CN115228491B - High-dispersion rhodium-based catalyst, preparation method thereof and application thereof in preparing ethanol from carbon dioxide - Google Patents
High-dispersion rhodium-based catalyst, preparation method thereof and application thereof in preparing ethanol from carbon dioxide Download PDFInfo
- Publication number
- CN115228491B CN115228491B CN202110440016.4A CN202110440016A CN115228491B CN 115228491 B CN115228491 B CN 115228491B CN 202110440016 A CN202110440016 A CN 202110440016A CN 115228491 B CN115228491 B CN 115228491B
- Authority
- CN
- China
- Prior art keywords
- rhodium
- carbon dioxide
- potassium
- reaction
- based catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 94
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 239000010948 rhodium Substances 0.000 title claims abstract description 57
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 56
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 39
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000006185 dispersion Substances 0.000 title abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 30
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 26
- 239000011591 potassium Substances 0.000 claims abstract description 26
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910039444 MoC Inorganic materials 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 48
- 238000001354 calcination Methods 0.000 claims description 29
- 239000002243 precursor Substances 0.000 claims description 27
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 229910001414 potassium ion Inorganic materials 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000012300 argon atmosphere Substances 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 239000000523 sample Substances 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- -1 aromatic amine compound Chemical class 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- 238000009396 hybridization Methods 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 claims description 2
- YWFDDXXMOPZFFM-UHFFFAOYSA-H rhodium(3+);trisulfate Chemical compound [Rh+3].[Rh+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YWFDDXXMOPZFFM-UHFFFAOYSA-H 0.000 claims description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 5
- 150000001340 alkali metals Chemical class 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 3
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 238000003780 insertion Methods 0.000 abstract description 2
- 230000037431 insertion Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910019626 (NH4)6Mo7O24 Inorganic materials 0.000 description 1
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- 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
- C07C29/156—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
- C07C29/157—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 containing platinum group metals or compounds thereof
- C07C29/158—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 containing platinum group metals or compounds thereof containing rhodium or compounds thereof
Abstract
The application discloses a high-dispersion supported rhodium-based catalyst, a preparation method thereof and application thereof in preparing ethanol from carbon dioxide, and mainly solves the problems of low conversion rate and poor high-carbon alcohol selectivity in a carbon dioxide hydrogenation reaction. The catalyst comprises molybdenum carbide, rhodium element and potassium element, wherein the rhodium element and the potassium element are supported on the molybdenum carbide. According to the application, the second active component rhodium with carbonyl insertion function is introduced into the molybdenum carbide catalyst for generating methanol by hydrogenating carbon dioxide, so that the double-active-center synergistic composite catalyst is formed, and under the modification of alkali metal auxiliary agents, high-selectivity hydrogenation of carbon dioxide to ethanol is realized, and meanwhile, the conversion rate of carbon dioxide is higher.
Description
Technical Field
The application relates to a high-dispersion rhodium-based catalyst, a preparation method thereof and application thereof in preparing ethanol by hydrogenating carbon dioxide, belonging to the field of petrochemical industry.
Background
At the same time of the rapid development of human society, a great deal of fossil energy is consumed, and a great deal of greenhouse gases such as carbon dioxide, methane and the like are discharged. This has led to the world facing increasingly severe energy and environmental crisis. Carbon dioxide is used as a cheap, nontoxic and widely available gas, and is recycled, and is catalytically converted into fuel with high industrial value such as formic acid, alcohols and even fuel oil, so that on one hand, the utilization rate of carbon resources can be improved, and on the other hand, the environmental problem of global warming can be solved.
Ethanol is used as a fuel with high energy density, and can be used as an automobile fuel additive in the current practical application, and can completely replace the traditional gasoline to realize the purpose of taking ethanol fuel as a main power source. Meanwhile, the modified starch is used as a common chemical solvent and has wide application in various aspects such as cosmetics, medicines, pesticides and the like. Thus, the conversion of carbon dioxide to ethanol is one of the most desirable products for achieving the "liquid sunlight" (Joule 2018,2 (10), 1925-1949) strategy for efficient use of renewable energy (solar energy).
In the existing preparation of ethanol by catalytic hydrogenation of CO 2, a homogeneous catalyst generally has relatively high activity and selectivity, but because of the metal complex catalyst (CN 104995161A,US 8912240B2) applied in the reaction process, the catalyst is expensive and poor in stability, and the separation of the catalyst and the reacted product is difficult. In view of these characteristics of homogeneous catalysis, scientists have been devoted to the study of efficient hydrogenation heterogeneous catalysts for CO 2. Among them, modified fischer-tropsch type catalysts (e.g., fe-based, co-based, etc.) have received much attention because of their high carbon chain growth capacity. However, the direct use of the CO hydrogenation catalyst in the CO 2 hydrogenation reaction still has more problems, because the mechanism of ethanol production by CO 2 hydrogenation is different from that of ethanol production by synthesis gas, and currently, the catalysts specifically developed for the hydrogenation characteristics of CO 2 are relatively few. When the traditional Fischer-Tropsch modified catalyst is applied to CO 2 hydrogenation reaction, the conversion rate of CO 2 is low, a large amount of low-carbon alkane is still generated in hydrogenation products, liquid-phase alcohol products after the reaction accord with ASF distribution, mixed alcohols such as methanol and propanol are added in the products except ethanol, and the carbon chain growth degree cannot be accurately controlled. While fischer-tropsch type catalysts are generally effective at catalyst onset temperatures of 300 ℃ and above, higher reaction temperatures also mean higher energy consumption and more byproducts.
In a word, the existing homogeneous catalyst for preparing ethanol by catalyzing CO 2 hydrogenation has high requirements on reaction equipment, complex process flow, poor stability and shorter service life of the catalyst; the heterogeneous catalyst needs high reaction temperature, high process energy consumption, more byproducts, low catalyst activity and low ethanol selectivity, and when the CO 2 conversion rate is more than 10%, the ethanol selectivity is less than 40%, so that in order to realize the recycling utilization of CO 2 and reduce the dependence on fossil energy, the high-efficiency heterogeneous catalyst with high activity and high ethanol selectivity for CO 2 conversion under mild conditions needs to be developed.
Disclosure of Invention
In the process of synthesizing ethanol by hydrogenating CO 2, the adsorption and activation of CO 2 and hydrogen are preconditions for reaction. CO 2 is used as a nonpolar molecule, has strong inertia and is not easy to activate. Due to the special electronic structure, the molybdenum carbide has the property of noble metal, so that the molybdenum carbide has stronger activation capability for CO 2 and hydrogen. The invention aims to provide a catalyst for preparing ethanol by hydrogenating CO 2, which has high activity and particularly higher selectivity, according to the characteristics of CO 2 hydrogenation reaction.
According to the invention, molybdenum carbide capable of effectively activating CO 2 and hydrogen is taken as a carrier, the capability of dissociating and adsorbing CO 2 to form carbonyl species and forming initial carbon-carbon bonds is utilized, and the noble metal rhodium is anchored on the molybdenum carbide carrier, so that a novel stable and good bifunctional catalyst with higher activity in CO 2 hydrogenation reaction is obtained.
Aiming at the problems that CO 2 is difficult to activate and the selectivity of ethanol which is a hydrogenation product is low, the preparation method of the catalyst is improved, alkali metal potassium is further introduced, the capacity of a molybdenum carbide carrier for adsorbing and activating CO 2 to generate an intermediate is regulated and controlled, and the selectivity and the activity of the catalyst in the reaction of preparing ethanol by hydrogenating carbon dioxide are further improved.
The invention provides a molybdenum carbide-based hydrogenation catalyst with high catalyst efficiency and a preparation method thereof, and the method is simple, easy to control and high in operability. According to the invention, the loading of the noble metal rhodium is regulated and controlled, and the stability of the catalyst is improved and the loading of the noble metal rhodium of the catalyst is reduced by combining the stabilizing effect of the molybdenum carbide carrier. The introduction of rhodium plays an important role in the establishment and stabilization of the bifunctional active center, and the addition amount thereof will directly affect the hydrogenation property thereof. The catalyst prepared by the invention has high reaction activity and high ethanol selectivity, and has a great application prospect in preparing ethanol by CO 2 hydrogenation.
According to one aspect of the present application, there is provided a supported rhodium-based catalyst comprising molybdenum carbide, rhodium element, potassium element, the rhodium element, potassium element being supported on the molybdenum carbide.
The rhodium element is an active element;
The potassium element is an auxiliary agent element;
the rhodium element is loaded on molybdenum carbide in a simple substance form;
The mass ratio of rhodium element to the carrier is 0.001:1-0.5:1;
The mass ratio of the potassium element to the carrier is 0.001:1-0.5:1.
Further alternatively, the upper mass ratio of rhodium element to carrier may be independently selected from 0.5:1, 0.4:1, 0.3:1; the lower limit of the mass ratio of rhodium element to the carrier can be independently selected from 0.001:1, 0.002:1 and 0.003:1.
Further alternatively, the upper mass ratio of potassium element to carrier may be independently selected from 0.5:1, 0.4:1, 0.3:1; the lower limit of the mass ratio of the potassium element to the carrier can be independently selected from 0.001:1, 0.002:1 and 0.003:1.
According to still another aspect of the present application, there is provided a preparation method for preparing the supported rhodium-based catalyst, the method comprising at least the steps of:
The precursor solution and the aromatic amine compound undergo an organic-inorganic hybridization reaction to prepare a compound;
step (2) mixing a precursor solution containing potassium element with the compound to prepare a supported rhodium-based catalyst;
optionally, the method of step (1) is selected from at least one of impregnation, co-precipitation or precipitation;
the method of step (2) is selected from at least one of impregnation, co-precipitation or deposition precipitation.
In the step (1), the precursor solution contains a precursor of rhodium element and a precursor of molybdenum element;
Optionally, the precursor of rhodium element is selected from at least one of rhodium chloride, rhodium nitrate and rhodium sulfate;
the precursor of the molybdenum element is at least one of molybdic acid, paramolybdic acid, molybdate and paramolybdate;
the aromatic amine compound is aniline; the concentration of the aniline is 0.1-10 mol/L;
Further alternatively, the upper concentration limit of the aniline may be independently selected from 8mol/L, 8.5mol/L, 9mol/L, 9.5mol/L, 10mol/L; the lower concentration limit of the aniline can be independently selected from 0.1mol/L, 0.5mol/L, 1.0mol/L, 1.5mol/L and 2mol/L.
The precursor containing the potassium element in the step (2) is at least one selected from potassium chloride, potassium carbonate and potassium nitrate;
the concentration of the potassium element is 0.1-10 mol/L, calculated by the concentration of potassium ions.
Further alternatively, the upper concentration limit of the potassium element may be independently selected from 8mol/L, 8.5mol/L, 9mol/L, 9.5mol/L, 10mol/L; the lower concentration limit of the potassium element can be independently selected from 0.5mol/L, 1.0mol/L, 2mol/L, 3mol/L and 4mol/L.
Optionally, the precursor solution in step (1) includes a solvent and hydrochloric acid;
the solvent is selected from deionized water;
the carbonization reaction adopts a stirring mode.
Optionally, in step (2), before the mixing, a step of pretreating the composite is further included;
the pretreatment comprises drying and calcining in sequence;
in the step (2), after the mixing, a post-treatment process is further included, and the post-treatment process sequentially includes stirring, calcining and reducing.
Optionally, in the step (1), the pH value of the precursor solution is 3 to 5;
further alternatively, the pH of the mixed solution may be independently selected from 3, 4, 5;
in the step (1), the stirring temperature is 25-80 ℃; the stirring time is 1-12 h;
Further alternatively, the stirring temperature may be independently selected from 25 ℃, 50 ℃, 80 ℃;
Further alternatively, the stirring time may be independently selected from 1h, 6h, 12h.
In the pretreatment in the step (2), the drying temperature is 60-100 ℃ and the drying time is 5-12 h;
Further alternatively, the drying temperature may be independently selected from 60 ℃, 80 ℃, 100 ℃;
Further alternatively, the drying time may be independently selected from 5 hours, 10 hours, 12 hours;
In the pretreatment in the step (2), the calcination temperature is 500-800 ℃; the calcination time is 3-6 h;
The temperature rising rate of the calcination is 2 ℃/min;
Further alternatively, the calcination temperature may be independently selected from 500 ℃, 600 ℃, 800 ℃;
further alternatively, the calcination time may be independently selected from 3h, 4h, 5h, 6h;
in the pretreatment of step (2), the calcination is performed under an inert atmosphere condition;
optionally, in the pretreatment in the step (2), the inactive atmosphere is an argon atmosphere.
Optionally, in the step (2), in the post-treatment procedure, the stirring temperature is 25-60 ℃;
the stirring time is 1-12 h;
Further alternatively, the stirring time may be independently selected from 1h, 6h, 12h;
Further alternatively, the stirring temperature may be independently selected from 25 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃;
Optionally, in the step (2), in the post-treatment procedure, the calcination temperature is 200-500 ℃; the calcination time is 3-6 h; the calcination heating rate is 2 ℃/min;
further alternatively, the calcination temperature may be independently selected from 200 ℃, 300 ℃, 400 ℃, 500 ℃;
further alternatively, the calcination time may be independently selected from 3h, 4h, 5h, 6h;
In the post-treatment step, the calcination is performed under an inert atmosphere condition;
in the post-treatment process, the inactive atmosphere is argon atmosphere;
In the post-treatment step, the reduction is performed under a hydrogen atmosphere.
Optionally, in the step (2), the reduction temperature is 200-400 ℃ in the post-treatment procedure; the reduction time is 1-3 h;
The reduction heating rate is 2 ℃/min;
further alternatively, the reduction temperature may be independently selected from 200 ℃, 300 ℃, 400 ℃;
further alternatively, the reduction time may be independently selected from 1h, 2h, 3h;
according to still another aspect of the present application, there is provided a method for preparing ethanol by hydrogenating carbon dioxide, wherein the supported rhodium-based catalyst or the supported rhodium-based catalyst prepared according to the method is mixed with a solvent, and the mixture gas containing carbon dioxide and hydrogen is contacted and reacted to prepare ethanol.
Optionally, the method at least comprises the steps of:
Placing the supported rhodium-based catalyst into a reaction kettle, adding a solvent, introducing carbon dioxide, replacing air in the reaction kettle, and introducing a mixed gas of carbon dioxide and hydrogen to reach the reaction pressure; carrying out contact reaction to prepare ethanol;
optionally, the mass ratio of the supported rhodium-based catalyst to the solvent is 0.01-0.1;
further alternatively, the upper mass ratio limit of the supported rhodium-based catalyst to the solvent may be independently selected from 0.06, 0.07, 0.08, 0.09, 0.1; the lower limit of the mass ratio of the supported rhodium-based catalyst to the solvent can be independently selected from 0.01, 0.02, 0.03, 0.04 and 0.05.
Optionally, the volume ratio of the carbon dioxide to the hydrogen is 1:1-1:6;
further alternatively, the upper limit of the volume ratio of carbon dioxide to hydrogen may be independently selected from 1:1, 1:1.5, 1:2, 1:2.5, 1:3; the lower limit of the volume ratio of carbon dioxide to hydrogen can be independently selected from 1:4, 1:4.5, 1:5, 1:5.5, 1:6.
Optionally, the reaction temperature is 100-300 ℃; the reaction time is 0.5 h-20 h.
Further alternatively, the reaction temperature may be independently selected from 100 ℃, 200 ℃, 300 ℃;
Further alternatively, the upper reaction time limit may be independently selected from 16h, 17h, 18h, 19h, 20h; the lower limit of the reaction time can be independently selected from 0.5h, 1.5h, 2.5h, 3.5h and 4.5h;
Optionally, the solvent is selected from at least one of water, N-dimethylformamide, cyclohexane, dichloromethane, 1,4 dioxane;
The mass ratio of the supported rhodium-based catalyst to the carbon dioxide is 1:10-1:1;
Further alternatively, the upper mass ratio of the supported rhodium-based catalyst and carbon dioxide may be independently selected from 1:1, 1:1.5, 1:2, 1:2.5, 1:3; the lower mass ratio limit of the supported rhodium-based catalyst and carbon dioxide can be independently selected from 1:8, 1:8.5, 1:9, 1:9.5 and 1:10;
the reaction pressure is 0.5-8 Mpa;
Further alternatively, the upper limit of the reaction pressure may be independently selected from 4.0Mpa, 5.0Mpa, 6.0Mpa, 7.0Mpa, 8.0Mpa; the lower limit of the reaction pressure can be independently selected from 0.5Mpa, 1.0Mpa, 1.5Mpa, 2.0Mpa and 2.5Mpa.
Compared with the prior art, the application has the following beneficial effects:
(1) Due to a special electronic structure, the molybdenum carbide has the property of noble metal, and the molybdenum carbide is used as a carrier, so that CO 2 and hydrogen can be effectively adsorbed and activated simultaneously; the second active component rhodium with carbonyl insertion function is introduced into the molybdenum carbide catalyst for generating methanol by hydrogenating carbon dioxide, rhodium element is loaded on the molybdenum carbide, and the content and valence state of metal rhodium are regulated to form a double-active-center synergistic composite catalyst, so that the catalyst has good catalytic activity in the carbon dioxide hydrogenation reaction, high-selectivity hydrogenation of carbon dioxide to ethanol is realized, and meanwhile, the conversion rate of carbon dioxide is higher.
(2) The introduction of the auxiliary component of alkali metal potassium further regulates and controls the surface electronic structure of the catalyst, on one hand, the introduction of the alkali metal promotes the adsorption and activation of acidic CO 2, and on the other hand, the auxiliary component of alkali metal potassium also plays a role in regulating the adsorption and activation of hydrogen to the carrier molybdenum carbide, so that higher catalyst stability is obtained, and higher catalytic activity and ethanol selectivity are obtained.
(3) The preparation method of the catalyst is simple, the catalytic efficiency is high, the method operability is strong, the control is easy, and the catalyst has wide development space and market application.
Drawings
FIG. 1 is an XRD pattern of molybdenum carbide in a catalyst sample prepared in example 1;
FIG. 2 is an XPS chart of elemental rhodium in a sample of the catalyst prepared in example 1.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
In the examples of the present application, the catalyst evaluation, conversion and selectivity calculation methods are as follows:
The activity evaluation of the catalyst in the ethanol synthesis reaction by CO 2 hydrogenation is carried out in a high-pressure closed reaction kettle. The specific experimental process is as follows:
50mg of the catalyst was charged into a high-pressure closed reaction vessel and 5ml of solvent was added. At room temperature, the air in the reaction kettle is replaced three times by high-purity CO 2, and then high-pressure H 2 (the molar ratio of carbon dioxide to hydrogen to nitrogen is 1:3:1, wherein the nitrogen is used as an internal standard substance) is introduced. The reaction was carried out at 150℃for 10h. After the reaction was completed, the reaction vessel was cooled to room temperature, the gas in the reaction vessel was collected with an air bag, and the remaining liquid was further centrifuged to obtain a supernatant. The gas and liquid phase products were analyzed off-line on an Agilent 7890B chromatograph, two detectors were configured for TCD and FID, two columns of TDX-01 (2.0 m x 2 mm) and FFAP (30.0 m x 0.32mm x 1 μm), wherein the TDX-01 column was used to detect and analyze the gas phase products and the FFAP column was used to detect and analyze CH 3 OH and CH 3CH2 OH.
The conversion of CO 2 was calculated from the reduction of CO 2 as follows:
The reaction product is mainly CH 3OH,CH3CH2 OH. The calculation formula of the selectivity of each product is as follows:
where x (in) (x represents CO 2、N2) represents the concentration of x in the feed gas and x (out) represents the concentration of x in the liquid phase product off-gas.
Example 1
And (2) in the step (1), 5.20g of RhCl 3·3H2O 0.04g、(NH4)6Mo7O24·4H2 O is respectively weighed and dissolved in 100ml of deionized water, aniline is added, the concentration of the aniline is 1mol/L, and stirring is continued. Slowly dripping 1mol/L HCl solution into the solution, adjusting the pH to 4, and then continuously stirring for 6 hours in a water bath kettle at 50 ℃; after the reaction is finished, the generated white solid is washed by 400ml of ethanol, filtered and dried for 10 hours at 80 ℃; after the drying was completed, the solid was placed in a tube furnace, heated to 600 ℃ at 2 ℃/min under an argon atmosphere and calcined for 5 hours to obtain a composite.
Completely dissolving soluble potassium carbonate in deionized water, wherein the concentration of potassium ions is 0.5mol/L, then adding the compound, stirring for 6 hours at 25 ℃, and evaporating to dryness; placing the evaporated solid into a tube furnace, heating to 400 ℃ at 2 ℃/min under the argon atmosphere, and calcining for 4 hours; cooling to room temperature, heating to 300 ℃ at 2 ℃/min under the hydrogen atmosphere, and reducing for 2 hours to finally obtain a supported rhodium-based catalyst sample.
As can be seen from fig. 1, the carrier is molybdenum carbide crystal, and the molybdenum carbide has high crystallinity, and as can be seen from fig. 2, rhodium exists in the catalyst in the form of simple substance.
Examples 2 to 23
The method is the same as in example 1, the preparation process conditions are respectively changed, and the method is used in the reaction for preparing ethanol by hydrogenating carbon dioxide under the conditions of 150 ℃, 5MPa and 1,4 dioxane, and the preparation conditions and the evaluation results which are different from those of example 1 are shown in Table 1.
TABLE 1 influence of different preparation process conditions on the performance of catalysts for the hydrogenation of carbon dioxide to ethanol
Example 24
Separately, weighing RhCl 3·3H2O 0.02g、(NH4)6Mo7O24·4H2 O5.20 g, dissolving in 100ml deionized water, adding aniline with an aniline concentration of 1mol/L, and continuously stirring. Slowly dripping 1mol/L HCl solution into the solution, adjusting the pH to 4, and then continuously stirring for 6 hours in a water bath kettle at 50 ℃; after the reaction is finished, the generated white solid is washed by 400ml of ethanol, filtered and dried for 10 hours at 80 ℃; after the drying is finished, placing the solid in a tube furnace, heating to 600 ℃ at 2 ℃/min under the argon atmosphere, and calcining for 5 hours to obtain a compound; completely dissolving soluble potassium carbonate in deionized water, wherein the concentration of potassium ions is 0.5mol/L, then adding the compound, stirring for 6 hours at 25 ℃, and evaporating to dryness; placing the evaporated solid into a tube furnace, heating to 400 ℃ at 2 ℃/min under the argon atmosphere, and calcining for 4 hours; cooling to room temperature, heating to 300 ℃ at 2 ℃/min under the hydrogen atmosphere, and reducing for 2 hours to finally obtain a supported rhodium-based catalyst sample.
Example 25
The procedure was as in example 1, except that the addition of RhCl 3·3H2 O was increased to 0.06g.
Example 26
The procedure was as in example 1, except that the addition of RhCl 3·3H2 O was increased to 0.08g.
Example 27
The preparation procedure was the same as in example 1, except that the potassium ion concentration was 1mol/L.
Example 28
The preparation procedure was the same as in example 1, except that the potassium ion concentration was 2mol/L.
Example 29
The preparation procedure was the same as in example 1, except that the potassium ion concentration was 4mol/L.
Example 30
The performance of the catalysts prepared in example 1 and examples 24, 25, 26, which were used in the hydrogenation of carbon dioxide to ethanol at 150℃under 5MPa and 1,4 dioxane conditions, are shown in Table 2.
TABLE 2 influence of different Rh loadings on the performance of catalysts for the hydrogenation of carbon dioxide to ethanol
Table 2 shows the catalytic activity of CO 2 hydrogenation: example 26> example 25> example 24> example 1; ethanol selectivity: example 26< example 25< example 24< example 1. It is shown that the preferred addition amount of RhCl 3·3H2 O is 0.02-0.04 g, and when the addition amount of RhCl 3·3H2 O is more than 0.04g, the hydrogenation capacity of the catalyst is enhanced along with the increase of rhodium loading, and the methanol forming speed is higher than the ethanol forming speed, so that the selectivity of ethanol is reduced along with the increase of rhodium content.
Example 31:
the performance of the catalysts prepared in example 1 and examples 27, 28, 29, used in the hydrogenation of carbon dioxide to ethanol at 150℃under 5MPa and 1,4 dioxane conditions, is shown in Table 3.
TABLE 3 influence of different K loadings on the performance of catalysts for the hydrogenation of carbon dioxide to ethanol
As can be seen from table 3, the catalytic activity of CO 2 hydrogenation: example 27> example 1> example 28> example 29; ethanol selectivity: example 27> example 1> example 28> example 29. This means that properly increasing the potassium content not only increases the catalytic activity of the hydrogenation of CO 2 but also increases the selectivity of ethanol, preferably with a potassium ion concentration of 0.5 to 1mol/L, when the potassium ion concentration is greater than 1mol/L, the activated conversion of CO 2 is inhibited, the hydrogenation efficiency is reduced, resulting in reduced activity, and too high potassium content also affects the carbon-carbon coupling process, resulting in reduced selectivity of ethanol.
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.
Claims (17)
1. A supported rhodium-based catalyst for preparing ethanol by carbon dioxide hydrogenation is characterized in that,
The catalyst comprises molybdenum carbide, rhodium element and potassium element;
the rhodium element and the potassium element are supported on the molybdenum carbide;
the rhodium element is loaded on molybdenum carbide in a simple substance form;
The mass ratio of rhodium to the carrier is 0.001:1-0.5:1;
the mass ratio of the potassium element to the carrier is 0.001:1-0.5:1;
the preparation method of the supported rhodium-based catalyst at least comprises the following steps:
Step (1): carrying out organic-inorganic hybridization reaction on the precursor solution and an aromatic amine compound to prepare a compound;
step (2): mixing a precursor solution containing potassium element with the compound to prepare a supported rhodium-based catalyst;
in the step (1), the precursor solution contains a precursor of rhodium element and a precursor of molybdenum element;
the aromatic amine compound is aniline; the concentration of the aniline is 0.1-10 mol/L;
The concentration of the potassium element is 0.5-1 mol/L, calculated by the concentration of potassium ions;
the precursor solution in the step (1) comprises a solvent and hydrochloric acid;
step (2), before mixing, further comprising a step of pretreating the composite;
The pretreatment comprises drying and calcination in sequence, wherein the calcination temperature is 500-800 ℃; the calcination time is 3-6 hours;
after mixing, the method further comprises a post-treatment procedure, wherein the post-treatment procedure sequentially comprises stirring, calcining and reducing;
the pH value of the precursor solution is 3-5.
2. A process for the preparation of the supported rhodium-based catalyst of claim 1, said process comprising at least the steps of:
Step (1): carrying out organic-inorganic hybridization reaction on the precursor solution and an aromatic amine compound to prepare a compound;
step (2): mixing a precursor solution containing potassium element with the compound to prepare a supported rhodium-based catalyst;
in the step (1), the precursor solution contains a precursor of rhodium element and a precursor of molybdenum element;
the aromatic amine compound is aniline; the concentration of the aniline is 0.1-10 mol/L;
The concentration of the potassium element is 0.5-1 mol/L, calculated by the concentration of potassium ions;
the precursor solution in the step (1) comprises a solvent and hydrochloric acid;
step (2), before mixing, further comprising a step of pretreating the composite;
the pretreatment comprises drying and calcination in sequence, wherein the calcination temperature is 500-800 ℃, and the calcination time is 3-6 hours;
after mixing, the method further comprises a post-treatment procedure, wherein the post-treatment procedure sequentially comprises stirring, calcining and reducing;
the pH value of the precursor solution is 3-5.
3. The method according to claim 2, wherein,
The precursor of rhodium element is at least one of rhodium chloride, rhodium nitrate and rhodium sulfate; the precursor of molybdenum element is at least one of molybdic acid, paramolybdic acid, molybdate and paramolybdate.
4. The method according to claim 2, wherein,
In the step (2), the precursor of the potassium element is at least one selected from potassium chloride, potassium carbonate and potassium nitrate.
5. The method according to claim 2, wherein,
In step (1), the solvent is selected from deionized water;
the organic-inorganic hybridization reaction adopts a stirring mode.
6. The method according to claim 5, wherein,
In the step (1), the stirring temperature is 25-80 ℃; the stirring time is 1-12 h.
7. The method according to claim 2, wherein,
In the step (2), the pretreatment conditions are as follows: the drying temperature is 60-100 ℃, and the drying time is 5-12 hours; the calcination is performed under inert atmosphere conditions.
8. The method according to claim 7, wherein,
The inactive atmosphere is an argon atmosphere.
9. The method according to claim 2, wherein,
In the step (2), in the post-treatment step, the stirring temperature is 25-60 ℃; stirring time is 1-12 h; the calcination temperature is 200-500 ℃; the calcination time is 3-6 hours; the calcination is performed under inert atmosphere conditions.
10. The method according to claim 9, wherein,
The inactive atmosphere is an argon atmosphere.
11. The method according to claim 2, wherein,
The reduction is carried out under the condition of hydrogen atmosphere; the reduction temperature is 200-400 ℃; the reduction time is 1-3 h.
12. A method for preparing ethanol by hydrogenating carbon dioxide is characterized by comprising the following steps: mixing the supported rhodium-based catalyst according to claim 1 or the supported rhodium-based catalyst prepared by the preparation method according to any one of claims 2-11 with a solvent, and performing contact reaction with a mixed gas containing carbon dioxide and hydrogen to prepare ethanol.
13. Method according to claim 12, characterized in that it comprises at least the following steps:
Placing the supported rhodium-based catalyst into a reaction kettle, adding a solvent, introducing carbon dioxide, replacing air in the reaction kettle, and introducing a mixed gas of carbon dioxide and hydrogen into the reaction kettle to reach the reaction pressure; and (3) carrying out contact reaction to prepare the ethanol.
14. The method of claim 12, wherein the step of determining the position of the probe is performed,
The volume ratio of the carbon dioxide to the hydrogen is 1:1-1:6.
15. The method of claim 12, wherein the step of determining the position of the probe is performed,
The reaction temperature is 100-300 ℃; the reaction time is 0.5 h-20 h.
16. The method of claim 12, wherein the step of determining the position of the probe is performed,
The solvent is at least one selected from water, N-dimethylformamide cyclohexane, dichloromethane and 1,4 dioxane.
17. The method of claim 13, wherein the step of determining the position of the probe is performed,
The reaction pressure is 0.5-8 mpa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110440016.4A CN115228491B (en) | 2021-04-23 | 2021-04-23 | High-dispersion rhodium-based catalyst, preparation method thereof and application thereof in preparing ethanol from carbon dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110440016.4A CN115228491B (en) | 2021-04-23 | 2021-04-23 | High-dispersion rhodium-based catalyst, preparation method thereof and application thereof in preparing ethanol from carbon dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115228491A CN115228491A (en) | 2022-10-25 |
| CN115228491B true CN115228491B (en) | 2024-04-19 |
Family
ID=83666162
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110440016.4A Active CN115228491B (en) | 2021-04-23 | 2021-04-23 | High-dispersion rhodium-based catalyst, preparation method thereof and application thereof in preparing ethanol from carbon dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115228491B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0717884A (en) * | 1993-07-05 | 1995-01-20 | Agency Of Ind Science & Technol | Production of ethanol |
| CN101367521A (en) * | 2008-10-13 | 2009-02-18 | 复旦大学 | Synthesis of stephanoporate molybdenum carbide nano-wire |
| CN104995161A (en) * | 2013-02-22 | 2015-10-21 | 伊士曼化工公司 | Production of methanol and ethanol from co or co2 |
| CN106311281A (en) * | 2015-07-02 | 2017-01-11 | 中国科学院大连化学物理研究所 | Catalyst for synthesis of low carbon alcohol by hydrogenation of carbon dioxide as well as preparation method and application thereof |
| CN109954507A (en) * | 2019-04-16 | 2019-07-02 | 宁夏大学 | Ni-Rh/αβ-MoXC composite catalyst and preparation and application |
| CN111185209A (en) * | 2018-11-14 | 2020-05-22 | 中国科学院大连化学物理研究所 | Preparation of molybdenum carbide supported nickel-based catalyst and application of catalyst in preparation of ethanol by hydrogenation of carbon dioxide |
| CN111420689A (en) * | 2020-03-26 | 2020-07-17 | 内蒙古大学 | Preparation method and application of catalyst for preparing low-carbon alcohol from synthesis gas |
| CN111434382A (en) * | 2019-01-15 | 2020-07-21 | 天津大学 | Carrier-supported vanadium oxide promoted Rh-based catalyst and preparation method and application thereof |
-
2021
- 2021-04-23 CN CN202110440016.4A patent/CN115228491B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0717884A (en) * | 1993-07-05 | 1995-01-20 | Agency Of Ind Science & Technol | Production of ethanol |
| CN101367521A (en) * | 2008-10-13 | 2009-02-18 | 复旦大学 | Synthesis of stephanoporate molybdenum carbide nano-wire |
| CN104995161A (en) * | 2013-02-22 | 2015-10-21 | 伊士曼化工公司 | Production of methanol and ethanol from co or co2 |
| CN106311281A (en) * | 2015-07-02 | 2017-01-11 | 中国科学院大连化学物理研究所 | Catalyst for synthesis of low carbon alcohol by hydrogenation of carbon dioxide as well as preparation method and application thereof |
| CN111185209A (en) * | 2018-11-14 | 2020-05-22 | 中国科学院大连化学物理研究所 | Preparation of molybdenum carbide supported nickel-based catalyst and application of catalyst in preparation of ethanol by hydrogenation of carbon dioxide |
| CN111434382A (en) * | 2019-01-15 | 2020-07-21 | 天津大学 | Carrier-supported vanadium oxide promoted Rh-based catalyst and preparation method and application thereof |
| CN109954507A (en) * | 2019-04-16 | 2019-07-02 | 宁夏大学 | Ni-Rh/αβ-MoXC composite catalyst and preparation and application |
| CN111420689A (en) * | 2020-03-26 | 2020-07-17 | 内蒙古大学 | Preparation method and application of catalyst for preparing low-carbon alcohol from synthesis gas |
Non-Patent Citations (1)
| Title |
|---|
| "Low temperature CO2 hydrogenation to alcohols and hydrocarbons over Mo2C supported metal catalysts‘;Yuan Chen等;《Journal of Catalysis》;第343卷;147-156 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115228491A (en) | 2022-10-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8697028B2 (en) | Catalytic method for obtaining hydrogen or a hydrogen-rich gas starting from bioethanol and/or ethanol | |
| CN101940958A (en) | Method for preparing low-carbon olefine catalyst by loading iron-based synthetic gas | |
| CN111215084A (en) | Copper-based catalyst for preparing methanol by carbon dioxide hydrogenation, preparation and application thereof | |
| CN101972656A (en) | Nickel-base catalyst used for autothermal reforming of ethanol for producing hydrogen and preparation method thereof | |
| CN101428229B (en) | Catalyst for synthesis of gas produced low-carbon mixed alcohol and production method thereof | |
| Fujitsuka et al. | Hydrogen Production from formic acid using Pd/C, Pt/C, and Ni/C catalysts prepared from Ion-exchange resins | |
| CN106861689B (en) | Pd-based catalyst and preparation and application thereof | |
| Tian et al. | Advances in hydrogen production by aqueous phase reforming of biomass oxygenated derivatives | |
| CN109999814A (en) | Nano metal Raney nickel and preparation method for carbon dioxide methanation reaction | |
| CN115228491B (en) | High-dispersion rhodium-based catalyst, preparation method thereof and application thereof in preparing ethanol from carbon dioxide | |
| CN111217673B (en) | Method for high-energy utilization of ethanol | |
| Qiu et al. | Hydrogen production by low-temperature steam reforming of bio-oil over Ni/HZSM-5 catalyst | |
| CN112237918A (en) | Dual-function supported catalyst for oxidative dehydrogenation and dry reforming of low-carbon alkane and preparation method thereof | |
| CN109847777A (en) | A kind of solid-carrying type Cu base catalyst and its preparation method and application | |
| CN114984952A (en) | Carbon-coated copper material and preparation method and application thereof | |
| CN112237926B (en) | Metal supported catalyst and preparation method thereof | |
| CN104710280B (en) | Method for producing methanol co-production C2 C4 alcohol | |
| Guo et al. | Conversion of Levulinic Acid and its Esters to 1, 5‐dimethyl‐2‐Pyrrolidone over a Nonnoble Metallic Ni@ CeOx Catalyst | |
| CN113979837A (en) | Application of cobalt-based catalyst in hydrogenolysis reaction of biomass and derivatives thereof | |
| CN109647492B (en) | Catalyst for directly producing low-carbon olefin by synthesis gas | |
| CN114602449B (en) | ZnZrO (zinc ZrO-rich alloy) 2 Surface solid solution catalyst, preparation method and application thereof | |
| CN115475626B (en) | Preparation method of catalyst for preparing long-chain hydrocarbon and co-producing low-carbon olefin through carbon dioxide hydrogenation | |
| CN115555021B (en) | Preparation method of catalyst for co-production of liquid hydrocarbon and low-carbon olefin by hydrogenation of carbon dioxide | |
| CN115197280B (en) | Metal cobalt complex with photocatalytic carbon dioxide reduction activity and preparation method and application thereof | |
| KR101220759B1 (en) | Nickel catalyst supported on xerogel alumina and method for amnufacturing the same, and method for manufacturing methane using said catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |