CN105195156A - Preparation method and application of high-dispersity copper-based catalyst - Google Patents
Preparation method and application of high-dispersity copper-based catalyst Download PDFInfo
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- CN105195156A CN105195156A CN201510695863.XA CN201510695863A CN105195156A CN 105195156 A CN105195156 A CN 105195156A CN 201510695863 A CN201510695863 A CN 201510695863A CN 105195156 A CN105195156 A CN 105195156A
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Abstract
The invention discloses a preparation method and application of a high-dispersity copper-based catalyst. The preparation method of the high-dispersity copper-based catalyst comprises the following steps: in a reaction vessel, taking divalent metal salt, trivalent metal salt and sodium acetate as raw materials to prepare a metal oxide precursor material through a homogeneous precipitation method, filtering, washing, drying, roasting and reducing to obtain the high-dispersity copper-based catalyst. The prepared copper-based catalyst is large in specific surface area and high in copper dispersity, and is beneficial to adsorption and activation of reactants. In addition, the raw materials of the catalyst are cheap in price and easy to get; the preparation method is simple and is easy to operate and low in process cost; the catalyst is good in performance and repeatability; furthermore, the defects of low conversion rate and low selectivity of methanol caused by a methanol synthesis catalyst from carbon dioxide hydrogenation in the prior art can be overcome; the prepared catalyst is stable in performance, so that the catalyst has a good application prospect.
Description
Technical field
The present invention relates to a kind of catalyst and preparation method and application, particularly relate to the catalyst based preparation method of a kind of high dispersing copper and at CO
2application in synthesizing methanol by hydrogenating.
Background technology
Carbon dioxide is the carbon-source cpd that occurring in nature exists in a large number, is translated into valuable chemicals or fuel and not only can alleviates the problem that energy shortage is also expected to solve greenhouse-gas control.In recent years, synthesizing methanol by hydrogenating carbon dioxide process gets the attention, this is because methyl alcohol is important industrial chemicals, is again non-petroleum base Clean synthesis fuel.Based on the significance of hydrogenation of carbon dioxide to generate methanol on environment and energy problem, Nobel chemistry Prize winner professor Olah proposes the concept of " methyl alcohol economy ".But carbon dioxide is highly stable, activation is difficult to, and therefore the key of this process is the exploitation of high activated catalyst.
Industrial with the synthesis gas containing carbon dioxide for raw material, adopt the Cu/ZnO/Al for preparing of coprecipitation
2o
3catalyst carries out methanol-fueled CLC, so copper-based catalysts receives extensive research in synthesizing methanol by hydrogenating carbon dioxide reaction.The decentralization of active copper plays vital effect to carbon dioxide hydrogenation reaction activity, many researchers improve the decentralization of copper by introducing metal promoter, as (AppliedcatalysisA:General.2013 such as Gao, 468:442-452.), by introducing the introducing of the metallic elements such as Mn, La, Ce, Zr and Y, effectively improve Cu/ZnO/Al
2o
3the catalytic performance of catalyst synthesizing methanol by hydrogenating carbon dioxide reaction, and find that carbon dioxide conversion increases with the increase of the decentralization of metallic copper.Except metal component, preparation method also has remarkable impact to the decentralization of copper.It is serious that the material specific surface area that conventional coprecipitation method obtains is lower, active component copper is reunited, and causes active principle utilization rate not high, and publication number is that the application for a patent for invention of CN102580750 reports traditional co-precipitation method synthesis Cu/ZnO/Al
2o
3catalyst, at 230 DEG C, 3MPa, air speed 3000h
-1, H
2/ CO
2under the reaction condition of mol ratio=3:1, carbon dioxide conversion is 19.6%, and methyl alcohol is selective is 69.3%.Publication number is that the application for a patent for invention of CN103263926A reports traditional co-precipitation method synthesis Cu/ZnO/Al
2o
3catalyst, at 250 DEG C, 5.0MPa, air speed 4000h
-1, H
2/ CO
2under the reaction condition of mol ratio=3:1, carbon dioxide conversion is 17.3%, and methyl alcohol is selective is 48.8%.But, material crystal phase structure prepared by homogeneous precipitation method is more complete, crystallite dimension is more homogeneous and and grain dispersion better, the method is expected to the specific area and the metal dispersity that promote copper-based catalysts.
Summary of the invention
The shortcoming of prior art in view of the above, the object of this invention is to provide the preparation method and application that a kind of high dispersing copper is catalyst based, for solving the problem that in prior art, copper-based catalysts active component decentralization is low, reactivity is low.
For achieving the above object and other relevant objects, the invention provides the preparation method that a kind of high dispersing copper is catalyst based, comprise the steps:
(1) take divalent metal salt, trivalent metal salt and sodium acetate in molar ratio, be configured to mixed aqueous solution, wherein, divalent metal salt is mantoquita and zinc salt;
(2) be placed in water heating kettle by described mixed aqueous solution, reaction generates sediment;
(3) described sediment carried out successively filter, wash, dry, roasting obtains metal oxide precursor, reduce described metal oxide precursor, obtain high dispersing copper catalyst based.
Step 1) described in sodium acetate as precipitating reagent.
As the scheme of a kind of optimization of the catalyst based preparation method of high dispersing copper of the present invention, described step 1) in, described mantoquita is copper nitrate or copper chloride, zinc nitrate or zinc chloride during described zinc salt.
As the scheme of a kind of optimization of the catalyst based preparation method of high dispersing copper of the present invention, in described step (1), described trivalent metal salt is metal nitrate or metal chloride.
As the scheme of a kind of optimization of the catalyst based preparation method of high dispersing copper of the present invention, described step 1) in, the metal cation of trivalent metal salt is Al
3+, Y
3+, Ga
3+, Cr
3+, Fe
3+, La
3+in one or more combination.
As the scheme of a kind of optimization of the catalyst based preparation method of high dispersing copper of the present invention, described step 1) in, the mol ratio of trivalent metal salt and divalent metal salt is (1 ~ 6): 1.
As the scheme of a kind of optimization of the catalyst based preparation method of high dispersing copper of the present invention, described step 1) in, total mol ratio of sodium acetate and divalent metal salt, trivalent metal salt is (0.5 ~ 2): 1.
As the scheme of a kind of optimization of the catalyst based preparation method of high dispersing copper of the present invention, described step 1) in, the concentration of mixed aqueous solution is 0.5 ~ 3M.
As the scheme of a kind of optimization of the catalyst based preparation method of high dispersing copper of the present invention, described step 2) in, be placed in the rotary oven of water heating kettle by described mixed aqueous solution, rotating speed is 10 ~ 25r/min, temperature is set to 80 ~ 160 DEG C, and the time is 12 ~ 72h.
As the scheme of a kind of optimization of the catalyst based preparation method of high dispersing copper of the present invention, in described step (3), described roasting condition is 300 ~ 700 DEG C, and the time is 2 ~ 10h.
As the scheme of a kind of optimization of the catalyst based preparation method of high dispersing copper of the present invention, in described step (3), after carrying out described roasting, described metal oxide precursor is at reducing gases H
2be warming up to 200 ~ 350 DEG C in atmosphere, it is catalyst based that reductase 12 ~ 10h obtains high dispersing copper.This reduction step completes in fixed bed reactors, can also by the step of low temperature calcination between drying and roasting.
The application that the present invention also provides a kind of high dispersing copper catalyst based, for CO
2in synthesizing methanol by hydrogenating reaction, reaction condition is: reaction pressure is 1.0 ~ 8.0MPa, and reaction temperature is 190 ~ 290 DEG C, and volume space velocity is 500 ~ 6000h
-1, H
2/ CO
2mol ratio is 2 ~ 4, and wherein reaction pressure is relative pressure.
As mentioned above, the invention discloses the application of the catalyst based preparation method of a kind of high dispersing copper and the direct synthesizing methanol of its hydrogenation of carbon dioxide.In reaction vessel, with divalent metal salt, trivalent metal salt, sodium acetate for raw material, obtain metal oxide precursor material by homogeneous precipitation method, then the copper-based catalysts of high dispersive can be obtained through filtration, washing, drying, roasting, reduction.The specific area of copper-based catalysts prepared by the present invention is large, and the decentralization of copper is high, is conducive to the absorption of reactant, activation.In addition, this method for preparing catalyst is simple, and easily operate, process costs is low, and cost of material is cheaply easy to get, and catalyst performance repeatability better.Moreover overcome existing synthesizing methanol by hydrogenating carbon dioxide catalyst carbon dioxide conversion low, the selective shortcoming such as poor of methyl alcohol, prepared catalyst performance stabilised, therefore has good application prospect.
Accompanying drawing explanation
The scanning electron microscope (SEM) photograph of unfired precursor samples in Fig. 1 embodiment 4.
Detailed description of the invention
Below by way of specific instantiation, embodiments of the present invention are described, those skilled in the art the content disclosed by this description can understand other advantages of the present invention and effect easily.The present invention can also be implemented or be applied by detailed description of the invention different in addition, and the every details in this description also can based on different viewpoints and application, carries out various modification or change not deviating under spirit of the present invention.
Notice, in the following example, the concrete process equipment that indicates or device all adopt conventional equipment in this area or device; All force value and scope all refer to relative pressure.
In addition should be understood that the one or more method steps mentioned in the present invention do not repel and can also to there is additive method step or can also insert additive method step before and after described combination step between these steps clearly mentioned, except as otherwise noted; Will also be understood that, the relation that is connected between the one or more equipment/devices mentioned in the present invention is not repelled and can also to be there are other equipment/devices or can also insert other equipment/devices before and after described unit equipment/device between these two equipment/devices clearly mentioned, except as otherwise noted.And, except as otherwise noted, the numbering of various method steps is only the convenient tool differentiating various method steps, but not be ordering or the enforceable scope of restriction the present invention of restriction various method steps, the change of its relativeness or adjustment, when changing technology contents without essence, when being also considered as the enforceable category of the present invention.
[embodiment 1]
Get appropriate copper nitrate, zinc nitrate, aluminum nitrate, yttrium nitrate and sodium acetate by Cu
2+: Zn
2+=1:1, (Al
3++ Y
3+): (Cu
2++ Zn
2+)=2:1, sodium acetate: total metal ion=0.5:1 (mol ratio) is mixed with the mixed aqueous solution of 0.5M.Solution is placed in autoclave and reacts 24h under 120 DEG C of conditions, baking oven rotating speed is 10r/min, and by sediment cooling, filtration, washing, drying, the solid sediment obtained calcines 12h through 80 DEG C, then through 500 DEG C of roasting 4h.Obtain Cu/ZnO/Al
2o
3metal oxide precursor, compressing tablet becomes 40 ~ 60 orders.After roasting, the physical and chemical performance of metal oxide precursor is as shown in table 1.Getting metal oxide precursor 1.5mL is loaded in fixed bed reactors, at 1MPa, reduces after 6h and is down to room temperature, be then switched to reactor feed gas (H at 280 DEG C
2and CO
2) react, reaction condition is as follows: T=190 DEG C, P=2.0MPa, volume space velocity GHSV=4000h
-1, H
2/ CO
2mol ratio=3:1, collects liquid product with cold-trap, and gas chromatographic analysis product forms.Reaction result is in table 2.
[embodiment 2]
Get appropriate copper nitrate, zinc nitrate, aluminum nitrate, gallium nitrate and sodium acetate by Cu
2+: Zn
2+=5:1, (Al
3++ Ga
3+): (Cu
2++ Zn
2+)=3:1, sodium acetate: total metal ion=0.8:1 (mol ratio) is mixed with 1.2M mixed aqueous solution.Solution is placed in autoclave and reacts 24h under 160 DEG C of conditions, baking oven rotating speed is 15r/min, and by sediment cooling, filtration, washing, drying, the solid sediment obtained calcines 12h through 80 DEG C, then through 500 DEG C of roasting 4h.Obtain Cu/ZnO/Al
2o
3metal oxide precursor, compressing tablet becomes 40 ~ 60 orders.After roasting, the physical and chemical performance of metal oxide precursor is as shown in table 1.Getting metal oxide precursor 1.5mL is loaded in fixed bed reactors, and at 1MPa, reduce at 280 DEG C after 6h and be down to room temperature, be then switched to reactor feed gas and react, reaction condition is as follows: T=210 DEG C, P=1.0MPa, GHSV=500h
-1, H
2/ CO
2mol ratio=2:1, collects liquid product with cold-trap, and gas chromatographic analysis product forms.Reaction result is in table 2.
[embodiment 3]
Get appropriate copper nitrate, zinc nitrate, aluminum nitrate and sodium acetate by Cu
2+: Zn
2+=2:1, Al
3+: (Cu
2++ Zn
2+)=6:1, sodium acetate: total metal ion=1.5:1 (mol ratio) is mixed with 2.0M mixed aqueous solution.Solution is placed in autoclave and reacts 24h under 80 DEG C of conditions, baking oven rotating speed is 20r/min, and by sediment cooling, filtration, washing, drying, the solid sediment obtained calcines 12h through 80 DEG C, then through 500 DEG C of roasting 4h.Obtain Cu/ZnO/Al
2o
3metal oxide precursor, compressing tablet becomes 40-60 order.After roasting, the physical and chemical performance of metal oxide precursor is as shown in table 1.Getting metal oxide precursor 1.5mL is loaded in fixed bed reactors, and at 1MPa, reduce at 280 DEG C after 6h and be down to room temperature, be then switched to reactor feed gas and react, reaction condition is as follows: T=290 DEG C, P=8.0MPa, GHSV=6000h
-1, H
2/ CO
2mol ratio=3:1, collects liquid product with cold-trap, and gas chromatographic analysis product forms.Reaction result is in table 2.
[embodiment 4]
Get appropriate copper nitrate, zinc nitrate, aluminum nitrate and sodium acetate by Cu
2+: Zn
2+=3:1, Al
3+: (Cu
2++ Zn
2+)=5:1, sodium acetate: total metal ion=1.0:1 (mol ratio) is mixed with 1.0M mixed solution.Solution is placed in autoclave and reacts 24h under 100 DEG C of conditions, baking oven rotating speed is 15r/min, and by sediment cooling, filtration, washing, drying, the sedimentary ESEM of dry rear acquisition as shown in Figure 1.The solid sediment obtained calcines 12h through 80 DEG C, then through 500 DEG C of roasting 4h.Obtain Cu/ZnO/Al
2o
3metal oxide precursor, compressing tablet becomes 40-60 order.After roasting, the physical and chemical performance of metal oxide precursor is as shown in table 1.Getting metal oxide precursor 1.5mL is loaded in fixed bed reactors, and at 1MPa, reduce at 280 DEG C after 6h and be down to room temperature, be then switched to reactor feed gas and react, reaction condition is as follows: T=250 DEG C, P=5.0MPa, GHSV=1500h
-1, H
2/ CO
2mol ratio=3:1, collects liquid product with cold-trap, and gas chromatographic analysis product forms.Reaction result is in table 2.
[embodiment 5]
Get appropriate copper nitrate, zinc nitrate, aluminum nitrate, lanthanum nitrate and sodium acetate by Cu
2+: Zn
2+=1:1, (Al
3++ La
3+): (Cu
2++ Zn
2+)=4:1, sodium acetate: total metal ion=2.0:1 (mol ratio) is mixed with 0.8M mixed solution.Solution is placed in autoclave and reacts 24h under 150 DEG C of conditions, baking oven rotating speed is 20r/min, and by sediment cooling, filtration, washing, drying, the solid sediment obtained calcines 12h through 80 DEG C, then through 500 DEG C of roasting 4h.Obtain Cu/ZnO/Al
2o
3metal oxide precursor, compressing tablet becomes 40-60 order.After roasting, the physical and chemical performance of metal oxide precursor is as shown in table 1.Getting metal oxide precursor 1.5mL is loaded in fixed bed reactors, and at 1MPa, reduce at 280 DEG C after 6h and be down to room temperature, be then switched to reactor feed gas and react, reaction condition is as follows: T=230 DEG C, P=6.0MPa, GHSV=1000h
-1, H
2/ CO
2mol ratio=4:1, collects liquid product with cold-trap, and gas chromatographic analysis product forms.Reaction result is in table 2.
[embodiment 6]
Get appropriate copper nitrate, zinc nitrate, aluminum nitrate and sodium acetate by Cu
2+: Zn
2+=3:1, Al
3+: (Cu
2++ Zn
2+)=1:1, sodium acetate: total metal ion=1.4:1 (mol ratio) is mixed with 2.5M mixed solution.Solution is placed in autoclave and reacts 24h under 110 DEG C of conditions, baking oven rotating speed is 10r/min, and by sediment cooling, filtration, washing, drying, the solid sediment obtained calcines 12h through 80 DEG C, then through 500 DEG C of roasting 4h.Obtain Cu/ZnO/Al
2o
3metal oxide precursor, compressing tablet becomes 40-60 order.After roasting, the physical and chemical performance of metal oxide precursor is as shown in table 1.Getting metal oxide precursor 1.5mL is loaded in fixed bed reactors, and at 1MPa, reduce at 280 DEG C after 6h and be down to room temperature, be then switched to reactor feed gas and react, reaction condition is as follows: T=270 DEG C, P=4.0MPa, GHSV=2000h
-1, H
2/ CO
2mol ratio=3:1, collects liquid product with cold-trap, and gas chromatographic analysis product forms.Reaction result is in table 2.
[embodiment 7]
Get appropriate copper nitrate, zinc nitrate, aluminum nitrate and sodium acetate by Cu
2+: Zn
2+=4:1, Al
3+: (Cu
2++ Zn
2+)=3:1, sodium acetate: total metal ion=1.8:1 (mol ratio) is mixed with 1.8M mixed solution.Solution is placed in autoclave and reacts 24h under 100 DEG C of conditions, baking oven rotating speed is 25r/min, and by sediment cooling, filtration, washing, drying, the solid sediment obtained calcines 12h through 80 DEG C, then through 500 DEG C of roasting 4h.Obtain Cu/ZnO/Al
2o
3metal oxide precursor, compressing tablet becomes 40-60 order.After roasting, the physical and chemical performance of metal oxide precursor is as shown in table 1.Getting metal oxide precursor 1.5mL is loaded in fixed bed reactors, and at 1MPa, reduce at 280 DEG C after 6h and be down to room temperature, be then switched to reactor feed gas and react, reaction condition is as follows: T=250 DEG C, P=3.0MPa, GHSV=5000h
-1, H
2/ CO
2mol ratio=3:1, collects liquid product with cold-trap, and gas chromatographic analysis product forms.Reaction result is in table 2.
[embodiment 8]
Get appropriate copper nitrate, zinc nitrate, aluminum nitrate, yttrium nitrate and sodium acetate by Cu
2+: Zn
2+=5:1, (Al
3++ Y
3+): (Cu
2++ Zn
2+)=2:1, sodium acetate: total metal ion=1.6:1 (mol ratio) is mixed with 3.0M mixed solution.Solution is placed in autoclave and reacts 24h under 130 DEG C of conditions, baking oven rotating speed is 20r/min, and by sediment cooling, filtration, washing, drying, the solid sediment obtained calcines 12h through 80 DEG C, then through 500 DEG C of roasting 4h.Obtain Cu/ZnO/Al
2o
3metal oxide precursor, compressing tablet becomes 40-60 order.After roasting, the physical and chemical performance of metal oxide precursor is as shown in table 1.Getting metal oxide precursor 1.5mL is loaded in fixed bed reactors, and at 1MPa, reduce at 280 DEG C after 6h and be down to room temperature, be then switched to reactor feed gas and react, reaction condition is as follows: T=290 DEG C, P=5.0MPa, GHSV=4000h
-1, H
2/ CO
2mol ratio=3:1, collects liquid product with cold-trap, and gas chromatographic analysis product forms.Reaction result is in table 2.
The physical and chemical performance of metallic oxide precursor sample after the roasting of table 1 embodiment
Table 2 embodiment catalyst reaction result
As can be seen from table 1,2, the specific area of the catalyst prepared by the present invention is large, and the decentralization of copper is high, is conducive to absorption and the activation of reactant, good stability.Further, in the application of synthesizing methanol by hydrogenating carbon dioxide, titanium dioxide charcoal percent conversion is high, methyl alcohol better selective.
The above; be only preferred embodiment of the present invention; not to any formal and substantial restriction of the present invention; should be understood that; for those skilled in the art; under the prerequisite not departing from the inventive method, also can make some improvement and supplement, these improve and supplement and also should be considered as protection scope of the present invention.All those skilled in the art, without departing from the spirit and scope of the present invention, a little change made when utilizing disclosed above technology contents, the equivalent variations of modifying and developing, be Equivalent embodiments of the present invention; Meanwhile, all according to substantial technological of the present invention to the change of any equivalent variations that above-described embodiment is done, modify and differentiation, all still belong in the scope of technical scheme of the present invention.
Claims (11)
1. the preparation method that high dispersing copper is catalyst based, is characterized in that, comprises the steps:
(1) take divalent metal salt, trivalent metal salt and sodium acetate in molar ratio, be configured to mixed aqueous solution, wherein, divalent metal salt is mantoquita and zinc salt;
(2) be placed in water heating kettle by described mixed aqueous solution, reaction generates sediment;
(3) described sediment carried out successively filter, wash, dry, roasting obtains metal oxide precursor, reduce described metal oxide precursor, obtain high dispersing copper catalyst based.
2. the preparation method that high dispersing copper as claimed in claim 1 is catalyst based, is characterized in that, described step 1) in, described mantoquita is copper nitrate or copper chloride, zinc nitrate or zinc chloride during described zinc salt.
3. the preparation method that high dispersing copper as claimed in claim 1 is catalyst based, it is characterized in that, in described step (1), described trivalent metal salt is metal nitrate or metal chloride.
4. the preparation method that high dispersing copper as claimed in claim 1 is catalyst based, is characterized in that, described step 1) in, the metal cation of trivalent metal salt is Al
3+, Y
3+, Ga
3+, Cr
3+, Fe
3+, La
3+in one or more combination.
5. the preparation method that high dispersing copper as claimed in claim 1 is catalyst based, is characterized in that, described step 1) in, the mol ratio of trivalent metal salt and divalent metal salt is (1 ~ 6): 1.
6. the preparation method that high dispersing copper as claimed in claim 1 is catalyst based, is characterized in that, described step 1) in, total mol ratio of sodium acetate and divalent metal salt, trivalent metal salt is (0.5 ~ 2): 1.
7. the preparation method that high dispersing copper as claimed in claim 1 is catalyst based, is characterized in that, described step 1) in, the concentration of mixed aqueous solution is 0.5 ~ 3M.
8. the preparation method that high dispersing copper as claimed in claim 1 is catalyst based, is characterized in that, described step 2) in, described mixed aqueous solution is placed in the rotary oven of water heating kettle, rotating speed is 10 ~ 25r/min, and temperature is set to 80 ~ 160 DEG C, and the time is 12 ~ 72h.
9. the preparation method that high dispersing copper as claimed in claim 1 is catalyst based, it is characterized in that, in described step (3), described roasting condition is 300 ~ 700 DEG C, and the time is 2 ~ 10h.
10. the preparation method that high dispersing copper as claimed in claim 1 is catalyst based, it is characterized in that, in described step (3), after carrying out described roasting, described metal oxide precursor is at reducing gases H
2be warming up to 200 ~ 350 DEG C in atmosphere, it is catalyst based that reductase 12 ~ 10h obtains high dispersing copper.
The application that high dispersing copper prepared by 11. 1 kinds of preparation methods as described in any one of claim 1 to 10 is catalyst based, is characterized in that, for CO
2in synthesizing methanol by hydrogenating reaction, reaction condition is: reaction pressure is 1.0 ~ 8.0MPa, and reaction temperature is 190 ~ 290 DEG C, and volume space velocity is 500 ~ 6000h
-1, H
2/ CO
2mol ratio is 2 ~ 4.
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| CN105521775A (en) * | 2016-01-28 | 2016-04-27 | 中国科学院上海高等研究院 | Carrier SiO2, preparation method of carrier SiO2, copper-based catalyst as well as preparation method and application of copper-based catalyst |
| CN105562009A (en) * | 2016-01-28 | 2016-05-11 | 中国科学院上海高等研究院 | Layer-structured copper-based catalyst and preparation method and application thereof |
| CN106180747A (en) * | 2016-07-07 | 2016-12-07 | 王荔 | A kind of palladium copper binary alloy nano material, its preparation method and reduce CO as catalyst electro-catalysis2application |
| CN108889303A (en) * | 2018-07-20 | 2018-11-27 | 太原理工大学 | The support type high dispersive copper-based catalysts and preparation method of carbon dioxide methanol and application |
| CN110787809A (en) * | 2019-11-11 | 2020-02-14 | 中国科学院上海高等研究院 | Copper-based catalyst, preparation method and application |
| CN111514893A (en) * | 2020-04-17 | 2020-08-11 | 中国科学院合肥物质科学研究院 | Catalyst with sub-nanometer composite structure and preparation method thereof |
| CN113198479A (en) * | 2021-04-26 | 2021-08-03 | 中国科学院上海高等研究院 | Catalyst for preparing methanol from carbon dioxide-rich synthesis gas and preparation method thereof |
| CN114349607A (en) * | 2022-03-01 | 2022-04-15 | 中国科学院上海高等研究院 | Method for synthesizing dimethoxymethane by selective hydrogenation of carbon dioxide |
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| CN105521775A (en) * | 2016-01-28 | 2016-04-27 | 中国科学院上海高等研究院 | Carrier SiO2, preparation method of carrier SiO2, copper-based catalyst as well as preparation method and application of copper-based catalyst |
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| CN105562009B (en) * | 2016-01-28 | 2018-05-04 | 中国科学院上海高等研究院 | A kind of layer structure copper-based catalysts and its preparation method and application |
| CN106180747A (en) * | 2016-07-07 | 2016-12-07 | 王荔 | A kind of palladium copper binary alloy nano material, its preparation method and reduce CO as catalyst electro-catalysis2application |
| CN108889303A (en) * | 2018-07-20 | 2018-11-27 | 太原理工大学 | The support type high dispersive copper-based catalysts and preparation method of carbon dioxide methanol and application |
| CN108889303B (en) * | 2018-07-20 | 2021-02-12 | 太原理工大学 | Supported high-dispersion copper-based catalyst for preparing methanol from carbon dioxide, preparation method and application thereof |
| CN110787809A (en) * | 2019-11-11 | 2020-02-14 | 中国科学院上海高等研究院 | Copper-based catalyst, preparation method and application |
| CN110787809B (en) * | 2019-11-11 | 2022-11-25 | 中国科学院上海高等研究院 | Copper-based catalyst, preparation method and application |
| CN111514893A (en) * | 2020-04-17 | 2020-08-11 | 中国科学院合肥物质科学研究院 | Catalyst with sub-nanometer composite structure and preparation method thereof |
| CN113198479A (en) * | 2021-04-26 | 2021-08-03 | 中国科学院上海高等研究院 | Catalyst for preparing methanol from carbon dioxide-rich synthesis gas and preparation method thereof |
| CN114349607A (en) * | 2022-03-01 | 2022-04-15 | 中国科学院上海高等研究院 | Method for synthesizing dimethoxymethane by selective hydrogenation of carbon dioxide |
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