CN116510761A - Method for preparing nitrogen-doped mesoporous carbon nano alloy catalyst by double-ligand MOFs and application - Google Patents
Method for preparing nitrogen-doped mesoporous carbon nano alloy catalyst by double-ligand MOFs and application Download PDFInfo
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- CN116510761A CN116510761A CN202310150327.6A CN202310150327A CN116510761A CN 116510761 A CN116510761 A CN 116510761A CN 202310150327 A CN202310150327 A CN 202310150327A CN 116510761 A CN116510761 A CN 116510761A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 118
- 238000000034 method Methods 0.000 title claims abstract description 42
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 30
- 239000000956 alloy Substances 0.000 title claims abstract description 30
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 22
- 239000003446 ligand Substances 0.000 title claims abstract description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims description 25
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 190
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims abstract description 110
- 238000006243 chemical reaction Methods 0.000 claims abstract description 99
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims description 52
- 229910052751 metal Inorganic materials 0.000 claims description 41
- 239000002184 metal Substances 0.000 claims description 41
- 239000013138 trimesic acid-based metal-organic framework Substances 0.000 claims description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
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- 238000003756 stirring Methods 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
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- 239000011949 solid catalyst Substances 0.000 claims description 13
- NVCZKUSRWBBGAH-UHFFFAOYSA-N methyl 4-[10,15,20-tris(4-methoxycarbonylphenyl)-21,23-dihydroporphyrin-5-yl]benzoate Chemical compound COC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(=O)OC)c2ccc([nH]2)c(-c2ccc(cc2)C(=O)OC)c2ccc(n2)c(-c2ccc(cc2)C(=O)OC)c2ccc1[nH]2 NVCZKUSRWBBGAH-UHFFFAOYSA-N 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 11
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- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000010813 internal standard method Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
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- 238000000227 grinding Methods 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims 1
- 150000004032 porphyrins Chemical class 0.000 abstract description 10
- 229910021645 metal ion Inorganic materials 0.000 abstract description 5
- 239000002028 Biomass Substances 0.000 abstract description 4
- 239000011943 nanocatalyst Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 3
- BGTOWKSIORTVQH-HOSYLAQJSA-N cyclopentanone Chemical class O=[13C]1CCCC1 BGTOWKSIORTVQH-HOSYLAQJSA-N 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 229910052723 transition metal Inorganic materials 0.000 abstract description 2
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- 238000005470 impregnation Methods 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 229910001428 transition metal ion Inorganic materials 0.000 abstract 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
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- 239000010453 quartz Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013084 copper-based metal-organic framework Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012847 fine chemical Substances 0.000 description 3
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- 238000006068 polycondensation reaction Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000013148 Cu-BTC MOF Substances 0.000 description 1
- 239000013147 Cu3(BTC)2 Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000013246 bimetallic metal–organic framework Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
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- 230000001737 promoting effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- NOSIKKRVQUQXEJ-UHFFFAOYSA-H tricopper;benzene-1,3,5-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1.[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 NOSIKKRVQUQXEJ-UHFFFAOYSA-H 0.000 description 1
- 239000002569 water oil cream 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
- C07C45/59—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of catalysts, and particularly relates to a method for preparing a nano mesoporous carbon-supported alloy nano catalyst with graded pores by using porphyrin-based MOFs (metal organic frameworks), and application of the catalyst in synthesizing cyclopentanone compounds by using the catalyst as biomass-based raw material furfural. According to the invention, porphyrin and trimesic acid are used as double ligands, firstly, M1-MOFs material is prepared by coordination with transition metal ion M1, and then, the other M2 metal ion is loaded by coordination with the center of porphyrin ring or impregnation adsorption, so that the M1-M2-MOFs precursor is prepared. The M1-M2-MOFs are annealed at high temperature to prepare the nitrogen-doped mesoporous carbon-supported transition metal alloy nano catalyst (hereinafter referred to as M1-M2-NPC). The obtained M1-M2-NPC can be applied to catalyzing the reaction of converting furfural into cyclopentanone.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a method for preparing a nano mesoporous carbon-supported alloy nano catalyst with graded pores by using porphyrin-based MOFs (metal organic frameworks), and application of the catalyst in synthesizing cyclopentanone compounds by using the catalyst as biomass-based raw material furfural.
Background
The use of biomass to produce valuable chemicals is an effective way to reduce fossil resource dependence and increase the supply of organic fine chemicals. Furfural (FFA) is an important bio-based platform compound, being located as a stable renewable source of organic non-chemical stone-like carbon, useful for the production of value-added chemicals and fuels. Furfural is a multifunctional compound (with furan ring and carbonyl), and various fine chemicals such as Cyclopentanone (CPO) and Cyclopentanol (CPL) can be prepared through various catalytic reduction, ring opening and other reactions, and can be efficiently synthesized through catalytic hydrogenation and isomerization reactions. Among them, cyclopentanone (CPO) is an important fine chemical raw material for the production of medicines, pesticides, dyes and fragrances.
In the process of converting furfural into cyclopentanone, researchers research and develop various catalysts in order to improve the conversion rate of raw materials and the selectivity of products and reduce the production cost. The 'Biomass-derived furfural conversion over Ni/CNT catalysts at the interface of water-oil emulsion droplets', HERRERA C and the like utilize liquid-liquid interface Ni nano particles, are distributed on the interface of emulsion liquid drops to form stable Pickering emulsion, and are loaded by carbon nano tubes to prepare the catalyst (Ni/CNTox for short). Ni/CNTox as effective catalyst for converting furfural into cyclopentanone under optimized conditions (using water as solvent, 200deg.C, 2MPa H 2 Under 1 h), the conversion rate of furfural is 35%, and the yield of cyclopentanone is 25%. The catalyst has low selectivity on converting furfural into cyclopentanone, and after three times of circulation, the CPO yield is obviously reduced, and the catalyst is difficult to continuously and effectively catalyze and is not suitable for industrial production and application.
“Pd/Cu-MOF as a highly efficient catalyst for synthesis ofcyclopentanone compounds frombiomass-derived furanic aldehydes ", DENG Q, etc. are prepared from Cu-MOFs of different chemical structures (e.g. Cu 3 (BTC) 2 ) And (3) preparing a Pd/Cu-MOFs precursor by using the carrier, and annealing to obtain the Pd/Cu-C bifunctional catalyst. Because Cu-BTC (metal ions are bridged by tripolyacid) has stronger acidity, cu and Pd metal ions can be effectively fixed, so that the Cu and Pd metal ions are uniformly and orderly dispersed. In the reaction of catalyzing furfural to convert cyclopentanone, the activity of the catalyst is reduced after the catalyst is circulated for 5 times. TEM analysis shows that the Pd nano-particles on the catalyst are seriously aggregated after being recycled for 5 times compared with the high dispersity of the Pd nano-particles on the unreacted catalyst. Catalyst is circulated for 5 times and then N 2 The adsorption-desorption process also shows that the specific surface area of the catalyst is greatly reduced, which is the cause of the reduction of the catalyst activity.
Therefore, the catalyst which has good selectivity and high stability and is used for promoting the conversion of furfural into cyclopentanone is prepared, and the industrial application is realized, so that the catalyst has important significance.
Disclosure of Invention
One of the purposes of the present invention is to provide a method for preparing a nitrogen-doped mesoporous carbon nano alloy catalyst by using tetra (4-methoxy carbonyl phenyl) porphyrin (T (4-COOCH) 3 ) PP), trimesic acid (BTC) is a double-ligand MOFs material (M-TCOPP-BTC-MOF for short), and is used as a precursor to prepare the nitrogen-doped mesoporous carbon-supported transition metal alloy nano catalyst which can be applied to catalyzing the reaction of converting furfural into cyclopentanone, has the characteristics of good selectivity and high stability, and can be applied to industry.
In order to achieve the above purpose, the present invention adopts the following technical scheme: a method for preparing a nitrogen-doped mesoporous carbon nano alloy catalyst by using double-ligand MOFs comprises the following steps:
s1, dissolving soluble metal salt M1 in an organic solvent, and adding tetra (4-methoxy carbonyl phenyl) porphyrin (T (4-COOCH) with the mol ratio of 1 (0.1-10) 3 ) Mixing PP and trimesic acid (BTC) to obtain mixed solution, stirring to dissolve completely, regulating pH to 2-4, transferring into polytetrafluoroethylene reaction kettle, continuously reacting at 50-140deg.C for 2-48 hr, and coolingSeparating to obtain precipitate, drying to obtain T (4-COOCH) 3 ) MOFs material with PP and BTC as double ligands, abbreviated as M 1 -TCOPP-BTC-MOFs；
S2, dissolving soluble metal salt M2 in ethanol solution, and adding M prepared in the step S1 1 -TCOPP-BTC-MOFs, said M 1 The molar ratio of the metal in the TCOPP-BTC-MOFs to the metal in the soluble metal salt M2 is 10:1-1:10, the mixture is stirred and mixed uniformly at normal temperature, and the solid catalyst precursor M1-M2-TCOPP-BTC-MOFs is obtained by vacuum drying;
s3, taking M1-M2-TCOPP-BTC-MOFs, crushing uniformly, placing in a tube furnace, annealing for 2-8 hours at 200-800 ℃ in the atmosphere of air, hydrogen or inert gas, cooling to room temperature, and grinding to obtain the nitrogen-doped mesoporous carbon nano alloy catalyst, namely M1-M2-NPC.
The method for preparing the nitrogen-doped mesoporous carbon nano alloy catalyst by using the double-ligand MOFs is further improved:
preferably, the porphyrin (T (4-COOCH) 3 ) PP) and trimesic acid (BTC) are in a molar ratio of 1 (1-3).
Preferably, the soluble metal salt M1 is one formed single metal salt of Cu, co, ni, zn, al, mn, pd.
Preferably, the soluble metal salt M2 is a single metal salt formed by one of Cu, co, ni, zn, al, mn, pd or a composite metal salt formed by two or more of Cu, co, ni, zn, al, mn, pd, or a combination of any two or more of a single metal salt and a composite metal salt.
Preferably, the organic solvent is one or more of N, N-Dimethylformamide (DMF), N-Diethylformamide (DEF), acetonitrile, dimethyl sulfoxide and triethanolamine.
Preferably, the organic solvent is a mixed solution of DMF and DEF, and the volume ratio of DMF to DEF is 1:1-1:10, preferably 1:7.
Preferably, the inert gas in step S3 is one or a combination of more than two of nitrogen, argon, carbon dioxide and helium.
Preferably, in step S1, the pH of the solution is adjusted with a hydrochloric acid solution, a nitric acid solution or a sulfuric acid solution; the concentration of the sulfuric acid solution is 1-10mol/L, preferably 3.3mol/L.
Preferably, the reaction temperature of the mixed solution in the step S1 in a polytetrafluoroethylene reaction kettle is 120-140 ℃, and the reaction time is 20-24 hours.
Preferably, the annealing temperature in step S3 is 400-500 ℃ and the annealing time is 2.5-4h.
The second purpose of the invention is to provide the application of the nitrogen-doped mesoporous carbon nano alloy catalyst prepared by the preparation method of any one of the above in catalyzing the water phase hydrogenation of furfural to prepare cyclopentanone.
The application of the catalyst as the nitrogen doped mesoporous carbon nano alloy is further improved:
preferably, the catalyst M1-M2-NPC and the furfural solution are mixed and then added into a high-pressure reaction kettle, and N is used in sequence 2 And H 2 Air in the high-pressure reaction kettle is replaced, the reaction kettle is sealed, and then H is introduced 2 And (3) starting stirring until the pressure reaches 1-20Mpa, and heating the reaction kettle to 80-200 ℃ for reaction for 0.5-8h.
Preferably, the ratio of the mass of the catalyst added to the mass of the furfural in the furfural solution is (10-30): 100, and preferably the ratio is (15-20): 100.
Preferably, hydrogen is introduced to a pressure of 1.5-3Mpa.
Preferably, the reaction kettle is heated to 140-180 ℃ for 4-6h.
Preferably, the solvent of the furfural solution is one or two of water and methanol, and the mass concentration of the furfural solution is 1-30%.
Preferably, after the reaction is finished, the content of furfural, furfuryl alcohol, cyclopentanone and the like in the reaction mixture is analyzed by a gas chromatograph internal standard method, the furfural conversion rate and the cyclopentanone yield are calculated, and the recovered M1-M2-NPC catalyst can be directly or circularly used after washing treatment.
Compared with the prior art, the invention has the beneficial effects that:
1) The invention provides a method for preparing a nitrogen-doped mesoporous carbon nano alloy catalyst by using double-ligand MOFs, which is characterized in that tetra (4-methoxycarbonyl phenyl) porphyrin and trimesic acid are designed as double ligands, double-metal MOFs are prepared as precursors, and then M1-M2-NPC carbon-based catalyst is prepared by annealing.
According to the preparation method, trimesic acid and tetra (4-methoxycarbonylphenyl) porphyrin are used as double ligands, bimetallic MOFs (metal oxide-organic frameworks) are prepared as precursors, rich metal active sites and metal ions can be provided for coordination, the prepared solid catalyst precursor has a hierarchical porous structure, and M1-M2-NPC obtained through annealing has a higher specific surface area and a good pore structure, so that mass transfer process in catalytic reaction is facilitated, and the activity of the catalyst is improved. The M1-M2-TCOPP-BTC-MOFs are formed by the trimesic acid and the tetra (4-methoxycarbonylphenyl) porphyrin double ligand, the metal atoms are distributed more uniformly through coordination, and under the pyrolysis condition, the highly dispersed M1 and M2 metals are converted into metal nano particles in situ, so that the obtained M1-M2-NPC catalyst has multiple active sites, uniform dispersion and better stability.
The N content in M1-M2-NPC can be conveniently regulated and controlled by changing the proportion of the two ligands of tetra (4-methoxy carbonyl phenyl) porphyrin and trimesic acid, the acid alkalinity, the site and the balance of the catalyst carrier are controlled, and in the reaction process of catalyzing the conversion of furfural into cyclopentanone, the self polymerization of furfural and the polycondensation of intermediate furfuryl alcohol in an aqueous phase system at high temperature can be effectively prevented, and the conversion rate and the selectivity of the catalytic reaction are improved.
2) The M1-M2@NPC catalyst prepared by the method is applied to the reaction process of catalyzing the conversion of furfural into cyclopentanone, and can be recycled for a plurality of times, the catalytic efficiency is not obviously reduced, the cycle performance is good, and the method meets the industrial production requirements. The catalyst is safe, nontoxic, green and efficient, is environment-friendly and harmless to human bodies, meets the industrial green production requirement, and has good application prospect.
Detailed Description
The present invention will be further described in detail with reference to the following examples, in order to make the objects, technical solutions and advantages of the present invention more apparent, and all other examples obtained by those skilled in the art without making any inventive effort are within the scope of the present invention based on the examples in the present invention.
In an embodiment, the furfural conversion and cyclopentanone selectivity are defined as:
furfural conversion= (amount of starting furfural-amount of remaining furfural in reaction)/amount of starting furfural x 100%,
cyclopentanone selectivity = amount of furfural converted to cyclopentanone/furfural consumed by the reaction x 100%.
Example 1
The embodiment provides a method for preparing a Cu-Co-NPC catalyst 1, which is applied to catalyzing furfural to prepare cyclopentanone, and specifically comprises the following steps:
s1, preparing a Cu-Co-NPC catalyst 1:
1.0473g Cu (NO) was weighed out 3 ) 2 ·6H 2 O is dissolved in 80mL of organic solvent, wherein the organic solvent is a mixed solvent of DMF and DEF in a volume ratio of 1:7, and 0.5012g of tetra (4-methoxy carbonyl phenyl) porphyrin (namely T (4-COOCH) 3 ) PP) and 0.1243g trimesic acid (i.e., BTC), wherein T (4-COOCH) 3 ) The molar ratio of PP to BTC is 1:1, and the mixture is stirred until Cu (NO 3 ) 2 ·6H 2 The materials such as O and the like are completely dissolved, and the solution is adjusted to pH=3 by using a sulfuric acid solution of 3.3mol/L. Transferring the mixed solution into polytetrafluoroethylene lining, sealing in stainless steel autoclave, reacting at 120deg.C for 24 hr, cooling to room temperature, separating the mixed solution to obtain precipitate, drying at 60deg.C overnight to obtain porphyrin (T (4-COOCH) 3 ) PP), trimesic acid (BTC) as a dual ligand MOFs material 0.6543g, cu-TCOPP-BTC-MOFs for short;
0.1054g of Co (NO) 3 ) 2 ·6H 2 O was dissolved in 20mL of ethanol solution, 0.1054g of the Cu-TCOPP-BTC-MOFs described above was added, and Cu and Co (NO) metals in the Cu-TCOPP-BTC-MOFs were added 3 ) 2 ·6H 2 The molar ratio of the metal Co in the O is 1:4, stirring is carried out for 16 hours at normal temperature, and the mixed solution is dried in vacuum at 80 ℃ to obtain the solid catalyst precursorBulk Cu-Co-TCOPP-BTC-MOFs;
the solid catalyst precursor Cu-Co-TCOPP-BTC-MOFs is crushed uniformly, placed in a quartz crucible, placed in a tube furnace, annealed for 3 hours at 500 ℃ under the atmosphere of nitrogen and hydrogen with the flow ratio of 2:1, cooled to room temperature, and ground and collected to obtain 0.1028g of the nitrogen doped mesoporous carbon nano alloy catalyst, namely the Cu-Co-NPC catalyst 1.
S2, preparing cyclopentanone by catalyzing furfural:
the Cu-Co-NPC catalyst 1 prepared by the method is 20mg in total, 0.1g of furfuraldehyde is added into 5mL of deionized water (the mass concentration of the furfuraldehyde solution is 2 percent), then the mixture is respectively added into a high-pressure reaction kettle, the mass of the added catalyst accounts for 20 percent of the mass of the furfuraldehyde in the furfuraldehyde solution, and N is sequentially used 2 And H 2 Air in the high-pressure reaction kettle is replaced, the reaction kettle is sealed, and then H is introduced 2 And (3) starting the autoclave to stir until the pressure reaches 3.0MPa, and heating the autoclave to 180 ℃ for reaction for 4 hours.
After the reaction is finished, cooling the reaction mixed solution to room temperature, adding 10mL of absolute ethyl alcohol, uniformly mixing, centrifugally filtering, separating and recovering the catalyst, and directly recycling the catalyst.
The obtained filtrate is detected by a gas chromatography internal standard method by taking cyclohexanone as an internal standard, and the furfural conversion rate is calculated to be 99.9%, and the selectivity of the cyclopentanone is 72%.
Example 2:
the embodiment provides a method for preparing a Cu-Co-NPC catalyst 2, and is applied to catalyzing furfural to prepare cyclopentanone, and specifically comprises the following steps:
s1, preparing a Cu-Co-NPC catalyst 2:
1.0324g Cu (NO) was weighed out 3 ) 2 ·6H 2 O is dissolved in 80mL of organic solvent, wherein the organic solvent is a mixed solvent of DMF and DEF in a volume ratio of 1:7, and 0.5012g of tetra (4-methoxy carbonyl phenyl) porphyrin (namely T (4-COOCH) 3 ) PP) and 0.2486g trimesic acid (i.e., BTC), wherein T (4-COOCH) 3 ) The molar ratio of PP to BTC was 1:2, and Cu (NO 3 ) 2 ·6H 2 The materials such as O and the like are completely dissolved, and 3.3mol/L sulfuric acid solution is used for adjusting the solution to pH value3. Transferring the mixed solution into polytetrafluoroethylene lining, sealing in stainless steel autoclave, reacting at 120deg.C for 24 hr, cooling to room temperature, separating the mixed solution to obtain precipitate, drying at 60deg.C overnight to obtain porphyrin (T (4-COOCH) 3 ) PP), trimesic acid (BTC) 0.5756g of dual ligand MOFs material, abbreviated Cu-TCOPP-BTC-MOFs.
0.2012g of Co (NO) 3 ) 2 ·6H 2 O was dissolved in 20mL of ethanol solution, 0.1076g of the Cu-TCOPP-BTC-MOFs was added, and Cu and Co (NO) were metals in the Cu-TCOPP-BTC-MOFs 3 ) 2 ·6H 2 The molar ratio of the metal Co in the O is 1:4, stirring is carried out for 16 hours at normal temperature, and the mixed solution is dried in vacuum at 80 ℃ to obtain the solid catalyst precursor Cu-Co-TCOPP-BTC-MOFs.
The solid catalyst precursor Cu-Co-TCOPP-BTC-MOFs is crushed uniformly, placed in a quartz crucible, placed in a tube furnace, annealed for 3 hours at 500 ℃ under the atmosphere of nitrogen and hydrogen with the flow ratio of 2:1, cooled to room temperature, and ground and collected to obtain 0.1423g of nitrogen doped mesoporous carbon nano alloy catalyst, namely Cu-Co-NPC catalyst 2.
S2, preparing cyclopentanone by catalyzing furfural:
the Cu-Co-NPC catalyst 2 prepared by the method is 20mg in total, 0.1g of furfuraldehyde is added into 5mL of deionized water (the mass concentration of the furfuraldehyde solution is 2 percent), then the mixture is respectively added into a high-pressure reaction kettle, the mass of the added catalyst accounts for 20 percent of the mass of the furfuraldehyde in the furfuraldehyde solution, and N is sequentially used 2 And H 2 Air in the high-pressure reaction kettle is replaced, the reaction kettle is sealed, and then H is introduced 2 And (3) starting the autoclave to stir until the pressure reaches 3.0MPa, and heating the autoclave to 180 ℃ for reaction for 4 hours.
After the reaction is finished, cooling the reaction mixed solution to room temperature, adding 10mL of absolute ethyl alcohol, uniformly mixing, centrifugally filtering, separating and recovering the catalyst, and directly recycling the catalyst.
As compared with example 1, the metal content in M1 after the reaction was increased due to the increase of the second ligand, and the addition amount of M2 was adjusted so that the ratio of the two metals was the same as in example 1. In the embodiment, the nitrogen content in the catalyst is reduced by adjusting the molar ratio of the two ligands in the catalyst, so that a more proper nitrogen content interval is achieved, and the selectivity of cyclopentanone is improved. The obtained filtrate is detected by a gas chromatography internal standard method by taking cyclohexanone as an internal standard, and the furfural conversion rate is calculated to be 99.9%, and the selectivity of the cyclopentanone is 86%.
Example 3:
the embodiment provides a method for preparing cyclopentanone by catalyzing furfural by using a Cu-Co-NPC catalyst 2, which comprises the following steps:
s1, preparing a Cu-Co-NPC catalyst 2: reference is made to the specific procedure in example 2.
S2, preparing cyclopentanone by catalyzing furfural:
10mg of Cu-Co-NPC catalyst 2 is prepared by the method, 0.1g of furfuraldehyde is added into 5mL of deionized water (the mass concentration of the furfuraldehyde solution is 2 percent), then the mixture is respectively added into a high-pressure reaction kettle, the mass of the added catalyst accounts for 10 percent of the mass of the furfuraldehyde in the furfuraldehyde solution, and N is sequentially used 2 And H 2 Air in the high-pressure reaction kettle is replaced, the reaction kettle is sealed, and then H is introduced 2 And (3) starting the autoclave to stir until the pressure reaches 3.0MPa, and heating the autoclave to 180 ℃ for reaction for 4 hours.
Compared with example 2, the present example adjusts the ratio of the mass of the catalyst added to the mass of furfural in the furfural solution. The obtained filtrate is detected by a gas chromatography internal standard method by taking cyclohexanone as an internal standard, and the furfural conversion rate is calculated to be 70%, and the selectivity of the cyclopentanone is 68%.
Example 4:
the embodiment provides a method for preparing cyclopentanone by catalyzing furfural by using a Cu-Co-NPC catalyst 2, which comprises the following steps:
s1, preparing a Cu-Co-NPC catalyst 2: reference is made to the specific procedure in example 2.
S2, preparing cyclopentanone by catalyzing furfural:
30mg of Cu-Co-NPC catalyst 2 prepared by the method is added into 5mL of deionized water (the mass concentration of the furfural solution is 2%) by 0.1g of furfural, and then the mixture is respectively added into a high-pressure reaction kettle, wherein the mass of the added catalyst accounts for the furfural in the furfural solutionThe mass ratio is 30%, and N is used in sequence 2 And H 2 Air in the high-pressure reaction kettle is replaced, the reaction kettle is sealed, and then H is introduced 2 And (3) starting the autoclave to stir until the pressure reaches 3.0MPa, and heating the autoclave to 180 ℃ for reaction for 4 hours.
Compared with example 2, the present example adjusts the ratio of the mass of the catalyst added to the mass of furfural in the furfural solution. The obtained filtrate is detected by a gas chromatography internal standard method by taking cyclohexanone as an internal standard, and the furfural conversion rate is calculated to be 99.9%, and the selectivity of the cyclopentanone is 84%.
Example 5:
the embodiment provides a method for preparing a Cu-Ni-NPC catalyst, which is applied to preparing cyclopentanone by catalyzing furfural, and specifically comprises the following steps:
s1, preparing a Cu-Ni-NPC catalyst:
1.0324g Cu (NO) was weighed out 3 ) 2 ·6H 2 O is dissolved in 80mL of organic solvent, wherein the organic solvent is a mixed solvent of DMF and DEF in a volume ratio of 1:7, and 0.5012g of tetra (4-methoxy carbonyl phenyl) porphyrin (namely T (4-COOCH) 3 ) PP) and 0.2486g trimesic acid (i.e., BTC), wherein T (4-COOCH) 3 ) The molar ratio of PP to BTC was 1:2, and Cu (NO 3 ) 2 ·6H 2 The materials such as O and the like are completely dissolved, and the solution is adjusted to pH=3 by using a sulfuric acid solution of 3.3mol/L. Transferring the mixed solution into polytetrafluoroethylene lining, sealing in stainless steel autoclave, reacting at 120deg.C for 24 hr, cooling to room temperature, separating the mixed solution to obtain precipitate, drying at 60deg.C overnight to obtain porphyrin (T (4-COOCH) 3 ) PP), trimesic acid (BTC) 0.5756g of dual ligand MOFs material, abbreviated Cu-TCOPP-BTC-MOFs.
0.1011g of Ni (NO) 3 ) 2 ·6H 2 O was dissolved in 20mL of ethanol solution, 0.1076g of the Cu-TCOPP-BTC-MOFs was added, and Cu and Ni (NO) as metals in the Cu-TCOPP-BTC-MOFs were added 3 ) 2 ·6H 2 The molar ratio of metal Ni in O is 1:2, stirring is carried out for 16h at normal temperature, and the mixed solution is dried in vacuum at 80 ℃ to obtain a solid catalyst precursor Cu-Ni-TCOPP-BTC-MOFs.
The solid catalyst precursor Cu-Ni-TCOPP-BTC-MOFs is crushed uniformly, placed in a quartz crucible, placed in a tube furnace, annealed for 3 hours at 500 ℃ under the atmosphere of nitrogen and hydrogen with the flow ratio of 2:1, cooled to room temperature, and ground and collected to obtain 0.1002g of nitrogen doped mesoporous carbon nano alloy catalyst, namely the Cu-Ni-NPC catalyst.
S2, preparing cyclopentanone by catalyzing furfural:
the Cu-Ni-NPC catalyst prepared by the method is 20mg in total, 0.1g of furfuraldehyde is added into 5mL of deionized water (the mass concentration of the furfuraldehyde solution is 2 percent), then the mixture is respectively added into a high-pressure reaction kettle, the mass of the added catalyst accounts for 20 percent of the mass of the furfuraldehyde in the furfuraldehyde solution, and N is sequentially used 2 Air in the high-pressure reaction kettle is replaced, the reaction kettle is sealed, and then H is introduced 2 And (3) starting the autoclave to stir until the pressure reaches 3.0MPa, and heating the autoclave to 180 ℃ for reaction for 4 hours.
After the reaction is finished, cooling the reaction mixed solution to room temperature, adding 10mL of absolute ethyl alcohol, uniformly mixing, centrifugally filtering, separating and recovering the catalyst, and directly recycling the catalyst.
The obtained filtrate is detected by a gas chromatography internal standard method by taking cyclohexanone as an internal standard, and the furfural conversion rate is calculated to be 99.9%, and the selectivity of the cyclopentanone is 80%.
Example 6:
the embodiment provides a method for preparing a Co-Ni-NPC catalyst, which is applied to catalyzing furfural to prepare cyclopentanone, and specifically comprises the following steps:
s1, preparation of Co-Ni-NPC catalyst:
1.0241g Co (NO) 3 ) 2 ·6H 2 O is dissolved in 80mL of organic solvent, wherein the organic solvent is a mixed solvent of DMF and DEF in a volume ratio of 1:7, and 0.5012g of tetra (4-methoxy carbonyl phenyl) porphyrin (namely T (4-COOCH) 3 ) PP) and 0.2486g trimesic acid (i.e., BTC), wherein T (4-COOCH) 3 ) The molar ratio of PP to BTC was 1:2, and Co (NO 3 ) 2 ·6H 2 The materials such as O and the like are completely dissolved, and the solution is adjusted to pH=3 by using a sulfuric acid solution of 3.3mol/L. The mixed solution is then transferred into a polytetrafluoroethylene lining and sealed in a stainless steel autoclaveIn the process, the reaction was continued at 120℃for 24 hours, and after cooling to room temperature, the reaction mixture was separated to obtain a precipitate, and the obtained precipitate was dried at 60℃overnight to obtain porphyrin (T (4-COOCH) 3 ) PP), trimesic acid (BTC) as a dual ligand, 0.4687g of MOFs material, abbreviated as Co-TCOPP-BTC-MOFs.
0.1123g of Ni (NO) 3 ) 2 ·6H 2 O was dissolved in 20mL of ethanol solution, 0.1025g of the above Co-TCOPP-BTC-MOFs was added, and Cu and Co (NO) were metals in the Cu-TCOPP-BTC-MOFs 3 ) 2 ·6H 2 The molar ratio of the metal Co in the O is 1:2, stirring is carried out for 16 hours at normal temperature, and the mixed solution is dried in vacuum at 80 ℃ to obtain the solid catalyst precursor Co-Ni-TCOPP-BTC-MOFs.
The solid catalyst precursor Co-Ni-TCOPP-BTC-MOFs is crushed uniformly, placed in a quartz crucible, placed in a tube furnace, annealed for 3 hours at 500 ℃ under the atmosphere of nitrogen and hydrogen with the flow ratio of 2:1, cooled to room temperature, and ground and collected to obtain 0.1002g of nitrogen doped mesoporous carbon nano alloy catalyst, namely Co-Ni-NPC catalyst 2.
S2, preparing cyclopentanone by catalyzing furfural:
the Co-Ni-NPC catalyst prepared by the method is 20mg in total, 0.1g of furfuraldehyde is added into 5mL of deionized water (the mass concentration of the furfuraldehyde solution is 2 percent), then the mixture is respectively added into a high-pressure reaction kettle, the mass of the added catalyst accounts for 20 percent of the mass of the furfuraldehyde in the furfuraldehyde solution, and N is sequentially used 2 And H 2 Air in the high-pressure reaction kettle is replaced, the reaction kettle is sealed, and then H is introduced 2 And (3) starting the autoclave to stir until the pressure reaches 3.0MPa, and heating the autoclave to 180 ℃ for reaction for 4 hours.
After the reaction is finished, cooling the reaction mixed solution to room temperature, adding 10mL of absolute ethyl alcohol, uniformly mixing, centrifugally filtering, separating and recovering the catalyst, and directly recycling the catalyst.
The obtained filtrate is detected by a gas chromatography internal standard method by taking cyclohexanone as an internal standard, and the furfural conversion rate is calculated to be 99.9%, and the selectivity of the cyclopentanone is 83%.
Example 7:
the embodiment provides a method for preparing cyclopentanone by catalyzing furfural by using a Cu-Co-NPC catalyst 2, which comprises the following steps:
s1, preparing a Cu-Co-NPC catalyst 2: reference is made to the specific procedure in example 2.
S2, preparing cyclopentanone by catalyzing furfural:
the Cu-Co-NPC catalyst 2 prepared by the method is 50mg in total, 0.25g of furfurol is added into 5mL of deionized water (the mass concentration of the furfurol solution is 5%), then the mixture is respectively added into a high-pressure reaction kettle, the mass of the added catalyst accounts for 20% of the mass of the furol in the furol solution, and N is sequentially used 2 And H 2 Air in the high-pressure reaction kettle is replaced, the reaction kettle is sealed, and then H is introduced 2 And (3) starting the autoclave to stir until the pressure reaches 3.0MPa, and heating the autoclave to 180 ℃ for reaction for 4 hours.
After the reaction is finished, cooling the reaction mixed solution to room temperature, adding 10mL of absolute ethyl alcohol, uniformly mixing, centrifugally filtering, separating and recovering the catalyst, and directly recycling the catalyst.
Compared with the embodiment 2, the embodiment increases the concentration of the reactant furfural in the preparation of the cyclopentanone by catalyzing the furfural, and the polycondensation side reaction is obvious in the reaction process, so that the furfural conversion rate and the cyclopentanone selectivity are reduced. The obtained filtrate is detected by a gas chromatography internal standard method by taking cyclohexanone as an internal standard, and the furfural conversion rate is calculated to be 90%, and the selectivity of the cyclopentanone is 40%.
Example 8:
the embodiment provides a method for preparing cyclopentanone by catalyzing furfural by using a Cu-Co-NPC catalyst 2, which comprises the following steps:
s1, preparing a Cu-Co-NPC catalyst 2: reference is made to the specific procedure in example 2.
S2, preparing cyclopentanone by catalyzing furfural:
the Cu-Co-NPC catalyst 2 prepared by the method is 50mg in total, 0.50g of furfuraldehyde is added into 5mL of deionized water (the mass concentration of the furfuraldehyde solution is 10 percent), then the mixture is respectively added into a high-pressure reaction kettle, the mass of the added catalyst accounts for 20 percent of the mass of the furfuraldehyde in the furfuraldehyde solution, and N is sequentially used 2 And H 2 Air in the high-pressure reaction kettle is replaced, the reaction kettle is sealed, and then H is introduced 2 And (3) starting the autoclave to stir until the pressure reaches 3.0MPa, and heating the autoclave to 180 ℃ for reaction for 4 hours.
Compared with examples 2 and 5, after the concentration of the reactant furfural is continuously increased, the polycondensation side reaction is obvious in the reaction process, so that the furfural conversion rate and the selectivity of cyclopentanone are reduced. The obtained filtrate is detected by a gas chromatography internal standard method by taking cyclohexanone as an internal standard, and the furfural conversion rate is calculated to be 65%, and the selectivity of the cyclopentanone is 16%.
Example 9:
the embodiment provides a method for preparing a Cu-Co-Ni-NPC catalyst, which is applied to catalyzing furfural to prepare cyclopentanone, and specifically comprises the following steps:
s1, preparing a Cu-Co-Ni-NPC catalyst:
1.0324g Cu (NO) was weighed out 3 ) 2 ·6H 2 O is dissolved in 80mL of organic solvent, wherein the organic solvent is a mixed solvent of DMF and DEF in a volume ratio of 1:7, and 0.5012g of tetra (4-methoxy carbonyl phenyl) porphyrin (namely T (4-COOCH) 3 ) PP) and 0.2486g trimesic acid (i.e., BTC), wherein T (4-COOCH) 3 ) The molar ratio of PP to BTC was 1:2, and Cu (NO 3 ) 2 ·6H 2 The materials such as O and the like are completely dissolved, and the solution is adjusted to pH=3 by using a sulfuric acid solution of 3.3mol/L. Transferring the mixed solution into polytetrafluoroethylene lining, sealing in stainless steel autoclave, reacting at 120deg.C for 24 hr, cooling to room temperature, separating the mixed solution to obtain precipitate, drying at 60deg.C overnight to obtain porphyrin (T (4-COOCH) 3 ) PP), trimesic acid (BTC) 0.5756g of dual ligand MOFs material, abbreviated Cu-TCOPP-BTC-MOFs.
0.2012g of Co (NO) 3 ) 2 ·6H 2 O and 0.2012g of Ni (NO) 3 ) 2 ·6H 2 O is dissolved in 20mL of ethanol solution, 0.1076g of Cu-TCOPP-BTC-MOFs is added, stirring is carried out for 16h at normal temperature, and the mixed solution is dried in vacuum at 80 ℃ to obtain solid catalyst precursor Cu-Co-Ni-TCOPP-BTC-MOFs.
The solid catalyst precursor Cu-Co-Ni-TCOPP-BTC-MOFs is crushed uniformly, placed in a quartz crucible, placed in a tube furnace, annealed for 3 hours at 500 ℃ under the atmosphere of nitrogen and hydrogen with the flow ratio of 2:1, cooled to room temperature, and ground and collected to obtain 0.1924g of nitrogen doped mesoporous carbon nano alloy catalyst, namely the Cu-Co-Ni-NPC catalyst.
S2, preparing cyclopentanone by catalyzing furfural:
the Cu-Co-Ni-NPC catalyst prepared by the method is 20mg in total, added into 5mL of deionized water (the mass concentration of the furfural solution is 2 percent), then respectively added into a high-pressure reaction kettle, the mass of the added catalyst accounts for 20 percent of the mass of the furfural in the furfural solution, and N is used in sequence 2 And H 2 Air in the high-pressure reaction kettle is replaced, the reaction kettle is sealed, and then H is introduced 2 And (3) starting the autoclave to stir until the pressure reaches 3.0MPa, and heating the autoclave to 180 ℃ for reaction for 4 hours.
After the reaction is finished, cooling the reaction mixed solution to room temperature, adding 10mL of absolute ethyl alcohol, uniformly mixing, centrifugally filtering, separating and recovering the catalyst, and directly recycling the catalyst.
In comparison with example 2, the soluble metal salt M2 of this example employs a combination of two single metal salts to prepare a three-component nano-alloy catalyst. The obtained filtrate is detected by a gas chromatography internal standard method by taking cyclohexanone as an internal standard, and the furfural conversion rate is calculated to be 99.9%, and the selectivity of the cyclopentanone is 80%.
Those skilled in the art will appreciate that the foregoing is merely a few, but not all, embodiments of the invention. It should be noted that many variations and modifications can be made by those skilled in the art, and all variations and modifications which do not depart from the scope of the invention as defined in the appended claims are intended to be protected.
Claims (10)
1. The method for preparing the nitrogen-doped mesoporous carbon nano alloy catalyst by using the double-ligand MOFs is characterized by comprising the following steps of:
s1, dissolving soluble metal salt M1 in an organic solvent, and adding tetra (4-methoxy carbonyl phenyl) porphyrin (T (4-COOCH) with the mol ratio of 1 (0.1-10) 3 ) PP and trimesic acid (BTC) are mixed to obtain mixed solution, and the mixed solution is stirred until the materials are completely dissolved, and the dissolution is regulatedThe pH value of the solution is 2-4, the mixed solution is transferred into a polytetrafluoroethylene reaction kettle to continuously react for 2-48 hours at the temperature of 50-140 ℃, the solution is cooled to room temperature and separated to obtain a precipitate, and the precipitate is dried to obtain the T (4-COOCH) 3 ) MOFs material with PP and BTC as double ligands, abbreviated as M 1 -TCOPP-BTC-MOFs；
S2, dissolving soluble metal salt M2 in ethanol solution, and adding M prepared in the step S1 1 -TCOPP-BTC-MOFs, said M 1 The molar ratio of the metal in the TCOPP-BTC-MOFs to the metal in the soluble metal salt M2 is 10:1-1:10, the mixture is stirred and mixed uniformly at normal temperature, and the solid catalyst precursor M1-M2-TCOPP-BTC-MOFs is obtained by vacuum drying;
s3, taking M1-M2-TCOPP-BTC-MOFs, crushing uniformly, placing in a tube furnace, annealing for 2-8 hours at 200-800 ℃ in the atmosphere of air, hydrogen or inert gas, cooling to room temperature, and grinding to obtain the nitrogen-doped mesoporous carbon nano alloy catalyst, namely M1-M2-NPC.
2. The method of preparing nitrogen-doped mesoporous carbon nano alloy catalysts according to claim 1, wherein said soluble metal salt M1 is a single metal salt of Cu, co, ni, zn, al, mn, pd.
3. The method for preparing the nitrogen-doped mesoporous carbon nano alloy catalyst according to claim 1, wherein the soluble metal salt M2 is a single metal salt formed by one of Cu, co, ni, zn, al, mn, pd or a composite metal salt formed by two or more of Cu, co, ni, zn, al, mn, pd, or a combination of any two or more of the single metal salt and the composite metal salt.
4. The method for preparing the nitrogen-doped mesoporous carbon nano alloy catalyst according to claim 1, wherein the organic solvent is one or more of N, N-Dimethylformamide (DMF), N-Diethylformamide (DEF), acetonitrile, dimethyl sulfoxide and triethanolamine.
5. The method for preparing nitrogen-doped mesoporous carbon nano alloy catalysts according to claim 1, wherein the inert gas in step S3 is one or a combination of more than two of nitrogen, argon, carbon dioxide and helium.
6. Use of the nitrogen-doped mesoporous carbon nano alloy catalyst prepared by the preparation method of any one of claims 1-5 in catalyzing water phase hydrogenation of furfural to prepare cyclopentanone.
7. The method for preparing the nitrogen-doped mesoporous carbon nano alloy catalyst according to claim 6, wherein the catalyst M1-M2-NPC and the furfural solution are mixed and then added into a high-pressure reaction kettle, and N is used sequentially 2 And H 2 Air in the high-pressure reaction kettle is replaced, the reaction kettle is sealed, and then H is introduced 2 And (3) starting stirring until the pressure reaches 1-20Mpa, and heating the reaction kettle to 80-200 ℃ for reaction for 0.5-8h.
8. The use of the nitrogen-doped mesoporous carbon nano alloy catalyst according to claim 7, wherein the ratio of the mass of the catalyst added to the mass of furfural in the furfural solution is (10-30): 100.
9. The use of the nitrogen-doped mesoporous carbon nano alloy catalyst according to claim 7, wherein the solvent of the furfural solution is one or two of water and methanol, and the mass concentration of the furfural solution is 1% -30%.
10. The use of the nitrogen-doped mesoporous carbon nano alloy catalyst according to claim 7, wherein after the reaction is finished, the content of furfural, furfuryl alcohol, cyclopentanone and the like in the reaction mixture is analyzed by a gas chromatograph internal standard method, the conversion rate of furfural and the yield of cyclopentanone are calculated, and the recovered M1-M2-NPC catalyst can be directly recycled or recycled after washing treatment.
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2023
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