CN109420486A - The ZnZrO of synthesizing methanol by hydrogenating carbon dioxidexSolid solution catalyst and preparation and application - Google Patents

The ZnZrO of synthesizing methanol by hydrogenating carbon dioxidexSolid solution catalyst and preparation and application Download PDF

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CN109420486A
CN109420486A CN201710756830.0A CN201710756830A CN109420486A CN 109420486 A CN109420486 A CN 109420486A CN 201710756830 A CN201710756830 A CN 201710756830A CN 109420486 A CN109420486 A CN 109420486A
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catalyst
znzro
solid solution
carbon dioxide
synthesizing methanol
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李�灿
王集杰
李泽龙
汤驰洲
韩哲
刘海龙
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics 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
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • B01J35/30—
    • 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
    • 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 present invention relates to a kind of ZnZrO for synthesizing methanol by hydrogenating carbon dioxidexSolid solution catalyst, the ZnZrOxSolid solution refers to ZrO2A certain amount of Zr in crystal4+Ion is by Zn2+It is replaced, but is not changed the structure and symmetry of entire crystal.The ZnOZrOxSolid solution catalyst is applied to hydrogenation of carbon dioxide reaction for preparing methanol, in 5MPa, 320 DEG C, and 24000h–1Under the conditions of, can make methanol selectivity is more than 88%, and keeps 10% or more conversion per pass.Catalyst the advantages that there are also high temperature resistants, sulfur resistive.

Description

The ZnZrO of synthesizing methanol by hydrogenating carbon dioxidexSolid solution catalyst and preparation and application
Technical field
The invention belongs to catalyst fields, and in particular to a kind of ZnZrO for synthesizing methanol by hydrogenating carbon dioxidexSolid solution Body catalyst and its preparation method and application.
Background technique
Catalyzed conversion CO2For fuel, chemicals, it can not only alleviate CO2Problem is brought, can also be obtained useful to the mankind Substance is the route of sustainable development.It is generated electricity using renewable energy, such as photovoltaic, photo-thermal, wind energy, nuclear energy, water energy, in turn It is electrolysed aquatic products hydrogen, with CO2Hydrogen addition technology catalyzes and synthesizes fuel and chemicals, is most typical catalyzed conversion CO2Example.
Methanol is one of most important raw material of industry, itself is also good fuel, utilizes CO2Synthesizing methanol by hydrogenating is real The existing above-mentioned most effective strategy of route.For CO2The catalyst research of synthesizing methanol by hydrogenating it is most be Cu base catalyst, research Most of is by CuZnO (ZrO2) it is supported on Al2O3、ZrO2、SiO2、TiO2On equal carriers, and add into catalyst Na, K, The metals such as Ce, Cs, Ca, Zr, La, Mn, Ti, Th, Mg, Ba are modified [Handbook of Heterogeneous as auxiliary agent Catalysis.Wiley,2008,2920].It is best the result is that Zr or Ti promoted from the point of view of current result of study CuZnAl catalyst (petrochemical industry, 2009,38 (5), 482；Chemistry of fuel journal, 2011,39 (12), 912).Grinding in recent years The performance for focusing primarily upon catalyst preparation mode to improve catalyst is studied carefully, such as Dalian University of Technology patent CN 101513615 A, 103263926 A of Shanxi coalification institute patent CN, 104383928 A of Rake Science and Technology Ltd. patent CN；Shanghai Hua Yigong Take charge of 102580750 A of patent CN, 102240553 A of Rake Science and Technology Ltd. patent CN, Xiamen University patent CN 101786001 A；Or surfactant is added in precipitated liquid salting liquid in advance, play peptizaiton, such as the research of Shanghai height 103272607 A of institute patent CN.These researchs all improve to some extent to the Cu base catalyst of synthesizing methanol by hydrogenating carbon dioxide, But methanol selectivity is also lower (being generally not more than 60%) on Cu base catalyst.In addition, hydrogenation of carbon dioxide methanol is heat release It reacts, a large amount of heat can be released in reaction process, and Cu base catalyst heat resistance is poor, easy-sintering.Also there is patent report recently It is methanol with two reactor chemical recycling of carbon dioxide, this method is by CO2It first passes through Reversed Water-gas Shift and is transformed to CO, Jin Erjin Row CO add hydrogen can highly selective generation methanol (105622344 A of CN), but the matching of two reaction pressures be need to overcome it is tired Difficulty or two reactors respectively carry out two reactions and directly increase operating cost again.Carbon dioxide one-step method direct hydrogenation Gao Xuan Selecting property synthesizing methanol is most effective process, but lacks efficient catalyst at present, and the present invention develops a kind of for CO2Add hydrogen The ZnZrO of synthesizing methanolxSolid solution catalyst, which can effectively inhibit reverse water-gas-shift reaction, to improve first The selectivity of alcohol.The catalyst also have many advantages, such as heat resistance it is strong, it is anti-sintering, stability it is good.
Summary of the invention
The present invention provides a kind of ZnZrO for synthesizing methanol by hydrogenating carbon dioxidexSolid solution catalyst and its preparation Methods and applications.Wherein 5%≤Zn/ (Zn+Zr)≤38% (catalyst structure feature is shown in Fig. 1).X represents the ligancy of oxygen, leads to Often between 2.8-3, there is individual ZnO to be precipitated as Zn/ (Zn+Zr) > 50%.
The ZnOZrO for synthesizing methanol by hydrogenating carbon dioxidexThe preparation method of solid solution catalyst, feature It is to include the following steps:
(1) Zn, Zr saline solution for preparing certain mol proportion, prepare the precipitating reagent aqueous solution of same concentrations, the two is in water It is precipitated in solution.Coprecipitation mode includes that precipitating reagent aqueous solution instills metal salt solution, metal salt solution instills precipitating reagent water Solution and the two co-precipitation.Zn, Zr salt used is one of nitrate, acetate, halide, sulfate or several Kind；Precipitating reagent used is ammonium hydroxide, ammonium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, saleratus, sodium hydroxide and hydroxide One or more of potassium.
(2) gained precipitating drying, roasting, obtain ZnZrOxSolid solution catalyst.
The activity rating that catalyst reacts synthesizing methanol by hydrogenating carbon dioxide is in pressurization static bed continuous flow reactor- It is carried out in GC combined system.It is activated with the hydrogen of pure hydrogen or nitrogen, argon gas or nitrogen, argon-dilution in 200~400 DEG C before reaction 0.5~12h.The condition of synthesizing methanol by hydrogenating carbon dioxide are as follows: 1~10MPa of reaction pressure, reaction temperature are 240~400 DEG C, Air speed is 3000~40000h–1, n (H2):n(CO2) molar ratio=1~8.Reaction end gas is unloaded through counterbalance valve to normal pressure, 150 DEG C of guarantors It is sampled under temperature through gas-chromatography ten-way valve, by the thermal conductivity detector (TCD) (TCD) of AgilentGC-7890 Type B gas chromatograph Combine with hydrogen flame detector (FID) and makees on-line analysis.The former chromatographic column is that 5A molecular sieve and Propark Q are combined (Agilent), Column length 3m, uses H2Make carrier gas, work at 85 DEG C, is used for separation detection CO2,Ar,CO；The latter's chromatographic column is TG-BOND Q capillary Tubing string (the silent winged generation that of match), specification is 30m × 0.32mm × 10 μm, uses N2Make carrier gas, is used for separation detection lower carbon number hydrocarbons, alcohol.CO2 Conversion ratio and the C based selective for generating the carbonaceous products such as CO, alcohol, hydrocarbon and space-time yield are by the calculating of C base normalization method.
Catalyst of the present invention can effectively improve the selectivity of hydrogenation of carbon dioxide methanol, optimum operating temperature It is 300~350 DEG C, is resistant to 400 DEG C of high temperature, anti-sintering and stability is good.In 5MPa, 320 DEG C, 24000h–1Under the conditions of, first can be made Alcohol is selectively more than 88%, and the conversion per pass of 10% or more holding.There are also high temperature resistant, sulfur resistive, stability are good for the catalyst The advantages that (see Fig. 2).
Detailed description of the invention
Fig. 1 is ZnZrOxSolid solution catalyst XRD spectra.
Fig. 2 is ZnZrOxHigh temperature resistant, the sulfur resistive of solid solution catalyst test (corresponding embodiment 4) figure, reaction condition: 2MPa, 320 DEG C, GHVS=24000mL/ (g h).
Specific embodiment
Embodiment 1
Weigh 15.0mmol Zr (NO3)4·5H2O is configured to 100mL aqueous solution and is placed in 500mL beaker, weighs 33.0mmol(NH4)2CO3It is configured to 100mL aqueous solution.The zirconium nitrate that prepared sal volatile is added dropwise to 70 DEG C is water-soluble In liquid, rate of addition about 3mL/min, mixing speed 600r/min, to (NH4)2CO3Solution consumption is complete, obtains mother liquor of precipitation of ammonium and in 70 Aging 2h at DEG C, cooling, natural filtration is washed with deionized 3 times, filters, and gained filter cake is dried in 60 DEG C, 500 DEG C of air Middle roasting 3h obtains catalyst oxidation state presoma, is denoted as ZrO2.Tabletting is crushed, and 40~80 mesh of screening are for evaluating.
It weighs the catalyst that 0.2g has been screened and is packed into the reaction tube that internal diameter is 6mm, in normal pressure, pure H2In 300 DEG C of reductase 12 h, Flow velocity is 30mL/min, imports unstripped gas n (H later2):n(CO2)=3, reaction is in 2MPa, and 300 DEG C (or 5MPa, 320 DEG C), GHSV=24000h–1) under the conditions of carry out.Evaluating catalyst the results are shown in Table 1.
Embodiment 2
Metal salt used in catalyst preparation is 0.8mmol Zn (NO3)2·6H2O、14.3mmol Zr(NO3)4·5H2O, institute It is 32.2mmol (NH with precipitating reagent4)2CO3, gained catalyst is denoted as 5%ZnZrOx.Other preparations and evaluation procedure and embodiment 1 is identical, and evaluating catalyst the results are shown in Table 1.
Embodiment 3
Metal salt used in catalyst preparation is 1.5mmol Zn (NO3)2·6H2O、13.5mmol Zr(NO3)4·5H2O, institute It is 31.4mmol (NH with precipitating reagent4)2CO3, gained catalyst is denoted as 10%ZnZrOx.Other preparations and evaluation procedure and implementation Example 1 is identical, and evaluating catalyst the results are shown in Table 1.
Embodiment 4
Metal salt used in catalyst preparation is 2.0mmol Zn (NO3)2·6H2O、13.0mmol Zr(NO3)4·5H2O, institute It is 32.2mmol (NH with precipitating reagent4)2CO3, gained catalyst is denoted as 13%ZnZrOx.Evaluating catalyst is respectively in 2MPa, and 300 DEG C, 2MPa, 320 DEG C, 5MPa carry out at 320 DEG C, other preparations are same as Example 1 with evaluation procedure, the results are shown in Table 1.Catalysis The high temperature resistant of agent the experimental results showed that, reaction temperature is risen to 400 DEG C and is down to 320 DEG C of reaction temperature again, catalyst performance is lossless It loses.In addition, 50ppm SO is added in reaction atmosphere2/ Ar or H2S/Ar, sustained response 12 hours, the catalyst was existing without inactivation As showing certain resistance to SO_2.The results are shown in attached figure 2.
Embodiment 5
Metal salt used in catalyst preparation is 2.6mmol Zn (NO3)2·6H2O、12.4mmol Zr(NO3)4·5H2O, institute It is 30.2mmol (NH with precipitating reagent4)2CO3, gained catalyst is denoted as 17%ZnZrOx.Other preparations and evaluation procedure and implementation Example 1 is identical, and evaluating catalyst the results are shown in Table 1.
Embodiment 6
Metal salt used in catalyst preparation is 3.0mmol Zn (NO3)2·6H2O、12.0mmol Zr(NO3)4·5H2O, institute It is 29.7mmol (NH with precipitating reagent4)2CO3, gained catalyst is denoted as 20%ZnZrOx.Other preparations and evaluation procedure and implementation Example 1 is identical, and evaluating catalyst the results are shown in Table 1.
Embodiment 7
Metal salt used in catalyst preparation is 3.8mmol Zn (NO3)2·6H2O、11.3mmol Zr(NO3)4·5H2O, institute It is 28.9mmol (NH with precipitating reagent4)2CO3, gained catalyst is denoted as 20%ZnZrOx.Other preparations and evaluation procedure and implementation Example 1 is identical, and evaluating catalyst the results are shown in Table 1.
Embodiment 8
Metal salt used in catalyst preparation is 5.0mmol Zn (NO3)2·6H2O、10.1mmol Zr(NO3)4·5H2O, institute It is 27.6mmol (NH with precipitating reagent4)2CO3, gained catalyst is denoted as 33%ZnZrOx.Other preparations and evaluation procedure and implementation Example 1 is identical, and evaluating catalyst the results are shown in Table 1.
Embodiment 9
Metal salt used in catalyst preparation is 5.7mmol Zn (NO3)2·6H2O、9.3mmol Zr(NO3)4·5H2O, institute It is 26.7mmol (NH with precipitating reagent4)2CO3, gained catalyst is denoted as 38%ZnZrOx.Other preparations and evaluation procedure and implementation Example 1 is identical, and evaluating catalyst the results are shown in Table 1.
Embodiment 10
Metal salt used in catalyst preparation is 7.5mmol Zn (NO3)2·6H2O、7.5mmol Zr(NO3)4·5H2O, institute It is 24.8mmol (NH with precipitating reagent4)2CO3, gained catalyst is denoted as 50%ZnZrOx.Other preparations and evaluation procedure and implementation Example 1 is identical, and evaluating catalyst the results are shown in Table 10.
Embodiment 11
Metal salt used in catalyst preparation is 10.1mmol Zn (NO3)2·6H2O、5.0mmol Zr(NO3)4·5H2O, institute It is 21.9mmol (NH with precipitating reagent4)2CO3, gained catalyst is denoted as 67%ZnZrOx.Other preparations and evaluation procedure and implementation Example 1 is identical, and evaluating catalyst the results are shown in Table 1.
Embodiment 12
Metal salt used in catalyst preparation is 12.0mmol Zn (NO3)2·6H2O、3.0mmol Zr(NO3)4·5H2O, institute It is 19.8mmol (NH with precipitating reagent4)2CO3, gained catalyst is denoted as 80%ZnZrOx.Other preparations and evaluation procedure and implementation Example 1 is identical, and evaluating catalyst the results are shown in Table 1.
Embodiment 13
Metal salt used in catalyst preparation is 15.0mmol Zn (NO3)2·6H2O, precipitating reagent used are 16.5mmol (NH4)2CO3, gained catalyst is denoted as ZnO.Other preparations are same as Example 1 with evaluation procedure, and evaluating catalyst the results are shown in Table 1。
Embodiment 14 (comparative example)
Mechanical mixing prepares 13%ZnZrOx(M), M=Mixed.Take 10mmol Zn (NO3)2·6H2O 12mmol (NH4)2CO3Precipitating, gained precipitating be filtered, washed, dry in 500 DEG C of air roast 3h obtain ZnO.Take 20mmol Zn (NO3)2·6H2O 40mmol (NH4)2CO3Precipitating, gained precipitating be filtered, washed, dry in 500 DEG C of air roast 3h obtain ZrO2.Take above-mentioned 1.3mmol ZnO and 8.7mmol ZrO2It is 13%ZnZrO through catalyst obtained by mechanical mixturex(M).Catalyst Evaluation procedure is same as Example 1, and evaluating catalyst the results are shown in Table 1.
Embodiment 15 (comparative example)
Infusion process prepares 13%ZnZrOx(S), S=Supported.Take 20mmol Zn (NO3)2·6H2O 40mmol (NH4)2CO3Precipitating, gained precipitating be filtered, washed, dry in 500 DEG C of air roast 3h obtain ZrO2.Weigh 1.3mmol Zn (NO3)2·6H2O is dissolved in 30mL deionized water, takes above-mentioned 8.7mmol ZrO2It is added in zinc nitrate aqueous solution, ultrasonic 10min, It stirs and is evaporated in 110 DEG C of oil baths, gained catalyst is 13%ZnZrOx(S).Evaluating catalyst step is same as Example 1, Evaluating catalyst the results are shown in Table 1.
1 embodiment of table and comparative example evaluating catalyst result
GHVS=24000mL/ (g h)
Illustrate: in hydrogenation of carbon dioxide reaction for preparing methanol while improving carbon dioxide conversion and methanol selectivity is great chooses War property, from embodiment 4 with comparative example 14,15 as can be seen that solid solution structure catalyst compared with mechanical mixture and support type Catalyst is with the obvious advantage in terms of improving carbon dioxide conversion and methanol selectivity；It can also be seen that performance is more excellent from table Its solutes content of solid solution catalyst be 10%≤Zn/ (Zn+Zr)≤33%.

Claims (10)

1. a kind of ZnZrO of synthesizing methanol by hydrogenating carbon dioxidexSolid solution catalyst, it is characterised in that: as 5%≤Zn/ (Zn+ Zr)≤38% there is solid solution structure (by mol), wherein ZnO is solute, ZrO2Solvent.
2. ZnZrO according to claim 1xSolid solution catalyst is applied to synthesizing methanol by hydrogenating carbon dioxide and reacts When, by mol, Zn/ (Zn+Zr) preferably 10%~33%.
3. a kind of ZnZrO described in claim 1xThe preparation method of solid solution catalyst, which is characterized in that use precipitation method packet It includes following steps: preparing Zn, Zr metal salt mixed aqueous solution of certain mol proportion, metal ion total concentration is 0.01~2mol/ L；Prepare the precipitating reagent aqueous solution of same concentrations；The two is precipitated in 0~90 DEG C of water, controls pH=6~10；Coprecipitation mode Metal salt solution is instilled including precipitating reagent aqueous solution, metal salt solution instills precipitating reagent aqueous solution or both co-precipitation；Institute Must be deposited in 60~130 DEG C drying 4~for 24 hours, 400~800 DEG C roasting 2~for 24 hours, obtain ZnZrOxSolid solution catalyst.
4. the preparation method of solid solution catalyst according to claim 3, it is characterised in that: Zn salt used is nitric acid One of salt, acetate, halide, sulfate or two kinds or more；
Precipitating reagent used is ammonium hydroxide, ammonium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, saleratus, sodium hydroxide and hydrogen-oxygen Change one of potassium or two kinds or more；
Zr salt used is nitrate, acetate, halide, sulfate, zirconyl nitrate, basic zirconium chloride, one in zirconium iso-propoxide Kind is two or more.
5. ZnZrO as claimed in claim 3xThe preparation method of solid solution catalyst, it is characterised in that roasting include static roasting or Flow atmosphere roasting, one of calcination atmosphere available air, oxygen, nitrogen or two kinds or more.
6. ZnZrO as claimed in claim 1 or 2xSolid solution catalyst is applied in synthesizing methanol by hydrogenating carbon dioxide.
7. according to application described in right 6, which comprises the steps of: the reaction of synthesizing methanol by hydrogenating carbon dioxide It is carried out on pressurization static bed continuous flow reactor, the condition of synthesizing methanol by hydrogenating carbon dioxide are as follows: raw gas pressure 1~ 10MPa, reaction temperature are 240~400 DEG C, and air speed is 3000~40000h–1, n (H2):n(CO2) molar ratio=1~8.
8. application according to claim 6 or 7, it is characterised in that: catalyst carries out the activation of catalyst before application, living Change condition are as follows: with one of pure hydrogen, nitrogen, argon gas or two kinds or more in 200~400 DEG C of 0.5~12h of activation.
9. application according to claim 7, it is characterised in that: the metal oxide solid solution catalyst is applied to two The reaction of carbonoxide preparing methanol by hydrogenation, reaction pressure 5MPa, 320 DEG C of reaction temperature, air speed 24000h–1, unstripped gas n (H2):n (CO2)=3.
10. application according to claim 7, it is characterised in that: the tabletting of gained catalyst, broken, screening 20~80 mesh use In evaluation.
CN201710756830.0A 2017-08-29 2017-08-29 The ZnZrO of synthesizing methanol by hydrogenating carbon dioxidexSolid solution catalyst and preparation and application Pending CN109420486A (en)

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CN110743609A (en) * 2019-11-21 2020-02-04 厦门大学 Combined catalyst and preparation method thereof, and method for preparing dimethylbenzene by carbon dioxide hydrogenation coupling toluene alkylation
CN111054323A (en) * 2020-02-25 2020-04-24 贵州大学 InZnOx solid solution structure catalyst and preparation method thereof
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CN110743609A (en) * 2019-11-21 2020-02-04 厦门大学 Combined catalyst and preparation method thereof, and method for preparing dimethylbenzene by carbon dioxide hydrogenation coupling toluene alkylation
CN111054323A (en) * 2020-02-25 2020-04-24 贵州大学 InZnOx solid solution structure catalyst and preparation method thereof
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CN111841524A (en) * 2020-08-04 2020-10-30 盐城工学院 Preparation of mesoporous ZnO-ZrO2Method for preparing solid solution catalyst and application thereof
CN113058583A (en) * 2021-03-26 2021-07-02 兰州大学 GaZrOxPreparation method and application of bimetallic oxide solid solution catalyst
CN113058583B (en) * 2021-03-26 2023-02-28 兰州大学 GaZrO x Preparation method and application of bimetallic oxide solid solution catalyst
CN113797939A (en) * 2021-08-31 2021-12-17 宁夏大学 ZnZrOx/MoS2Composite catalyst, preparation and application thereof
CN113797939B (en) * 2021-08-31 2024-01-05 宁夏大学 ZnZrO (zinc ZrO-rich alloy) x /MoS 2 Composite catalyst, preparation and application thereof
CN115770563B (en) * 2021-09-06 2024-02-02 中国科学院大连化学物理研究所 Bimetallic catalyst for high-temperature methanol steam reforming hydrogen production and preparation method and application thereof
CN115770563A (en) * 2021-09-06 2023-03-10 中国科学院大连化学物理研究所 Bimetallic catalyst for hydrogen production by high-temperature methanol steam reforming and preparation method and application thereof
CN113893843A (en) * 2021-11-04 2022-01-07 中国船舶重工集团公司第七一九研究所 For CO2Zn for preparing methanol by catalytic hydrogenation1Zr2O3Process for preparing catalyst
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CN116328773A (en) * 2021-12-15 2023-06-27 中国科学院大连化学物理研究所 Catalyst for synthesizing liquid state sunlight methanol by carbon dioxide hydrogenation, preparation method and application thereof
CN114433059A (en) * 2022-01-20 2022-05-06 上海工程技术大学 CO2Catalyst for synthesizing low-carbon olefin compound by hydrogenation, preparation and application thereof
CN115318298A (en) * 2022-08-01 2022-11-11 天津大学 Copper-based ternary catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method and application thereof
CN115845830A (en) * 2022-08-30 2023-03-28 宁夏大学 Preparation and application of solid solution In-ZnZrOx catalyst doped with In element

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