CN111036262A - Supported monatomic rhodium-based catalyst and preparation method and application thereof - Google Patents
Supported monatomic rhodium-based catalyst and preparation method and application thereof Download PDFInfo
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- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 79
- 239000010948 rhodium Substances 0.000 title claims abstract description 79
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000002135 nanosheet Substances 0.000 claims abstract description 39
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 27
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 27
- 238000007037 hydroformylation reaction Methods 0.000 claims abstract description 24
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 7
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 14
- 239000003638 chemical reducing agent Substances 0.000 claims description 14
- 238000004108 freeze drying Methods 0.000 claims description 13
- 150000003283 rhodium Chemical class 0.000 claims description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- 239000000725 suspension Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000007833 carbon precursor Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 238000000703 high-speed centrifugation Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 7
- 150000001299 aldehydes Chemical class 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- MBVAQOHBPXKYMF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MBVAQOHBPXKYMF-LNTINUHCSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 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 description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- -1 aldehyde compound Chemical class 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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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
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention particularly relates to a supported monatomic rhodium-based catalyst, a preparation method thereof and application in propylene hydroformylation reaction, wherein the catalyst is two-dimensional ultrathin g-C3N4The nano sheet is a carrier, and the noble metal rhodium is uniformly dispersed in the two-dimensional ultrathin g-C in an atomic scale mode3N4The nano-chip is prepared by the following method: mixing the blocks g-C3N4Peeling into two-dimensional ultra-thin g-C3N4Nanosheets, then supported and reduced at low temperature to said two-dimensional ultrathin g-C3N4Monatomic rhodium particles grow on the surface of the nanosheet in situ to obtain the supported monatomic rhodium-based catalyst. Catalyst of the inventionThe catalyst has excellent catalytic activity and stability for propylene hydroformylation reaction, high selectivity for n-butyraldehyde, easily available raw materials, simple operation and easy industrialization.
Description
Technical Field
The invention belongs to the technical field of catalyst synthesis, and particularly relates to a supported monatomic rhodium-based catalyst, a preparation method thereof and application thereof in propylene hydroformylation.
Background
The hydroformylation reaction utilizes an olefin and synthesis gas (CO and H)2) Is the process of synthesizing aldehyde with the material under the action of catalyst. The aldehyde compound of the hydroformylation reaction product is a fine chemical with high added value, and is widely applied to the preparation of chemical products such as spices, gasoline additives, resins, surfactants and the like. Since the discovery of this reaction by professor Otto Roelen in 1938, hydroformylation has become one of the most important chemical reactions in industrial applications today. In the hydroformylation of olefins, taking propylene to butyraldehyde as an example, two aldehydes, namely linear aldehyde (n-butyraldehyde) with terminal aldehyde group and branched aldehyde (i-butyraldehyde) with non-terminal aldehyde group, can be obtained, therefore, the selection of a high-activity and high-selectivity catalyst is the key for preparing linear aldehyde by hydroformylation of olefins.
Patent document CN107537481A discloses a preparation method of a supported monatomic rhodium-based catalyst and an application of the supported monatomic rhodium-based catalyst in an olefin hydroformylation reaction. The main active component of the catalyst is rhodium, and the carrier is nano zinc oxide. The rhodium is dispersed on the carrier in an atomic level, and the content of the rhodium is 0.005-2 wt% of the total mass of the catalyst. The catalyst shows higher catalytic activity and stability in the olefin hydroformylation reaction, and the highest yield of a target product is 90% under the optimal reaction condition, which still needs to be improved.
The choice of support has a certain influence on the activity and selectivity of the catalyst. Graphitic carbon nitride (g-C)3N4) The material is a novel functional material with a layered two-dimensional structure, has the characteristics of nonmetallicity, high electron mobility, low energy gap (2.73eV), high chemical stability and thermal stability, low cost, environmental friendliness, simple preparation process and the like, and is widely applied to the field of photocatalysts. g-C3N4The preparation method mainly comprises a liquid phase reaction method and a solid phase reaction method. However, these processes generally produce bulk g-C3N4There is a problem that the specific surface area is small. By mixing the g-C of the block3N4Peeling into two-dimensional ultra-thin g-C3N4After the nanosheet, it may be enlargedSpecific surface area, and enhanced adsorption capacity. On the basis of this, more g-C will be derived3N4Nanoplatelet based composites (CN104801329A, CN103934012A, CN 103785434A). However, based on g-C3N4The supported monatomic rhodium-based catalyst is constructed by the nanosheets and the noble metal rhodium and is applied to the hydroformylation reaction, which is not reported at present.
Disclosure of Invention
The invention aims to provide a supported monatomic rhodium-based catalyst, a preparation method thereof and application thereof in hydroformylation reaction, wherein the catalyst is two-dimensional ultrathin g-C3N4The nano sheet is a carrier, the active component noble metal rhodium is in a monoatomic dispersion state, the catalyst has excellent catalytic activity and stability for propylene hydroformylation reaction, and the selectivity for n-butyraldehyde is high.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a load type monatomic rhodium-based catalyst consists of a carrier and an active component loaded on the carrier, wherein the active component is noble metal rhodium, and the catalyst is characterized in that the carrier is two-dimensional ultrathin g-C3N4Nanosheets, the noble metal rhodium being uniformly dispersed in the two-dimensional ultrathin g-C in an atomic scale3N4And (4) nano-chips.
Preferably, the loading amount of the noble metal rhodium is 0.05-0.5 wt%, and the particle size is 0.01-1 nm.
The preparation method of the supported monatomic rhodium-based catalyst comprises the following steps: mixing the blocks g-C3N4Peeling into two-dimensional ultra-thin g-C3N4Nanosheets, then supported and reduced at low temperature to said two-dimensional ultrathin g-C3N4Monatomic rhodium particles grow on the surface of the nanosheet in situ to obtain the supported monatomic rhodium-based catalyst.
Preferably, the preparation method specifically comprises the following steps:
(1) calcining, cooling and grinding the nitrogen-rich carbon precursor to obtain a block g-C3N4；
(2) Mixing the blocks g-C of step (1)3N4Adding the mixture into an organic solvent, and performing ultrasonic treatment to form dispersed suspension; removing precipitate by high-speed centrifugation, and freeze-drying the remaining suspension to obtain two-dimensional ultrathin g-C3N4Nanosheets;
(3) subjecting the two-dimensional ultrathin g-C obtained in the step (2)3N4The nano sheet is dipped in rhodium salt solution, then reducing agent solution is added under the condition of low temperature, the reaction is fully completed, and the obtained product is filtered, washed and dried to obtain the load type monatomic rhodium-based catalyst.
Preferably, the nitrogen-rich carbon precursor in step (1) is any one or a mixture of more than one of cyanamide, dicyandiamide, melamine, urea and thiourea.
Preferably, the calcination in step (1) is carried out under an inert gas atmosphere.
Preferably, the calcining temperature in the step (1) is 450-600 ℃, and the calcining time is 3-5 h.
Preferably, the temperature rise rate of the calcination in the step (1) is 2-5 ℃/min, the temperature is raised to 450-600 ℃, and the temperature is kept for 3-5 h.
Preferably, the organic solvent in step (2) is any one or a mixture of more than one of water, ethanol, isopropanol, N-dimethylformamide, tetrahydrofuran and acetone.
Preferably, the ultrasonic time in the step (2) is 5-20 h.
Preferably, the centrifugal speed in the step (2) is 1000-5000 rpm, and the centrifugal time is 1-10 min.
Preferably, the freeze-drying temperature in the step (2) is-40 to-20 ℃, and the freeze-drying time is 6 to 24 hours.
Preferably, the rhodium salt in step (3) is a soluble salt of rhodium.
Preferably, the concentration of the rhodium salt solution in the step (3) is 0.0002-0.003 mol/L.
Preferably, the rhodium salt is reacted with ultra-thin g-C in step (3)3N4The mass ratio of the nano sheets is calculated according to the mass ratio of the noble gold in the finally prepared catalystThe loading amount of rhodium is 0.05-0.5 wt%.
Preferably, the dipping in the step (3) is carried out under stirring, the stirring speed is 100-1000 rpm, and the dipping time is 3-6 h.
Preferably, the reaction in the step (3) is carried out for 1-5 h at-40 to-20 ℃, and then is carried out for 1-5 h at 20-30 ℃.
Preferably, the reducing agent in step (3) is any one or a mixture of more than one of sodium borohydride, hydrazine hydrate and ascorbic acid.
Preferably, the molar ratio of the reducing agent to the noble metal rhodium in the rhodium salt in the step (3) is (5-100): 1.
preferably, the concentration of the reducing agent solution in the step (3) is 0.001-0.3 mol/L.
Preferably, the solvent of the solution in the step (3) is water and ethanol, and the ethanol accounts for 0-100% of the solvent by volume and does not include 0 and 100%.
Preferably, the drying temperature is 20-70 ℃, and the drying time is 6-24 h.
The application of the supported monatomic rhodium-based catalyst in the propylene hydroformylation reaction comprises the following steps: under the action of the supported monatomic rhodium-based catalyst, propylene and synthesis gas (CO and H)2) In the liquid phase, n-butyraldehyde is formed.
Compared with the prior art, the invention has the following beneficial effects:
the catalyst of the invention is two-dimensional ultrathin g-C3N4The nano sheet is used as a carrier, noble metal rhodium is used as an active component, the noble metal rhodium is in a monoatomic dispersion state, the loading amount is 0.5-0.5 wt%, and the nano sheet is used in a propylene hydroformylation reaction, has high catalytic activity and stability and has high selectivity on n-butyraldehyde. The preparation method has the advantages of easily available raw materials, simple operation and easy industrialization.
1. Two-dimensional ultrathin g-C3N4The nano-sheet has the characteristics of developed pore passages and large specific surface area, is favorable for dispersing the monatomic noble metal rhodium, and simultaneously, the N atom doped on the graphite carbon skeleton is favorable for anchoring the monatomicThe size of the single-atom noble metal particles is reduced, the dispersion degree of the active components is improved, and the acting force between the metal and the carrier is improved.
2. The reducing environment combining low temperature and normal temperature effectively avoids the agglomeration and growth of the single atom noble metal rhodium, so that the rhodium is uniformly dispersed in a two-dimensional ultrathin g-C in an atomic scale mode3N4On the nano sheet, the dispersion degree of the noble metal rhodium is high, and the atom utilization rate is high.
Drawings
Fig. 1 is a transmission electron micrograph of the supported monatomic rhodium-based catalyst of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
The invention relates to a supported monatomic rhodium-based catalyst, which consists of a carrier and an active component loaded on the carrier, wherein the active component is noble metal rhodium, and the supported monatomic rhodium-based catalyst is characterized in that the carrier is two-dimensional ultrathin g-C3N4Nanosheets, the noble metal rhodium being uniformly dispersed in the two-dimensional ultrathin g-C in an atomic scale3N4And (4) nano-chips.
Preferably, the noble metal rhodium is supported in an amount of 0.05 to 0.5 wt%, for example, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, and has a particle diameter of 0.01 to 1nm, for example, 0.01nm, 0.1nm, 0.2nm, 0.3nm, 0.4nm, 0.5nm, 0.6nm, 0.7nm, 0.8nm, 0.9nm, 1.0 nm.
The preparation method of the supported monatomic rhodium-based catalyst comprises the following steps: mixing the blocks g-C3N4Peeling into two-dimensional ultra-thin g-C3N4Nanosheets, then supported and reduced at low temperature to said two-dimensional ultrathin g-C3N4Monatomic rhodium particles grow on the surface of the nanosheet in situ to obtain the supported monatomic rhodium-based catalyst.
Preferably, the preparation method specifically comprises the following steps:
(1) calcining, cooling and grinding the nitrogen-rich carbon precursor to obtain a block g-C3N4；
(2) Mixing the blocks g-C of step (1)3N4Adding the mixture into an organic solvent, and performing ultrasonic treatment to form dispersed suspension; removing precipitate by high-speed centrifugation, and freeze-drying the remaining suspension to obtain two-dimensional ultrathin g-C3N4Nanosheets;
(3) subjecting the two-dimensional ultrathin g-C obtained in the step (2)3N4The nano sheet is dipped in rhodium salt solution, then reducing agent solution is added under the condition of low temperature, the reaction is fully completed, and the obtained product is filtered, washed and dried to obtain the load type monatomic rhodium-based catalyst.
Preferably, the nitrogen-rich carbon precursor in step (1) is any one or a mixture of more than one of cyanamide, dicyandiamide, melamine, urea and thiourea.
Preferably, the calcination in step (1) is carried out under an inert gas atmosphere, which may be, for example, nitrogen or argon.
Preferably, the calcination temperature in step (1) is 450-600 ℃, for example, 450 ℃, 500 ℃, 550 ℃, 600 ℃, and the calcination time is 3-5 hours, for example, 3 hours, 4 hours, 5 hours.
Preferably, the temperature rise rate of the calcination in the step (1) is 2-5 ℃/min, for example, 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min, and the temperature is raised to 450-600 ℃, for example, 450 ℃, 500 ℃, 550 ℃, 600 ℃, and the temperature is kept constant for 3-5 h, for example, 3h, 4h, 5 h.
Preferably, the organic solvent in step (2) is any one or a mixture of more than one of water, ethanol, isopropanol, N-dimethylformamide, tetrahydrofuran and acetone.
Preferably, the ultrasonic time in the step (2) is 5-20 h.
Preferably, the centrifugation speed in step (2) is 1000-5000 rpm, such as 1000rpm, 2000rpm, 3000rpm, 4000rpm, 5000rpm, and the centrifugation time is 1-10 min, such as 1min, 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min, 10 min.
Preferably, the freeze-drying temperature in the step (2) is-40 to-20 ℃, for example, -40 to-30 to-20 ℃, and the freeze-drying time is 6 to 24 hours, for example, 6 hours, 9 hours, 12 hours, 15 hours, 18 hours, 21 hours and 24 hours.
Preferably, the rhodium salt in step (3) is a soluble salt of rhodium, and may be any one or a mixture of more than one of rhodium chloride, rhodium nitrate and rhodium acetylacetonate, for example.
Preferably, the concentration of the rhodium salt solution in the step (3) is 0.0002-0.003 mol/L, for example, 0.0002mol/L, 0.001mol/L, 0.002mol/L, 0.003 mol/L.
Preferably, the rhodium salt is reacted with ultra-thin g-C in step (3)3N4The mass ratio of the nanosheets is such that the loading amount of the noble metal rhodium in the finally prepared catalyst is 0.05-0.5 wt%, for example, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%.
Preferably, the dipping in the step (3) is carried out under stirring, the stirring speed is 100-1000 rpm, such as 100rpm, 200rpm, 300rpm, 400rpm, 500rpm, 600rpm, 700rpm, 800rpm, 900rpm, 1000rpm, and the dipping time is 3-6 h, such as 3h, 4h, 5h, 6 h.
Preferably, the reaction in the step (3) is carried out for 1-5 h at-40 to-20 ℃, and then is carried out for 1-5 h at 20-30 ℃.
Preferably, the reducing agent in step (3) is any one or a mixture of more than one of sodium borohydride, hydrazine hydrate and ascorbic acid.
Preferably, the molar ratio of the reducing agent to the noble metal rhodium in the rhodium salt in the step (3) is (5-100): 1, for example, may be 5: 1. 10:1, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1, 100: 1.
Preferably, the concentration of the reducing agent solution in the step (3) is 0.001-0.3 mol/L, for example, 0.001mol/L, 0.01mol/L, 0.1mol/L, 0.2mol/L, 0.3 mol/L.
Preferably, the solvent of the solution in the step (3) is water and ethanol, and the ethanol accounts for 0-100% of the solvent by volume and does not include 0 and 100%, and for example, the solvent can be 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%.
Preferably, the drying temperature is 20-70 ℃, for example, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃ and 70 ℃, and the drying time is 6-24 h, for example, 6h, 9h, 12h, 15h, 18h, 21h and 24 h.
The application of the supported monatomic rhodium-based catalyst in the propylene hydroformylation reaction comprises the following steps: under the action of the supported monatomic rhodium-based catalyst, propylene and synthesis gas (CO and H)2) Linear aldehydes are formed in the liquid phase.
The performance evaluation of the catalyst is carried out in a 100mL high-pressure reaction kettle, and the method specifically comprises the following steps: propylene and 50mg catalyst were added to 20mL of isopropanol and charged with 160KPa propylene, 1.5MPa CO and 1.5MPa H2Heating to 100 ℃, reacting for 2h under the condition of heat preservation, and maintaining the rotating speed of 300rpm in the heat preservation process. After the reaction system was cooled to room temperature, the remaining gas was released, and the reaction solution was subjected to GC analysis.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention. The experimental methods in the examples are conventional methods unless otherwise specified; the materials used, unless otherwise specified, were purchased from conventional biochemical manufacturers.
Example 1
(1) Preparation of blocks g-C3N4: weighing 5g of dicyandiamide, grinding, uniformly mixing, filling into an alumina crucible, covering, putting into a muffle furnace, heating to 450 ℃ at the speed of 2 ℃/min under the nitrogen atmosphere, keeping for 3h, naturally cooling to room temperature, taking out, and grinding to obtain blocky g-C3N4。
(2) Preparation of ultra-thin g-C3N4Nanosheet: weighing 2g of the block g-C prepared in step (1)3N4Putting into a narrow-mouth bottle, adding 500mL of acetone, and screwing down the bottle cap. Placing the bottle containing the sample in an ultrasonic machine, ultrasonically treating for 5 hr to obtain suspension, centrifuging at 1000rpm for 1min to remove precipitate, and freeze drying at-40 deg.CAnd (5) freeze-drying for 6h to obtain the ultrathin g-C3N4 nanosheet.
(3) Preparation of a monatomic rhodium-based catalyst: adding 1g of the ultrathin g-C3N4 nanosheet obtained in the step (2) into 20mL of 0.00025mol/L rhodium acetylacetonate solution (the solvent is a mixture of water and ethanol in a volume ratio of 1: 9) at room temperature, stirring and soaking for 3h at 100rmp, then placing the mixture into a low-temperature box, simultaneously placing 20mL of 0.001mol/L sodium borohydride solution (the solvent is a mixture of water and ethanol in a volume ratio of 1: 9) into the low-temperature box, setting the temperature in the low-temperature box to be-40 ℃, adding a reducing agent solution into the soaking solution when the temperature of the low-temperature box is reduced to-40 ℃, reacting for 1h at-40 ℃, then taking out the mixture, continuing to react for 1h at 20 ℃, then performing suction filtration and washing, and drying for 6h at 20 ℃ to obtain the supported monatomic rhodium-based catalyst with the rhodium loading capacity of 0.05 wt%.
In the propylene hydroformylation reaction catalyzed by the catalyst, the conversion rate of propylene is 41.1 percent, and the selectivity of n-butyl aldehyde in the product is 93 percent. Meanwhile, after the catalyst is used for 5 times of catalysis on propylene hydroformylation reaction, the conversion rate of propylene is 39.5%, and the selectivity of n-butyl aldehyde in a product is 91%.
Example 2
(1) Preparation of blocks g-C3N4: weighing 5g of melamine, grinding, uniformly mixing, filling into an alumina crucible, covering, putting into a muffle furnace, heating to 550 ℃ at the speed of 2 ℃/min under the nitrogen atmosphere, keeping for 4h, naturally cooling to room temperature, taking out, and grinding to obtain blocky g-C3N4。
(2) Preparation of ultra-thin g-C3N4Nanosheet: weighing 2g of the block g-C prepared in step (1)3N4Put into a narrow-mouth bottle, 500mL of isopropanol is added, and the bottle cap is screwed down. Placing the bottle containing the sample in an ultrasonic machine, ultrasonically treating for 10 hr to obtain suspension, centrifuging at 3000rpm for 10min to remove precipitate, and freeze drying at-40 deg.C for 12 hr to obtain ultrathin g-C3N4Nanosheets.
(3) Preparation of a monatomic rhodium-based catalyst: rhodium chloride solution (solvent is water and ethanol according to the volume ratio of 2: 8) of 20mL and 0.0005mol/L at room temperatureMixture of (3) with 1g of ultrathin g-C of step (2)3N4Stirring and soaking 500rmp of nanosheet for 3 hours, putting the nanosheet into a low-temperature box, simultaneously putting 10mL of 0.02mol/L hydrazine hydrate solution (the solvent is a mixture of water and ethanol in a volume ratio of 2: 8) into the low-temperature box, setting the temperature in the low-temperature box to be-30 ℃, adding a reducing agent solution into the soaking solution when the temperature of the low-temperature box is reduced to-40 ℃, reacting for 2 hours at-30 ℃, taking out, continuing to react for 1 hour at 25 ℃, then performing suction filtration and washing, and drying for 12 hours at 30 ℃ to obtain the supported monatomic rhodium-based catalyst with the rhodium loading of 0.1 wt%.
In the propylene hydroformylation reaction catalyzed by the catalyst, the conversion rate of propylene is 42.3 percent, and the selectivity of n-butyl aldehyde in the product is 95 percent. Meanwhile, after the catalyst is used for 5 times of catalysis on propylene hydroformylation reaction, the conversion rate of propylene is 40.3%, and the selectivity of n-butyl aldehyde in a product is 93%.
Example 3
(1) Preparation of blocks g-C3N4: weighing 5g of urea, grinding, uniformly mixing, filling into an alumina crucible, covering, putting into a muffle furnace, heating to 600 ℃ at the speed of 5 ℃/min under the argon atmosphere, keeping for 5h, naturally cooling to room temperature, taking out, and grinding to obtain blocky g-C3N4。
(2) Preparation of ultra-thin g-C3N4Nanosheet: weighing 2g of the block g-C prepared in step (1)3N4Putting the mixture into a narrow-mouth bottle, adding 500mL of N, N-dimethylformamide, and screwing the bottle cap. Placing the bottle containing the sample in an ultrasonic machine, ultrasonically treating for 20 hr to obtain suspension, centrifuging the suspension at 5000rpm for 10min to remove precipitate, and freeze drying the remaining suspension in a-20 deg.C freeze dryer for 24 hr to obtain ultrathin g-C3N4Nanosheets.
(3) Preparation of a monatomic rhodium-based catalyst: adding 1g of the ultrathin g-C in the step (2) into 20mL of 0.0025mol/L rhodium nitrate solution (the solvent is a mixture of water and ethanol according to the volume ratio of 9: 1) at room temperature3N4Stirring and soaking the nano-sheets at 100rmp for 6h, putting the nano-sheets into a low-temperature box, and simultaneously adding 20mL of 0.25mol/L ascorbic acid solution (the solvent is water and B)A mixture of alcohol according to the volume ratio of 9: 1) is also put into a low-temperature box, the temperature in the low-temperature box is set to be minus 20 ℃, a reducing agent solution is added into the dipping solution when the temperature in the low-temperature box is reduced to minus 20 ℃, the solution is taken out after 5 hours of reaction at minus 20 ℃, the reaction is continued for 5 hours at 30 ℃, then the solution is filtered and washed, and dried for 24 hours at 70 ℃, so as to obtain the load type monoatomic rhodium-based catalyst with the rhodium load of 0.5wt percent.
In the propylene hydroformylation reaction catalyzed by the catalyst, the conversion rate of propylene is 45.3 percent, and the selectivity of n-butyl aldehyde in the product is 98 percent. Meanwhile, after the catalyst is used for 5 times of catalysis on propylene hydroformylation reaction, the conversion rate of propylene is 43.2%, and the selectivity of n-butyl aldehyde in a product is 95%.
The embodiment shows that the load type monatomic rhodium-based catalyst of the invention is used in propylene hydroformylation reaction, shows the characteristic of high activity, has high selectivity to n-butyraldehyde, keeps high catalytic activity and selectivity after multiple catalytic reactions, has stable catalytic property and is convenient for recycling the catalyst, and the catalytic conversion rate and the selectivity of the load type monatomic rhodium-based catalyst are not greatly reduced.
The above embodiments describe the technical solutions of the present invention in detail. It will be clear that the invention is not limited to the described embodiments. Based on the embodiments of the present invention, those skilled in the art can make various changes, but any changes equivalent or similar to the present invention are within the protection scope of the present invention.
Claims (10)
1. A load type monatomic rhodium-based catalyst consists of a carrier and an active component loaded on the carrier, wherein the active component is noble metal rhodium, and the catalyst is characterized in that the carrier is two-dimensional ultrathin g-C3N4Nanosheets, the noble metal rhodium being uniformly dispersed in the two-dimensional ultrathin g-C in an atomic scale3N4And (4) nano-chips.
2. The supported monatomic rhodium-based catalyst of claim 1, wherein the noble metal rhodium is supported at a level of 0.05 to 0.5 wt.% and has a particle size of 0.01 to 1 nm.
3. A process for the preparation of a supported monatomic rhodium-based catalyst according to claim 1 or 2, characterized by comprising the steps of: mixing the blocks g-C3N4Peeling into two-dimensional ultra-thin g-C3N4Nanosheets, then supported and reduced at low temperature to said two-dimensional ultrathin g-C3N4Monatomic rhodium particles grow on the surface of the nanosheet in situ to obtain the supported monatomic rhodium-based catalyst.
4. A process for the preparation of a supported monatomic rhodium-based catalyst of claim 3, characterized by specifically comprising the steps of:
(1) calcining, cooling and grinding the nitrogen-rich carbon precursor to obtain a block g-C3N4；
(2) Mixing the blocks g-C of step (1)3N4Adding the mixture into an organic solvent, and performing ultrasonic treatment to form dispersed suspension; removing precipitate by high-speed centrifugation, and freeze-drying the remaining suspension to obtain two-dimensional ultrathin g-C3N4Nanosheets;
(3) subjecting the two-dimensional ultrathin g-C obtained in the step (2)3N4The nano sheet is dipped in rhodium salt solution, then reducing agent solution is added under the condition of low temperature, the reaction is fully completed, and the obtained product is filtered, washed and dried to obtain the load type monatomic rhodium-based catalyst.
5. The preparation method of the supported monatomic rhodium-based catalyst according to claim 4, characterized in that in step (1), the nitrogen-rich carbon precursor is any one or a mixture of more than one of cyanamide, dicyandiamide, melamine, urea and thiourea; the calcination in the step (1) is carried out in an inert gas atmosphere, the calcination temperature is 450-600 ℃, and the calcination time is 3-5 h.
6. The process of claim 4 wherein the organic solvent in step (2) is any one or more of water, ethanol, isopropanol, N-dimethylformamide, tetrahydrofuran, and acetone.
7. The preparation method of the supported monatomic rhodium-based catalyst according to claim 4, characterized in that the ultrasonic time in the step (2) is 5 to 20 hours; in the step (2), the centrifugal rotating speed is 1000-5000 rpm, and the centrifugal time is 1-10 min; in the step (2), the freeze drying temperature is-40 to-20 ℃, and the freeze drying time is 6 to 24 hours.
8. The process of claim 4 wherein the rhodium salt of step (3) is a soluble salt of rhodium with said ultra-thin g-C3N4The mass ratio of the nanosheets is based on the loading amount of noble metal rhodium in the finally prepared catalyst being 0.05-0.5 wt%; the reducing agent in the step (3) is any one or a mixture of more than one of sodium borohydride, hydrazine hydrate and ascorbic acid, and the molar ratio of the reducing agent to the noble metal rhodium in the rhodium salt is (5-100): 1.
9. the preparation method of the supported monatomic rhodium-based catalyst according to claim 4, characterized in that, in the step (3), the reaction is carried out at-40 to-20 ℃ for a period of time, and then the reaction is transferred to 20 to 30 ℃ for continuing the reaction to be complete.
10. Use of a supported monatomic rhodium-based catalyst according to claim 1 or 2, in the hydroformylation of propylene, comprising the steps of: under the action of the supported monatomic rhodium-based catalyst, n-butyraldehyde is generated from propylene and synthesis gas in a liquid phase.
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