CN114507200A - Method for preparing 2, 5-furan diformate by heterogeneous catalysis - Google Patents
Method for preparing 2, 5-furan diformate by heterogeneous catalysis Download PDFInfo
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- CN114507200A CN114507200A CN202011272195.7A CN202011272195A CN114507200A CN 114507200 A CN114507200 A CN 114507200A CN 202011272195 A CN202011272195 A CN 202011272195A CN 114507200 A CN114507200 A CN 114507200A
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- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000007210 heterogeneous catalysis Methods 0.000 title abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 239000002131 composite material Substances 0.000 claims abstract description 29
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 26
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 26
- PXJJKVNIMAZHCB-UHFFFAOYSA-N 2,5-diformylfuran Chemical compound O=CC1=CC=C(C=O)O1 PXJJKVNIMAZHCB-UHFFFAOYSA-N 0.000 claims abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- CHTHALBTIRVDBM-UHFFFAOYSA-N dehydromucic acid Natural products OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 230000001590 oxidative effect Effects 0.000 claims abstract description 13
- -1 2, 5-furandicarboxylic acid ester Chemical class 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 64
- 239000010941 cobalt Substances 0.000 claims description 64
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 64
- 239000000126 substance Substances 0.000 claims description 30
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 12
- 150000001298 alcohols Chemical class 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 5
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 3
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 33
- 238000007254 oxidation reaction Methods 0.000 abstract description 11
- 230000003647 oxidation Effects 0.000 abstract description 10
- 230000032050 esterification Effects 0.000 abstract description 5
- 238000005886 esterification reaction Methods 0.000 abstract description 5
- 239000007800 oxidant agent Substances 0.000 abstract description 3
- 239000002028 Biomass Substances 0.000 abstract description 2
- YDVGDXLABZAVCP-UHFFFAOYSA-N azanylidynecobalt Chemical compound [N].[Co] YDVGDXLABZAVCP-UHFFFAOYSA-N 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 abstract description 2
- 229940125782 compound 2 Drugs 0.000 abstract description 2
- 239000007791 liquid phase Substances 0.000 abstract description 2
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 14
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 6
- UWQOPFRNDNVUOA-UHFFFAOYSA-N dimethyl furan-2,5-dicarboxylate Chemical compound COC(=O)C1=CC=C(C(=O)OC)O1 UWQOPFRNDNVUOA-UHFFFAOYSA-N 0.000 description 6
- 238000006709 oxidative esterification reaction Methods 0.000 description 6
- LARLSBWABHVOTC-UHFFFAOYSA-N 1,1-bis(4-chlorophenyl)-2,2,2-trifluoroethanol Chemical compound C=1C=C(Cl)C=CC=1C(C(F)(F)F)(O)C1=CC=C(Cl)C=C1 LARLSBWABHVOTC-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 238000004993 emission spectroscopy Methods 0.000 description 4
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 2
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 2
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- KDPOOUQFAUOHHX-UHFFFAOYSA-N methyl 5-formylfuran-2-carboxylate Chemical compound COC(=O)C1=CC=C(C=O)O1 KDPOOUQFAUOHHX-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- NNNRGWOWXNCGCV-UHFFFAOYSA-N 4-(2-bromoethyl)benzonitrile Chemical compound BrCCC1=CC=C(C#N)C=C1 NNNRGWOWXNCGCV-UHFFFAOYSA-N 0.000 description 1
- PCSKKIUURRTAEM-UHFFFAOYSA-N 5-hydroxymethyl-2-furoic acid Chemical compound OCC1=CC=C(C(O)=O)O1 PCSKKIUURRTAEM-UHFFFAOYSA-N 0.000 description 1
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 1
- 229910020676 Co—N Inorganic materials 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- HDJLSECJEQSPKW-UHFFFAOYSA-N Methyl 2-Furancarboxylate Chemical compound COC(=O)C1=CC=CO1 HDJLSECJEQSPKW-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000006359 acetalization reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000004849 alkoxymethyl group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229940049699 cobalt gluconate Drugs 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- GAYAMOAYBXKUII-UHFFFAOYSA-L cobalt(2+);dibenzoate Chemical compound [Co+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 GAYAMOAYBXKUII-UHFFFAOYSA-L 0.000 description 1
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- FXJUUMGKLWHCNZ-UHFFFAOYSA-N dimethyl furan-2,3-dicarboxylate Chemical compound COC(=O)C=1C=COC=1C(=O)OC FXJUUMGKLWHCNZ-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000002663 humin Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing 2, 5-furan diformate by heterogeneous catalysis. The method for preparing the 2, 5-furan diformate by using a biomass-based platform compound 2, 5-diformyl furan (DFF) as a raw material, using a cobalt-nitrogen doped carbon nanotube composite catalyst and using air or oxygen as an oxidant through liquid-phase oxidation esterification. The reaction has the advantages of simple operation, mild conditions, high conversion rate of raw materials, high yield of the product 2, 5-furandicarboxylic acid ester and important application prospect.
Description
Technical Field
The invention relates to a method for preparing 2, 5-furan diformate by heterogeneous catalytic molecular oxygen oxidation of 2, 5-diformylfuran, belonging to the technical field of chemical synthesis.
Background
Polyethylene terephthalate (PET) is a widely used polyester compound, and the furan analog of the PET is polyethylene 2, 5-furandicarboxylate (PEF), and due to the rigid structure of furan rings, the furan ring is superior to petroleum-based PET (Macromolecules,2014,47, 1383-. There are two main methods for preparing PEF, one is a direct esterification method of furandicarboxylic acid (FDCA) with ethylene glycol; secondly, the transesterification of dimethyl Furandicarboxylate (FDMC) with ethylene glycol (Energy environ. Sci.,2012,5, 6407-. The literature reports that the performance of PEF prepared by the ester exchange method is better than that of the PEF prepared by the direct esterification method (Macromolecules,2018,51, 3515-3526). The reason is that: 1)2, 5-furan diformate is easy to purify; 2)2, 5-furandicarboxylate has better thermal stability, and is not easy to decarboxylate during polymerization to generate chain terminator methyl furoate, which makes PEF have higher polymerization degree on one hand and better color on the other hand (J.Polym.Sci., Part A: Polym.chem.,2015,53, 2617-2632).
FDMC can be prepared by oxidative esterification of 5-Hydroxymethylfurfural (HMF). Catalytic systems have been reported as noble metal catalysts represented by gold (ChemSusChem,2008,1, 75-78; j.catal.,2009,265, 109-116; j.catal.,2014,319, 61-70). Although these noble metal catalysts can efficiently synthesize dimethyl 2, 5-Furandicarboxylate (FDMC), their further applications are limited due to limitations such as high price and rarity. To this end, researchers have developed Co-N/C catalyst systems for the oxidative esterification of HMF to prepare FDMC (ChemSusChem,2014,7, 3334-3340; ChemCisChemCi, 2016,8, 2907-2911; ACS Sustainable Chem. Eng.,2019,7, 12061-12068). But at the same time requires another catalyst component, e.g. K-OMS-2, MnO2Or Ru @ C promotes oxidation of hydroxymethyl groups in HMF molecules.
Furthermore, HMF is prone to side reactions to humins during oxidation due to its own instability (angelw. chem. int. ed.,2016,55, 8338-. To address this problem, researchers have modified the two highly reactive functional groups of HMF, either hydroxymethyl or formyl, using functional group modification strategies. Researchers of Avantium use etherified HMF generated in situ, such as 5-alkoxymethylfurfural and 2, 5-di (alkoxymethyl) furan, as raw materials, and perform oxidation to obtain FDCA monoesters, followed by esterification to obtain furandicarboxylate (CN101400666A, CN101827833A, CN 102666521A). In addition, researchers have performed acetalization modifications on the formyl functional group of HMF (ACS cat., 2019,9,4277-4285) to improve the stability of HMF during oxidative esterification.
The inventor finds that the instability of HMF is related to the difference of reactivity of two functional groups (hydroxymethyl and formyl) in the molecular structure, and 5-hydroxymethyl furan-2-carboxylic acid or ester thereof can be generated in the oxidation process and is easy to generate self-polymerization. Compared with HMF, DFF is a derivative product of selective oxidation of HMF, and only formyl is a functional group in the molecular structure, so that side reactions are relatively less in the oxidation process (chem. -Asian J.2019,14, 3329-3334). And the inventors have developed a method for efficiently preparing DFF, preparing kilogram-grade DFF (ChemSusChem,2011,4, 51-54; appl.catal.a,2014,482, 231-.
Disclosure of Invention
The invention aims to provide a method for preparing 2, 5-furan diformate by efficiently carrying out heterogeneous catalytic oxidation esterification on DFF. The method overcomes the defects in the prior art, can avoid side reactions caused by instability of HMF, and can prepare the 2, 5-furan dicarboxylic acid ester with high selectivity under mild conditions.
According to one aspect of the invention, the 2, 5-furandicarboxylate is prepared by preparing 2 to obtain the 2, 5-furandicarboxylate by taking a cobalt-nitrogen doped carbon nanotube composite material as a catalyst and taking a compound containing 2, 5-diformylfuran and alcohols as raw materials in an oxidizing atmosphere (preferably molecular oxygen), and the distribution of main products is shown as a formula 1.
Formula 1 product distribution for catalytic preparation of 2, 5-furandicarboxylate
The term "alcohol compound" as used herein is C containing at least one hydroxyl group1～8The organic compound of (2) is preferably one or more alcohols having 1 to 8 carbon atoms and at least one hydroxyl group, and the alcohols may be primary, secondary or tertiary alcohols, and may be linear, branched, aliphatic or aromatic ring-containing alcohols or diols. Preferably at least one of methanol, ethanol, isopropanol, n-butanol, tert-butanol, isoamyl alcohol, isooctyl alcohol, benzyl alcohol, cyclohexanol and ethylene glycol. The reaction being in the liquid phaseThe method is carried out, the type of the added alcohol is determined according to the type of the target product 2, 5-furan dicarboxylic acid ester, and the product is prepared through liquid-phase oxidative esterification.
The proportion of the alcohol to the 2, 5-diformylfuran can be selected by those skilled in the art according to actual needs, and generally an alcohol excess manner is adopted according to the reaction formula, and the general selection range is that the molar ratio of the alcohol compound to the 2, 5-diformylfuran is 2-500.
Preferably, the oxidizing atmosphere comprises at least one of oxygen and air. In the catalytic conversion process, air or oxygen is used as an oxidant, and preferably, the oxygen pressure of the oxidizing atmosphere is 0.1-3.0 MPa.
Preferably, the catalytic reaction temperature of the method is 60-160 ℃. Increasing the reaction temperature can shorten the reaction time, but can lead to increased side reactions.
Preferably, the reaction time of the method is 1-24 h, the conversion rate is increased along with the reaction time within a certain time range, the product yield is improved, but the conversion rate and the product selectivity are stable after the reaction time is prolonged to a certain time.
Preferably, the catalyst of the method is used in an amount of 0.05 to 60 mol% based on the content of cobalt in the 2, 5-diformylfuran.
The skilled person can select the compound containing cobalt element according to the actual requirement, and usually can dissolve cobalt salt or organic cobalt compound in the corresponding solvent, and the common choices are: at least one of cobalt acetate tetrahydrate, cobalt nitrate, cobalt sulfate, cobaltosic oxide, cobalt acetylacetonate, cobalt gluconate, cobalt benzoate, cobalt stearate, cobalt isooctanoate and cobalt oxalate.
According to another aspect of the invention, a cobalt-based nitrogen-doped carbon nanotube composite material is prepared by performing heat treatment on a mixture containing a cobalt-containing compound, activated carbon and a nitrogen-containing substance in a non-oxidizing atmosphere.
The non-oxidizing atmosphere is preferably an inert atmosphere; most preferably nitrogen;
preferably, the temperature of the heat treatment is 600-1200 ℃; the time is 0.5-12 h. The heat treatment procedure and temperature have a direct influence on the catalytic effect of the catalyst.
Preferably, the nitrogen-containing substance is melamine, dicyanodiamine, urea, g-C3N4At least one of 1, 10-phenanthroline, 2-methylimidazole and ammonium oxalate;
preferably, the mass ratio of the nitrogen-containing substance to the cobalt-containing compound is 1-200.
Preferably, the cobalt-based nitrogen-doped carbon nanotube composite material is prepared by performing primary heat treatment on a mixture of a compound containing cobalt (i.e., a cobalt-containing precursor), activated carbon and a nitrogen-containing substance; or firstly carrying out heat treatment on the mixture and the activated carbon, then mixing the mixture and the nitrogenous substance, and then carrying out secondary heat treatment; or firstly carrying out heat treatment on the compound containing the cobalt element and the nitrogenous substance, then mixing the compound containing the cobalt element and the nitrogenous substance with the activated carbon, and then carrying out secondary heat treatment; or the material can be obtained by firstly carrying out heat treatment on the nitrogenous substance and the activated carbon, then mixing the nitrogenous substance and the activated carbon with the compound containing the cobalt element and then carrying out secondary heat treatment. Most preferably, the composite material is prepared by simultaneously carrying out primary heat treatment on a mixture of a compound containing cobalt (i.e. a cobalt-containing precursor), activated carbon and a nitrogen-containing substance. The cobalt content in the cobalt-based nitrogen-doped carbon nanotube composite material is 0.1-60 wt.%, and the cobalt agglomeration can occur in the subsequent heat treatment process along with the increase of the cobalt content in the precursor in a certain range, so that the activity of the catalyst is reduced.
According to still another aspect of the present invention, there is provided a cobalt-based nitrogen-doped carbon nanotube composite material obtained by the above-mentioned preparation method.
In the composite material, Co nanoparticles are wrapped in carbon nanotubes.
The content of cobalt in the composite material is 0.1-60 wt.%.
The invention can produce the beneficial effects that:
(1) the invention relates to a method for preparing 2, 5-furan diformate by taking a more stable bio-based platform compound 2, 5-diformyl furan as a raw material through oxidative esterification.
(2) The raw material 2, 5-diformylfuran can be obtained by selective oxidation of 5-hydroxymethylfurfural, can also be converted from biomass platform compounds or carbohydrates such as glucose, fructose, sucrose, starch, cellulose and the like, and has the advantage of wide sources.
(3) The invention aims to directly catalyze 2, 5-diformylfuran to prepare 2, 5-furandicarboxylic acid by one step, and prepares a cobalt-based nitrogen-doped carbon nanotube composite material (Co @ N-CNT) by carrying out heat treatment on a cobalt-containing precursor, activated carbon and a nitrogen-containing substance under a certain condition through catalyst innovation.
(4) The invention takes molecular oxygen as an oxidant, is clean, cheap and environment-friendly; the oxidation reaction condition is mild (60-160 ℃), and the reaction process is simple and easy to operate.
Drawings
FIG. 1 is an XRD characterization spectrum of Co @ N-CNT-800-1 prepared in example 1 of the present invention.
FIG. 2 is an XPS characterization spectrum of Co @ N-CNT-800-1 prepared in example 1 of the present invention.
FIG. 3 is an SEM and TEM characterization spectrum of Co @ N-CNT-800-1 prepared in example 1 of the present invention, wherein (a) is an SEM image of Co @ N-CNT-800-1 of the cobalt-based nitrogen-doped carbon nanotube composite material, and (b, c) is a TEM image.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The starting materials in the examples of the present invention were all purchased commercially.
The analysis method in the examples of the present invention is as follows:
the main products are qualitatively analyzed by GC-MS and the retention time of gas chromatography of standard substances; the product was quantitatively analyzed by gas chromatography internal standard quantitation.
The examples of the present invention calculated the conversion of 2, 5-diformylfuran and the yield of dimethyl 2, 5-furandicarboxylate, respectively, according to the following formulas.
Conversion [ mol% ]]＝(n0-n)/n0×100％
The yield is [ mol%]＝nx/n0×100％
In the formula, n0Before reactionAmount of substance to which 2, 5-diformylfuran is added [ mol ]]And n is the amount of the substance of 2, 5-diformylfuran remaining after the reaction [ mol]，nxThe amount of a substance which is a product formed during the reaction [ mol ]]。
Preparation of nitrogen-doped cobalt-based carbon nanotube composite material
Example 1 preparation of Co-based N-doped carbon nanotube composite Co @ N-CNT-800-1
0.68mmol (0.1693g) of cobalt acetate tetrahydrate is dissolved in 20mL of ethanol, 3.2g of melamine are added and stirred for 30 minutes, followed by 1.0g of activated carbon and reflux in an oil bath at 80 ℃ for 4 hours, after which the ethanol is removed by rotary evaporation. The resulting product was dried under vacuum at 80 ℃ for 12 hours. Then, at 70mL/min N2Under protection, the temperature is raised to 800 ℃ from room temperature, and the mixture is roasted for 1 hour. And obtaining the cobalt-based nitrogen-doped carbon nanotube composite material Co @ N-CNT-800-1, wherein 800 and 1 respectively represent the roasting temperature and the roasting time in the catalyst preparation process.
The mass fraction of cobalt in the cobalt based catalyst was 4.1 wt.% as measured by inductively coupled plasma emission spectroscopy (ICP-OES).
XRD characterization of the prepared Co @ N-CNT-800-1 is shown in FIG. 1, XPS characterization is shown in FIG. 2, and SEM and TEM characterization is shown in FIG. 3. As can be seen from FIGS. 1 and 2, the prepared Co @ N-CNT-800-1 contains the metal Co, C and N species, i.e., N is doped into the catalyst. As can be seen from FIG. 3, the prepared Co @ N-CNT-800-1 contains a large number of carbon nanotubes, and Co nanoparticles are encapsulated in the carbon nanotubes.
EXAMPLE 2 preparation of Nitrogen-doped cobalt-based carbon nanotube composite Co @ N-CNT-1200-0.5
0.09mmol (0.0171g) of cobalt oxalate was dissolved in 20mL of ethanol, 3.4213g of urea was added and stirred for 30 minutes, then 5.2023g of activated carbon was added and refluxed in an oil bath at 80 ℃ for 4 hours, and then ethanol was removed by rotary evaporation. The resulting product was dried under vacuum at 80 ℃ for 12 hours. Then, at 70mL/min N2Under protection, the temperature is raised to 1200 ℃ from room temperature, and the mixture is roasted for 0.5 hour. Thus obtaining Co @ N-CNT-1200-0.5. The mass fraction of cobalt in Co @ N-CNT-1200-0.5 was 0.1 wt.% as measured by inductively coupled plasma emission spectroscopy (ICP-OES).
EXAMPLE 3 preparation of Nitrogen-doped cobalt-based carbon nanotube composite Co @ N-CNT-600-12
g-C3N4The preparation of (1): 5.0095g of melamine or dicyanodiamine or urea is put into a muffle furnace to be heated to 550 ℃ from room temperature at 1.5 ℃/min under the semi-closed condition in the air atmosphere, and then the mixture is roasted for 3 hours. 2.3247g of yellow powder g-C were obtained3N4。
2.1mmol (0.5415g) of cobalt acetylacetonate were dissolved in 20mL of ethanol and 0.5426g g-C was added3N4After stirring for 30 minutes, 0.2183g of activated carbon were added and refluxed in an oil bath at 100 ℃ for 6 hours, and then ethanol was removed by rotary evaporation. The resulting product was dried under vacuum at 80 ℃ for 12 hours. Then, at 70mL/min N2Under protection, the temperature is raised to 600 ℃ from room temperature, and the mixture is roasted for 12 hours. Co @ N-CNT-600-12 was obtained. The mass fraction of cobalt in Co @ N-CNT-600-12 was 60.0 wt.% as measured by inductively coupled plasma emission spectroscopy (ICP-OES).
Examples 4-7 preparation of Nitrogen-doped cobalt-based carbon nanotube composite Material by different baking methods
Examples 4-7 the process for preparing the catalyst differs from example 1 in that the calcination manner for preparing the catalyst is different; are respectively (A): roasting the three precursors at 750 ℃ for 2 hours at the same time to prepare a cobalt-based catalyst, and marking the cobalt-based catalyst as Co @ N-CNT-750-2-A; (B) the method comprises the following steps Firstly, roasting a cobalt-containing precursor and activated carbon at 750 ℃, then mixing the cobalt-containing precursor and the activated carbon with a nitrogen-containing substance, and then roasting at 750 ℃ for the second time to prepare the cobalt-based catalyst: co @ N-CNT-750-2-B; (C) the method comprises the following steps Firstly, roasting a cobalt-containing precursor and a nitrogen-containing substance at 750 ℃, then mixing the cobalt-containing precursor and the nitrogen-containing substance with activated carbon at 750 ℃ and then carrying out secondary roasting to prepare the cobalt-based catalyst: co @ N-CNT-750-2-C; (D) the method comprises the following steps Firstly, roasting nitrogen-containing substances and activated carbon at 750 ℃, then mixing the nitrogen-containing substances and the activated carbon with a cobalt-containing precursor, and then roasting at 750 ℃ for the second time to obtain the cobalt-based catalyst: co @ N-CNT-750-2-D. The mass fractions of cobalt in the prepared cobalt-based catalyst were 4.1, 4.0, 4.2, 3.9 wt.%, respectively, as measured by inductively coupled plasma emission spectroscopy (ICP-OES).
Catalytic preparation of 2, 5-furandicarboxylic acid ester
EXAMPLE 8 catalytic preparation of dimethyl 2, 5-Furanedicarboxylate
62mg (0.5mmol) of 2, 5-diformylfuran, 160mg (20 mol% Co) of the Co @ N-CNT-800-1 catalyst prepared in example 1 was charged into a 30mL reaction vessel, 10mL of methanol was added, the vessel was closed, oxygen was substituted 6 times while introducing oxygen pressure of 2.0MPa, and the temperature was raised to 140 ℃ with stirring and held for 1 hour. After the reaction was completed, the reaction mixture was cooled to room temperature and carefully reduced to normal pressure. All products were transferred to a 25mL volumetric flask, added with 1mL internal standard (mesitylene) and then subjected to constant volume analysis by gas chromatography internal standard quantitative method.
The conversion of 2, 5-diformylfuran was calculated to be > 99% and the yield of dimethyl 2, 5-furandicarboxylate was 93.0%.
Example 9
62mg (0.5mmol) of 2, 5-diformylfuran, 15mg (0.05 mol% Co) of the Co @ N-CNT-1200-0.5 catalyst prepared in example 2, was charged into a 30mL reaction vessel, 10mL of methanol was added, the vessel was closed, oxygen was substituted 6 times while introducing oxygen at a pressure of 3.0MPa, and the temperature was raised to 160 ℃ with stirring and held for 12 hours. After the reaction was completed, the product was quantitatively analyzed as in example 8.
The conversion of 2, 5-diformylfuran was calculated to be 90.7%, the yield of dimethyl 2, 5-furandicarboxylate was 83.5%, and the yield of methyl 5-formylfuran-2-carboxylate was 4.0%.
Example 10
62mg (0.5mmol) of 2, 5-diformylfuran, 30mg (60 mol% Co) of the Co @ N-CNT-600-12 catalyst prepared in example 3 was charged into a 30mL reaction vessel, 10mL of methanol was added, the vessel was closed, oxygen was substituted 6 times while charging oxygen pressure 0.1MPa, and the temperature was raised to 60 ℃ with stirring and maintained for 24 hours. After the reaction was completed, the product was quantitatively analyzed as in example 8.
The conversion of 2, 5-diformylfuran was calculated to be 93.2%, the yield of dimethyl 2, 5-furandicarboxylate was 81.4%, and the yield of methyl 5-formylfuran-2-carboxylate was 7.5%.
Examples 11-17 catalytic Effect of Nitrogen-doped cobalt-based carbon nanotube composites made with different Nitrogen-containing substances
Examples 11-17 differ from example 1 in the nitrogen-containing species used in the preparation of the catalyst. Reaction conditions are as follows: 62mg (0.5mmol) of 2, 5-diformylfuran and 80mg (10 mol% of Co) of nitrogen-doped cobalt-based carbon nanotube composite material are added into a 30mL reaction kettle, 10mL of methanol is added, the kettle is closed, oxygen is filled into the reaction kettle under the pressure of 1.0MPa, the temperature is raised to 120 ℃ under stirring, and the reaction kettle is kept for 16 hours. After the reaction was completed, the product was quantitatively analyzed as in example 8, and the results are shown in table one:
TABLE 1 Co @ N-CNT catalytic Effect of different nitrogen containing species
And (4) conclusion: g-C3N4The cobalt-based nitrogen-doped carbon nanotube composite catalyst prepared by roasting melamine, dicyanodiamine and the like as nitrogen sources has good catalytic effect, wherein g-C3N4Most preferred.
Examples 18-21 catalytic Effect of Nitrogen-doped cobalt-based carbon nanotube composites prepared by different calcination methods
Reaction conditions are as follows: 62mg (0.5mmol) of 2, 5-diformylfuran was added to a 30mL reaction vessel, 120mg (15 mol% Co) of the catalyst prepared in examples 4 to 7 was added, 10mL of methanol was added, the vessel was closed, oxygen pressure was charged at 0.8MPa, the temperature was raised to 100 ℃ with stirring, and the reaction was maintained for 12 hours. After the reaction was completed, the product was quantitatively analyzed according to the method of example 8, and the results are shown in table two:
TABLE 2 Co @ N-CNT catalytic effect of catalysts prepared by different heat treatment modes
And (4) conclusion: the different treatment modes of the catalyst have great influence on the effect, and the Co @ N-CNT-750-2-A catalytic effect of the nitrogen-doped cobalt-based carbon nanotube composite material prepared by simultaneously roasting three precursors at 750 ℃ for 2 hours under the nitrogen condition is optimal.
Examples 22-30 preparation of 2, 5-Furanodicarboxylic acid esters of different alcohols
The result of the oxidative esterification of 2, 5-diformylfuran with different alcohols to prepare 2, 5-furandicarboxylic acid ester. The method comprises the following specific steps: adding 62mg (0.5mmol) of 2, 5-diformylfuran and 40mg (5 mol% Co) Co @ N-CNT-800-1 catalyst into a 30mL reaction kettle, respectively adding 10mL of ethanol, isopropanol, N-butanol, tert-butanol, isoamylol, isooctanol, benzyl alcohol, cyclohexanol and ethylene glycol, closing the kettle, filling air pressure to be 1.5MPa, heating to 120 ℃ under stirring, and keeping for 18 hours. After the reaction was completed, the product was quantitatively analyzed according to the method in example 8, and the results are shown in table 3:
TABLE 3 preparation of 2, 5-furandicarboxylic acid esters of different alcohols
And (4) conclusion: the nitrogen-doped cobalt-based carbon nanotube composite material Co @ N-CNT-800-1 used in the invention can catalyze 2, 5-diformylfuran to be oxidized and esterified with different alcohols, and 2, 5-furandicarboxylate with high yield is prepared.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A method of making 2, 5-furandicarboxylate, comprising: in an oxidizing atmosphere, preparing 2, 5-furan diformate by using a cobalt-based nitrogen-doped carbon nanotube composite material as a catalyst and using a compound containing 2, 5-diformyl furan and alcohols as raw materials.
2. The method of claim 1, wherein: the alcohol compound is C containing at least one hydroxyl1～8Is provided withAn organic compound;
preferably, the alcohol compound is at least one selected from methanol, ethanol, isopropanol, n-butanol, tert-butanol, isoamyl alcohol, isooctyl alcohol, benzyl alcohol, cyclohexanol and ethylene glycol.
3. The method of claim 1, wherein: the oxidizing atmosphere comprises at least one of oxygen and air;
preferably, the oxygen pressure of the oxidizing atmosphere is 0.1 to 3.0 MPa.
4. The method of claim 1, wherein: the catalytic reaction temperature of the method is 60-160 ℃, and the reaction time is 1-24 h.
5. The method of claim 1, wherein: the dosage of the catalyst in the method is 0.05-60 mol% of 2, 5-diformylfuran based on the content of cobalt.
6. A preparation method of a cobalt-based nitrogen-doped carbon nanotube composite material is characterized by comprising the following steps: and carrying out heat treatment on the mixture containing the compound containing the cobalt element, the activated carbon and the nitrogen-containing substance in a non-oxidizing atmosphere to obtain the composite material.
7. The method of claim 6, wherein: the non-oxidizing atmosphere is preferably an inert atmosphere; most preferably nitrogen;
preferably, the temperature of the heat treatment is 600-1200 ℃; the time is 0.5-12 h.
Preferably, the nitrogen-containing substance is melamine, dicyanodiamine, urea, g-C3N4At least one of 1, 10-phenanthroline, 2-methylimidazole and ammonium oxalate;
preferably, the mass ratio of the nitrogen-containing substance to the cobalt-containing compound is 1-200.
Preferably, the heat treatment method is at least one of the following methods;
simultaneously carrying out primary heat treatment on a mixture of a compound containing cobalt (namely a cobalt-containing precursor), activated carbon and a nitrogen-containing substance; or firstly carrying out heat treatment on the mixture and the activated carbon, then mixing the mixture and the nitrogenous substance, and then carrying out secondary heat treatment; or firstly carrying out heat treatment on the compound containing the cobalt element and the nitrogenous substance, then mixing the compound containing the cobalt element and the nitrogenous substance with the activated carbon, and then carrying out secondary heat treatment; and firstly carrying out heat treatment on the nitrogenous substance and the activated carbon, then mixing the nitrogenous substance and the activated carbon with a compound containing cobalt element, and then carrying out secondary heat treatment to obtain the cobalt-containing cobalt oxide.
8. The cobalt-based nitrogen-doped carbon nanotube composite material obtained by the preparation method of claim 6 or 7.
9. The cobalt-based nitrogen-doped carbon nanotube composite material of claim 8, wherein: in the composite material, Co nanoparticles are wrapped in carbon nanotubes.
10. The composite material according to claim 9, characterized in that: the content of cobalt in the composite material is 0.1-60 wt.%.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104383953A (en) * | 2014-11-24 | 2015-03-04 | 武汉纺织大学 | Active carbon-loaded nitrogen-doped cobalt catalyst and preparation method and application thereof |
| CN104953135A (en) * | 2015-04-30 | 2015-09-30 | 北京化工大学 | N-doped carbon nano tube loaded cobalt-based electro-catalytic material and preparation method thereof |
| CN108084123A (en) * | 2016-11-22 | 2018-05-29 | 中国科学院大连化学物理研究所 | A kind of method for preparing 2,5- furandicarboxylic acid dimethyl esters |
| CN108666584A (en) * | 2018-04-13 | 2018-10-16 | 东莞理工学院 | A kind of Co-N-C/ carbon nano-tube catalysts and its preparation method and application |
| CN108910859A (en) * | 2018-07-16 | 2018-11-30 | 东华大学 | A kind of preparation method of Metal Supported N doping bulk porous carbon materials |
| CN111250126A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Catalyst, preparation method and application thereof |
| CN111253353A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Method for preparing 2, 5-furandicarboxylic acid dimethyl ester by catalyzing oxidation esterification of 5-hydroxymethylfurfural |
| CN111408392A (en) * | 2019-01-08 | 2020-07-14 | 南京理工大学 | Cobalt-nitrogen co-doped porous carbon material catalyst and preparation method and application thereof |
| CN111558391A (en) * | 2020-05-26 | 2020-08-21 | 福州大学 | Heteroatom-doped cobalt metal catalyst and preparation method thereof |
-
2020
- 2020-11-14 CN CN202011272195.7A patent/CN114507200A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104383953A (en) * | 2014-11-24 | 2015-03-04 | 武汉纺织大学 | Active carbon-loaded nitrogen-doped cobalt catalyst and preparation method and application thereof |
| CN104953135A (en) * | 2015-04-30 | 2015-09-30 | 北京化工大学 | N-doped carbon nano tube loaded cobalt-based electro-catalytic material and preparation method thereof |
| CN108084123A (en) * | 2016-11-22 | 2018-05-29 | 中国科学院大连化学物理研究所 | A kind of method for preparing 2,5- furandicarboxylic acid dimethyl esters |
| CN108666584A (en) * | 2018-04-13 | 2018-10-16 | 东莞理工学院 | A kind of Co-N-C/ carbon nano-tube catalysts and its preparation method and application |
| CN108910859A (en) * | 2018-07-16 | 2018-11-30 | 东华大学 | A kind of preparation method of Metal Supported N doping bulk porous carbon materials |
| CN111250126A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Catalyst, preparation method and application thereof |
| CN111253353A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Method for preparing 2, 5-furandicarboxylic acid dimethyl ester by catalyzing oxidation esterification of 5-hydroxymethylfurfural |
| CN111408392A (en) * | 2019-01-08 | 2020-07-14 | 南京理工大学 | Cobalt-nitrogen co-doped porous carbon material catalyst and preparation method and application thereof |
| CN111558391A (en) * | 2020-05-26 | 2020-08-21 | 福州大学 | Heteroatom-doped cobalt metal catalyst and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| YUXIA SUN: "A High-Performance Base-Metal Approach for the Oxidative Esterification of 5-Hydroxymethylfurfural", CHEMCATCHEM, vol. 8, no. 18, 25 August 2016 (2016-08-25), pages 2909 - 2911 * |
| YUXIA SUN: "A High-Performance Base-Metal Approach for the Oxidative Esterification of 5-Hydroxymethylfurfural", CHEMCATCHEM, vol. 8, no. 18, pages 2907 - 2911 * |
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