CN110465302A - A kind of CO2Hydrogen is added to prepare low-carbon alcohol catalyst and its preparation method and application - Google Patents
A kind of CO2Hydrogen is added to prepare low-carbon alcohol catalyst and its preparation method and application Download PDFInfo
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- CN110465302A CN110465302A CN201910694348.8A CN201910694348A CN110465302A CN 110465302 A CN110465302 A CN 110465302A CN 201910694348 A CN201910694348 A CN 201910694348A CN 110465302 A CN110465302 A CN 110465302A
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- 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
- B01J23/83—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 rare earths or actinides
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- C—CHEMISTRY; METALLURGY
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
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Abstract
The present invention relates to catalyst technical fields, and in particular to a kind of CO2Hydrogen is added to prepare low-carbon alcohol catalyst and its preparation method and application, which is quaternary metallic oxide, is denoted as x%Cs-CuyFezZn1, x% is that metal Cs accounts for Cu in formulayFezZn1Mass fraction, y and z be respectively Ni metal and Fe using metal Zn as the molar ratio of reference, wherein x=1-5, y=0.2-1.5, z=0.1-1.CO of the invention2Add hydrogen to prepare low-carbon alcohol catalyst, is used for CO2Hydrogen is added to prepare low-carbon alcohols, CO2Conversion per pass is up to 37.9%, and low-carbon alcohols yield is up to 7.6%, and low-carbon alcohols mass fraction is 93.9% in total alcohol, much higher than the result of existing report.
Description
Technical field
The present invention relates to catalyst technical fields, and in particular to a kind of CO2Hydrogen is added to prepare low-carbon alcohol catalyst and its preparation
Methods and applications.
Background technique
Being widely used for fossil fuel has resulted in a large amount of greenhouse gases CO2Discharge, by CO2Caused environmental problem
It is outstanding day by day.Simultaneously as a kind of important carbon resource, by CO2Before high valuable chemicals are converted into important application
The important channel of scape and sustainable development.
Low carbon mixed alcohol (abbreviation low-carbon alcohols) generally refers to C2-C4 mixed alcohol, their octane numbers with higher can be used as
Clean fuel uses, and simultaneously can be used for gasoline additive, the ethanol petrol such as widelyd popularize.Low-carbon alcohols are also good
Solvent and the raw material of industry are widely used in all kinds of chemical industries.Industrial low-carbon alcohols mostly come from grain fermentation, but the mistake at present
Journey inefficiency and with solve food problem run in the opposite direction, therefore utilize greenhouse gases CO2Directly preparation low-carbon alcohols have good
Prospect.But with CO2Preparing methanol by hydrogenation is different, and synthesis of low-carbon alcohol is related to multistep reaction and multiple activated centres, and product is complicated, such as
What highly selective preparation low-carbon alcohols is a stern challenge, thus very harsh for the selection of catalyst.
CO2The heterogeneous catalyst of hydrogenation synthesizing low carbon alcohol mainly includes three classes, and one kind is Rh base catalyst, and wherein RhFe has
There is preferable ethanol selectivity, but noble metal Rh fancy price restricts its application；Second class is Mo base catalyst, and Mo base is urged
Agent is cheap, carbon accumulation resisting ability is good, but active lower, severe reaction conditions, need further to explore；Third class is
CuFe base catalyst, CuFe bimetallic catalyst are provided simultaneously with the ability of CO insertion and the coupling of carbon carbon, are a kind of ideal synthesis
The catalyst of low-carbon alcohols, while Cu base catalyst and Fe base catalyst are widely used in methanol-fueled CLC and F- T synthesis, valence respectively
Lattice are cheap, skilled, have good research and application prospect.
Summary of the invention
One of the objects of the present invention is to provide a kind of CO2Add hydrogen to prepare low-carbon alcohol catalyst, is used for CO2Hydrogen is added to prepare low
Carbon alcohol, CO2Conversion per pass is high, low-carbon alcohols high income, and low-carbon alcohols mass fraction is higher in total alcohol.
The second object of the present invention is to provide a kind of CO2Add hydrogen to prepare the preparation method of low-carbon alcohol catalyst, prepares
Simply, low in cost, it is suitble to industrialized production.
The third object of the present invention is to provide a kind of CO2Hydrogen is added to prepare the application of low-carbon alcohol catalyst.
The present invention realizes technical solution used by the first purpose are as follows: a kind of CO2Hydrogen is added to prepare low-carbon alcohol catalyst, it is described
Catalyst is quaternary metallic oxide, is denoted as x%Cs-CuyFezZn1, x% is that metal Cs accounts for Cu in formulayFezZn1Quality point
Number, y and z are respectively Ni metal and Fe using metal Zn as the molar ratio of reference, wherein x=1-5, y=0.2-1.5, z=0.1-1.
Preferably, the catalyst obtains metal oxidation with calcining after the co-precipitation of mantoquita, molysite, zinc salt and precipitating reagent first
Then object introduces alkali metal Cs by infusion process, most obtains afterwards through high-temperature calcination.
The present invention realizes technical solution used by the second purpose are as follows: CO described in one kind2Hydrogen is added to prepare low-carbon alcohol catalysis
The preparation method of agent, comprising the following steps:
(1) a certain amount of mantoquita, molysite are weighed and zinc salt is soluble in water is configured to solution A；
(2) weigh that a certain amount of precipitating reagent is soluble in water to be configured to solution B；
(3) solution B is added drop-wise in solution A under certain temperature, certain mixing speed, controls pH, continues after dripping
Ageing obtains centrifugation after the crystal of uniform-dimension, washing, dry, calcining obtain metal oxide；
(4) it weighs that a certain amount of cesium salt is soluble in water to be configured to solution C, Cs is loaded into metal oxide with infusion process
On, dry, calcining obtains x%Cs-CuyFezZn1Catalyst.
Preferably, in the step (1), total concentration of metal ions is 0.2mol/L in solution A, wherein copper ion
Concentration is 18-95mmol/L, and the concentration of iron ion is 9.5-91mmol/L, and the concentration of zinc ion is 57-95mmol/L.
Preferably, in the step (1), mantoquita is copper nitrate, and molysite is ferric nitrate, and zinc salt is zinc nitrate.
Preferably, in the step (2), precipitating reagent is ammonium carbonate, and the concentration of solution B is 0.24mol/L.
Preferably, in the step (3), the volume ratio of solution A and solution B is 1:1-1.5, and solution B is added drop-wise to solution A
In speed be 3-4mL/min, it is 8-9 that reaction temperature, which be 70 DEG C, mixing speed 400-600r/min, precipitating pH, is dried warm
Degree is 80 DEG C, and calcination temperature is 400 DEG C.
Preferably, in the step (4), cesium salt is cesium carbonate, and the concentration of solution C is 0.4-4.1g/L, and drying temperature is
110 DEG C, calcination temperature is 400 DEG C.
The present invention realizes technical solution used by the third purpose are as follows: CO described in one kind2Hydrogen is added to prepare low-carbon alcohol catalysis
The application of agent.
Preferably, CO2The reaction of hydrogen preparation low-carbon alcohols is added to carry out in fixed-bed micro-reactor-gas-chromatography combination,
By catalyst in 10%H before reaction2350 DEG C of reduction 1h in/Ar atmosphere, cooling starts to react after reduction, and reaction pressure is
5MPa, reaction temperature are 260-330 DEG C, and unstrpped gas group becomes CO2/H2/N2=24/72/4, air speed 4500mL/gcat/ h,
The low-carbon alcohols are methanol, ethyl alcohol, propyl alcohol, butanol etc..
Compared with the prior art, the invention has the following advantages:
(1) CO of the invention2Add hydrogen to prepare low-carbon alcohol catalyst, is used for CO2Hydrogen is added to prepare low-carbon alcohols, CO2Conversion per pass
Up to 37.9%, low-carbon alcohols yield is up to 7.6%, and low-carbon alcohols mass fraction is 93.9% in total alcohol, is much higher than existing report
Result；
(2) preparation method of catalyst of the invention is easy to operate, the period is short, low in cost, easy to industrialized production.
Specific embodiment
For a better understanding of the present invention, the following examples are to further explanation of the invention, but the contents of the present invention
It is not limited solely to the following examples.
Embodiment 1
1%Cs-Cu1Fe0.1Zn1The preparation of catalyst and its CO2The catalytic performance of hydrogenation synthesizing low carbon alcohol:
It weighs copper nitrate 2.42g, zinc nitrate 2.98g, ferric nitrate 0.404g to be dissolved in 105mL water, is configured to solution A, claim
It takes 2.48g ammonium carbonate to be dissolved in 108mL water, is configured to solution B, it will at a temperature of the mixing speed of 400-600r/min, 70 DEG C
Solution B is slowly added dropwise with the speed of 3-4mL/min into solution A, and it is 8-9 that rear pH value of solution, which is added dropwise, continues to stir 1h ageing
Obtain the crystal of uniform-dimension.It is centrifuged, washes after reaction, 12h is dried in vacuo at 80 DEG C, then with 2 in Muffle furnace
DEG C/heating rate of min rises to 400 DEG C of calcining 2-3h, metal oxide is obtained after grinding.0.0123g cesium carbonate is weighed to be dissolved in
It is made into aqueous solution C in 15mL distilled water, is added in 1g metal oxide and impregnates 6h, 110 DEG C of removings are heated to after dipping
Distilled water, obtained solid are pulverized after rising to 400 DEG C of one section of calcinings in Muffle furnace with the heating rate of 2 DEG C/min, are obtained
Final product 1%Cs-Cu1Fe0.1Zn1Catalyst.
Catalyst is to CO2The catalytically active assessment of hydrogenation synthesizing low carbon alcohol is gas chromatography combined in fixed-bed micro-reactor-
It is carried out in system.Enter ten-way valve after 180 DEG C of reaction end gas heat preservations to sample, by outfit thermal conductivity detector (TCD) (TCD) and hydrogen flame
The gas-chromatography (GC) of ion detector (FID) carries out on-line analysis.In being packed into after 0.2g catalyst and the mixing of 0.4g quartz sand
Diameter is in the reaction tube of 10mm, in 10%H2350 DEG C of reduction 1h are risen to 4 DEG C/min in/Ar atmosphere, are cooled down after reduction.
Using gas composition instead is CO2/H2/N2For=24/72/4 reaction gas back pressure to 5MPa, control air speed is 4500mL/gcat/ h, reaction
Temperature is 260-330 DEG C.The catalyst is best in 310 DEG C of catalytic performances, CO2Conversion ratio is 27.4%, and low-carbon alcohols yield is
0.12mmol/gcat/ h, low-carbon alcohols mass fraction in total alcohol is 20.5%.Detailed catalytic result such as table 1.
1 1%Cs-Cu of table1Fe0.1Zn1Catalyst result
Embodiment 2
2%Cs-Cu1Fe0.1Zn1The preparation of catalyst and its CO2The catalytic performance of hydrogenation synthesizing low carbon alcohol:
Method for preparing catalyst is identical as implementing 1, and only cesium carbonate dosage is 0.0246g.CO at 310 DEG C2Conversion ratio is
25.4%, low-carbon alcohols yield is 0.29mmol/gcat/ h, low-carbon alcohols mass fraction in total alcohol is 57.2%.Detailed catalytic result
Such as table 2.
2 2%Cs-Cu of table1Fe0.1Zn1Catalyst result
Embodiment 3
3%Cs-Cu1Fe0.1Zn1The preparation of catalyst and its CO2The catalytic performance of hydrogenation synthesizing low carbon alcohol:
Method for preparing catalyst is identical as implementing 1, and only cesium carbonate dosage is 0.0369g.CO at 330 DEG C2Conversion ratio is
29.3%, low-carbon alcohols yield is 1.05mmol/gcat/ h, low-carbon alcohols mass fraction in total alcohol is 90.5%.Detailed catalytic result
Such as table 3.
3 3%Cs-Cu of table1Fe0.1Zn1Catalyst result
Embodiment 4
5%Cs-Cu1Fe0.1Zn1The preparation of catalyst and its CO2The catalytic performance of hydrogenation synthesizing low carbon alcohol:
Method for preparing catalyst is identical as implementing 1, and only cesium carbonate dosage is 0.0613g.CO at 330 DEG C2Conversion ratio is
24.9%, low-carbon alcohols yield is 0.68mmol/gcat/ h, low-carbon alcohols mass fraction in total alcohol is 87.0%.Detailed catalytic result
Such as table 4.
4 5%Cs-Cu of table1Fe0.1Zn1Catalyst result
Embodiment 5
3%Cs-Cu1Fe0.2Zn1The preparation of catalyst and its CO2The catalytic performance of hydrogenation synthesizing low carbon alcohol:
Method for preparing catalyst is same as Example 1, weighs copper nitrate 2.42g, zinc nitrate 2.98g, ferric nitrate 0.808g
It is dissolved in 110mL water, is configured to solution A, weigh 2.65g ammonium carbonate and be dissolved in 115mL water, be configured to solution B, cesium carbonate dosage
For 0.0369g.CO at 330 DEG C2Conversion ratio is 32.6%, and low-carbon alcohols yield is 1.19mmol/gcat/ h, low-carbon alcohols are in total alcohol
Mass fraction is 92.4%.Detailed catalytic result such as table 5.
5 3%Cs-Cu of table1Fe0.2Zn1Catalyst result
Embodiment 6
3%Cs-Cu1Fe0.5Zn1The preparation of catalyst and its CO2The catalytic performance of hydrogenation synthesizing low carbon alcohol:
Method for preparing catalyst is same as Example 1, and it is molten to weigh copper nitrate 2.42g, zinc nitrate 2.98g, ferric nitrate 2.02g
In 125mL water, it is configured to solution A, 3.17g ammonium carbonate is weighed and is dissolved in 138mL water, is configured to solution B, cesium carbonate dosage is
0.0369g.CO at 330 DEG C2Conversion ratio is 37.4%, and low-carbon alcohols yield is 1.30mmol/gcat/ h, low-carbon alcohols matter in total alcohol
Measuring score is 94.2%.Detailed catalytic result such as table 6.
6 3%Cs-Cu of table1Fe0.5Zn1Catalyst result
Embodiment 7
3%Cs-Cu1Fe1Zn1The preparation of catalyst and its CO2The catalytic performance of hydrogenation synthesizing low carbon alcohol:
Method for preparing catalyst is same as Example 1, and it is molten to weigh copper nitrate 2.42g, zinc nitrate 2.98g, ferric nitrate 4.04g
In 150mL water, it is configured to solution A, 4.03g ammonium carbonate is weighed and is dissolved in 175mL water, is configured to solution B, cesium carbonate dosage is
0.0369g.CO at 330 DEG C2Conversion ratio is 36.6%, and low-carbon alcohols yield is 1.47mmol/gcat/ h, low-carbon alcohols matter in total alcohol
Measuring score is 93.9%.Detailed catalytic result such as table 7.
7 3%Cs-Cu of table1Fe1Zn1Catalyst result
Embodiment 8
3%Cs-Cu0.2Fe1Zn1The preparation of catalyst and its CO2The catalytic performance of hydrogenation synthesizing low carbon alcohol:
Method for preparing catalyst is same as Example 1, weighs copper nitrate 0.484g, zinc nitrate 2.98g, ferric nitrate 4.04g
It is dissolved in 110mL water, is configured to solution A, weigh 3.11g ammonium carbonate and be dissolved in 135mL water, be configured to solution B, cesium carbonate dosage
For 0.0369g.CO at 330 DEG C2Conversion ratio is 26.6%, and low-carbon alcohols yield is 0.73mmol/gcat/ h, low-carbon alcohols are in total alcohol
Mass fraction is 94.9%.Detailed catalytic result such as table 8.
8 3%Cs-Cu of table0.2Fe1Zn1Catalyst result
Embodiment 9
3%Cs-Cu0.5Fe1Zn1The preparation of catalyst and its CO2The catalytic performance of hydrogenation synthesizing low carbon alcohol:
Method for preparing catalyst is same as Example 1, and it is molten to weigh copper nitrate 1.21g, zinc nitrate 2.98g, ferric nitrate 4.04g
In 125mL water, it is configured to solution A, 3.46g ammonium carbonate is weighed and is dissolved in 150mL water, is configured to solution B, cesium carbonate dosage is
0.0369g.CO at 330 DEG C2Conversion ratio is 33.7%, and low-carbon alcohols yield is 1.20mmol/gcat/ h, low-carbon alcohols matter in total alcohol
Measuring score is 93.5%.Detailed catalytic result such as table 9.
9 3%Cs-Cu of table0.5Fe1Zn1Catalyst result
Embodiment 10
3%Cs-Cu1.5Fe1Zn1The preparation of catalyst and its CO2The catalytic performance of hydrogenation synthesizing low carbon alcohol:
Method for preparing catalyst is same as Example 1, and it is molten to weigh copper nitrate 3.63g, zinc nitrate 2.98g, ferric nitrate 4.04g
In 175mL water, it is configured to solution A, 4.608g ammonium carbonate is weighed and is dissolved in 200mL water, is configured to solution B, cesium carbonate dosage
For 0.0369g.CO at 330 DEG C2Conversion ratio is 37.9%, and low-carbon alcohols yield is 1.46mmol/gcat/ h, low-carbon alcohols are in total alcohol
Mass fraction is 94.3%.Detailed catalytic result such as table 10.
10 3%Cs-Cu of table1.5Fe1Zn1Catalyst result
Comprehensively consider, filtering out optimum catalyst is 3%Cs-Cu1Fe1Zn1, 330 DEG C of low-carbon alcohols yields are up to
1.47mmol/gcat/ h, low-carbon alcohols mass fraction 93.9% in total alcohol, for result peak has been reported.
The above is a preferred embodiment of the present invention, cannot limit the right model of the present invention with this certainly
It encloses, it is noted that for those skilled in the art, without departing from the principle of the present invention, may be used also
To make several improvement and variation, these, which improve and change, is also considered as protection scope of the present invention.
Claims (10)
1. a kind of CO2Hydrogen is added to prepare low-carbon alcohol catalyst, it is characterised in that: the catalyst is quaternary metallic oxide, is denoted as
X%Cs-CuyFezZn1, x% is that metal Cs accounts for Cu in formulayFezZn1Mass fraction, y and z be respectively Ni metal and Fe with metal
Zn is the molar ratio of reference, wherein x=1-5, y=0.2-1.5, z=0.1-1.
2. CO as described in claim 12Hydrogen is added to prepare low-carbon alcohol catalyst, it is characterised in that: the catalyst uses copper first
Calcining obtains metal oxide after salt, molysite, zinc salt and precipitating reagent co-precipitation, then introduces alkali metal Cs by infusion process, most
It is obtained by high-temperature calcination.
3. a kind of CO as claimed in claim 1 or 22Hydrogen is added to prepare the preparation method of low-carbon alcohol catalyst, it is characterised in that: packet
Include following steps:
(1) a certain amount of mantoquita, molysite are weighed and zinc salt is soluble in water is configured to solution A；
(2) weigh that a certain amount of precipitating reagent is soluble in water to be configured to solution B；
(3) solution B is added drop-wise in solution A under certain temperature, certain mixing speed, controls pH, continues to be aged after dripping
Obtain centrifugation after the crystal of uniform-dimension, washing, dry, calcining obtain metal oxide；
(4) it weighs that a certain amount of cesium salt is soluble in water to be configured to solution C, is loaded to Cs on metal oxide with infusion process, do
Dry, calcining obtains x%Cs-CuyFezZn1Catalyst.
4. CO as claimed in claim 32Hydrogen is added to prepare the preparation method of low-carbon alcohol catalyst, it is characterised in that: the step
(1) in, total concentration of metal ions is 0.2mol/L in solution A, wherein the concentration of copper ion is 18-95mmol/L, iron ion
Concentration be 9.5-91mmol/L, the concentration of zinc ion is 57-95mmol/L.
5. CO as claimed in claim 42Hydrogen is added to prepare the preparation method of low-carbon alcohol catalyst, it is characterised in that: the step
(1) in, mantoquita is copper nitrate, and molysite is ferric nitrate, and zinc salt is zinc nitrate.
6. CO as claimed in claim 32Hydrogen is added to prepare the preparation method of low-carbon alcohol catalyst, it is characterised in that: the step
(2) in, precipitating reagent is ammonium carbonate, and the concentration of solution B is 0.24mol/L.
7. CO as claimed in claim 32Hydrogen is added to prepare the preparation method of low-carbon alcohol catalyst, it is characterised in that: the step
(3) in, the volume ratio of solution A and solution B is 1:1-1.5, and it is 3-4mL/min that solution B, which is added drop-wise to the speed in solution A, instead
It is 8-9 that answer temperature, which be 70 DEG C, mixing speed 400-600r/min, precipitating pH, and drying temperature is 80 DEG C, calcination temperature 400
℃。
8. CO as claimed in claim 32Hydrogen is added to prepare the preparation method of low-carbon alcohol catalyst, it is characterised in that: the step
(4) in, cesium salt is cesium carbonate, and the concentration of solution C is 0.4-4.1g/L, and drying temperature is 110 DEG C, and calcination temperature is 400 DEG C.
9. a kind of CO of any of claims 1 or 22Hydrogen is added to prepare low-carbon alcohol catalyst or the described in any item systems of claim 3-8
The CO of Preparation Method preparation2Hydrogen is added to prepare the application of low-carbon alcohol catalyst.
10. as right 9 requires the application, it is characterised in that: CO2Add the reaction of hydrogen preparation low-carbon alcohols miniature anti-in fixed bed
It answers and is carried out in device-gas-chromatography combination, by catalyst in 10%H before reaction2350 DEG C of reduction 1h in/Ar atmosphere, after reduction
Cooling starts to react, reaction pressure 5MPa, and reaction temperature is 260-330 DEG C, and unstrpped gas group becomes CO2/H2/N2=24/
72/4, air speed 4500mL/gcat/ h, the low-carbon alcohols are methanol, ethyl alcohol, propyl alcohol, butanol etc..
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| CN110947386A (en) * | 2019-11-21 | 2020-04-03 | 太原理工大学 | Preparation method of catalyst for synthesizing low-carbon alcohol by carbon dioxide hydrogenation |
| CN111659432A (en) * | 2020-05-22 | 2020-09-15 | 北京化工大学 | CO2Iron-based catalyst for preparing ethanol by hydrogenation, preparation method and application |
| CN111659402A (en) * | 2020-05-21 | 2020-09-15 | 中国科学院广州能源研究所 | CO (carbon monoxide)2Catalyst for preparing low-carbon alcohol by hydrogenation, preparation method and application thereof |
| CN112430472A (en) * | 2020-11-06 | 2021-03-02 | 武汉大学 | CO (carbon monoxide)2Method for directly preparing low-carbon alcohol and co-producing gasoline by hydrogenation |
| CN115722228A (en) * | 2021-08-31 | 2023-03-03 | 赤壁市高质量发展研究院有限公司 | Series catalyst and high-selectivity preparation method of low-carbon alcohol |
| CN115999555A (en) * | 2022-12-02 | 2023-04-25 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | For CO 2 Catalyst for preparing higher alcohol by hydrogenation, preparation method and application thereof |
| CN116135306A (en) * | 2021-11-18 | 2023-05-19 | 赤壁市高质量发展研究院有限公司 | High-performance alkali metal modified CuFeZr catalytic material and preparation method thereof |
| CN116393134A (en) * | 2023-03-29 | 2023-07-07 | 武汉科立凯科技有限公司 | High-performance alkali metal modified Fe/ZrO 2 Method for preparing catalytic material |
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| CN110947386A (en) * | 2019-11-21 | 2020-04-03 | 太原理工大学 | Preparation method of catalyst for synthesizing low-carbon alcohol by carbon dioxide hydrogenation |
| CN111659402A (en) * | 2020-05-21 | 2020-09-15 | 中国科学院广州能源研究所 | CO (carbon monoxide)2Catalyst for preparing low-carbon alcohol by hydrogenation, preparation method and application thereof |
| CN111659432A (en) * | 2020-05-22 | 2020-09-15 | 北京化工大学 | CO2Iron-based catalyst for preparing ethanol by hydrogenation, preparation method and application |
| CN112430472A (en) * | 2020-11-06 | 2021-03-02 | 武汉大学 | CO (carbon monoxide)2Method for directly preparing low-carbon alcohol and co-producing gasoline by hydrogenation |
| CN115722228A (en) * | 2021-08-31 | 2023-03-03 | 赤壁市高质量发展研究院有限公司 | Series catalyst and high-selectivity preparation method of low-carbon alcohol |
| CN116135306A (en) * | 2021-11-18 | 2023-05-19 | 赤壁市高质量发展研究院有限公司 | High-performance alkali metal modified CuFeZr catalytic material and preparation method thereof |
| CN115999555A (en) * | 2022-12-02 | 2023-04-25 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | For CO 2 Catalyst for preparing higher alcohol by hydrogenation, preparation method and application thereof |
| CN116393134A (en) * | 2023-03-29 | 2023-07-07 | 武汉科立凯科技有限公司 | High-performance alkali metal modified Fe/ZrO 2 Method for preparing catalytic material |
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