CN107442177B - Method for synthesizing 2, 5-furandimethanol by selective hydrogenation of 5-hydroxymethylfurfural - Google Patents
Method for synthesizing 2, 5-furandimethanol by selective hydrogenation of 5-hydroxymethylfurfural Download PDFInfo
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- CN107442177B CN107442177B CN201710640261.3A CN201710640261A CN107442177B CN 107442177 B CN107442177 B CN 107442177B CN 201710640261 A CN201710640261 A CN 201710640261A CN 107442177 B CN107442177 B CN 107442177B
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- organic
- hydroxymethylfurfural
- coordination polymer
- magnetic metal
- reaction
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- DSLRVRBSNLHVBH-UHFFFAOYSA-N 2,5-furandimethanol Chemical compound OCC1=CC=C(CO)O1 DSLRVRBSNLHVBH-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 29
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 title claims abstract description 27
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title abstract description 12
- 230000002194 synthesizing effect Effects 0.000 title abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000013256 coordination polymer Substances 0.000 claims abstract description 26
- 229920001795 coordination polymer Polymers 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000003197 catalytic effect Effects 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 239000003446 ligand Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 229910001510 metal chloride Inorganic materials 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052735 hafnium Inorganic materials 0.000 claims description 6
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 3
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical group Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 3
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000004971 Cross linker Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000000852 hydrogen donor Substances 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 230000001588 bifunctional effect Effects 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 238000009901 transfer hydrogenation reaction Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 7
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 4
- 150000001728 carbonyl compounds Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OUDFNZMQXZILJD-UHFFFAOYSA-N 5-methyl-2-furaldehyde Chemical compound CC1=CC=C(C=O)O1 OUDFNZMQXZILJD-UHFFFAOYSA-N 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 229940040102 levulinic acid Drugs 0.000 description 3
- 238000012552 review Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 2
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229940058352 levulinate Drugs 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 229940068041 phytic acid Drugs 0.000 description 2
- 235000002949 phytic acid Nutrition 0.000 description 2
- 239000000467 phytic acid Substances 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- JHDJUJAFXNIIIW-UHFFFAOYSA-N (4-phosphonophenyl)phosphonic acid Chemical compound OP(O)(=O)C1=CC=C(P(O)(O)=O)C=C1 JHDJUJAFXNIIIW-UHFFFAOYSA-N 0.000 description 1
- VOZFDEJGHQWZHU-UHFFFAOYSA-N (5-methylfuran-2-yl)methanol Chemical compound CC1=CC=C(CO)O1 VOZFDEJGHQWZHU-UHFFFAOYSA-N 0.000 description 1
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- JOOXCMJARBKPKM-UHFFFAOYSA-M 4-oxopentanoate Chemical compound CC(=O)CCC([O-])=O JOOXCMJARBKPKM-UHFFFAOYSA-M 0.000 description 1
- CSGQJHQYWJLPKY-UHFFFAOYSA-N CITRAZINIC ACID Chemical compound OC(=O)C=1C=C(O)NC(=O)C=1 CSGQJHQYWJLPKY-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 229940120146 EDTMP Drugs 0.000 description 1
- GMEONFUTDYJSNV-UHFFFAOYSA-N Ethyl levulinate Chemical compound CCOC(=O)CCC(C)=O GMEONFUTDYJSNV-UHFFFAOYSA-N 0.000 description 1
- 229910015189 FeOx Inorganic materials 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- -1 levulinate ester Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B01J35/33—
-
- 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
- C07D307/38—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
-
- 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
- C07D307/38—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
- C07D307/44—Furfuryl alcohol
-
- 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
- C07D307/58—One oxygen atom, e.g. butenolide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
- B01J2531/0216—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/31—Aluminium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/42—Tin
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/49—Hafnium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
- B01J2531/57—Niobium
Abstract
The invention discloses a method for synthesizing 2, 5-furandimethanol by selective hydrogenation of 5-hydroxymethylfurfural, which takes a magnetic metal organic coordination polymer as an acid-base bifunctional catalyst, takes low-carbon alcohol which is cheap and easy to obtain as an in-situ hydrogen donor, efficiently converts the 5-hydroxymethylfurfural into the 2, 5-furandimethanol by selective transfer hydrogenation reaction under mild operation conditions, and has the highest yield of 98.6 percent. The magnetic metal organic coordination polymer used in the invention has the advantages of high acid-base strength, more acid-base sites, larger specific surface area and proper pore size, and is simple in preparation process, easy to separate and recycle, and excellent in catalytic activity and catalytic stability. In addition, the invention uses low carbon alcohol as in-situ hydrogen donor, which not only can avoid the use of molecular hydrogen and increase the safety of the reaction process, but also can be used as reaction solvent, reduce the introduction of exogenous substances and further reduce the production cost.
Description
Technical Field
The invention belongs to the field of biomass energy chemical industry, and particularly relates to a method for synthesizing 2, 5-furandimethanol by selective hydrogenation of 5-hydroxymethylfurfural.
Background
In recent years, the conversion of renewable biomass resources into high value-added bio-based chemicals has become an important approach to reduce the excessive dependence on non-renewable fossil resources in today's society (Chemical Reviews, 2014, 114: 1827-6880; Chemical Reviews, 2017, 117: 6834-6880). Among various bio-based chemicals, 5-hydroxymethylfurfural is considered to be one of the ten major platform compounds currently based on biomass resources, because it can produce a range of derivatives that are of high quality and can replace fossil-based products (Renewable and susteable Energy Reviews, 2017,74: 230-. Among them, 2, 5-furandimethanol obtained by selective hydrogenation of 5-hydroxymethylfurfural is attracting attention, and it can be used as a softener, a wetting agent, a binder, a plasticizer, a surfactant, a medical intermediate, etc., and also as a polymer material (ACS Catalysis,2015, 5: 722-733) such as a monomer synthetic resin material, a fiber material, a foam material, a crown ether material, etc., and has a very wide application prospect.
As is known, 5-hydroxymethylfurfural molecules simultaneously contain an aldehyde group, an alcoholic hydroxyl group and a furan ring, so that the chemical properties of the 5-hydroxymethylfurfural are very active, and the product generated during the hydrogenation reaction is relatively complex, so that how to ensure the preferential hydrogenation of the aldehyde group and avoid the excessive hydrogenation of the alcoholic hydroxyl group and the furan ring as much as possible is the problem which needs to be solved firstly in the process of synthesizing 2, 5-furandimethanol by selective hydrogenation of 5-hydroxymethylfurfural, and the development of a proper catalytic reaction system plays a crucial role in solving the problem. For the moment, supported noble metals (such as Pt/C, Ru/C, Ru/SiO2, Ru/Al2O3, Ir/TiO2, Ir/ReOx, Au/Al2O3, Au/FeOx and the like) and hydrogen are the most commonly used catalysts and hydrogen donors, respectively, for the selective hydrogenation synthesis of 2, 5-furandimethanol from 5-hydroxymethylfurfural (RSC Advances, 2013, 3: 1033-. However, it should be particularly pointed out that the catalytic reaction system composed of the supported noble metal and hydrogen has a series of inevitable disadvantages in the process of converting 5-hydroxymethylfurfural into 2, 5-furandimethanol through selective hydrogenation, for example, the supported noble metal catalyst has high manufacturing cost and complicated preparation process; the use amount of the load-type noble metal is large, and the reusability is poor; hydrogen has high dispersibility and inflammability, and has larger potential safety hazard; the solubility of hydrogen in various solvents is not high, and the atom utilization rate is low. In order to overcome the disadvantages of the catalytic reaction system, a disproportionation reaction system (Green Chemistry, 2013, 15: 2849-. Although these novel catalytic reaction systems can be carried out with non-noble metal catalysts and without exogenous hydrogen, their catalytic efficiency, including substrate conversion and product yield, tends to be low, which greatly limits the practical production and subsequent use of 2, 5-furandimethanol.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for synthesizing 2, 5-furandimethanol by selective hydrogenation of 5-hydroxymethylfurfural, aims to provide a mild, efficient, economical and safe method for synthesizing 2, 5-furandimethanol by selective hydrogenation of 5-hydroxymethylfurfural, and further provides a novel magnetic metal organic coordination polymer as an acid-base bifunctional catalyst and application of the catalyst in selective hydrogenation conversion of various carbonyl compounds such as 5-methylfurfural, furfural, levulinic acid and levulinate.
In a first aspect of the present invention, there is provided:
a magnetic metal organic coordination polymer catalyst is a high molecular polymer which is obtained by taking magnetic ferroferric oxide as a carrier and carrying organic polyacid ligands and a cross-linking agent on the surface of the carrier for polymerization, wherein catalytic active metal is complexed on the organic polyacid ligands.
The catalytically active metal is selected from zinc, aluminium, tin, zirconium, hafnium or niobium; more preferably zirconium or hafnium.
The organic polyacid ligand is selected from one of phytic acid, cyanuric acid, citrazinic acid, ethylene diamine tetraacetic acid, diethylenetriamine pentaacetic acid, aminotrimethylene phosphonic acid, p-phenylene diphosphonic acid, ethylene diamine tetramethylene phosphonic acid or diethylenetriamine pentamethylene phosphonic acid; more preferably phytic acid, cyanuric acid or aminotrimethylene phosphonic acid.
The cross-linking agent is preferably polyamine; more preferably triethylamine.
In a second aspect of the present invention, there is provided:
a preparation method of a magnetic metal organic coordination polymer catalyst comprises the following steps:
step 1, adding nano ferroferric oxide into an organic solution mixed with metal chloride, and ultrasonically stirring and uniformly dispersing;
step 2, respectively dripping an organic solvent and a cross-linking agent dissolved with an organic polyacid ligand, and stirring for reaction;
and 3, carrying out solid-liquid separation on the solids by using a magnet, and washing, drying and grinding the solids to obtain the catalyst.
In the step 1, the concentration of the metal chloride in the organic solution is 30-120 mmol/L, and the molar ratio of the metal chloride to the iron is 1-3: 1.
The metal chloride is one of zinc dichloride, aluminum trichloride, tin tetrachloride, zirconium tetrachloride, hafnium tetrachloride or niobium pentachloride, and is preferably zirconium tetrachloride or hafnium tetrachloride.
In the step 1, the molar ratio of the metal ions to the organic polyacid ligands is 3: 4-6: 1, and the molar ratio of the metal ions to the triethylamine is 1: 10-1: 4.
In the step 2, the dropping speed of the organic solvent dissolved with the organic polyacid ligand is 2-8 mL/min, and the dropping speed of the organic solvent dissolved with the crosslinking agent is 0.5-1.5 mL/min.
In the step 2, the stirring reaction is carried out for 2-12 h at room temperature, and the temperature is raised to 60-90 ℃ for standing and aging for 2-12 h.
In the step 3, the washing step refers to repeatedly washing the precipitate with ethanol and diethyl ether in sequence until no chloride ion exists; the drying step is vacuum drying at 75-85 ℃ for 8-16 h.
In a third aspect of the present invention, there is provided:
the magnetic metal organic coordination polymer is used as a catalyst in the selective hydrogenation synthesis of 2, 5-furandimethanol from 5-hydroxymethylfurfural.
In the application, the magnetic metal organic coordination polymer has the effects of improving the yield and selectivity of the product and the using times of the catalyst.
In a fourth aspect of the present invention, there is provided:
a method for synthesizing 2, 5-furandimethanol by selective hydrogenation of 5-hydroxymethylfurfural comprises the following steps:
adding low-carbon alcohol, 5-hydroxymethyl furfural and magnetic metal organic coordination polymer into a reaction kettle, replacing with nitrogen, reacting to obtain 2, 5-furandimethanol.
The lower alcohol is one of isopropanol, sec-butyl alcohol, sec-amyl alcohol or cyclopentanol.
The dosage of the 5-hydroxymethylfurfural is 1-3 wt% of that of the lower alcohol, and the dosage of the magnetic metal organic coordination polymer is 20-60 wt% of that of the 5-hydroxymethylfurfural.
The stirring speed in the reaction kettle is 300-500 rpm, the reaction temperature is 120-150 ℃, and the reaction time is 2-10 h.
Hair brushIn a fifth aspect of the invention, there is provided:
the active metal is used as an active center of the magnetic metal organic coordination polymer catalyst for improving the reaction yield and reaction selectivity of the selective hydrogenation synthesis of 2, 5-furandimethanol from 5-hydroxymethylfurfural and the application frequency of the catalyst.
The active metal is selected from zinc, aluminum, tin, zirconium, hafnium or niobium; more preferably zirconium or hafnium.
In a sixth aspect of the present invention, there is provided:
the magnetic metal organic coordination polymer is used as a catalyst in the selective hydrogenation synthesis of 5-methylfurfural into 5-methylfurfuryl alcohol.
The magnetic metal organic coordination polymer is used as a catalyst in the furfural selective hydrogenation synthesis of furfuryl alcohol.
The magnetic metal organic coordination polymer is used as a catalyst in the synthesis of valerolactone by selective hydrogenation of levulinic acid.
The magnetic metal organic coordination polymer is used as a catalyst in the synthesis of valerolactone by selective hydrogenation of ethyl levulinate.
Advantageous effects
On the basis of researching the reaction mechanism of synthesizing 2, 5-furandimethanol by selective hydrogenation of 5-hydroxymethylfurfural, the magnetic metal organic coordination polymer catalyst with the acid-base bifunctional catalytic action is creatively prepared, and has the advantages of high acid-base strength, more acid-base sites, larger specific surface area and proper pore size, simple manufacturing process, easiness in separation and recovery, and excellent catalytic activity and catalytic stability; in addition, the low carbon alcohol is used as the in-situ hydrogen donor, so that the use of molecular hydrogen can be avoided, the safety of the reaction process is improved, the low carbon alcohol can be used as a reaction solvent, the introduction of exogenous substances is reduced, and the production cost can be further reduced. More importantly, the method provided by the invention can be used for catalyzing various carbonyl compounds such as 5-methylfurfural, furfural, levulinic acid, levulinate ester and the like to be selectively converted into corresponding products, has strong substrate universality, and has good application value and industrial prospect.
Detailed Description
EXAMPLE 1 preparation of magnetic Metal organic coordination Polymer
Adding nano ferroferric oxide into 400mL of dimethylformamide solution containing 30mmol of metal chloride according to the molar ratio of the metal chloride to the iron of 2:1, and stirring for 30min under the assistance of ultrasound; respectively and slowly dripping 400mL of dimethylformamide solution containing 10mmol of organic polybasic acid and 240mmol of triethylamine into the mixed solution at the dripping speed of 5mL/min and 1 mL/min; continuously stirring for 4 hours at room temperature, heating to 70 ℃, and then standing and aging for 4 hours; separating the solid precipitate by means of a magnet, and repeatedly washing the precipitate with ethanol and diethyl ether until no chloride ions are detected; and (3) drying the washed solid precipitate for 12h at 80 ℃ in vacuum, and grinding and crushing the solid precipitate to about 120 meshes to obtain the magnetic metal organic coordination polymer catalyst.
The amounts of the raw materials and the reaction species in the preparation using different metal chlorides and organic polybasic acids as the raw materials are shown in the following table:
the characterization data of the catalyst are shown in the following table:
example 2
The magnetic metal organic coordination polymer catalyst is adopted to carry out selective hydrogenation on 5-hydroxymethylfurfural to synthesize 2, 5-furandimethanol. The synthesis method comprises the following steps:
adding 20g of isopropanol, 0.4g of 5-hydroxymethylfurfural and 0.16g of magnetic metal organic coordination polymer catalyst into a 50mL reaction kettle, sealing, and continuously replacing air in the kettle for 6 times by using nitrogen; heating to 130 ℃ at the stirring speed of 400 rpm, and carrying out selective hydrogenation reaction for 8 hours to obtain the 2, 5-furandimethanol.
In order to examine the reusability of the catalyst, after the reaction is finished, MZPCP is separated from the reaction liquid by adding a magnet, and then the MZPCP is washed and dried to perform the next selective hydrogenation reaction according to the reaction conditions.
Compared with the catalyst and the hydrogenation synthesis method provided by the invention, the synthesis reaction and the catalyst in the prior art are adopted as a reference:
comparative example 1: the synthetic procedures in examples 1-3 of patent CN 106008414A.
It can be seen from the above table that the synthesis process provided by the present invention has higher product yield and reaction selectivity, particularly zirconium and hafnium show better catalytic effect as active metals, and the catalyst can still maintain higher reaction activity after being used for many times, which is superior to the magnetic zirconium hydroxide catalyst used in the comparative example.
Examples 3-8 Selective hydroconversion of catalysts in other carbonyl Compounds
Adding low-carbon alcohol, carbonyl-containing compound and magnetic metal organic coordination polymer catalyst into a 50mL reaction kettle, sealing, and continuously replacing air in the kettle with nitrogen for 6 times; heating at the stirring speed of 400 rpm, and performing selective hydrogenation reaction to obtain a corresponding product.
Wherein, the adopted reaction substrates, catalysts and reaction conditions are summarized as follows:
as can be seen from the above table, the catalyst provided by the invention is also suitable for the selective hydrogenation reaction of other carbonyl compounds, and has better reaction yield.
Claims (5)
1. The application of a magnetic metal organic coordination polymer as a catalyst in the selective hydrogenation synthesis of 2, 5-furandimethanol from 5-hydroxymethylfurfural is characterized in that the magnetic metal organic coordination polymer takes magnetic ferroferric oxide as a carrier, a high molecular polymer obtained by polymerization of an organic polyacid ligand and a crosslinking agent is loaded on the surface of the magnetic metal organic coordination polymer, and a catalytic active metal is complexed on the organic polyacid ligand; the catalytically active metal is selected from zirconium or hafnium; the organic polyacid ligand is selected from cyanuric acid or aminotrimethylene phosphonic acid; the crosslinker is triethylamine.
2. The use according to claim 1, wherein the preparation method of the magnetic metal organic coordination polymer comprises the following steps:
step 1, adding nano ferroferric oxide into an organic solution mixed with metal chloride, and ultrasonically stirring and uniformly dispersing;
step 2, respectively dripping an organic solvent and a cross-linking agent dissolved with an organic polyacid ligand, and stirring for reaction;
and 3, carrying out solid-liquid separation on the solids by using a magnet, and washing, drying and grinding the solids to obtain the catalyst.
3. The use of claim 2, wherein in the step 1, the concentration of the metal chloride in the organic solution is 30-120 mmol/L, and the molar ratio of the metal chloride to the iron is 1-3: 1; the metal chloride is zirconium tetrachloride or hafnium tetrachloride; in the step 1, the molar ratio of the metal ions to the organic polyacid ligand is 3: 4-6: 1, and the molar ratio of the metal ions to the triethylamine is 1: 10-1: 4; in the step 2, the dropping speed of the organic solvent dissolved with the organic polyacid ligand is 2-8 mL/min, and the dropping speed of the cross-linking agent is 0.5-1.5 mL/min; in the step 2, stirring for 2-12 h at room temperature, heating to 60-90 ℃, standing and aging for 2-12 h; in the step 3, the washing step refers to repeatedly washing the precipitate with ethanol and diethyl ether in sequence until no chloride ion exists; the drying step is vacuum drying at 75-85 ℃ for 8-16 h.
4. Use according to claim 1, characterized in that it comprises the following steps: adding low-carbon alcohol, 5-hydroxymethyl furfural and magnetic metal organic coordination polymer into a reaction kettle, replacing with nitrogen, reacting to obtain 2, 5-furandimethanol.
5. The use according to claim 4, wherein the lower alcohol is one of isopropanol, sec-butanol, sec-pentanol or cyclopentanol; the dosage of the 5-hydroxymethylfurfural is 1-3 wt% of that of the lower alcohol, and the dosage of the magnetic metal organic coordination polymer is 20-60 wt% of that of the 5-hydroxymethylfurfural; the stirring speed in the reaction kettle is 300-500 rpm, the reaction temperature is 120-150 ℃, and the reaction time is 2-10 h.
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| CN115779896A (en) * | 2022-11-23 | 2023-03-14 | 河南省生物基材料产业研究院有限公司 | Catalyst for preparing 2, 5-furandimethanol by selective hydrogenation of 5-hydroxymethylfurfural and preparation method thereof |
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