CN111514938A - 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

Info

Publication number
CN111514938A
CN111514938A CN202010514932.3A CN202010514932A CN111514938A CN 111514938 A CN111514938 A CN 111514938A CN 202010514932 A CN202010514932 A CN 202010514932A CN 111514938 A CN111514938 A CN 111514938A
Authority
CN
China
Prior art keywords
catalyst
thf
bpy
uio
solid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202010514932.3A
Other languages
Chinese (zh)
Other versions
CN111514938B (en
Inventor
王晓龙
程阿超
王琪
郜时旺
肖天存
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huaneng Clean Energy Research Institute
China Huaneng Group Co Ltd
Original Assignee
Huaneng Clean Energy Research Institute
China Huaneng Group Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huaneng Clean Energy Research Institute, China Huaneng Group Co Ltd filed Critical Huaneng Clean Energy Research Institute
Priority to CN202010514932.3A priority Critical patent/CN111514938B/en
Publication of CN111514938A publication Critical patent/CN111514938A/en
Priority to PCT/CN2021/098987 priority patent/WO2021249403A1/en
Application granted granted Critical
Publication of CN111514938B publication Critical patent/CN111514938B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • B01J35/61—
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
    • B01J2231/625—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2 of CO2
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/48—Zirconium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22—Organic complexes
    • 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 discloses a catalyst for preparing methanol by carbon dioxide hydrogenation and a preparation method thereof, wherein graphene oxide with high specific surface area is used as a carrier, copper nitrate and the carrier form a complex through pyridine nitrogen in UO-bpy to enhance the interaction of the copper nitrate and the carrier, and the CuZn @ UO-bpy/GO catalyst with ultra-small Cu/ZnOx nano particles is obtained by utilizing Zr-MOFs confinement effect while excessive loss of active component copper is prevented, so that the stability and the dispersibility of the CuZn @ UO-bpy catalyst are further improved, and the yield of methanol is improved on the basis of ensuring ultrahigh selectivity; at the same time, GO has strongerThermal stability, avoidance of CO2Higher reaction temperatures during the conversion lead to carbon deposition deactivation of the catalyst.

Description

Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof
Technical Field
The invention relates to the field of methanol synthesis, in particular to a catalyst for preparing methanol by carbon dioxide hydrogenation and a preparation method thereof.
Background
CO2As a gas causing greenhouse effect, it is a great harm to the natural environment. By using CO2The nontoxic and nonflammable raw material can be used for obtaining products with high added value such as methanol, meets the requirement of green chemistry, and has great environmental effect and economic effect. In addition, the methanol has wide application prospect as a basic organic chemical raw material and a power fuel, and can be used for preparing products such as low-carbon olefin, formic acid, methyl formate, acetic acid and the like.
1、Cu/ZnO/Al2O3The (CZA) catalyst was a commercial catalyst for methanol production invented by ICI corporation in the 70 th century. Due to the conventional CZA catalyst to CO2The catalytic performance of hydrogenation for preparing methanol is not high enough, and researches mainly focus on improving the performance of the catalyst by adding an auxiliary agent or changing a preparation mode. For example, Chinese patents CN101983765A, CN102000578A, CN102302934A, CN101513615A and CN104549299A respectively disclose CO modified by auxiliary agent2Catalyst for preparing methanol by hydrogenation and preparation method thereof, wherein the main body of the catalyst is CZA catalyst, and the auxiliary agent is ZrO2、SiO2And MgO and the like; as reported in CN 104383928A, the rake science and technology ltd, first performs cocurrent precipitation on an active component salt solution and a precipitant to prepare an active component slurry a, performs cocurrent precipitation on a carrier component salt solution and a precipitant to prepare a carrier slurry B, adds the slurry a into the slurry B, performs vigorous pulping, and then adds the active component salt solution and the precipitant to prepare a catalyst slurry. The catalyst performance can be improved by introducing the auxiliary agent in a coprecipitation mode, but for gas-solid heterogeneous catalysis, the auxiliary agent embedded in a catalyst body phase cannot be fully and effectively utilized; changing the preparation method only for CO2The CZA catalyst for preparing methanol by hydrogenation is improved.
2. With Al2O3Compared with ZrO2Has weak hydrophilicity, can inhibit the toxic action of water on active sites in the methanol synthesis process, and is Cu/ZnO/ZrO2(CZZ) catalysts are receiving increasing attention. Naturecommunications,2019,10(1):1166-1175]Reports a Cu/ZnO/ZrO2Catalyst, application thereof to CO2The selectivity of the methanol can reach 80.2 percent after reaction. But under the reaction conditions of high temperature and high pressure, Cu/ZnO/ZrO2The catalyst is prone to surface reconstruction and particle growth, thereby reducing catalytic activity and selectivity.
3. Woodne and Wang teaching topic of Xiamen university [ Journal of the American chemical society,2017,139(10),3834-]The CuZn @ UiO-bpy catalyst with the ultra-small Cu/ZnOx nano particles is obtained by utilizing the Zr-MOFs confinement effect and is used for CO2The selectivity of the methanol can reach 100 percent. However, the powder catalyst has the defects of easy loss, increased pressure drop in the reactor, easy sintering and the like. Changzhou university Von Sheng teacher [ Fine chemical engineering, 2018,35(11):1942-]A nano composite material UiO-66/graphene oxide (UiO-66/GO) is synthesized, the catalyst takes graphene oxide with a 2D structure as a carrier, and the liquid phase adsorption performance of the catalyst is greatly improved while the stability and the dispersibility of the catalyst are improved. Thus, the construction of stable catalysts is currently CO2One of the hot spots in the research of hydrogenation to methanol.
Disclosure of Invention
The invention provides a catalyst for preparing methanol by carbon dioxide hydrogenation and a preparation method thereof, aiming at overcoming the defects of the prior art and improving CO content2The stability and the dispersity of the catalyst used for preparing the methanol by hydrogenation improve the yield of the methanol on the basis of ensuring ultrahigh selectivity.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a catalyst for preparing methanol by carbon dioxide hydrogenation comprises the following steps:
s1, adding GO into DMF and carrying out ultrasonic treatment for 6h to obtain a GO mixture; weighing zirconium salt, 2 '-bipyridyl-5, 5' -dicarboxylic acid and formic acid, adding the zirconium salt, the 2,2 '-bipyridyl-5, 5' -dicarboxylic acid and the formic acid into the GO mixture, and uniformly stirring to obtain a mixed solution of GO and UiO-bpy, wherein the molar ratio of the zirconium salt to the 2,2 '-bipyridyl-5, 5' -dicarboxylic acid to the formic acid to DMF is 0.106: 0.104: 0.018: 0.145, the added GO accounts for 0.23 to 5 wt percent of the solid phase mass of the UiO-bpy;
s2, reacting the reaction solution which is evenly stirred in S1 at the temperature of 100 ℃ and 160 ℃ for 12-36 h;
s3, after the reaction is finished, washing and drying the collected solid phase by using a mixed solvent of DMF and THF to obtain a solid sample;
s4, dissolving the copper salt solid into THF to obtain a copper salt solution, adding the obtained solid sample into the copper salt solution, fully and uniformly stirring, centrifuging, washing with THF, placing the obtained precipitate into THF, and preserving in an inert atmosphere, wherein the copper salt solid accounts for (25-75) wt% of the mass fraction of the solid sample obtained from S3;
s5, dissolving zinc salt solid into hexane to obtain a zinc salt solution, adding the zinc salt solution into the precipitate obtained in S4 in an inert atmosphere, adding THF, stirring uniformly, centrifuging, washing with THF, and drying to obtain a solid sample, and storing in the inert atmosphere, wherein the zinc salt solid accounts for (25-60) wt% of the mass fraction of the solid sample obtained in S3;
s6, placing the solid sample obtained in the S5 in a reducing atmosphere, and carrying out in-situ reduction at the temperature of 200-260 ℃ to obtain the catalyst for preparing the methanol from the carbon dioxide.
Further, the zirconium salt is one of zirconium nitrate, zirconium chloride and zirconium sulfate.
Further, the copper salt solid is one of copper nitrate, copper chloride dihydrate and copper sulfate.
Further, the zinc salt is one of zinc nitrate hexahydrate, diethyl zinc and zinc sulfate.
Further, the reducing atmosphere in S6 is H2Or H2With CO2The mixed gas of (1).
A catalyst for preparing methanol by carbon dioxide hydrogenation is prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial technical effects:
the inventionThe preparation method comprises the steps of adopting graphene oxide with high specific surface area as a carrier, enabling copper salt and the carrier to form a complex through pyridine nitrogen in the UiO-bpy to enhance the interaction of the copper salt and the carrier, preventing excessive loss of active component copper, and obtaining the CuZn @ UiO-bpy/GO catalyst with ultra-small Cu/ZnOx nano particles by utilizing a Zr-MOFs confinement effect so as to further improve the stability and the dispersibility of the CuZn @ UiO-bpy catalyst and improve the yield of methanol on the basis of ensuring ultrahigh selectivity; meanwhile, GO has stronger thermal stability, and CO is avoided2Higher reaction temperatures during the conversion lead to carbon deposition deactivation of the catalyst.
Detailed Description
The invention is described in further detail below for a better understanding of the invention.
A preparation method of a catalyst for preparing methanol by carbon dioxide hydrogenation comprises the following steps:
s1, adding GO (graphene oxide) into DMF (N, N-dimethylformamide) and carrying out ultrasonic treatment for 6 hours to obtain a GO mixture; weighing a zirconium salt, 2 '-bipyridyl-5, 5' -dicarboxylic acid and formic acid, adding the zirconium salt, the 2,2 '-bipyridyl-5, 5' -dicarboxylic acid and the formic acid into the GO mixture, and uniformly stirring to obtain a mixed solution of GO and UiO-bpy (UiO-67-bpy type zirconium metal organic framework material), wherein the zirconium salt is one or more of zirconium nitrate, zirconium chloride and zirconium sulfate, and the molar ratio of the zirconium salt, the 2,2 '-bipyridyl-5, 5' -dicarboxylic acid, the formic acid and DMF is 0.106: 0.104: 0.018: 0.145, the added GO accounts for 0.23 to 5 wt percent of the solid phase mass of the UiO-bpy;
s2, transferring the reaction solution with the S1 uniformly stirred into a bottle, and reacting for 12-36h at the temperature of 100-160 ℃;
s3, after the reaction is finished, washing and drying the collected solid phase by using DMF and THF (tetrahydrofuran) to obtain a solid sample UiO-bpy/GO;
s4, dissolving a copper salt solid into THF to obtain a copper salt solution, adding the obtained solid sample into the copper salt solution, fully and uniformly stirring, centrifuging, washing with THF, and placing the obtained precipitate into THF to be stored in an inert atmosphere, wherein the copper salt solid is one of copper nitrate, copper chloride dihydrate and copper sulfate, and the mass ratio of the copper salt solid to the solid sample obtained in S3 is (25-75) wt%;
s5, dissolving a zinc salt solid into hexane to obtain a zinc salt solution, adding the zinc salt solution into the precipitate obtained in S4 in an inert atmosphere, adding THF, stirring uniformly, centrifuging, washing with THF, and drying to obtain a solid sample, and storing the solid sample in the inert atmosphere, wherein the zinc salt is one of zinc nitrate hexahydrate, diethyl zinc and zinc sulfate, and the mass ratio of the zinc salt solid to the solid sample obtained in S3 is (25-60) wt%;
s6, placing the solid sample obtained in the S5 in a reducing atmosphere, and carrying out in-situ reduction at the temperature of 200-260 ℃ to obtain the CuZn @ UiO-bpy/GO catalyst for preparing methanol from carbon dioxide, wherein the reducing atmosphere is H2Or H2With CO2The mixed gas of (1).
The present invention will be described in detail with reference to examples. It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
The following detailed description is illustrative of the embodiments and is intended to provide further details of the invention. Unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention.
Comparative example
The preparation method of the catalyst for preparing methanol by hydrogenating carbon dioxide comprises the following steps:
1. reacting ZrCl4(24.5mg,0.106mmol), 2 '-bipyridine-5, 5' -dicarboxylic acid (bpydc,26mg,0.104mmol), formic acid (1mL) and DMF (10mL) were stirred well; transferring the uniformly stirred reaction solution into a bottle, and heating for 24 hours at 120 ℃; after the reaction was complete, the collected solid phase was washed with DMF and THF and a solid sample UiO-bpy was obtained in a vacuum oven overnight at 60 ℃.
2. Adding CuCl2·2H2O (53.0mg,0.30mmol) was dissolved in 20mL THF; weighing 100mg UiO-bpy washed 5 times with THF and added to CuCl2In solution; slowly stirring the obtained mixed solution at room temperature for overnight; after centrifugation and 5-time THF washes, the solid UiO-bpy-Cu sample was placed in THF and transferred to a glove box for storage.
3. In a glove box, a bottle containing UiO-bpy-Cu was charged with 0.42mL of a hexane solution of diethyl zinc (1 mol/L); slowly stirring the obtained mixed solution for 4 hours; the solid sample Zn @ UiO-bpy-Cu obtained by centrifugation, washing with THF for 5 times and vacuum drying was stored in a glove box.
4. The obtained solid sample Zn @ UiO-bpy-Cu is added in H2/CO2(3:1) heating to 250 ℃ in the atmosphere, and carrying out in-situ reduction to obtain the CuZn @ UiO-bpy catalyst for preparing methanol from carbon dioxide.
Example 1
The embodiment of the invention relates to a preparation method of a catalyst for preparing methanol by hydrogenating carbon dioxide, which comprises the following steps:
1. 0.5mg GO was added to 15mL DMF and sonicated for 6h, ZrCl4(24.5mg,0.106mmol), 2 '-bipyridine-5, 5' -dicarboxylic acid (bpydc,26mg,0.104mmol) and formic acid (1mL) were added to the GO mixture and stirred well; transferring the uniformly stirred reaction solution into a bottle, and heating for 24 hours at 120 ℃; after the reaction was complete, the collected solid phase was washed with DMF and THF and solid sample UiO-bpy/GO was obtained in a vacuum oven overnight at 60 ℃.
2. Adding CuCl2·2H2O (53.0mg,0.30mmol) was dissolved in 20mL THF; 100mg of UiO-bpy/GO is weighed, washed with THF for 3 times and added to CuCl2In solution; slowly stirring the obtained mixed solution at room temperature for overnight; after centrifugation and 5 THF washes, the resulting solid sample UiO-bpy-Cu/GO was placed in THF and transferred to a glove box for storage.
3. In a glove box, to a bottle containing UiO-bpy-Cu/GO was added 0.42mL of a hexane solution of diethyl zinc (1 mol/L); slowly stirring the obtained mixed solution for 4 hours; centrifuging, washing with THF for 5 times, and vacuum drying to obtain solid sample Zn @ UiO-bpy-Cu/GO which is stored in a glove box.
4. The obtained solid sample Zn @ UiO-bpy-Cu/GO is subjected to H2/CO2(3:1) heating to 250 ℃ in the atmosphere, and carrying out in-situ reduction to obtain the CuZn @ UiO-bpy/GO catalyst for preparing methanol from carbon dioxide.
Example 2
The embodiment of the invention relates to a preparation method of a catalyst for preparing methanol by hydrogenating carbon dioxide, which comprises the following steps:
1. 2.5mg GO was added to 15mL DMF and sonicated for 6h, ZrCl4(24.5mg,0.106mmol), 2 '-bipyridine-5, 5' -dicarboxylic acid (bpydc,26mg,0.104mmol) and formic acid (1mL) were added to the GO mixture and stirred well; transferring the uniformly stirred reaction solution into a bottle, and heating for 24 hours at 120 ℃; after the reaction was complete, the collected solid phase was washed with DMF and THF and solid sample UiO-bpy/GO was obtained in a vacuum oven overnight at 60 ℃.
2. Adding CuCl2·2H2O (53.0mg,0.30mmol) was dissolved in 20mL THF; 100mg of UiO-bpy/GO is weighed, washed with THF for 5 times, and added to CuCl2In solution; slowly stirring the obtained mixed solution at room temperature for overnight; after centrifugation and 5 THF washes, the resulting solid sample UiO-bpy-Cu/GO was placed in THF and transferred to a glove box for storage.
3. In a glove box, taking out UiO-bpy-Cu/GO, and adding into a bottle containing 30mL of THF solvent; to the bottle was added 0.42mL of a hexane solution of diethyl zinc (1 mol/L); slowly stirring the obtained mixed solution for 4 hours; centrifuging, washing with THF for 5 times, and vacuum drying to obtain solid sample Zn @ UiO-bpy-Cu/GO which is stored in a glove box.
4. The obtained solid sample Zn @ UiO-bpy-Cu/GO is subjected to H2/CO2(3:1) heating to 250 ℃ in the atmosphere, and carrying out in-situ reduction to obtain the CuZn @ UiO-bpy/GO catalyst for preparing methanol from carbon dioxide.
Example 3
The embodiment of the invention relates to a preparation method of a catalyst for preparing methanol by hydrogenating carbon dioxide, which comprises the following steps:
1. add 5mg GO to 15mL DMF and sonicate for 6h, ZrCl4(24.5mg,0.106mmol), 2 '-bipyridine-5, 5' -dicarboxylic acid (bpydc,26mg,0.104mmol) and formic acid (1mL) were added to the GO mixture and stirred well; will stir the reaction evenlyTransferring the solution into a bottle, and heating at 120 deg.C for 24 hr; after the reaction was complete, the collected solid phase was washed with DMF and THF and solid sample UiO-bpy/GO was obtained in a vacuum oven overnight at 60 ℃.
2. Adding CuCl2·2H2O (53.0mg,0.30mmol) was dissolved in 20mL THF; 100mg of UiO-bpy/GO is weighed, washed with THF for 6 times and added to CuCl2In solution; slowly stirring the obtained mixed solution at room temperature for overnight; after centrifugation and 5 THF washes, the resulting solid sample UiO-bpy-Cu/GO was placed in THF and transferred to a glove box for storage.
3. In a glove box, taking out UiO-bpy-Cu/GO, and adding into a bottle containing 30mL of THF solvent; to the bottle was added 0.42mL of a hexane solution of diethyl zinc (1 mol/L); slowly stirring the obtained mixed solution for 4 hours; centrifuging, washing with THF for 5-8 times, and vacuum drying to obtain solid sample Zn @ UiO-bpy-Cu/GO, and storing in a glove box.
4. The obtained solid sample Zn @ UiO-bpy-Cu/GO is subjected to H2/CO2(3:1) heating to 250 ℃ in the atmosphere, and carrying out in-situ reduction to obtain the CuZn @ UiO-bpy/GO catalyst for preparing methanol from carbon dioxide.
Example 4
The embodiment of the invention relates to a preparation method of a catalyst for preparing methanol by hydrogenating carbon dioxide, which comprises the following steps:
1. add 10.9mg GO to 15mL DMF and sonicate for 6h, ZrCl4(24.5mg,0.106mmol), 2 '-bipyridine-5, 5' -dicarboxylic acid (bpydc,26mg,0.104mmol) and formic acid (1mL) were added to the GO mixture and stirred well; transferring the uniformly stirred reaction solution into a bottle, and heating for 24 hours at 120 ℃; after the reaction was complete, the collected solid phase was washed with DMF and THF and solid sample UiO-bpy/GO was obtained in a vacuum oven overnight at 60 ℃.
2. Adding CuCl2·2H2O (53.0mg,0.30mmol) was dissolved in 20mL THF; 100mg of UiO-bpy/GO is weighed, washed with THF for 5 times, and added to CuCl2In solution; slowly stirring the obtained mixed solution at room temperature for overnight; after centrifugation and 5 THF washes, the resulting solid sample UiO-bpy-Cu/GO was placed in THF and transferred to a glove box for storage.
3. In a glove box, taking out UiO-bpy-Cu/GO, and adding into a bottle containing 30mL of THF solvent; to the bottle was added 0.42mL of a hexane solution of diethyl zinc (1 mol/L); slowly stirring the obtained mixed solution for 4 hours; centrifuging, washing with THF for 5 times, and vacuum drying to obtain solid sample Zn @ UiO-bpy-Cu/GO which is stored in a glove box.
4. The obtained solid sample Zn @ UiO-bpy-Cu/GO is subjected to H2/CO2(3:1) heating to 250 ℃ in the atmosphere, and carrying out in-situ reduction to obtain the CuZn @ UiO-bpy/GO catalyst for preparing methanol from carbon dioxide.
Example 5
The embodiment of the invention relates to a preparation method of a catalyst for preparing methanol by hydrogenating carbon dioxide, which comprises the following steps:
1. 2.5mg GO was added to 15mL DMF and sonicated for 6h, Zr (NO)3)4(45.5mg,0.106mmol), 2 '-bipyridine-5, 5' -dicarboxylic acid (bpydc,26mg,0.104mmol) and formic acid (1mL) were added to the GO mixture and stirred well; transferring the uniformly stirred reaction solution into a bottle, and heating for 24 hours at 120 ℃; after the reaction was complete, the collected solid phase was washed with DMF and THF and solid sample UiO-bpy/GO was obtained in a vacuum oven overnight at 60 ℃.
2. Copper nitrate (25.0mg,0.13mmol) was dissolved in 20mL THF; 100mg of UiO-bpy/GO is weighed, washed with THF for 6 times and added to CuCl2In solution; slowly stirring the obtained mixed solution at room temperature for overnight; after centrifugation and 5 THF washes, the resulting solid sample UiO-bpy-Cu/GO was placed in THF and transferred to a glove box for storage.
3. In a glove box, taking out UiO-bpy-Cu/GO, and adding into a bottle containing 30mL of THF solvent; to the bottle was added zinc nitrate hexahydrate (25.0mg,0.08mmol) as a solid; slowly stirring the obtained mixed solution for 4 hours; centrifuging, washing with THF for 5-8 times, and vacuum drying to obtain solid sample Zn @ UiO-bpy-Cu/GO, and storing in a glove box.
4. The obtained solid sample Zn @ UiO-bpy-Cu/GO is subjected to H2And heating to 200 ℃ in the atmosphere, and carrying out in-situ reduction to obtain the CuZn @ UiO-bpy/GO catalyst for preparing methanol from carbon dioxide.
Example 6
The embodiment of the invention relates to a preparation method of a catalyst for preparing methanol by hydrogenating carbon dioxide, which comprises the following steps:
1. 2.5mg GO was added to 15mL DMF and sonicated for 6h, Zr (SO)4)2(30.0mg,0.106mmol), 2 '-bipyridine-5, 5' -dicarboxylic acid (bpydc,26mg,0.104mmol) and formic acid (1mL) were added to the GO mixture and stirred well; transferring the uniformly stirred reaction solution into a bottle, and heating for 24 hours at 120 ℃; after the reaction was complete, the collected solid phase was washed with DMF and THF and solid sample UiO-bpy/GO was obtained in a vacuum oven overnight at 60 ℃.
2. Copper sulfate (75.0mg,0.47mmol) was dissolved in 20mL THF; 100mg of UiO-bpy/GO is weighed, washed with THF for 6 times and added to CuCl2In solution; slowly stirring the obtained mixed solution at room temperature for overnight; after centrifugation and 5 THF washes, the resulting solid sample UiO-bpy-Cu/GO was placed in THF and transferred to a glove box for storage.
3. In a glove box, taking out UiO-bpy-Cu/GO, and adding into a bottle containing 30mL of THF solvent; to the bottle was added zinc sulfate (60.0mg,0.37mmol) as a solid; slowly stirring the obtained mixed solution for 4 hours; centrifuging, washing with THF for 5-8 times, and vacuum drying to obtain solid sample Zn @ UiO-bpy-Cu/GO, and storing in a glove box.
4. The obtained solid sample Zn @ UiO-bpy-Cu/GO is subjected to H2/CO2(1:3) heating to 260 ℃ in the atmosphere, and carrying out in-situ reduction to obtain the CuZn @ UiO-bpy/GO catalyst for preparing methanol from carbon dioxide.
TABLE 1 Table of specific reaction conditions for comparative examples and examples 1 to 6
Figure BDA0002529782190000101
a, the adding amount of copper salt is the mass ratio of the copper salt to [ UiO-bpy/GO ];
and b, the adding amount of the zinc salt is the mass ratio of the zinc salt to the [ UiO-bpy/GO ].
Results of Activity evaluation
The comparative example and the activity of the catalyst for preparing methanol by hydrogenating carbon dioxide prepared in the example 1 to 3 were tested:
0.3g of each of the catalysts obtained in comparative example and examples 1 to 3 was placed in CO2In a miniature fixed bed reactor for preparing methanol by hydrogenation. First in H2/CO2(3) Reducing at a constant temperature of 250 ℃ for 8h under the atmosphere of 1, wherein the heating rate is 1 ℃/min; space velocity GHSV of 3000h-1The evaluation temperature is 200-; finally, the tail gas and liquid phase products were detected and analyzed by Agilent technologies 7980B Gas Chromatography (GC) to calculate CO2Conversion and CH3Selectivity of OH product. The results are shown in Table 2.
Table 2 evaluation data of the activity of the catalysts in the different examples
Figure BDA0002529782190000111
As can be seen from Table 1, the powdered CuZn @ UiO-bpy catalyst is easy to accumulate and has poor catalytic activity; after loading, the use amount of GO is increased, the stability and the dispersibility of the CuZn @ UiO-bpy catalyst can be improved, and further the influence on CO is caused2Conversion rate of (2) and CH3OH yield; when the dosage of the graphene oxide is 2.5mg, the highest methanol yield can reach 17.42%.
It will be appreciated by those skilled in the art that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The embodiments disclosed above are therefore to be considered in all respects as illustrative and not restrictive. All changes which come within the scope of or equivalence to the invention are intended to be embraced therein.

Claims (6)

1. A preparation method of a catalyst for preparing methanol by carbon dioxide hydrogenation is characterized by comprising the following steps:
s1, adding GO into DMF and carrying out ultrasonic treatment for 6h to obtain a GO mixture; weighing zirconium salt, 2 '-bipyridyl-5, 5' -dicarboxylic acid and formic acid, adding the zirconium salt, the 2,2 '-bipyridyl-5, 5' -dicarboxylic acid and the formic acid into the GO mixture, and uniformly stirring to obtain a mixed solution of GO and UiO-bpy, wherein the molar ratio of the zirconium salt to the 2,2 '-bipyridyl-5, 5' -dicarboxylic acid to the formic acid to DMF is 0.106: 0.104: 0.018: 0.145, the added GO accounts for 0.23 to 5 wt percent of the solid phase mass of the UiO-bpy;
s2, reacting the reaction solution which is evenly stirred in S1 at the temperature of 100 ℃ and 160 ℃ for 12-36 h;
s3, after the reaction is finished, washing and drying the collected solid phase by using a mixed solvent of DMF and THF to obtain a solid sample;
s4, dissolving the copper salt solid into THF to obtain a copper salt solution, adding the obtained solid sample into the copper salt solution, fully and uniformly stirring, centrifuging, washing with THF, placing the obtained precipitate into THF, and preserving in an inert atmosphere, wherein the copper salt solid accounts for (25-75) wt% of the mass fraction of the solid sample obtained from S3;
s5, dissolving zinc salt solid into hexane to obtain a zinc salt solution, adding the zinc salt solution into the precipitate obtained in S4 in an inert atmosphere, adding THF, stirring uniformly, centrifuging, washing with THF, and drying to obtain a solid sample, and storing in the inert atmosphere, wherein the zinc salt solid accounts for (25-60) wt% of the mass fraction of the solid sample obtained in S3;
s6, placing the solid sample obtained in the S5 in a reducing atmosphere, and carrying out in-situ reduction at the temperature of 200-260 ℃ to obtain the catalyst for preparing the methanol from the carbon dioxide.
2. The method according to claim 1, wherein the zirconium salt is one of zirconium nitrate, zirconium chloride and zirconium sulfate.
3. The method of claim 1, wherein the copper salt solid is one of copper nitrate, copper chloride dihydrate and copper sulfate.
4. The method for preparing the catalyst for preparing methanol by hydrogenating carbon dioxide according to claim 1, wherein the zinc salt is one of zinc nitrate hexahydrate, diethyl zinc and zinc sulfate.
5. According to the claimsThe preparation method of the catalyst for preparing methanol by carbon dioxide hydrogenation according to claim 1, wherein the reducing atmosphere in S6 is H2Or H2With CO2The mixed gas of (1).
6. A catalyst for preparing methanol by hydrogenating carbon dioxide, which is prepared by the preparation method of any one of claims 1 to 5.
CN202010514932.3A 2020-06-08 2020-06-08 Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof Active CN111514938B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN202010514932.3A CN111514938B (en) 2020-06-08 2020-06-08 Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof
PCT/CN2021/098987 WO2021249403A1 (en) 2020-06-08 2021-06-08 Catalyst for preparing methanol by means of hydrogenation of carbon dioxide, and preparation method therefor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010514932.3A CN111514938B (en) 2020-06-08 2020-06-08 Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof

Publications (2)

Publication Number Publication Date
CN111514938A true CN111514938A (en) 2020-08-11
CN111514938B CN111514938B (en) 2021-12-14

Family

ID=71909979

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010514932.3A Active CN111514938B (en) 2020-06-08 2020-06-08 Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof

Country Status (2)

Country Link
CN (1) CN111514938B (en)
WO (1) WO2021249403A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021249403A1 (en) * 2020-06-08 2021-12-16 中国华能集团清洁能源技术研究院有限公司 Catalyst for preparing methanol by means of hydrogenation of carbon dioxide, and preparation method therefor
CN114099716A (en) * 2021-11-30 2022-03-01 上海交通大学医学院附属第九人民医院 Bimodal imaging compositions and their use in lung nodule localization
CN114160104A (en) * 2021-11-29 2022-03-11 昆岳互联环境技术(江苏)有限公司 Kiln flue gas CO2Trapping and utilizing coupling material and application thereof
CN115646546A (en) * 2022-09-13 2023-01-31 中国石油大学(华东) Preparation method of carbon-based bimetallic site catalytic material for producing formic acid by carbon dioxide hydrogenation

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114908370B (en) * 2022-03-31 2023-11-10 西湖大学 Copper-based CO 2 Preparation method and application of reduced molecular catalyst
CN116422378B (en) * 2023-03-24 2024-04-05 大连理工大学 Cu (copper) alloy 2 O-CuXbpy composite material CO 2 Preparation method and application of photoreduction catalyst

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103736523A (en) * 2014-01-10 2014-04-23 南京工业大学 High-stability metal-organic framework composite material, and preparation method and application thereof
CN105344380A (en) * 2015-12-08 2016-02-24 镇江市高等专科学校 Metal organic frame/graphene carried palladium nano-composite catalyst and preparing method and application thereof
CN106622252A (en) * 2016-11-28 2017-05-10 宁夏大学 Catalyst for production of methanol by CO2 hydrogenation
CN107096536A (en) * 2017-04-26 2017-08-29 山东师范大学 A kind of controllable method for preparing of the monatomic catalyst of base metal
CN111167518A (en) * 2020-01-06 2020-05-19 上海应用技术大学 Catalyst CuZn/UiO-66 for synthesizing methanol by carbon dioxide hydrogenation and preparation method thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10978718B2 (en) * 2017-08-29 2021-04-13 Uchicago Argonne, Llc Carbon dioxide reduction electro catalysts prepared for metal organic frameworks
CN108940254B (en) * 2018-06-27 2021-02-02 天津大学 Preparation method of catalyst for synthesizing methanol by carbon dioxide hydrogenation
CN110170308B (en) * 2019-06-25 2021-04-02 湖南大学 Functionalized zirconium-based metal organic framework/graphene oxide composite material and preparation method and application thereof
CN111514938B (en) * 2020-06-08 2021-12-14 中国华能集团有限公司 Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103736523A (en) * 2014-01-10 2014-04-23 南京工业大学 High-stability metal-organic framework composite material, and preparation method and application thereof
CN105344380A (en) * 2015-12-08 2016-02-24 镇江市高等专科学校 Metal organic frame/graphene carried palladium nano-composite catalyst and preparing method and application thereof
CN106622252A (en) * 2016-11-28 2017-05-10 宁夏大学 Catalyst for production of methanol by CO2 hydrogenation
CN107096536A (en) * 2017-04-26 2017-08-29 山东师范大学 A kind of controllable method for preparing of the monatomic catalyst of base metal
CN111167518A (en) * 2020-01-06 2020-05-19 上海应用技术大学 Catalyst CuZn/UiO-66 for synthesizing methanol by carbon dioxide hydrogenation and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BING AN等: ""Confinement of Ultrasmall Cu/ZnOx Nanoparticles in Metal−Organic Frameworks for Selective Methanol Synthesis from Catalytic Hydrogenation of CO2"", 《J. AM. CHEM. SOC.》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021249403A1 (en) * 2020-06-08 2021-12-16 中国华能集团清洁能源技术研究院有限公司 Catalyst for preparing methanol by means of hydrogenation of carbon dioxide, and preparation method therefor
CN114160104A (en) * 2021-11-29 2022-03-11 昆岳互联环境技术(江苏)有限公司 Kiln flue gas CO2Trapping and utilizing coupling material and application thereof
CN114099716A (en) * 2021-11-30 2022-03-01 上海交通大学医学院附属第九人民医院 Bimodal imaging compositions and their use in lung nodule localization
CN114099716B (en) * 2021-11-30 2023-04-07 上海交通大学医学院附属第九人民医院 Bimodal imaging compositions and their use in lung nodule localization
CN115646546A (en) * 2022-09-13 2023-01-31 中国石油大学(华东) Preparation method of carbon-based bimetallic site catalytic material for producing formic acid by carbon dioxide hydrogenation
CN115646546B (en) * 2022-09-13 2024-04-16 中国石油大学(华东) Preparation method of carbon-based bimetallic site catalytic material for producing formic acid by carbon dioxide hydrogenation

Also Published As

Publication number Publication date
CN111514938B (en) 2021-12-14
WO2021249403A1 (en) 2021-12-16

Similar Documents

Publication Publication Date Title
CN111514938B (en) Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof
CN111889132B (en) Metal oxide-molecular sieve catalyst, and preparation method and application thereof
CN105921148A (en) Catalyst for preparing olefins from saturated alkanes through dehydrogenation and preparing method and application thereof
CN112169799A (en) Method for synthesizing low-carbon olefin by carbon dioxide hydrogenation by iron-based catalyst
CN101966460B (en) Supported catalyst for synthesis of dimethyl carbonate, preparation method and using method thereof
CN112755996A (en) Catalyst for synthesizing methanol by carbon dioxide hydrogenation, preparation method and application
CN107552056B (en) Catalyst for preparing carbon monoxide by carbon dioxide hydrogenation, preparation method and application thereof
CN114829004A (en) Method for preparing Ni-X-based oxide catalyst and application thereof in transfer hydrogenation
CN102500382B (en) Catalyst used in synthesis of methanol and preparation method thereof
CN106607050B (en) The fluid catalyst and preparation method thereof of one-step method from syngas producing light olefins
CN113058613B (en) Zirconium-manganese-zinc composite oxide supported nickel-based catalyst for methane dry gas reforming reaction and preparation and application thereof
CN112169817B (en) Perovskite type composite oxygen carrier and application
CN109701634B (en) Catalyst composition for preparing low-carbon hydrocarbon from synthesis gas and application thereof
CN105582931B (en) Cobalt-based Fischer-Tropsch synthesis catalyst loaded by mixed oxide carrier and preparation method thereof
WO2016180000A1 (en) Two-step ethylene glycol and 1,2-propylene glycol preparation method using cellulose
CN112973761A (en) Graphite phase carbon nitride composite material and preparation method and application thereof
CN109851473B (en) Method for preparing 1,3-propylene glycol by hydrogenolysis of glycerol solution
CN102911693B (en) Fischer-Tropsch synthesis method by employing mixed catalyst
CN111054384B (en) Catalyst for organic liquid hydrogen storage material dehydrogenation and preparation method thereof
CN112374968B (en) Application of supported catalyst in selective hydrogenation reaction of naphthalene derivatives
CN102039133B (en) Fischer-Tropsch synthesized Co-based fluidized bed catalyst and preparation method thereof
CN106423202A (en) Preparation method of rhodium-ruthenium composite catalyst for preparing ethyl alcohol through acetic acid hydrogenation
WO2019183841A1 (en) Composite catalyst, preparation method therefor, and method for preparing ethylene
CN106607049B (en) Catalyst of preparation of low carbon olefines by synthetic gas and preparation method thereof
CN106268815A (en) A kind of loaded nano Co catalysts and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
CB03 Change of inventor or designer information
CB03 Change of inventor or designer information

Inventor after: Wang Xiaolong

Inventor after: Cheng Achao

Inventor after: Xu Shisen

Inventor after: Wang Qi

Inventor after: Gao Shiwang

Inventor after: Xiao Tiancun

Inventor before: Wang Xiaolong

Inventor before: Cheng Achao

Inventor before: Wang Qi

Inventor before: Gao Shiwang

Inventor before: Xiao Tiancun

GR01 Patent grant
GR01 Patent grant