CN115646547B - Rhodium-cobalt loaded monoatomic alloy catalyst for hydroformylation of high-carbon olefin and preparation and application methods thereof - Google Patents
Rhodium-cobalt loaded monoatomic alloy catalyst for hydroformylation of high-carbon olefin and preparation and application methods thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 118
- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 48
- 239000000956 alloy Substances 0.000 title claims abstract description 44
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 44
- SUCYXRASDBOYGB-UHFFFAOYSA-N cobalt rhodium Chemical compound [Co].[Rh] SUCYXRASDBOYGB-UHFFFAOYSA-N 0.000 title claims abstract description 42
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 14
- 238000006772 olefination reaction Methods 0.000 title description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 93
- 238000006243 chemical reaction Methods 0.000 claims abstract description 80
- 239000010948 rhodium Substances 0.000 claims abstract description 40
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 28
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 27
- 239000010941 cobalt Substances 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 239000011259 mixed solution Substances 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000000047 product Substances 0.000 claims abstract description 16
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 14
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002244 precipitate Substances 0.000 claims abstract description 13
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 10
- 238000001291 vacuum drying Methods 0.000 claims abstract description 10
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 4
- 150000001336 alkenes Chemical class 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 26
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 20
- 239000010453 quartz Substances 0.000 claims description 19
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000002105 nanoparticle Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 125000004429 atom Chemical group 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 8
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 8
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 claims description 8
- 238000011010 flushing procedure Methods 0.000 claims description 8
- 239000005457 ice water Substances 0.000 claims description 8
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 8
- 238000010926 purge Methods 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000006004 Quartz sand Substances 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 3
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910003450 rhodium oxide Inorganic materials 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- HSSMNYDDDSNUKH-UHFFFAOYSA-K trichlororhodium;hydrate Chemical compound O.Cl[Rh](Cl)Cl HSSMNYDDDSNUKH-UHFFFAOYSA-K 0.000 claims description 3
- FEQPHYCEZKWPNE-UHFFFAOYSA-K trichlororhodium;triphenylphosphane Chemical compound Cl[Rh](Cl)Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FEQPHYCEZKWPNE-UHFFFAOYSA-K 0.000 claims description 3
- FERQZYSWBVOPNX-UHFFFAOYSA-N carbonyl dichloride;rhodium;triphenylphosphane Chemical compound [Rh].ClC(Cl)=O.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FERQZYSWBVOPNX-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 10
- 238000000926 separation method Methods 0.000 abstract description 6
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- 239000012847 fine chemical Substances 0.000 abstract description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- GSOLWAFGMNOBSY-UHFFFAOYSA-N cobalt Chemical compound [Co][Co][Co][Co][Co][Co][Co][Co] GSOLWAFGMNOBSY-UHFFFAOYSA-N 0.000 abstract 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 150000001299 aldehydes Chemical class 0.000 description 17
- 230000000694 effects Effects 0.000 description 15
- 230000009257 reactivity Effects 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 5
- 239000002815 homogeneous catalyst Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- YVSTYWRWPBKPTR-UHFFFAOYSA-N [Zn].[Rh] Chemical compound [Zn].[Rh] YVSTYWRWPBKPTR-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- SGULOPRLUCGLSH-UHFFFAOYSA-M Cl[Rh].[C]=O.c1ccc(cc1)P(c1ccccc1)c1ccccc1.c1ccc(cc1)P(c1ccccc1)c1ccccc1 Chemical compound Cl[Rh].[C]=O.c1ccc(cc1)P(c1ccccc1)c1ccccc1.c1ccc(cc1)P(c1ccccc1)c1ccccc1 SGULOPRLUCGLSH-UHFFFAOYSA-M 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- FXHGMKSSBGDXIY-UHFFFAOYSA-N heptanal Chemical compound CCCCCCC=O FXHGMKSSBGDXIY-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- WJIBZZVTNMAURL-UHFFFAOYSA-N phosphane;rhodium Chemical compound P.[Rh] WJIBZZVTNMAURL-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 2
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
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- 150000001728 carbonyl compounds Chemical class 0.000 description 1
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- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 description 1
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Abstract
The invention relates to the field of fine chemical engineering, and discloses a high-carbon olefin hydroformylation carbon-supported rhodium-cobalt monoatomic alloy catalyst and a preparation and application method thereof. The catalyst comprises active metal rhodium, auxiliary agent cobalt and nitrogen atom doped porous carbon carrier; the preparation method comprises the following steps: respectively dissolving cobalt nitrate hexahydrate and 2-methylimidazole in methanol; mixing, stirring, centrifuging, washing with ethanol, collecting the produced precipitate, vacuum drying to obtain a metal organic framework material, and dispersing in a methanol solution to obtain a mixed solution I; dissolving rhodium source compound in methanol solution to obtain mixed solution II; and mixing the solution I and the solution II, performing full reaction, drying in an oil bath to obtain a catalyst precursor, and then roasting to obtain a finished product. The preparation process of the carbon-supported rhodium-cobalt monoatomic alloy catalyst is simple and reliable, green and environment-friendly, and the production cost is low; the dosage is small, and the raw material conversion rate and the aldehyde yield are very high; easy separation and recovery, good cycle performance and remarkable industrial application advantages.
Description
Technical Field
The invention relates to the technical fields of fine chemical engineering and heterogeneous catalysis, in particular to a rhodium-cobalt loaded monoatomic alloy catalyst for high-carbon olefin hydroformylation and a preparation and application method thereof.
Background
The hydroformylation reaction is also known as OXO reactionBy this is meant the feed olefins and synthesis gas (H) 2 The catalytic process of reacting to generate aldehyde with one more carbon has 100% of atom economy and meets the green development requirement. The aldehydes, alcohols and derivatives thereof thus produced are used in large amounts in the industries of plasticizers, rubbers, surfactants, cosmetics, pharmaceutical intermediates, and flavoring agents. The hydroformylation reaction is one of the largest application of the soluble homogeneous metal catalyst in industry, the aldehyde and the derivative thereof generated by the reaction reach 1200 ten thousand tons each year, and the hydroformylation reaction has wide research and development prospects for the synthesis of basic organic raw materials matched with large quantities of products or the production of fine chemicals related to various aspects of modern life.
For olefin hydroformylation, all transition metals capable of forming carbonyl compounds are potential catalysts, but the catalytic activities of the metals are different, and only complex catalysts based on rhodium and cobalt are applied to industrial production at present, and the development of other transition metals is in the laboratory research stage. Commercial hydroformylation catalysts undergo four stages of evolution: (1) a cobalt carbonyl catalyst; (2) a tertiary phosphine ligand modified cobalt carbonyl catalyst; (3) an oil-soluble rhodium-phosphine complex catalyst; (4) a water-soluble rhodium-phosphine complex catalyst. Among the industrially applied hydroformylation catalysts, the homogeneous rhodium-based catalyst gradually replaces the cobalt-based catalyst by the characteristics of high catalytic activity, good chemical selectivity, mild reaction conditions, low energy consumption and the like, and becomes the most main catalyst for hydroformylation. However, for olefin hydroformylation processes for the production of higher aldehydes and alcohols, homogeneous cobalt-based catalysts are still mainly employed because higher aldehydes and alcohols have higher boiling points and, when separated from the catalyst by distillation at elevated temperatures, the homogeneous rhodium-based catalyst will decompose and deactivate. Meanwhile, the homogeneous hydroformylation reaction has a series of problems of difficult separation and recovery of the catalyst, complex ligand synthesis, serious metal/ligand loss, phosphorus-containing wastewater and the like, and the development of the catalyst is greatly limited.
In contrast, heterogeneous catalysts have the advantages of easy separation and recycling, etc., and are the mainstream of industrial catalysis, however, the activity and selectivity of the currently reported heterogeneous catalysts in olefin hydroformylation reactions are still to be improved. For example: patent publication No. CN115007180A discloses a heterogeneous catalyst prepared by loading active metal Rh with phosphorus-containing oxide as a carrier; in the optimal embodiment, the conversion rate of the 1-octene is up to 100%, the selectivity of the product aldehyde is up to 96%, and the hydroformylation activity and the selectivity are not reduced after 12 times of recycling, so that the catalyst has good stability. And the following steps: the patent with publication number CN112844488A uses phosphine ligand polymer pellets as a carrier, and utilizes the P atoms with high concentration on the surface of the carrier to match with active metal Rh to synthesize an eggshell catalyst; the synthesized catalyst has high active center utilization rate, good mass and heat transfer effect and high mechanical strength, and meets the requirements of industrial production. However, both catalysts require the addition of phosphine ligands during the preparation process, the preparation process is complicated, and the requirements on the operation environment are high, resulting in an increase in the catalyst cost.
As a novel catalyst, active metal atoms in the single-atom catalyst are loaded on a carrier in a monodisperse form, no traditional metal-metal bond is generated, the utilization rate of the metal atoms is improved to the greatest extent, the novel catalyst shows high activity and high selectivity in hydrogenation reaction by virtue of unique electronic effect and coordination effect, and the activation of hydrogen has important role in olefin hydroformylation reaction. The patent with publication number of CN114163318A discloses an application of rhodium monoatomic catalyst taking molecular sieve as carrier in olefin hydroformylation reaction, compared with rhodium nanoparticle catalyst, the proportion of normal aldehyde in the product is obviously improved, but the conversion rate of the product is lower. Therefore, how to design and prepare a single-atom catalyst with high performance, high atom utilization and low cost for the hydroformylation of olefins has become a research hotspot and difficulty in this field.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a high-carbon olefin hydroformylation carbon-supported rhodium-cobalt monoatomic alloy catalyst and a preparation and application method thereof, and the technical scheme is as follows:
the structural formula of the carbon-supported rhodium-cobalt monoatomic alloy catalyst is Rh-M/NCF, wherein Rh is an active metal component, M is an auxiliary component, and NCF is a porous carbon carrier doped with nitrogen atoms; the active metal component is rhodium which is uniformly distributed on the porous carbon carrier in a single atom form; the auxiliary component is cobalt, which is uniformly distributed on the porous carbon support in the form of nanoparticles.
The mass fraction of the active metal component rhodium relative to the porous carbon carrier is 0.1-0.3wt%, the mass fraction of the auxiliary component cobalt relative to the porous carbon carrier is 20-40wt%, and the size of the cobalt nano particles is 5-20nm.
The rhodium monoatoms are prepared from rhodium source compounds, wherein the rhodium source compounds comprise rhodium dicarbonyl acetylacetonate, rhodium trichloride hydrate, anhydrous rhodium oxide, triphenylphosphine rhodium chloride and bis (triphenylphosphine) carbonyl rhodium chloride (I); the cobalt nanoparticles are prepared from a cobalt source compound comprising cobalt nitrate hexahydrate.
The preparation method of the carbon-supported rhodium-cobalt monoatomic alloy catalyst comprises the following steps:
(1) Respectively dissolving cobalt nitrate hexahydrate and 2-methylimidazole in methanol;
(2) Mixing the methanol solution of cobalt nitrate hexahydrate prepared in the step (1) with the methanol solution of 2-methylimidazole, stirring at room temperature, centrifuging, washing with ethanol, and collecting the produced precipitate;
(3) Vacuum drying the precipitate obtained in the step (2) to obtain a metal organic framework material;
(4) Uniformly dispersing the metal organic framework material obtained in the step (3) in a methanol solution to obtain a mixed solution I;
(5) Dissolving rhodium source compound in methanol solution to obtain mixed solution II;
(6) Slowly dripping the mixed solution II into the mixed solution I in a stirring state, and continuously mixing and stirring to perform full reaction after dripping is completed;
(7) Oil bath drying is carried out on the reaction liquid obtained in the step (6) to obtain a catalyst precursor;
(8) And (3) placing the catalyst precursor obtained in the step (7) into a quartz boat, placing the quartz boat into a tubular heating furnace, heating the quartz boat to a roasting target temperature from room temperature under the atmosphere of inert gas, and keeping the quartz boat at the roasting target temperature for a certain time to obtain the carbon-supported rhodium-cobalt monoatomic alloy catalyst.
The molar ratio of the cobalt nitrate hexahydrate to the 2-methylimidazole in the step (1) is 1:4; the mass ratio of the metal organic framework material in the step (4) to the rhodium source compound in the step (5) is 500 (3-10).
Stirring for 24 hours in the step (2); the step (3) of vacuum drying is carried out for 10 hours under the condition of 60 ℃; continuously mixing and stirring for 24 hours after the dripping of the step (6) is completed; the oil bath drying temperature in the step (7) is 80 ℃; the inert gas in the step (8) is any one or more of nitrogen and argon, and is heated to the target temperature of 550-950 ℃ from room temperature at a speed of 5 ℃/min and kept for 4 hours.
The application of the carbon-supported rhodium-cobalt monoatomic alloy catalyst prepared by the preparation method in the hydroformylation of olefins comprises the following specific application methods: sequentially adding a catalyst, a solvent and olefin into a quartz sand reaction tube; the reaction tube is arranged in the corresponding position of the high-pressure parallel reaction kettle, is connected with a stirrer and a temperature measuring device and is sealed; connecting a synthetic gas steel bottle, flushing synthetic gas to purge air in the autoclave, and then introducing synthetic gas with certain pressure; checking that each valve of the reaction kettle is in a closed state, opening the high-pressure reaction kettle device, heating to a set temperature, stirring by using a stirrer, and reacting for a certain time; after the reaction is finished, the reaction kettle is placed in an ice water bath for cooling, and pressure is slowly released.
The solvent is one or more of toluene, tetrahydrofuran, diethylene glycol dimethyl ether, acetonitrile, methylene dichloride, N-dimethylformamide and anisole; the olefin comprises one or any of 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and styrene.
The synthesis gas is a mixed gas of carbon monoxide and hydrogen with the volume ratio of 1:1 of 1.0 MPa; flushing the synthesis gas, and repeating the purging for 3 times; the stirrer rotation speed was set at 600rpm; the reaction time is 6-24h, the reaction temperature is 50-200 ℃, and the reaction pressure is 1-6MPa; cooling to below 10deg.C in ice water bath.
The carbon-supported rhodium-cobalt monoatomic alloy catalyst is applied to a slurry bed, is easy to separate from a product and is convenient to recycle; the catalyst can also be used in a fixed bed.
Compared with the prior art, the invention has the following beneficial technical effects:
1. the invention adopts the strategy of dipping-adsorption-carbonization to successfully prepare the carbon-supported rhodium-cobalt monoatomic alloy catalyst, the rhodium atom dispersity is high, and the rhodium and the cobalt have obvious synergistic catalytic effect; any phosphine ligand is not needed to be added in the preparation process, the process is simple and reliable, green and environment-friendly, no loss of metal active components is caused, and the production cost is low.
2. The carbon-supported rhodium-cobalt monoatomic alloy catalyst prepared by the invention has high activity and strong selectivity, and is convenient for separation and recovery.
3. The carbon-supported rhodium-cobalt monoatomic alloy catalyst prepared by the invention is particularly suitable for the hydroformylation reaction of high-carbon olefin, the catalyst consumption is small, the conversion rate of 1-hexene is up to 99.56%, the heptanal yield is up to 94.24%, and the turnover frequency is up to 2778.65h -1 。
4. The carbon-supported rhodium-cobalt monoatomic alloy catalyst prepared by the invention has stable structure in the preparation and reaction processes, the active component rhodium atoms, the auxiliary agent cobalt and the nitrogen-doped porous carbon carrier have strong coordination synergistic effect, the catalyst is repeatedly used for 6 times, the hydroformylation reaction activity is not obviously reduced, the key problems of high catalyst raw material price, rhodium metal loss and the like in the current olefin hydroformylation homogeneous catalyst industrialization application are effectively solved, and the catalyst has remarkable advantages in industrial application.
Drawings
Fig. 1 is a spherical aberration correction scanning transmission electron microscope photograph of the carbon-supported rhodium-cobalt monoatomic alloy catalyst provided by the invention (a plurality of isolated bright spots, namely Rh monoatoms, can be obviously observed from fig. 1, which shows that Rh species in the carbon-supported rhodium-cobalt monoatomic alloy catalyst are in a monoatomic dispersion state).
Detailed Description
In order that those skilled in the art will better understand the technical scheme of the present invention, the following description will further illustrate the present invention with reference to examples, but the present invention is not limited to the following examples.
First, the conversion, selectivity, and positive differential analysis methods involved in the examples will be briefly described:
the conversion rate, selectivity and positive-differential ratio analysis method adopts a GC-7820 gas chromatograph, a chromatographic column model HP-5 capillary column (with the inner diameter of 0.25nm and the length of 30 m) is assembled, and a hydrogen Flame Ion Detector (FID) is adopted to analyze the product, wherein the specific measurement method comprises the following steps:
the sample injection amount is 0.2 mu L, and the chromatographic column is heated according to the program: the initial temperature is 60 ℃, the column temperature is raised to 120 ℃ at 8 ℃/min after the residence time is 2min, the column temperature is raised to 240 ℃ at 12 ℃/min after the retention time is 6 min, and the retention time is 10 min; the temperature of the vaporization chamber is 230 ℃ and the temperature of the detector is 280 ℃; the carrier gas being N 2 The flow rate was 1.6mL/min, the pressure was 5.4psi, the average linear velocity was 21.793cm/sec, and the residence time was 2.29min.
And quantitatively analyzing the reacted mixture by adopting an internal standard method, and selecting dodecane as an internal standard.
The raw material conversion (C), the product selectivity (S) and the yield (Y) and the normal-to-iso ratio are calculated as follows:
conversion rate:
selectivity is as follows:
yield:
positive-to-iso ratio:
wherein:
c-conversion;
s-selectivity;
a 0 -amount of 1-hexene species in the feedstock;
a 1 -amount of 1-hexene species in the product;
a x -the amount of a substance of a certain product;
a-amount of material of the total product;
a n -the amount of linear aldehyde species;
a i -amount of branched aldehyde species.
Next, general embodiments of the present invention will be briefly described:
the structural formula of the carbon-supported rhodium-cobalt monoatomic alloy catalyst is Rh-M/NCF, wherein Rh is an active metal component, M is an auxiliary component, and NCF is a porous carbon carrier doped with nitrogen atoms; the active metal component is rhodium which is uniformly distributed on the porous carbon carrier in a form of single atom; the adjunct component is cobalt, which is uniformly distributed on the porous carbon support in the form of nanoparticles. The mass fraction of the active metal component rhodium relative to the porous carbon carrier is 0.1-0.3wt%, the mass fraction of the auxiliary component cobalt relative to the porous carbon carrier is 20-40wt%, and the size of the cobalt nano particles is 5-20nm. Rhodium monoatoms are prepared from rhodium source compounds, wherein the rhodium source compounds comprise rhodium dicarbonyl acetylacetonate, rhodium trichloride hydrate, anhydrous rhodium oxide, triphenylphosphine rhodium chloride and bis (triphenylphosphine) carbonyl rhodium (I) chloride; the cobalt nanoparticles are prepared from a cobalt source compound comprising cobalt nitrate hexahydrate.
The preparation method of the carbon-supported rhodium-cobalt monoatomic alloy catalyst comprises the following steps: (1) Respectively dissolving cobalt nitrate hexahydrate and 2-methylimidazole in methanol; (2) Mixing the methanol solution of cobalt nitrate hexahydrate prepared in the step (1) with the methanol solution of 2-methylimidazole, stirring at room temperature, centrifuging, washing with ethanol, and collecting the produced precipitate; (3) Vacuum drying the precipitate obtained in the step (2) to obtain a metal organic framework material; (4) Uniformly dispersing the metal organic framework material obtained in the step (3) in a methanol solution to obtain a mixed solution I; (5) Dissolving rhodium source compound in methanol solution to obtain mixed solution II; (6) Slowly dripping the mixed solution II into the mixed solution I in a stirring state, and continuously mixing and stirring to perform full reaction after dripping is completed; (7) Oil bath drying is carried out on the reaction liquid obtained in the step (6) to obtain a catalyst precursor; (8) And (3) placing the catalyst precursor obtained in the step (7) into a quartz boat, placing the quartz boat into a tubular heating furnace, heating the quartz boat to a roasting target temperature from room temperature under the atmosphere of inert gas, and keeping the quartz boat at the roasting target temperature for a certain time to obtain the carbon-supported rhodium-cobalt monoatomic alloy catalyst. The molar ratio of the cobalt nitrate hexahydrate to the 2-methylimidazole in the step (1) is 1:4; the mass ratio of the metal organic framework material in the step (4) to the rhodium source compound in the step (5) is 500 (3-10). Step (2) stirring for 24 hours; the step (3) of vacuum drying is carried out for 10 hours at 60 ℃; continuously mixing and stirring for 24 hours after the dripping of the step (6) is completed; the oil bath drying temperature in the step (7) is 80 ℃; and (8) the inert gas is one or more of nitrogen and argon, and the temperature is raised to the target temperature of 550-950 ℃ from room temperature at a speed of 5 ℃/min and maintained for 4 hours.
The application of the carbon-supported rhodium-cobalt monoatomic alloy catalyst prepared by the preparation method in the hydroformylation of olefins comprises the following specific application methods: sequentially adding a catalyst, a solvent and olefin into a quartz sand reaction tube; the reaction tube is arranged in the corresponding position of the high-pressure parallel reaction kettle, is connected with a stirrer and a temperature measuring device and is sealed; connecting a synthetic gas steel bottle, flushing synthetic gas to purge air in the autoclave, and then introducing synthetic gas with certain pressure; checking that each valve of the reaction kettle is in a closed state, opening the high-pressure reaction kettle device, heating to a set temperature, stirring by using a stirrer, and reacting for a certain time; after the reaction is finished, the reaction kettle is placed in an ice water bath for cooling, and pressure is slowly released. The solvent is one or more of toluene, tetrahydrofuran, diethylene glycol dimethyl ether, acetonitrile, methylene dichloride, N-dimethylformamide and anisole; the olefin comprises one or any of 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and styrene. The synthesis gas is a mixed gas of carbon monoxide and hydrogen with the volume ratio of 1:1 of 1.0 MPa; flushing the synthesis gas, and repeating the purging for 3 times; the stirrer rotation speed was set at 600rpm; the reaction time is 6-24h, the reaction temperature is 50-200 ℃, and the reaction pressure is 1-6MPa; cooling to below 10deg.C in ice water bath. The carbon-supported rhodium-cobalt monoatomic alloy catalyst is applied to a slurry bed, is easy to separate from a product and is convenient to recycle; the catalyst can also be used in a fixed bed.
Embodiments of the invention are then illustrated:
example 1
And (3) preparing a catalyst: based on the above-mentioned catalyst characteristics, a method for preparing the catalyst will now be exemplified. Cobalt nitrate hexahydrate (5.82 g) and 2-methylimidazole (6.16 g) were each dissolved in methanol (150 mL) to form two methanol solutions; mixing the two methanol solutions, stirring at room temperature for 24 hours, centrifuging, washing with ethanol, and collecting the precipitate; vacuum drying the precipitate obtained by centrifugation at 60 ℃ for 10 hours to obtain a metal organic frame material ZIF-67; ZIF-67 (0.5 g) was uniformly dispersed in a methanol solution to obtain a mixed solution I; rhodium dicarbonyl acetylacetonate (3 mg) was dissolved in a methanol solution to obtain a mixed solution II; slowly dropwise adding the mixed solution II into the solution I under the stirring state of the mixed solution I, and continuously mixing and stirring for 24 hours after the dropwise adding is completed to perform full reaction; oil bath drying the reaction liquid at 80 ℃ to obtain a catalyst precursor; and placing the obtained precursor into a quartz boat, placing the quartz boat into a tubular heating furnace, and heating the quartz boat from room temperature to 750 ℃ at a heating rate of 5 ℃/min under the atmosphere of nitrogen, wherein the roasting time is 4 hours, thus obtaining the carbon-supported rhodium-cobalt monoatomic alloy catalyst.
Hydroformylation reactivity evaluation: a certain amount of catalyst (40 mg), toluene (2 mL) and 1-hexene (15 mmol) were sequentially added to a 20mL quartz sand reaction tube: the reaction tube is arranged in the corresponding position of the high-pressure parallel reaction kettle, is connected with a stirrer and a temperature measuring device and is sealed; connecting a synthetic gas steel bottle, flushing synthetic gas of 1.0MPa to purge air in the autoclave, repeating for 3 times, and then introducing synthetic gas of 4 MPa; checking that each valve of the reaction kettle is in a closed state, opening the high-pressure reaction kettle device, heating to 100 ℃, setting 600rpm for the rotation speed of a stirrer, and reacting for 12 hours; after the reaction is finished, the reaction kettle is placed in ice water bath to be cooled to below 10 ℃ and slowly depressurized; 0.1g of dodecane was added to the reaction mixture as an internal standard, and the mixture after the reaction was centrifuged to obtain a liquid product, which was analyzed by gas chromatography to determine the conversion, selectivity, yield and the n-iso ratio.
Example 2
And (3) preparing a catalyst: referring to example 1, the precursor of the carbon-supported rhodium cobalt monoatomic alloy catalyst was calcined at 550 ℃ in a nitrogen atmosphere.
Hydroformylation reactivity evaluation: referring to example 1, the results are shown in Table 1.
Example 3
And (3) preparing a catalyst: referring to example 1, the precursor of the carbon-supported rhodium cobalt monoatomic alloy catalyst was calcined at 650 ℃ in a nitrogen atmosphere.
Hydroformylation reactivity evaluation: referring to example 1, the results are shown in Table 1.
Example 4
And (3) preparing a catalyst: referring to example 1, the precursor of the carbon-supported rhodium cobalt monoatomic alloy catalyst was calcined at 850 ℃ in a nitrogen atmosphere.
Hydroformylation reactivity evaluation: referring to example 1, the results are shown in Table 1.
Example 5
And (3) preparing a catalyst: referring to example 1, the precursor of the carbon-supported rhodium cobalt monoatomic alloy catalyst was calcined at 950 ℃ in a nitrogen atmosphere.
Hydroformylation reactivity evaluation: referring to example 1, the results are shown in Table 1.
Example 6
And (3) preparing a catalyst: referring to example 1, rhodium dicarbonyl acetylacetonate was added in an amount of 10mg during the preparation of the carbon-supported rhodium-cobalt monoatomic alloy catalyst.
The hydroformylation activity was evaluated in accordance with example 1, and the results are shown in Table 1.
Comparative example 1
And (3) preparing a catalyst: cobalt nitrate hexahydrate (5.82 g) and 2-methylimidazole (6.16 g) were each dissolved in methanol (150 mL) to form two methanol solutions; mixing the two methanol solutions, stirring at room temperature for 24 hours, centrifuging, washing with ethanol, and collecting the precipitate; vacuum drying the precipitate obtained by centrifugation at 60 ℃ for 10 hours to obtain a metal organic frame material ZIF-67; and placing the obtained ZIF-67 in a quartz boat, placing in a tubular heating furnace, and heating from room temperature to 750 ℃ at a heating rate of 5 ℃/min under the atmosphere of nitrogen, wherein the roasting time is 4 hours, so as to obtain the carbon-supported cobalt nanoparticle catalyst.
Hydroformylation reactivity evaluation: referring to example 1, the results are shown in Table 1.
Comparative example 2
And (3) preparing a catalyst: zinc nitrate hexahydrate (5.58 g) and 2-methylimidazole (6.16, g) were each dissolved in methanol (150 mL) to form two methanol solutions; mixing the two methanol solutions, stirring at room temperature for 24 hours, centrifuging, washing with ethanol, and collecting the precipitate; vacuum drying the precipitate obtained by centrifugation at 60 ℃ for 10 hours to obtain a metal organic frame material ZIF-8; ZIF-8 (0.5 g) is uniformly dispersed in a methanol solution to obtain a mixed solution I; rhodium dicarbonyl acetylacetonate (3 mg) was dissolved in a methanol solution to obtain a mixed solution II; slowly dripping the mixed solution II into the solution I under the stirring state of the mixed solution I, and mixing and stirring for 24 hours; the mixed reaction liquid is dried in an oil bath at the temperature of 80 ℃ to obtain a catalyst precursor; and placing the obtained precursor into a quartz boat, placing the quartz boat into a tubular heating furnace, and heating the quartz boat from room temperature to 750 ℃ at a heating rate of 5 ℃/min under the atmosphere of nitrogen, wherein the roasting time is 4 hours, thus obtaining the carbon-supported rhodium-zinc monoatomic alloy catalyst.
Hydroformylation reactivity evaluation: referring to example 1, the results are shown in Table 1.
Comparative example 3
And (3) preparing a catalyst: a homogeneous catalyst of tris (triphenylphosphine) rhodium (I) chloride is selected for comparison.
Hydroformylation reactivity evaluation: referring to example 1, the catalyst addition amount was 4 mg, and the results are shown in table 1.
TABLE 1 olefin hydroformylation reactivity of example/comparative catalyst
Analysis of table 1 shows that:
(1) Example 1 compared with example 6, the conversion of the raw material in example 6 was 1% lower than that in example 1, the aldehyde yield was 1.4% lower, and it was revealed that the hydroformylation reaction activity of the olefin of the catalyst was slightly lower when 10mg of rhodium dicarbonyl acetylacetonate was added than when 3mg of rhodium dicarbonyl acetylacetonate was added, because rhodium metal was mainly present in the form of atomic clusters and the atom utilization ratio was greatly lowered when rhodium metal was present in the form of single atom.
(2) Example 1 compared with examples 2-5, the conversion of the raw material of example 1 is 23.6% -51.9% higher than that of examples 2-5, the aldehyde yield is 22.1% -55.3% higher, which shows that the catalyst has the highest specific surface area at 750 ℃ in the range of 550-950 ℃ of roasting temperature, and the contact area of the reactant and the catalyst is the largest, so that the hydroformylation reaction activity of olefin is the highest.
(3) Compared with comparative example 1, the conversion rate of the raw material of example 1 is 39.5% higher than that of comparative example 1, the aldehyde yield is 37.9%, which shows that the activity of the carbon-supported rhodium-cobalt monoatomic alloy catalyst for hydroformylation of olefins is obviously improved compared with that of the carbon-supported cobalt nanoparticle catalyst, and the catalyst activity is obviously improved due to the synergistic effect of rhodium-cobalt bimetallic in the carbon-supported rhodium-cobalt monoatomic alloy catalyst.
(4) Compared with comparative example 2, the conversion rate of the raw material of example 1 is 98.3% higher than that of comparative example 2, the yield of the product aldehyde is 93.6%, which shows that the promoting effect of the zinc nano particles in the carbon-supported rhodium-zinc monoatomic alloy catalyst is far smaller than that of the cobalt nano particles, and further proves that the synergistic effect between rhodium and cobalt in the carbon-supported rhodium-cobalt monoatomic alloy catalyst obviously improves the catalytic efficiency of the catalyst on olefin.
(5) Example 1 compared with comparative example 3, the conversion of the raw material and the yield of the product aldehyde were both substantially equal, but the positive-to-negative ratio of the product aldehyde in example 1 was 6.9 times that of comparative example 3, demonstrating that the catalytic activity of the carbon-supported rhodium-zinc monoatomic alloy catalyst was comparable to that of the homogeneous catalyst, but the regioselectivity was significantly higher than that of the homogeneous catalyst.
Test example 1
Catalyst preparation reference example 1.
Hydroformylation reactivity evaluation: referring to example 1, the reaction substrate was 1-pentene (15 mmol), and the results are shown in Table 2.
Test example 2
Catalyst preparation reference example 1.
Hydroformylation reactivity evaluation: referring to example 1, the reaction substrate was 1-heptene (15 mmol), and the results are shown in Table 2.
Test example 3
Catalyst preparation reference example 1.
Hydroformylation reactivity evaluation: referring to example 1, the reaction substrate was 1-octene (15 mmol), and the results are shown in Table 2.
Test example 4
Catalyst preparation reference example 1.
Hydroformylation reactivity evaluation: referring to example 1, the reaction substrate was 1-decene (15 mmol) and the results are shown in Table 2.
Table 2 comparison of hydroformylation reactivity of catalysts for different higher olefins
As can be seen from Table 2, from example 1, test example 1 to test example 4, the raw material conversion, aldehyde yield, turnover frequency TOF (h -1 ) All show obvious descending trend, which shows that the hydroformylation reaction activity of the catalyst gradually decreases with the increase of the carbon chain length of the high-carbon olefin serving as a reaction substrate.
Test example 5
This test example was run in a cyclic reaction using the catalyst and reaction conditions of example 1.
Specifically, in the first reaction, a rhodium-cobalt single-atom alloy catalyst (40 mg), toluene (2 mL) and 1-hexene (15 mmol) carried by carbon are sequentially added into a 20mL quartz sand reaction tube; the reaction tube is arranged in the corresponding position of the high-pressure parallel reaction kettle, is connected with a stirrer and a temperature measuring device and is sealed; connecting a synthetic gas steel bottle, flushing synthetic gas of 1.0MPa to purge air in the autoclave, repeating for 3 times, and then introducing synthetic gas of 4 MPa; checking that each valve of the reaction kettle is in a closed state, opening the high-pressure reaction kettle device, heating to 100 ℃, setting 600rpm for the rotation speed of a stirrer, and reacting for 12 hours; after the reaction is finished, the reaction kettle is placed in ice water bath to be cooled to below 10 ℃ and slowly depressurized; 0.1g of dodecane was added to the reaction mixture as an internal standard, and the mixture after the reaction was centrifuged to obtain a liquid product, which was analyzed by gas chromatography to determine the conversion, selectivity, yield and the n-iso ratio.
The catalyst thus separated was subjected to a cycle, and the number of cycles and the corresponding conversion, selectivity, yield and positive-to-negative ratio results are shown in Table 3.
TABLE 3 hydroformylation reactivity of olefins for different cycle times of catalyst
As seen from Table 3, the catalyst was recycled 6 times, and the single recycle conversion, selectivity and aldehyde yield were substantially unchanged from those of the first reaction. After the reaction is finished, the catalyst is recovered by simple filtering means such as centrifugal separation, so that the problem of difficult recovery and separation of the catalyst is solved, and the catalyst has certain application value.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description of the present specification.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention.
Claims (7)
1. The preparation method of the carbon-supported rhodium-cobalt monoatomic alloy catalyst is characterized in that the structural formula of the catalyst is Rh-M/NCF, wherein Rh is an active metal component, M is an auxiliary agent component, and NCF is a porous carbon carrier doped with nitrogen atoms; the active metal component is rhodium which is uniformly distributed on the porous carbon carrier in a single atom form; the auxiliary agent component is cobalt which is uniformly distributed on the porous carbon carrier in the form of nano particles; the mass fraction of the active metal component rhodium relative to the porous carbon carrier is 0.1-0.3wt%, the mass fraction of the auxiliary component cobalt relative to the porous carbon carrier is 20-40wt%, and the size of the cobalt nano particles is 5-20nm; the active metal component rhodium is prepared from rhodium source compounds, wherein the rhodium source compounds comprise rhodium dicarbonyl acetylacetonate, rhodium trichloride hydrate, anhydrous rhodium oxide, triphenylphosphine rhodium chloride and bis (triphenylphosphine) rhodium (I) carbonyl chloride; the cobalt nanoparticles are prepared from a cobalt source compound, wherein the cobalt source compound comprises cobalt nitrate hexahydrate;
the preparation of the catalyst comprises the following steps:
(1) Respectively dissolving cobalt nitrate hexahydrate and 2-methylimidazole in methanol;
(2) Mixing the methanol solution of cobalt nitrate hexahydrate prepared in the step (1) with the methanol solution of 2-methylimidazole, stirring at room temperature, centrifuging, washing with ethanol, and collecting the produced precipitate;
(3) Vacuum drying the precipitate obtained in the step (2) to obtain a metal organic framework material;
(4) Uniformly dispersing the metal organic framework material obtained in the step (3) in a methanol solution to obtain a mixed solution I;
(5) Dissolving rhodium source compound in methanol solution to obtain mixed solution II;
(6) Slowly dripping the mixed solution II into the mixed solution I in a stirring state, and continuously mixing and stirring to perform full reaction after dripping is completed;
(7) Oil bath drying is carried out on the reaction liquid obtained in the step (6) to obtain a catalyst precursor;
(8) And (3) placing the catalyst precursor obtained in the step (7) into a quartz boat, placing the quartz boat into a tubular heating furnace, heating the quartz boat to a roasting target temperature from room temperature under the atmosphere of inert gas, and keeping the quartz boat at the roasting target temperature for a certain time to obtain the carbon-supported rhodium-cobalt monoatomic alloy catalyst.
2. The method for preparing a carbon-supported rhodium-cobalt monoatomic alloy catalyst according to claim 1, wherein the molar ratio of cobalt nitrate hexahydrate to 2-methylimidazole in the step (1) is 1:4; the mass ratio of the metal organic framework material in the step (4) to the rhodium source compound in the step (5) is 500 (3-10).
3. The method for preparing a carbon-supported rhodium-cobalt monoatomic alloy catalyst according to claim 2, wherein the step (2) is stirred for 24 hours; the step (3) of vacuum drying is carried out for 10 hours under the condition of 60 ℃; continuously mixing and stirring for 24 hours after the dripping of the step (6) is completed; the oil bath drying temperature in the step (7) is 80 ℃; the inert gas in the step (8) is any one or more of nitrogen and argon, and is heated to the target temperature of 550-950 ℃ from room temperature at a speed of 5 ℃/min and kept for 4 hours.
4. The use of a carbon-supported rhodium-cobalt monoatomic alloy catalyst prepared by the preparation method according to any one of claims 1 to 3 in the hydroformylation of olefins, wherein the specific application method is as follows: sequentially adding a catalyst, a solvent and olefin into a quartz sand reaction tube; the reaction tube is arranged in the corresponding position of the high-pressure parallel reaction kettle, is connected with a stirrer and a temperature measuring device and is sealed; connecting a synthetic gas steel bottle, flushing synthetic gas to purge air in the autoclave, and then introducing synthetic gas with certain pressure; checking that each valve of the reaction kettle is in a closed state, opening the high-pressure reaction kettle device, heating to a set temperature, stirring by using a stirrer, and reacting for a certain time; after the reaction is finished, the reaction kettle is placed in an ice water bath for cooling, and pressure is slowly released.
5. The application of the carbon-supported rhodium-cobalt monoatomic alloy catalyst in the hydroformylation of olefins, according to claim 4, wherein the solvent is one or more of toluene, tetrahydrofuran, diethylene glycol dimethyl ether, acetonitrile, dichloromethane, N-dimethylformamide and anisole; the olefin comprises one or any of 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and styrene.
6. The application of the carbon-supported rhodium-cobalt monoatomic alloy catalyst in the hydroformylation of olefins according to claim 4, wherein the synthesis gas is a mixed gas of 1.0MPa composed of carbon monoxide and hydrogen according to a volume ratio of 1:1; flushing the synthesis gas, and repeating the purging for 3 times; the stirrer rotation speed was set at 600rpm; the reaction time is 6-24h, the reaction temperature is 50-200 ℃, and the reaction pressure is 1-6MPa; cooling to below 10deg.C in ice water bath.
7. The application of the carbon-supported rhodium-cobalt monoatomic alloy catalyst in the hydroformylation of olefins, according to claim 4, wherein the carbon-supported rhodium-cobalt monoatomic alloy catalyst is applied to a slurry bed, is easy to separate from products and is convenient to recycle.
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| CN115301270A (en) * | 2022-07-21 | 2022-11-08 | 北京大学深圳研究生院 | Catalyst and preparation method and application thereof |
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