduction, H is turned on2/CO2The reaction is carried out on the raw material gas with the space velocity GSHV of 4000 mL/(g)catH), the pressure P is 5MPa, the evaluation is carried out at a temperature of 170 to 250 ℃, and the results are shown in tables 1 to 3.
Example 2
Adding Cu (NO)3)2、Zn(NO3)2And Pd (NO)3)2Dissolving the solution in deionized water according to Cu/Zn 2 (molar ratio) and the noble metal loading accounting for 0.1 wt% of the total mass of the catalyst to prepare 1mol/L metal mixed salt solution, and adding NaOH and Na2CO3Dissolving the mixture in a certain deionized water according to a molar ratio of 1:0.4 to prepare a 2mol/L precipitator solution.
100mL of deionized water was added to the beaker, and the mixed metal salt and precipitant solution were added dropwise to the beaker simultaneously, and stirred and mixed. The temperature of coprecipitation was 25 ℃ and the pH of coprecipitation was 9.5. After titration, the mixture is aged at 65 ℃ for 20h, the aged product is centrifugally washed by deionized water until the pH value is 7, then the dried product is placed in an oven at 65 ℃ for drying for 12h, and finally the dried product is roasted in a muffle furnace at 500 ℃ for 4 h.
The above catalyst was evaluated for catalytic performance in a fixed bed. Weighing 1.5g of the catalyst and 4.5g of quartz sand particles, and mixing the catalyst and the quartz sand40-60 meshes. High purity H2Reducing at GSHV 4000 mL/(g)catH), the reduction temperature is 300 ℃ and is maintained for 5 h. After reduction, H is turned on2/CO2The reaction is carried out on the raw material gas with the space velocity GSHV of 4000 mL/(g)catH), the pressure P is 5MPa, the evaluation is carried out at a temperature of 170 to 250 ℃, and the results are shown in tables 1 to 3.
Example 3
Adding Cu (NO)3)2、Zn(NO3)2And HAuCl4Dissolving the solution in deionized water according to Cu/Zn 2 (molar ratio) and the noble metal loading accounting for 0.1 wt% of the total mass of the catalyst to prepare 1mol/L metal mixed salt solution, and adding NaOH and Na2CO3Dissolving the mixture in a certain deionized water according to a molar ratio of 1:0.4 to prepare a 2mol/L precipitator solution.
100mL of deionized water was added to the beaker, and the mixed metal salt and precipitant solution were added dropwise to the beaker simultaneously, and stirred and mixed. The temperature of coprecipitation was 25 ℃ and the pH of coprecipitation was 9.5. After titration, the mixture is aged at 65 ℃ for 20h, the aged product is centrifugally washed by deionized water until the pH value is 7, then the dried product is placed in an oven at 65 ℃ for drying for 12h, and finally the dried product is roasted in a muffle furnace at 500 ℃ for 4 h.
The above catalyst was evaluated for catalytic performance in a fixed bed. 1.5g of the catalyst and 4.5g of quartz sand particles are weighed and mixed, and the catalyst and the quartz sand are 40-60 meshes. High purity H2Reducing at GSHV 4000 mL/(g)catH), the reduction temperature is 300 ℃ and is maintained for 5 h. After reduction, H is turned on2/CO2The reaction is carried out on the raw material gas with the space velocity GSHV of 4000 mL/(g)catH), the pressure P is 5MPa, the evaluation is carried out at a temperature of 170 to 250 ℃, and the results are shown in tables 1 to 3.
Example 4
Adding Cu (NO)3)2、Zr(NO3)2And Pd (NO)3)2Dissolving the solution in deionized water according to the molar ratio of Cu/Zr to 2 and the noble metal loading accounting for 0.1 wt% of the total mass of the catalyst to prepare 1mol/L metal mixed salt solution, and adding NaOH and Na2CO3In mole ratioDissolving the mixture in deionized water in a ratio of 1:0.4 to prepare a 2mol/L precipitant solution.
100mL of deionized water was added to the beaker, and the mixed metal salt and precipitant solution were added dropwise to the beaker simultaneously, and stirred and mixed. The temperature of coprecipitation was 25 ℃ and the pH of coprecipitation was 9.5. After titration, the mixture is aged at 65 ℃ for 20h, the aged product is centrifugally washed by deionized water until the pH value is 7, then the dried product is placed in an oven at 65 ℃ for drying for 12h, and finally the dried product is roasted in a muffle furnace at 500 ℃ for 4 h.
The above catalyst was evaluated for catalytic performance in a fixed bed. 1.5g of the catalyst and 4.5g of quartz sand particles are weighed and mixed, and the catalyst and the quartz sand are 40-60 meshes. High purity H2Reducing at GSHV 4000 mL/(g)catH), the reduction temperature is 300 ℃ and is maintained for 5 h. After reduction, H is turned on2/CO2The reaction is carried out on the raw material gas with the space velocity GSHV of 4000 mL/(g)catH), the pressure P is 5MPa, the evaluation is carried out at a temperature of 170 to 250 ℃, and the results are shown in tables 1 to 3.
Example 5
Adding Cu (NO)3)2、H8MoN2O4And Pd (NO)3)2Dissolving the solution in deionized water according to the molar ratio of Cu/Mo to 2, wherein the loading of the noble metal accounts for 0.1 wt% of the total mass of the catalyst to prepare a metal mixed salt solution with the concentration of 1mol/L, and adding NaOH and Na2CO3Dissolving the mixture in a certain deionized water according to a molar ratio of 1:0.4 to prepare a 2mol/L precipitator solution.
100mL of deionized water was added to the beaker, and the mixed metal salt and precipitant solution were added dropwise to the beaker simultaneously, and stirred and mixed. The temperature of coprecipitation was 25 ℃ and the pH of coprecipitation was 9.5. After titration, the mixture is aged at 65 ℃ for 20h, the aged product is centrifugally washed by deionized water until the pH value is 7, then the dried product is placed in an oven at 65 ℃ for drying for 12h, and finally the dried product is roasted in a muffle furnace at 500 ℃ for 4 h.
The above catalyst was evaluated for catalytic performance in a fixed bed. 1.5g of the catalyst and 4.5g of quartz sand particles are weighed and mixed, and the catalyst and the quartz sand are 40-60 meshes. High purity H2Go on and go backOriginal, space velocity GSHV 4000 mL/(g)catH), the reduction temperature is 300 ℃ and is maintained for 5 h. After reduction, H is turned on2/CO2The reaction is carried out on the raw material gas with the space velocity GSHV of 4000 mL/(g)catH), the pressure P is 5MPa, the evaluation is carried out at a temperature of 170 to 250 ℃, and the results are shown in tables 1 to 3.
TABLE 1
Figure RE-GDA0002979771210000061
TABLE 2
Figure RE-GDA0002979771210000062
Figure RE-GDA0002979771210000071
TABLE 3
Figure RE-GDA0002979771210000072
As can be seen from the results shown in tables 1-3, the catalyst of the present invention has higher CO under milder conditions than the results reported in the literature and shown in the patent cited in the prior art2The conversion rate, the methanol selectivity and the methanol space-time yield prove that the synthetic method can prepare the high-performance low-temperature Cu-based catalyst.

Claims (14)

1. The catalyst for synthesizing the methanol by hydrogenating the carbon dioxide is characterized in that a catalyst precursor corresponding to the catalyst is obtained by reduction post-treatment, the catalyst precursor comprises Cu and a metal auxiliary M1, and the metal auxiliary M1 adopts transition metal.
2. The catalyst for synthesizing methanol by hydrogenating carbon dioxide according to claim 1, wherein the molar ratio of the Cu to the metal promoter M1 is (1-20): 1; the transition metal is any one or more of zinc, molybdenum, zirconium, cerium, titanium and cobalt.
3. The catalyst for the carbon dioxide hydrogenation synthesis of methanol according to claim 1, wherein the catalyst precursor further comprises a noble metal promoter M2.
4. The catalyst for synthesizing methanol by hydrogenating carbon dioxide according to claim 3, wherein the mass percent of the noble metal assistant M2 is 0.05-5%; the noble metal assistant M2 is any one or more of gold, platinum, palladium, ruthenium and silver.
5. The catalyst for the carbon dioxide hydrogenation synthesis of methanol according to any one of claims 1 to 4, wherein the catalyst precursor further comprises an alkali metal promoter M3.
6. The catalyst for synthesizing methanol by hydrogenating carbon dioxide as claimed in claim 5, wherein the alkali metal promoter M3 is any one or more of lithium, sodium, potassium, rubidium and cesium.
7. The method for preparing a catalyst for the synthesis of methanol by hydrogenation of carbon dioxide according to claim 5 or 6, comprising the steps of:
step 1): dripping a mixed solution containing a copper source, a metal assistant M1 and a noble metal assistant M2 and a precipitator containing an alkali metal assistant M3 into water to react to form a coprecipitation solution;
step 2): aging, washing, drying and roasting the coprecipitation solution to obtain a catalyst precursor;
step 3): and (3) placing the catalyst precursor in a reducing gas atmosphere for heating and reducing.
8. The preparation method according to claim 7, wherein the molar concentration of the copper source in the mixed solution in the step 1) is not more than 5 mol/L; the molar concentration of the precipitant in the coprecipitation solution is not more than 3 mol/L.
9. The preparation method according to claim 7, wherein in the mixed solution in the step 1), the source of the metal promoter M1 is at least one of nitrate, chloride and sulfate of M1, the source of the noble metal promoter M2 is at least one of nitrate, chloride and sulfate of M2, and the copper source is at least one of nitrate, chloride and sulfate containing copper; the precipitant is LiOH or Na2CO3、NaHCO3、NaOH、KOH、Rb2CO3And Cs2CO3At least one of (1).
10. The preparation method according to claim 7, wherein the volume ratio of the mixed solution to the precipitant in the step 1) is 1:2 to 5: 1; the reaction temperature is 10-80 ℃, and the pH is 6-12.
11. The preparation method of claim 7, wherein the aging temperature in the step 2) is 10 to 90 ℃ and the aging time is 1 to 50 hours; drying at the temperature of 40-100 ℃ for 12-48 h, roasting at the temperature of 200-600 ℃ for 1-24 h; the atmosphere for drying and baking is air atmosphere, nitrogen atmosphere or argon atmosphere.
12. The method according to claim 7, wherein the reducing atmosphere in the step 3) is H2The space velocity of the synthetic gas and CO or the mixed gas of the synthetic gas and inert gas is 1000-20000 mL/(gcat.h); reducing and heating to 200-600 ℃, wherein the reduction time is 2-15 h.
13. Use of the catalyst for the synthesis of methanol by hydrogenation of carbon dioxide according to claims 1 to 5, characterized in that CO is reacted using a fixed bed reactor as reaction unit2And H2The formed raw material gas is synthesized into methanol under the action of the catalyst; the reaction conditions are as follows: temperature 170The temperature is 250 ℃ below zero, the pressure is 2-7 MPa, and the space velocity is 500-20000 mL/(gcat h).
14. The use according to claim 13, wherein the feed gas comprises CO2And H2The volume ratio of (1) to (10).
CN202011437598.2A 2020-12-11 2020-12-11 Catalyst for synthesizing methanol by carbon dioxide hydrogenation, preparation method and application Withdrawn CN112755996A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113663678A (en) * 2021-08-11 2021-11-19 清华大学 Cu-based spinel catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method and application thereof
CN113842914A (en) * 2021-10-29 2021-12-28 中国华能集团清洁能源技术研究院有限公司 Catalyst for synthesizing methanol from carbon dioxide, and preparation method and application thereof
CN113856688A (en) * 2021-11-16 2021-12-31 扬州大学 For CO2Preparation method of Cu-based catalyst for preparing methanol by hydrogenation
CN114349607A (en) * 2022-03-01 2022-04-15 中国科学院上海高等研究院 Method for synthesizing dimethoxymethane by selective hydrogenation of carbon dioxide
CN114602477A (en) * 2022-03-29 2022-06-10 扬州大学 For CO2Double-shell hollow copper-zinc-based catalyst for preparing methanol at low temperature and preparation method thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113663678A (en) * 2021-08-11 2021-11-19 清华大学 Cu-based spinel catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method and application thereof
CN113842914A (en) * 2021-10-29 2021-12-28 中国华能集团清洁能源技术研究院有限公司 Catalyst for synthesizing methanol from carbon dioxide, and preparation method and application thereof
CN113856688A (en) * 2021-11-16 2021-12-31 扬州大学 For CO2Preparation method of Cu-based catalyst for preparing methanol by hydrogenation
CN113856688B (en) * 2021-11-16 2023-11-10 扬州大学 For CO 2 Preparation method of Cu-based catalyst for preparing methanol by hydrogenation
CN114349607A (en) * 2022-03-01 2022-04-15 中国科学院上海高等研究院 Method for synthesizing dimethoxymethane by selective hydrogenation of carbon dioxide
CN114602477A (en) * 2022-03-29 2022-06-10 扬州大学 For CO2Double-shell hollow copper-zinc-based catalyst for preparing methanol at low temperature and preparation method thereof
CN114602477B (en) * 2022-03-29 2023-10-20 扬州大学 For CO 2 Double-shell hollow copper-zinc-based catalyst for preparing methanol at low temperature and preparation method thereof

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