CN115228491A - High-dispersion rhodium-based catalyst, preparation method thereof and application thereof in preparation of ethanol from carbon dioxide - Google Patents
High-dispersion rhodium-based catalyst, preparation method thereof and application thereof in preparation of ethanol from carbon dioxide Download PDFInfo
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- CN115228491A CN115228491A CN202110440016.4A CN202110440016A CN115228491A CN 115228491 A CN115228491 A CN 115228491A CN 202110440016 A CN202110440016 A CN 202110440016A CN 115228491 A CN115228491 A CN 115228491A
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- rhodium
- carbon dioxide
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- potassium
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 90
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 239000010948 rhodium Substances 0.000 title claims abstract description 56
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 55
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 38
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 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 34
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910039444 MoC Inorganic materials 0.000 claims abstract description 23
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 22
- 239000011591 potassium Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims description 42
- 238000001354 calcination Methods 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 22
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 239000012298 atmosphere Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910001414 potassium ion Inorganic materials 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 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 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- -1 aromatic amine compound Chemical class 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
- 239000008246 gaseous mixture Substances 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 4
- 150000001340 alkali metals Chemical class 0.000 abstract description 4
- 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
- 239000002131 composite material 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 1
- 230000004048 modification Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 238000011161 development Methods 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
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 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
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000001914 filtration 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
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 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
- 239000012071 phase Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 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
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect 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
- 230000001276 controlling effect Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 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
- 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
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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 preparation of ethanol from carbon dioxide, and mainly solves the problems of low conversion rate and poor selectivity of high-carbon alcohols in a carbon dioxide hydrogenation reaction. The catalyst comprises molybdenum carbide, rhodium and potassium, wherein the rhodium and the potassium are loaded on the molybdenum carbide. According to the invention, the second active component rhodium with carbonyl insertion function is introduced into the molybdenum carbide catalyst for hydrogenating carbon dioxide to generate methanol to form the composite catalyst with the synergy of double active centers, and the carbon dioxide is hydrogenated to ethanol with high selectivity under the modification of the alkali metal auxiliary agent, and simultaneously, the carbon dioxide conversion rate is higher.
Description
Technical Field
The application relates to a high-dispersion rhodium-based catalyst, a preparation method thereof and application thereof in preparation of ethanol by hydrogenation of carbon dioxide, belonging to the field of petrochemical industry.
Background
While the human society is rapidly developing, a large amount of fossil energy is consumed, and simultaneously, a large amount of greenhouse gases such as carbon dioxide, methane and the like are emitted. This has led to the world facing increasingly severe energy and environmental crisis. Carbon dioxide is used as a gas which is cheap, nontoxic and wide in source, and is recycled and catalytically converted into fuels with high industrial value such as formic acid, alcohols and even fuel oil, so that the utilization rate of carbon resources can be improved on one hand, and the environmental problem of global warming can be solved on the other hand.
Ethanol is used as a fuel with high energy density, and in the current practical application, the ethanol not only can be used as an automobile fuel additive, but also can completely replace the traditional gasoline, and the ethanol fuel is used as a main power source. Meanwhile, the compound is used as a common chemical solvent and has wide application in various aspects such as cosmetics, medicines, pesticides and the like. Therefore, the conversion of carbon dioxide to ethanol is one of the most desirable products to achieve the "liquid sunlight" (Joule 2018,2 (10), 1925-1949) strategy for efficient utilization of renewable energy (solar energy).
At present, CO 2 In the preparation of ethanol by catalytic hydrogenation, homogeneous catalysts generally have relatively high activity and selectivity, but due to the metal complex catalyst (CN 104995161a, us 8912240B2) used in the reaction process, the catalyst is expensive and has poor stability, and the difficulty in separation from the reacted product is an unavoidable problem. In view of these features of homogeneous catalysis, scientists have been working on CO 2 Research on high-efficiency hydrogenation heterogeneous catalysts. Among them, the modified fischer-tropsch catalysts (such as Fe-based, co-based, etc.) are receiving much attention because of their higher carbon chain extension ability. But directly applying CO hydrogenation catalyst to CO 2 In the hydrogenation reaction, there are still more problems because of CO 2 The mechanism of ethanol preparation by hydrogenation is different from that of ethanol preparation by synthesis gas, and the method aims at CO at present 2 The hydrogenation characteristics of the catalyst are relatively less in targeted development. Application of traditional Fischer-Tropsch modified catalyst to CO 2 During the hydrogenation reaction, CO 2 The conversion rate is low, a large amount of low-carbon alkane is still generated in the hydrogenation product, the liquid-phase alcohol product after reaction accords with ASF distribution, the product contains mixed alcohol such as methanol and propanol besides ethanol, and the carbon chain growth degree cannot be accurately controlled. Meanwhile, the initial temperature of the general effective catalyst of the Fischer-Tropsch catalyst is 300 ℃ or above, and is higherThe reaction temperature also means higher energy consumption and more by-products.
In summary, CO is currently catalyzed 2 The homogeneous catalyst for preparing ethanol by hydrogenation has high requirements on reaction equipment, complex process flow, poor stability and short service life of the catalyst; the heterogeneous catalyst needs high reaction temperature, large process energy consumption, more byproducts, low catalyst activity and low ethanol selectivity, and when CO is used 2 After a conversion of more than 10%, the ethanol selectivity will be less than 40%, and therefore, in order to achieve CO 2 Resource utilization, reduction of dependence on fossil energy, and development of CO under mild conditions 2 High-efficiency heterogeneous catalyst with high activity and high selectivity for conversion.
Disclosure of Invention
CO 2 In the process of synthesizing ethanol by hydrogenation, CO 2 And adsorption activation of hydrogen is a prerequisite for the reaction to occur. CO 2 2 As a non-polar molecule, it is highly inert and not easily activated. Due to the special electronic structure of the molybdenum carbide, the molybdenum carbide has the property of being similar to noble metal, thereby being used for CO 2 And both the catalyst and hydrogen have stronger activation capability. The object of the invention is to obtain a catalyst based on CO 2 The characteristic of hydrogenation reaction provides CO with high activity, especially higher selectivity 2 A catalyst for preparing ethanol by hydrogenation.
The invention can effectively activate CO 2 And hydrogen-containing molybdenum carbide as carrier, and noble metal rhodium is used for dissociative adsorption of CO 2 The ability to form carbonyl species, form initial carbon-carbon bonds, anchor the noble metal rhodium to the molybdenum carbide support, is obtained in the presence of CO 2 A novel bifunctional catalyst with high activity and good stability in hydrogenation reaction.
The technical problem to be solved by the invention is to aim at CO 2 The catalyst is difficult to activate and the selectivity of the hydrogenation product ethanol is not high, the preparation method of the catalyst is improved, the alkali metal potassium is further introduced, and the molybdenum carbide carrier is regulated and controlled to adsorb and activate CO 2 The ability of generating intermediate, and further improve the selectivity and activity of the catalyst in the reaction of preparing ethanol by carbon dioxide hydrogenation.
The invention providesThe molybdenum carbide-based hydrogenation catalyst with high catalyst efficiency and the preparation method thereof are simple, easy to control and strong in operability. According to the invention, the stability of the catalyst is improved and the loading of the noble metal rhodium of the catalyst is reduced by regulating and controlling the loading of the noble metal rhodium and combining the stabilizing effect of the molybdenum carbide carrier on the noble metal rhodium. The introduction of rhodium plays an important role in establishing and stabilizing the bifunctional active center, and the addition amount of rhodium directly influences the hydrogenation property of the bifunctional active center. The catalyst prepared by the method has high reaction activity, high ethanol selectivity and CO resistance 2 The hydrogenation for preparing the ethanol has a larger application prospect.
According to one aspect of the application, a supported rhodium-based catalyst is provided, the catalyst comprises molybdenum carbide, rhodium element and potassium element, and the rhodium element and the potassium element are 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 the molybdenum carbide in a simple substance form;
the mass ratio of the rhodium element to the carrier is 0.001-0.5;
the mass ratio of the potassium element to the carrier is 0.001.
Further alternatively, the upper limit of the mass ratio of the rhodium element to the support may be independently selected from 0.5; the lower mass ratio limit of the rhodium element to the carrier can be independently selected from 0.001.
Further alternatively, the upper limit of the mass ratio of the potassium element to the carrier may be independently selected from 0.5; the lower limit of the mass ratio of the potassium element to the carrier can be independently selected from 0.001.
According to yet another aspect of the present application, there is provided a process for the preparation of the supported rhodium-based catalyst, the process at least comprising the steps of:
carrying out organic-inorganic hybrid 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;
optionally, the method of step (1) is selected from at least one of impregnation, co-precipitation or precipitation;
the method of the step (2) is at least one of impregnation, coprecipitation or deposition precipitation.
In the step (1), the precursor solution contains a precursor of rhodium and a precursor of molybdenum;
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 selected from 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 can be independently selected from 8mol/L, 8.5mol/L, 9mol/L, 9.5mol/L, 10mol/L; the lower limit of the concentration 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 potassium element in the step (2) is selected from at least one of potassium chloride, potassium carbonate and potassium nitrate;
the concentration of the potassium element is 0.1-10 mol/L, and is calculated by the concentration of potassium ions.
Further alternatively, the upper concentration limit of the potassium element can be independently selected from 8mol/L, 8.5mol/L, 9mol/L, 9.5mol/L, 10mol/L; the lower limit of the concentration 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 the step (2), before the mixing, a step of pretreating the compound is further included;
the pretreatment sequentially comprises drying and calcining;
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 of 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 5h, 10h, 12h;
in the pretreatment of the step (2), the calcination temperature is 500-800 ℃; the calcination time is 3-6 h;
the calcination heating rate 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 the step (2), the calcination is carried out under the condition of an inactive atmosphere;
optionally, in the pretreatment of step (2), the inert atmosphere is an argon atmosphere.
Optionally, in the step (2), in the post-treatment process, the stirring temperature is 25 ℃ to 60 ℃;
the stirring time is 1-12 h;
further alternatively, the stirring time may be independently selected from 1h, 6h, 12h;
further optionally, the stirring temperature may be independently selected from 25 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃;
optionally, in the step (2), in the post-treatment process, the calcination temperature is 200 to 500 ℃; the calcination time is 3-6 h; the heating rate of calcination 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;
in the post-treatment process, the inert atmosphere is argon atmosphere;
in the post-treatment step, the reduction is performed under a hydrogen atmosphere.
Optionally, in the step (2), in the post-treatment process, the reduction temperature is 200 to 400 ℃; 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 another aspect of the application, the supported rhodium-based catalyst or the supported rhodium-based catalyst prepared by the method is mixed with a solvent, and is contacted and reacted with a mixed gas containing carbon dioxide and hydrogen to prepare the ethanol.
Optionally, the method comprises at least the steps of:
putting 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 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 limit of the mass ratio of the mass of the supported rhodium-based catalyst to the mass of 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 mass of the supported rhodium-based catalyst to the mass of the solvent can be independently selected from 0.01, 0.02, 0.03, 0.04 and 0.05.
Optionally, the volume ratio of carbon dioxide to hydrogen is 1;
further alternatively, the upper limit of the volume ratio of carbon dioxide and hydrogen can be independently selected from 1, 1.5, 1, 2, 1, 2.5, 1; the lower limit of the volume ratio of carbon dioxide to hydrogen can be independently selected from 1.
Optionally, the reaction temperature is 100-300 ℃; the reaction time is 0.5 to 20 hours.
Further optionally, 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 carbon dioxide is 1;
further optionally, the upper mass ratio limit of the supported rhodium-based catalyst to carbon dioxide may be independently selected from 1, 1.5, 1, 2, 1, 2.5, 1; the lower mass ratio limit of the supported rhodium-based catalyst to carbon dioxide can be independently selected from 1;
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 method has the following beneficial effects:
(1) Molybdenum carbide is due to its special characteristicsWith electronic structure, the material has the property of noble-like metal, and can effectively adsorb and activate CO by taking molybdenum carbide as a carrier 2 And hydrogen; the second active component rhodium with carbonyl insertion function is introduced into the molybdenum carbide catalyst which can hydrogenate carbon dioxide to generate methanol, rhodium element is loaded on the molybdenum carbide, and the composite catalyst with the synergetic double active centers is formed by regulating the content and valence state of metal rhodium, so that the catalyst has good catalytic activity in the carbon dioxide hydrogenation reaction, and has higher carbon dioxide conversion rate while realizing the high-selectivity hydrogenation of carbon dioxide to ethanol.
(2) The introduction of alkali metal potassium as an auxiliary component further regulates and controls the surface electronic structure of the catalyst, and on one hand, the introduction of alkali metal promotes acidic CO 2 The other side of the adsorption and activation of the molybdenum carbide also plays a role in regulating the adsorption and activation of hydrogen on the carrier, so that the higher catalytic activity and the higher ethanol selectivity can be obtained while the higher catalyst stability is obtained.
(3) The preparation method of the catalyst is simple, high in catalytic efficiency, strong in method operability, easy to control, and wide in development space and market application.
Drawings
FIG. 1 is an XRD pattern of molybdenum carbide in a sample of the catalyst prepared in example 1;
fig. 2 is an XPS plot of elemental rhodium in a sample of the catalyst prepared in example 1.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
In the examples of the present application, the methods for catalyst evaluation, conversion and selectivity calculation were as follows:
CO 2 the activity evaluation of the catalyst in the hydrogenation synthesis ethanol reaction is carried out in a high-pressure closed reaction kettle. The specific experimental process is as follows:
50mg of catalyst is filled into a high-pressure closed reaction kettleAnd 5ml of solvent was added. At room temperature with high purity CO 2 The air in the reaction kettle is replaced for three times, and then high pressure H is introduced 2 (the molar ratio of carbon dioxide, hydrogen, nitrogen is 1. 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 by a gas bag, and the remaining liquid was further centrifuged to take the supernatant. Gas phase product and liquid phase product are detected and analyzed off line on Agilent 7890B chromatogram, two detectors of TCD and FID are configured, two chromatographic columns of TDX-01 (2.0 m multiplied by 2 mm) and FFAP (30.0 m multiplied by 0.32mm multiplied by 1 μm) are configured, wherein, the TDX-01 chromatographic column is used for detecting and analyzing the gas phase product, the FFAP chromatographic column is used for detecting and analyzing CH 3 OH and CH 3 CH 2 OH。
CO 2 Conversion according to CO 2 Is calculated by the formula:
the reaction product is mainly CH 3 OH，CH 3 CH 2 And (5) OH. The calculation formula for each product selectivity is as follows:
wherein x (in) (x represents CO) 2 、N 2 ) Represents the concentration of x in the feed gas and x (out) represents the concentration of x in the liquid phase product tail gas.
Example 1
Respectively weighing RhCl in step (1) 3 ·3H 2 O 0.04g、(NH 4 ) 6 Mo 7 O 24 ·4H 2 O5.20 g is dissolved in 100ml of deionized water, aniline is added, the aniline concentration is 1mol/L, and stirring is continued. Slowly dropwise adding 1mol/L HCl into the solutionAdjusting the pH value of the solution to 4, and then continuously stirring the solution in a water bath kettle at the temperature of 50 ℃ for 6 hours; after the reaction is finished, washing the generated white solid by 400ml of ethanol, filtering, and drying for 10h at 80 ℃; after drying, the solid was placed in a tube furnace, heated to 600 ℃ at 2 ℃/min under argon atmosphere and calcined for 5h to obtain the 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; further putting the dried solid into a tubular furnace, heating to 400 ℃ at the speed of 2 ℃/min under the atmosphere of argon, and calcining for 4h; after cooling to room temperature, heating to 300 ℃ at the speed of 2 ℃/min under the atmosphere of hydrogen, and reducing for 2h to finally obtain the supported rhodium-based catalyst sample.
As can be seen from fig. 1, the carrier is a molybdenum carbide crystal, and the molybdenum carbide has high crystallinity, and as can be seen from fig. 2, the rhodium element exists in the catalyst in the form of a simple substance.
Examples 2 to 23
The method is the same as example 1, the preparation process conditions are respectively changed, and the method is used for the reaction of preparing ethanol by carbon dioxide hydrogenation under the conditions of 150 ℃, 5MPa and 1,4 dioxane, and the details of the preparation conditions and the evaluation results which are different from example 1 are shown in Table 1.
TABLE 1 influence of different preparation process conditions on the performance of catalyst for preparing ethanol by carbon dioxide hydrogenation
Example 24
Separately weighing RhCl 3 ·3H 2 O 0.02g、(NH 4 ) 6 Mo 7 O 24 ·4H 2 O5.20 g is dissolved in 100ml of deionized water, aniline is added, the aniline concentration is 1mol/L, and stirring is continued. Slowly dripping 1mol/L HCl solution into the solution,adjusting the pH value to 4, and then continuously stirring for 6 hours in a water bath kettle at the temperature of 50 ℃; after the reaction is finished, washing the generated white solid with 400ml of ethanol, filtering, and drying at 80 ℃ for 10h; after drying, putting the solid into a tubular furnace, heating to 600 ℃ at the speed of 2 ℃/min under the atmosphere of argon, 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 6h at 25 ℃, and evaporating to dryness; further putting the dried solid into a tube furnace, heating to 400 ℃ at the speed of 2 ℃/min under the argon atmosphere, and calcining for 4h; cooling to room temperature, heating to 300 ℃ at the speed of 2 ℃/min under the atmosphere of hydrogen, and reducing for 2h to obtain the supported rhodium-based catalyst sample.
Example 25
The procedure is as in example 1, except that RhCl is increased 3 ·3H 2 O was added in an amount of 0.06g.
Example 26
The procedure is as in example 1, except that RhCl is increased 3 ·3H 2 O was added in an amount of 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 properties of the catalysts prepared in example 1 and examples 24, 25 and 26, which were used in the reaction of producing ethanol by hydrogenation of carbon dioxide under the conditions of 150 ℃ and 5MPa in 1,4 dioxane, are shown in Table 2.
TABLE 2 influence of different Rh loadings on the performance of catalysts for carbon dioxide hydrogenation to ethanol
As can be seen from Table 2, CO 2 Catalytic activity of hydrogenation: example 26>Example 25>Example 24>Example 1; ethanol selectivity: example 26<Example 25<Example 24<Example 1. Illustrating the preferred RhCl 3 ·3H 2 The addition amount of O is 0.02-0.04 g when RhCl is added 3 ·3H 2 After the addition amount of O is more than 0.04g, the hydrogenation capacity of the catalyst is enhanced along with the increase of the loading amount of rhodium, the speed of generating methanol is higher than that of generating ethanol, and the selectivity of the ethanol is reduced along with the increase of the rhodium content.
Example 31:
the properties of the catalysts prepared in example 1 and examples 27, 28 and 29, which were used in the hydrogenation of carbon dioxide to ethanol at 150 ℃ and 5MPa in the presence of 1,4 dioxane, are given in Table 3.
TABLE 3 influence of different K-loading on the performance of catalyst for preparing ethanol by carbon dioxide hydrogenation
As can be seen from Table 3, CO 2 Catalytic activity of hydrogenation: example 27>Example 1>Example 28>Example 29; ethanol selectivity: example 27>Example 1>Example 28>Example 29. This indicates that not only CO can be increased by appropriately increasing the content of potassium metal 2 The catalytic activity of hydrogenation can also improve the selectivity of ethanol, the preferred concentration of potassium ions is 0.5-1 mol/L, and when the concentration of potassium ions is more than 1mol/L, CO 2 The activation conversion is suppressed, the hydrogenation efficiency is reduced, resulting in a reduction in activity, and an excessively high potassium content also affects the process of carbon-carbon coupling, resulting in a reduction in the selectivity of ethanol.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A supported rhodium-based catalyst characterized in that,
the catalyst comprises molybdenum carbide, rhodium and potassium;
the rhodium element and the potassium element are loaded on the molybdenum carbide.
2. The catalyst according to claim 1,
the mass ratio of the rhodium element to the carrier is 0.001-0.5;
the mass ratio of the potassium element to the carrier is 0.001 to 0.5.
3. A method for preparing the catalyst of claim 1, comprising at least the steps of:
step (1): carrying out organic-inorganic hybrid reaction on the precursor solution and the 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;
preferably, the precursor solution in step (1) contains a precursor of rhodium element and a precursor of molybdenum element; the precursor of the rhodium element is at least one of rhodium chloride, rhodium nitrate and rhodium sulfate; the precursor of the molybdenum element is selected from 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;
preferably, in the step (2), the precursor of potassium element is selected from at least one of potassium chloride, potassium carbonate and potassium nitrate; the concentration of the potassium element is 0.1-10 mol/L, and is calculated by the concentration of potassium ions.
4. The method of claim 3,
the precursor solution in the step (1) comprises a solvent and hydrochloric acid;
the solvent is selected from deionized water;
the organic-inorganic hybrid reaction adopts a stirring mode.
5. The method of claim 3,
in the step (2), before the mixing, a step of pretreating the compound is further included;
the pretreatment sequentially comprises drying and calcining;
after the mixing, the method also comprises a post-treatment process, wherein the post-treatment process sequentially comprises stirring, calcining and reducing.
6. The method of claim 4,
in the step (1), the pH value of the precursor solution is 3-5; the stirring temperature is 25-80 ℃; the stirring time is 1-12 h.
7. The method of claim 5,
in the step (2), the pretreatment conditions are as follows: the drying temperature is 60-100 ℃, and the drying time is 5-12 h; the calcining temperature is 500-800 ℃; the calcination time is 3-6 h; the calcination is carried out under non-reactive atmosphere conditions; preferably, the inert atmosphere is an argon atmosphere.
8. The method of claim 5,
in the step (2), in the working procedure of post-treatment, the stirring temperature is 25-60 ℃; the stirring time is 1 to 12 hours; the calcining temperature is 200-500 ℃; the calcination time is 3-6 h; the calcination is carried out under non-reactive atmosphere conditions; preferably, the inert atmosphere is an argon atmosphere; the reduction is carried out under the condition of hydrogen atmosphere; the reduction temperature is 200-400 ℃; the reduction time is 1-3 h.
9. A method for preparing ethanol by carbon dioxide hydrogenation is characterized by comprising the following steps: a supported rhodium-based catalyst as defined in claims 1-2 or as prepared by a process as defined in any of claims 3-8 is mixed with a solvent and reacted in contact with a gaseous mixture comprising carbon dioxide and hydrogen to produce ethanol.
10. Method according to claim 9, characterized in that it comprises at least the following steps:
putting 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 a reaction pressure; carrying out contact reaction to prepare ethanol;
preferably, the mass ratio of the supported rhodium-based catalyst to the solvent is 0.01-0.1;
preferably, the volume ratio of the carbon dioxide to the hydrogen is 1;
preferably, the reaction temperature is 100-300 ℃; the reaction time is 0.5 to 20 hours;
preferably, the solvent is selected from at least one of water, N-dimethylformamide cyclohexane, dichloromethane and 1,4 dioxane;
preferably, the mass ratio of the supported rhodium-based catalyst to the carbon dioxide is 1;
preferably, the reaction pressure is 0.5 to 8MPa.
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