CN109999833A - A kind of catalyst and preparation method thereof for synthesizing methanol by hydrogenating carbon dioxide - Google Patents
A kind of catalyst and preparation method thereof for synthesizing methanol by hydrogenating carbon dioxide Download PDFInfo
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- CN109999833A CN109999833A CN201910374508.0A CN201910374508A CN109999833A CN 109999833 A CN109999833 A CN 109999833A CN 201910374508 A CN201910374508 A CN 201910374508A CN 109999833 A CN109999833 A CN 109999833A
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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
- B01J23/89—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
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- 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
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- 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 catalyst and preparation method thereof that the present invention provides a kind of for synthesizing methanol by hydrogenating carbon dioxide, the catalyst carries Cu-ZrO2 catalyst by precious metals pd and obtains, the preparation method comprises the following steps: preparing Cu/ZrO2 catalyst first with sol-gel method, precious metals pd is then loaded to by Cu/ZrO2 catalyst preparation by infusion process and goes out double activated component Pd-Cu/ZrO2 catalyst.The catalyst that the present invention obtains has many advantages, such as that large specific surface area, catalytic activity are high, carbon dioxide conversion is high, methanol selectivity is high, and preparation method is simply, rapidly and efficiently.
Description
Technical field
The invention belongs to chemical industry catalysis technical fields, and in particular to a kind of catalysis for synthesizing methanol by hydrogenating carbon dioxide
Agent and preparation method thereof.
Background technique
In recent years, as the rapid growth of economic development, fossil fuel rapidly deplete, CO2 emissions are also more next
It is bigger, caused by " greenhouse effects " and weather variation, the mankind and natural environment are posed a serious threat, are compromised
The benign development of social economy causes the special attention of domestic and foreign scholars, therefore how to reduce CO2Discharge and realization are to it
The utilization of recycling becomes one of the difficult point that current researcher needs to solve.In recent years, for the emission reduction of carbon dioxide,
Recycling and activation utilization, various countries it is unremitting always seek effective method and approach, and achieve some breakthroughs.By CO2Add hydrogen
The organic matters such as methanol, methane and dimethyl ether are converted to, are all the effective and reasonable approach of current reduction carbon dioxide, and achieve
Certain effect.
Methanol is used as the alternative fuel of gasoline as a kind of ideal clean fuel, and when burning generates carbon dioxide and water
Steam, and generated almost without the solid particle for forming smog, the pernicious gas discharged is less.Methanol is a kind of very heavy
The Organic Ingredients wanted, can also produce methane chloride, terephthalic acid (TPA) dioctyl phthalate, methyl acrylate etc. as synthesis material has
Chemical machine product；The organic synthesis intermediates such as formic acid and acetic acid can also be produced by the carbonylation of methanol, they be manufacture fuel,
The main raw material such as explosive, pesticide.
Carbon dioxide discharge-reduction and resource utilization are related to the sustainable development of the mankind, and hydrogenation of carbon dioxide methanol quilt
It is considered one of the Land use systems of most Research Prospects.Currently, the catalyst for the reaction system is mainly cupper-based catalyst
Agent, however there is the disadvantages of low activity, poor selectivity, easy-sintering in copper-based catalysts, since synthesizing methanol by hydrogenating carbon dioxide is anti-
The Thermodynamics limitation answered, titanium dioxide charcoal percent conversion is difficult breakthrough 20% at present, and research worker is often from the group of catalyst
At come the activity of improving catalyst, loads a small amount of noble metal and form alloy catalyst, Lai Tigao catalytic activity and selectivity.But
It is currently, the catalyst for hydrogenation of carbon dioxide methanol is not yet mature, realization industrialization still has great difficulty.
Summary of the invention
To solve the above problems, the present invention provides a kind of, and the hydrogenation of carbon dioxide that is used for high activity and stability closes
At the catalyst and preparation method thereof of methanol.The catalyst that the present invention obtains is high with catalytic activity, carbon dioxide conversion is high,
The advantages that methanol selectivity is high.
To achieve the above object, first technical solution that the present invention uses are as follows: one kind is synthesized for hydrogenation of carbon dioxide
The catalyst of methanol carries Cu-ZrO by precious metals pd2Catalyst obtains.
A kind of second technical solution that the present invention uses are as follows: system of the catalyst for synthesizing methanol by hydrogenating carbon dioxide
Preparation Method, which comprises the following steps:
(1) copper nitrate and zirconium nitrate are mixed and is dissolved in deionized water, delay aqueous citric acid solution under the action of magnetic agitation
Slowly it is added drop-wise in nitrate mixed solution, obtains uniformly mixed sol solution；
(2) sol solution keeps the evaporation of sol solution aqueous solvent under magnetic agitation effect, and stirring is fixed to glassy nothing is obtained
Type product；
(3) product obtained in (2) is moved in vacuum oven, is dried, obtains gelatinous catalyst precursor；
(4) gel catalyst precursor obtained in (3) is put into tube furnace and carries out high-temperature roasting, temperature programming is set,
It keeps the temperature, is ground after cooling, compression molding crosses 40~80 meshes and obtains catalyst Precursors under maturing temperature.
Further, the metallic atom molar ratio of copper nitrate and zirconium nitrate is 1:(1 ~ 8 in the step (1)), metal is former
Sub mole summation and citric acid molar ratio are 1:(1 ~ 1.5).
Further, the metallic atom molar ratio of the copper nitrate and zirconium nitrate is 1:1,1:2,1:4,1:8.
Further, step (1) the magnetic agitation temperature control is between 75 DEG C ~ 95 DEG C.
Further, step (2) the magnetic agitation temperature control is between 75 DEG C ~ 95 DEG C.
Further, it is that for 24 hours, being dried temperature is 80~120 DEG C that the time is dried in the step (3).
Further, maturing temperature is 350 DEG C ~ 500 DEG C in the step (4), soaking time 4h.
The invention has the following advantages over the prior art:
The present invention uses sol-gel method to prepare Cu/ZrO first2Catalyst, control metallic atom molar ratio are Cu:Zr=1:
(1 ~ 8), by regulate and control metallic copper zirconium molar ratio, probe into influence of the metallic copper zirconium molar ratio to catalytic activity, develop activity compared with
Good Cu/ZrO2Then precious metals pd is loaded to Cu/ZrO by infusion process by catalyst2Pd-Cu/ is prepared on catalyst
ZrO2Catalyst, the obtained Pd-Cu/ZrO of the present invention2The catalytic activity of catalyst is high, has preferable methanol selectivity.
Detailed description of the invention
Fig. 1 is the XRD spectrum of the catalyst for synthesizing methanol by hydrogenating carbon dioxide of different Cu zirconium molar ratio preparation.
Specific embodiment
Combined with specific embodiments below and comparative example the present invention will be further described.According to following embodiments, Ke Yigeng
The good understanding present invention.However, as it will be easily appreciated by one skilled in the art that specific material proportion, work described in embodiment
Skill condition and its result are merely to illustrate the present invention, without that should will not limit this hair described in detail in claims
It is bright.
The present invention uses sol-gel method to prepare Cu/ZrO first2Catalyst, control metallic atom molar ratio are Cu:
Zr=1:(1 ~ 8), it is respectively 1:1,1:2,1:4,1:8 by regulating and controlling metallic copper zirconium molar ratio, probes into metallic copper zirconium molar ratio to urging
Change active influence, develops the preferable Cu/ZrO of activity2Then precious metals pd is loaded to Cu/ by infusion process by catalyst
ZrO2Pd-Cu/ZrO is prepared on catalyst2Catalyst, specific preparation step are as follows:
(1) Pd (C of 0.013g is weighed2H3O2)2, it is dissolved in acetone soln, ultrasound 10 minutes；
(2) palladium acetate solution is added drop-wise to the 0.6g Cu/ZrO prepared2On catalyst, stand for 24 hours；
(3) solid after standing, which moves in vacuum oven, to be dried for 24 hours, and drying temperature is 80~120 DEG C, is obtained
Pd-Cu/ZrO2Gelatinous catalyst precursor；
(4) Pd-Cu/ZrO that will be obtained2Catalyst precursor, which is put into tube furnace, carries out high-temperature roasting, and maturing temperature is 350 DEG C
Between ~ 500 DEG C, and temperature programming is set, is kept the temperature under maturing temperature, obtains Pd-Cu/ZrO2Catalyst.
The Cu/ZrO that following comparative example 2-5 is prepared2The corresponding metallic copper zirconium molar ratio of catalyst is respectively 1:1,1:
2,1:4,1:8, what comparative example 1 obtained is free from the ZrO of Cu2Catalyst, embodiment 1 are in comparative example 1-5 active testing data
On the basis of select the optimal metallic copper zirconium molar ratio 1:2 of activity to carry out precious metals pd to carry Cu/ZrO2The sheet that catalyst obtains
The Pd-Cu/ZrO of invention2Catalyst still taking the above-mentioned ideal embodiment according to the present invention as inspiration, passes through above-mentioned explanation
Content, relevant staff completely can without departing from the scope of the technological thought of the present invention', carry out multiplicity change and
Modification.The technical scope of the present invention is not limited to the contents of the specification, it is necessary to according to scope of the claims come really
Its fixed technical scope.
The ZrO that the present invention also obtains following comparative example and embodiment2Catalyst, Cu/ZrO2Catalyst, Pd-Cu/ZrO2
Catalyst structure is characterized.
Comparative example 1:
(1) pure zirconium oxide is prepared.Weigh Zr (NO3)4·5H2O 1.07g is dissolved in deionization, C6H8O7·H2O 3.9g is dissolved in
In deionized water；
(2) under 90 DEG C of reaction temperature, citric acid solution is moved in constant pressure funnel, citric acid is slowly dropped to zirconium nitrate
Solution in, while carrying out magnetic agitation, form sol solution after titration, continuation is stirred at 90 DEG C, and sol form is molten
Liquid is stirred to glassy unformed product；
(3) drying for 24 hours, obtains spawn ZrO in 120 DEG C of vacuum oven2Catalyst precursor；
(4) will it is dry after in gained catalyst precursor merging tube furnace, temperature programming is set, with 5 DEG C/min of speed from room
Temperature rise roasts 4h, grinds after cooling, compression molding crosses 40~80 meshes, obtains ZrO to 350 DEG C2Catalyst sample is denoted as
ZrO2。
Comparative example 2
(1) Cu/ZrO is prepared2Catalyst.Weigh Cu (NO3)2·3H2O 0.60g and Zr (NO3)4·5H2O 1.07g be dissolved in from
In son, C6H8O7·H2O 1.26g is dissolved in deionized water；
(2) under 90 DEG C of reaction temperature, citric acid solution is moved in constant pressure funnel, citric acid is slowly dropped to zirconium nitrate
Solution in, while carrying out magnetic agitation, form sol solution after titration, continuation is stirred at 90 DEG C, and sol form is molten
Liquid is stirred to glassy unformed product；
(3) drying for 24 hours, obtains spawn Cu/ZrO in 110 DEG C of vacuum oven2Catalyst precursor；
(4) will it is dry after gained catalyst precursor in merging tube furnace, temperature programming is set, with 5 DEG C/min of speed from
Room temperature is raised to 350 DEG C, roasts 4h, grinds after cooling, compression molding crosses 40~80 meshes, obtains Cu/ZrO2Catalyst sample, note
For Cu/Zr 1/1.
Comparative example 3
(1) Cu/ZrO is prepared2Catalyst.Weigh Cu (NO3)2·3H2O 0.60g and Zr (NO3)4·5H2O 2.15g be dissolved in from
In son, C6H8O7·H2O 1.89g is dissolved in deionized water；
(2) under 75 DEG C of reaction temperature, citric acid solution is moved in constant pressure funnel, citric acid is slowly dropped to zirconium nitrate
Solution in, while carrying out magnetic agitation, form sol solution after titration, continuation is stirred at 90 DEG C, and sol form is molten
Liquid is stirred to glassy unformed product；
(3) drying for 24 hours, obtains spawn Cu/ZrO in 90 DEG C of vacuum oven2Catalyst precursor；
(4) will it is dry after in resulting catalyst precursor merging tube furnace, temperature programming is set, with 5 DEG C/min of speed from
Room temperature is raised to 450 DEG C, roasts 4h, grinds after cooling, compression molding crosses 40~80 meshes, obtains Cu/ZrO2Catalyst sample, note
For Cu/Zr 1/2.
Comparative example 4
(1) Cu/ZrO is prepared2Catalyst.Weigh Cu (NO3)2·3H2O 0.60g and Zr (NO3)4·5H2O 4.29g be dissolved in from
In son, C6H8O7·H2O 3.15g is dissolved in deionized water；
(2) under 90 DEG C of reaction temperature, citric acid solution is moved in constant pressure funnel, citric acid is slowly dropped to zirconium nitrate
Solution in, while carrying out magnetic agitation, form sol solution after titration, continuation is stirred at 90 DEG C, and sol form is molten
Liquid is stirred to glassy unformed product；
(3) drying for 24 hours, obtains spawn Cu/ZrO in 100 DEG C of vacuum oven2Catalyst precursor；
(4) will it is dry after in resulting catalyst precursor merging tube furnace, temperature programming is set, with 5 DEG C/min of speed from
Room temperature is raised to 500 DEG C, roasts 4h, grinds after cooling, compression molding crosses 40~80 meshes, obtains Cu/ZrO2Catalyst sample, note
For Cu/Zr 1/4.
Comparative example 5
(1) Cu/ZrO is prepared2Catalyst.Weigh Cu (NO3)2·3H2O 0.60g and Zr (NO3)4·5H2O 8.59g be dissolved in from
In son, C6H8O7·H2O 5.67g is dissolved in deionized water；
(2) under 90 DEG C of reaction temperature, citric acid solution is moved in constant pressure funnel, citric acid is slowly dropped to zirconium nitrate
Solution in, while carrying out magnetic agitation, form sol solution after titration, continuation is stirred at 90 DEG C, and sol form is molten
Liquid is stirred to glassy unformed product；
(3) glassy unformed product is moved to drying in 110 DEG C of vacuum oven and for 24 hours, obtains spawn Cu/ZrO2
Catalyst precursor；
(4) will it is dry after in resulting catalyst precursor merging tube furnace, temperature programming is set, with 5 DEG C/min of speed from
Room temperature is raised to 350 DEG C, roasts 4h, grinds after cooling, compression molding crosses 40~80 meshes, obtains Cu/ZrO2Catalyst sample, note
For Cu/Zr 1/8.
Embodiment 1
(1) Pd-Cu/ZrO is prepared2Catalyst.Weigh Cu/ZrO2Catalyst 0.6g and palladium acetate 0.013g, palladium acetate is dissolved in
In acetone soln, ultrasound 10 minutes；
(2) palladium acetate solution is added drop-wise to Cu/ZrO2On catalyst, stand for 24 hours；
(3) solid after standing is moved in 110 DEG C of vacuum oven and is dried for 24 hours, obtains Pd-Cu/ZrO2Catalyst precursor；
(4) after dry in gained catalyst precursor merging tube furnace, temperature programming is set, with 5 DEG C/min of speed from room temperature
350 DEG C are raised to, 4h is roasted, is ground after cooling, compression molding crosses 40~80 meshes, obtains Pd-Cu/ZrO of the invention2Catalyst
Sample is denoted as Pd-Cu/Zr.
Test example 1
This test example is to Pd-Cu/ZrO made from the embodiment of the present invention 12Cu/ZrO made from catalyst and comparative example 1-52Catalysis
Agent carries out active testing, and specific test method and result are as follows:
The active testing of above-mentioned catalyst carries out (stainless steel reaction bore 10mm), Catalyst packing on fixed bed reactors
Amount is 0.5g, is mixed with 0.5g quartz sand, before catalyst reaction, in H2/N2Normal pressure is living in the gas that volume ratio is 10%~50%
Change 4h.Reduction temperature (270 DEG C) is slightly above reaction temperature, when being cooled to 250 DEG C of reaction temperature, is passed through H2:CO2:N2Volume ratio
The gaseous mixture of=69:23:8, reaction pressure 2MPa.Product is analyzed with gas-chromatography after reaction, is detected with TCD detector
CO、CO2, with hydrocarbon gas such as fid detector detection methanol.Contained using lattice component in correction area normalization quantitative analysis tail gas
Amount.The results are shown in Table 1 for the catalytic performance test for the various catalyst that the embodiment of the present invention 1 and comparative example 1-5 are prepared.
The various catalyst activity test results of table 1
Reaction condition: P=2MPa, T=250 DEG C, H2/CO2Volume ratio=3/1, GHSV=12,000ml/ (g h).
It is found by table 1: relative to comparative example 1-3 and 5, selecting Cu/Zr molar ratio to be prepared for 1/4 in comparative example 4
Cu/ZrO2Catalyst shows preferable catalytic activity, the Cu/ZrO further obtained in comparative example 42It is loaded on catalyst expensive
Metal Pd obtains Pd-Cu/ZrO described in the embodiment of the present invention 12Catalyst sample, CO2Conversion ratio, CO selectivity, CH3OH choosing
Selecting property and methanol yield are obviously improved relative to comparative example 1-5, illustrate that the present invention is prepared using sol-gel method
Cu/ZrO2Catalyst passes through the Pd-Cu/ZrO that infusion process will be prepared on catalyst that precious metals pd loads to again2It urges
Agent has many advantages, such as that large specific surface area, catalytic activity are high, carbon dioxide conversion is high, methanol selectivity is high.
Test example 2
This test example is to Pd-Cu/ZrO made from the embodiment of the present invention 12Cu/ZrO obtained by catalyst and comparative example 1-52It urges
Agent carries out X-ray diffraction test, and test result is as shown in Figure 1.
As seen from Figure 1, Pd-Cu/ZrO produced by the present invention2In catalyst XRD spectrum, 2 θ be 30.3 °, 35.3 °,
50.4 °, 60.2 ° of diffraction maximum belong to t-ZrO2(011), (110), (112), (121) crystal face, wherein most strong diffraction crystal face
For (011) crystal face.2 θ are 38.7 °, 48.7 ° of diffraction maximum is respectively belonging to (111) of CuO, (202) crystal face.In Cu/ZrO2It urges
Due to the addition of CuO species in agent, ZrO in map2Diffraction maximum obviously weaken, illustrate that the addition of CuO reduces ZrO2Crystallization
Degree；With gradually decreasing for Cu content, the diffraction maximum of Cu gradually weakens, and when Cu/Zr molar ratio is 1/4, sees in XRD spectrum
The faint diffraction maximum of Cu is observed, when Cu/Zr molar ratio is 1/8, not it is observed that the diffraction maximum of Cu in XRD spectrum, Cu at this time
ZrO is mainly dispersed in unbodied CuO2On carrier.And Pd-Cu/ZrO produced by the present invention2Fail to see Pd's in catalyst
Diffraction maximum, main cause may be lower load capacity, but and Cu/ZrO2Catalyst is compared, and catalyst is substantially reduced
Crystallization degree can be uniformly dispersed in the surface of carrier to make active component more, show preferable catalytic activity.
Claims (8)
1. a kind of catalyst for synthesizing methanol by hydrogenating carbon dioxide, which is characterized in that carry Cu-ZrO by precious metals pd2It urges
Agent obtains.
2. a kind of preparation method of the catalyst for synthesizing methanol by hydrogenating carbon dioxide, which comprises the following steps:
(1) copper nitrate and zirconium nitrate are mixed and is dissolved in deionized water, delay aqueous citric acid solution under the action of magnetic agitation
Slowly it is added drop-wise in nitrate mixed solution, obtains uniformly mixed sol solution；
(2) sol solution keeps the evaporation of sol solution aqueous solvent under magnetic agitation effect, and stirring is fixed to glassy nothing is obtained
Type product；
(3) product obtained in (2) is moved in vacuum oven, is dried, obtains gelatinous catalyst precursor；
(4) gel catalyst precursor obtained in (3) is put into tube furnace and carries out high-temperature roasting, temperature programming is set,
It keeps the temperature, is ground after cooling, compression molding crosses 40~80 meshes and obtains catalyst Precursors under maturing temperature.
3. the preparation method of the catalyst according to claim 1 for synthesizing methanol by hydrogenating carbon dioxide, feature
Be: in the step (1) the metallic atom molar ratio of copper nitrate and zirconium nitrate be 1:(1 ~ 8), metallic atom mole summation with
Citric acid molar ratio is 1:(1 ~ 1.5).
4. the preparation method of the catalyst according to claim 1 for synthesizing methanol by hydrogenating carbon dioxide, feature
It is, the metallic atom molar ratio of the copper nitrate and zirconium nitrate is 1:1,1:2,1:4,1:8.
5. the preparation method of the catalyst according to claim 1 for synthesizing methanol by hydrogenating carbon dioxide, feature
Be: step (1) the magnetic agitation temperature control is between 75 DEG C ~ 95 DEG C.
6. the preparation method of the catalyst according to claim 1 for synthesizing methanol by hydrogenating carbon dioxide, feature
Be: step (2) the magnetic agitation temperature control is between 75 DEG C ~ 95 DEG C.
7. the preparation method of the catalyst according to claim 1 for synthesizing methanol by hydrogenating carbon dioxide, feature
Be: it is that for 24 hours, being dried temperature is 80~120 DEG C that the time is dried in the step (3).
8. the preparation method of the catalyst according to claim 1 for synthesizing methanol by hydrogenating carbon dioxide, feature
Be: maturing temperature is 350 DEG C ~ 500 DEG C in the step (4), soaking time 4h.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1651139A (en) * | 2004-11-30 | 2005-08-10 | 中国科学院山西煤炭化学研究所 | Cu/ZrO2 radical synthesizing methanol catalyst and its making method and application |
| CN102091618A (en) * | 2011-01-12 | 2011-06-15 | 厦门大学 | Copper-zirconium catalyst used in process of preparing methanol by hydrogenation of carbon dioxide and preparation method thereof |
| CN102921420A (en) * | 2012-11-09 | 2013-02-13 | 上海应用技术学院 | Cu/ZrO2 catalytic agent, preparation method of Cu/ZrO2 catalytic agent and application of Cu/ZrO2 catalytic agent |
| CN105498756A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Catalyst for preparation of methanol by carbon dioxide hydrogenation |
-
2019
- 2019-05-07 CN CN201910374508.0A patent/CN109999833A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1651139A (en) * | 2004-11-30 | 2005-08-10 | 中国科学院山西煤炭化学研究所 | Cu/ZrO2 radical synthesizing methanol catalyst and its making method and application |
| CN102091618A (en) * | 2011-01-12 | 2011-06-15 | 厦门大学 | Copper-zirconium catalyst used in process of preparing methanol by hydrogenation of carbon dioxide and preparation method thereof |
| CN102921420A (en) * | 2012-11-09 | 2013-02-13 | 上海应用技术学院 | Cu/ZrO2 catalytic agent, preparation method of Cu/ZrO2 catalytic agent and application of Cu/ZrO2 catalytic agent |
| CN105498756A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Catalyst for preparation of methanol by carbon dioxide hydrogenation |
Non-Patent Citations (2)
| Title |
|---|
| 李文泽: "碳一化学品转化反应及催化剂的研究", 《中国博士学位论文全文数据库(工程科技Ⅰ辑)》 * |
| 黄纯洁等: "柠檬酸盐凝胶法制备纳米CuO-ZnO-ZrO2的工艺分析及CO2加氢制甲醇的性能", 《燃料化学学报》 * |
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Application publication date: 20190712 |