CN108554451A - 一种过渡金属天然高分子杂化催化剂及其制备方法与应用 - Google Patents
一种过渡金属天然高分子杂化催化剂及其制备方法与应用 Download PDFInfo
- Publication number
- CN108554451A CN108554451A CN201810318748.4A CN201810318748A CN108554451A CN 108554451 A CN108554451 A CN 108554451A CN 201810318748 A CN201810318748 A CN 201810318748A CN 108554451 A CN108554451 A CN 108554451A
- Authority
- CN
- China
- Prior art keywords
- transition metal
- natural polymer
- polymer hybrid
- preparation
- hybrid catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 229920005615 natural polymer Polymers 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 33
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 229920005610 lignin Polymers 0.000 claims abstract description 26
- 238000009901 transfer hydrogenation reaction Methods 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical class CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000002576 ketones Chemical class 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- -1 transition metal salt Chemical class 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 7
- 229920001732 Lignosulfonate Polymers 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229920005551 calcium lignosulfonate Polymers 0.000 claims description 2
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 150000002362 hafnium Chemical class 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 7
- 150000001298 alcohols Chemical class 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 230000001172 regenerating effect Effects 0.000 abstract 1
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 57
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 32
- 239000002585 base Substances 0.000 description 23
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 20
- 229910052726 zirconium Inorganic materials 0.000 description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- 239000007788 liquid Substances 0.000 description 15
- 238000004458 analytical method Methods 0.000 description 12
- 238000001514 detection method Methods 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 8
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 8
- 238000005070 sampling Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 4
- GMEONFUTDYJSNV-UHFFFAOYSA-N Ethyl levulinate Chemical compound CCOC(=O)CCC(C)=O GMEONFUTDYJSNV-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910007932 ZrCl4 Inorganic materials 0.000 description 4
- KVFDZFBHBWTVID-UHFFFAOYSA-N cyclohexanecarbaldehyde Chemical compound O=CC1CCCCC1 KVFDZFBHBWTVID-UHFFFAOYSA-N 0.000 description 4
- 229910052735 hafnium Inorganic materials 0.000 description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 4
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 4
- 229940100595 phenylacetaldehyde Drugs 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 208000035126 Facies Diseases 0.000 description 3
- 229910007926 ZrCl Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 235000013985 cinnamic acid Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical group Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 3
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical group CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 229930016911 cinnamic acid Natural products 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- WJUFSDZVCOTFON-UHFFFAOYSA-N veratraldehyde Chemical compound COC1=CC=C(C=O)C=C1OC WJUFSDZVCOTFON-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- PXJJKVNIMAZHCB-UHFFFAOYSA-N 2,5-diformylfuran Chemical class O=CC1=CC=C(C=O)O1 PXJJKVNIMAZHCB-UHFFFAOYSA-N 0.000 description 1
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 241000522254 Cassia Species 0.000 description 1
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- 229910003865 HfCl4 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- GQOPHGWADRIBIR-UHFFFAOYSA-J O.[Cl-].[Cl-].[Cl-].[Cl-].Cl.Cl.[Hf+4] Chemical compound O.[Cl-].[Cl-].[Cl-].[Cl-].Cl.Cl.[Hf+4] GQOPHGWADRIBIR-UHFFFAOYSA-J 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 description 1
- 150000003935 benzaldehydes Chemical class 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- WZUQMOGWPIRDHH-UHFFFAOYSA-N butyl 2-methyl-3-oxobutanoate Chemical compound CCCCOC(=O)C(C)C(C)=O WZUQMOGWPIRDHH-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229940043350 citral Drugs 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- VSSAZBXXNIABDN-UHFFFAOYSA-N cyclohexylmethanol Chemical compound OCC1CCCCC1 VSSAZBXXNIABDN-UHFFFAOYSA-N 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 1
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 description 1
- NXKAMHRHVYEHER-UHFFFAOYSA-J hafnium(4+);disulfate Chemical compound [Hf+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O NXKAMHRHVYEHER-UHFFFAOYSA-J 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229940058352 levulinate Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
-
- 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
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
-
- 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
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明属于杂化催化剂的制备技术领域,具体涉及一种过渡金属天然高分子杂化催化剂及其制备方法与应用。该方法将木质素与第VB族的过渡金属盐溶液进行水热反应,制备方法简单,由此获得的过渡金属天然高分子杂化催化剂稳定性好,可高效催化醛类、酮类或乙酰丙酸酯类与醇类有机物的转移氢化反应,其中由醛类制备醇类的转化率高达84~99%,醇类的选择性高达80~100%。此外,该催化剂在应用过程中的底物适用性好,反应后易于分离。由于其以木质素为原料,因此该催化剂安全,成本低,可将低价值的木质素高值化,绿色环保,且可循环再生,易于工业化。
Description
技术领域
本发明属于杂化催化剂的制备技术领域,具体涉及一种过渡金属天然高分子杂化催化剂及其制备方法与应用。
背景技术
糠醛是一类重要的可再生生物质平台分子,可以通过催化转化生产各种高附加值的呋喃衍生物,以及生产液体烷烃和燃料的添加剂。其中糠醇是最具吸引力的产物之一。糠醇作为一种重要的化工原料,主要用于生产恒温树脂、耐腐蚀杂化混凝土等,也被广泛地用作溶剂和重要中间体,例如粘合剂和润湿剂等。糠醛加氢还原制备糠醇反应在温和条件下难以发生,催化剂对反应的转化起到了关键作用。目前,工业上采用的糠醛加氢催化剂主要为Cu-Cr系列催化剂,由于该系列催化剂有毒致癌,废弃后会产生严重的环境污染,因此开发高效、环保且可回收的糠醛加氢催化剂具有重要意义。
木质素是陆地上仅次于纤维素的第二大天然高分子化合物。每年来源于制浆造纸废液和生物乙醇的工业木质素高达4×107~5×107t,然而只有不到10%的木质素得到了有效利用,90%以上的木质素都会被直接烧掉,既污染环境,又浪费资源。可以工业利用的木质素主要来自于制浆造纸工业,主要分为木质素磺酸盐(主要由亚硫酸盐酸法造纸红液浓缩而得或由碱木质素磺化制备)和碱木质素(碱法造纸黑液酸析而得)。其中酸法制浆废液中的木质素磺酸盐是工业木质素的主要应用形式,其分子结构中含有大量的磺酸基、羧基、酚羟基等基团。开发工业木质素的高值化应用领域,不仅能推动造纸行业的清洁生产,更有利于解决目前环境污染、资源浪费和能源危机的困境。
发明内容
为克服现有技术的缺点和不足,本发明的首要目的在于提供一种过渡金属天然高分子杂化催化剂的制备方法。
本发明的另一目的在于提供一种由上述方法制备而得的过渡金属天然高分子杂化催化剂。
本发明的再一目的在于提供一种上述过渡金属天然高分子杂化催化剂的应用。
为实现上述目的,本发明采用的技术方案如下:
一种过渡金属天然高分子杂化催化剂的制备方法,包括以下步骤:
将木质素和金属盐分别溶于水中,得到均一的木质素溶液和金属盐溶液,然后将两种溶液混合,得到均一的悬浊液,进行水热反应,反应后分离出沉淀,洗涤沉淀至滤液无色透明并呈中性后,干燥沉淀,即得过渡金属天然高分子杂化催化剂;
所述金属盐为第VB族的过渡金属盐。
优选的,所述的过渡金属盐为锆盐或铪盐。
优选的,所述的木质素为木质素磺酸钠、木质素磺酸钙、碱性木质素或磺化木质素。
优选的,所述的过渡金属盐为硫酸盐、硝酸盐或氯化物。
更优选的,所述的过渡金属盐为四氯化锆、二氯氧锆、硫酸锆、硝酸锆、氯化铪、氧氯化铪、硫酸铪或硝酸氧铪。
优选的,所述的木质素溶液的浓度为5~50wt.%。
优选的,所述的金属盐溶液的浓度为5~50wt.%。
优选的,所述的悬浊液中,木质素与金属盐的质量比为10:1~1:10。
更优选的,所述的悬浊液中,木质素与金属盐的质量比为1:1。
优选的,所述的水热反应的温度为25~160℃。
更优选的,所述的水热反应的温度为120~160℃。
优选的,所述的水热反应的时长为2~20h。
本发明进一步提供一种上述方法制备而得的过渡金属天然高分子杂化催化剂。
本发明进一步提供一种上述过渡金属天然高分子杂化催化剂的应用,将所述催化剂用于醛类、酮类或乙酰丙酸酯类与醇类有机物的转移氢化反应。
优选的,所述的醛类为糠醛、5-羟甲基糠醛、5-甲基呋喃醛、2,5-二甲酰呋喃、肉桂醛、柠檬醛、香草醛、巴豆醛、藜芦醛、丙醛、丁醛、苯甲醛、对甲氧基苯甲醛、苯乙醛、环己基甲醛或正己醛。
优选的,所述的酮类为2-己酮、环己酮、环戊酮或苯乙酮。
优选的,所述的乙酰丙酸酯类为乙酰丙酸甲酯、乙酰丙酸乙酯、乙酰丙酸异丙酯、乙酰丙酸正丙酯或乙酰丙酸丁酯。
优选的,所述的醇类有机物为甲醇、乙醇、正丙醇、异丙醇、正丁醇、仲丁醇、叔丁醇、正戊醇、环戊醇或环己醇。
优选的,所述的转移氢化反应包括以下步骤:
将所述的醛类、酮类或乙酰丙酸酯类与催化剂和醇类有机物混合,在50~200℃下反应0.1~20h,过滤分离,得到产物;
本发明与现有技术相比,具有如下优点和有益效果:
(1)本发明以制浆造纸中的副产物木质素为原料,制备过渡金属天然高分子杂化催化剂,可将低价值的木质素高值化,其安全,成本低,制备方法简单,绿色环保,且可循环再生,易于工业化。
(2)本发明制备的过渡金属天然高分子杂化催化剂稳定性好,尤其是锆基或铪基的天然高分子杂化催化剂,可高效催化醛类、酮类或乙酰丙酸酯类与醇类有机物的转移氢化反应,其中由醛类制备醇类的转化率高达84~99%,醇类的选择性高达80~100%,此外,该催化剂应用过程中的底物适用性好,反应后易于分离。
具体实施方式
下面结合实施例对本发明作进一步地详细说明,但本发明的实施方式不限于此。对于未特别注明的工艺参数,可参照常规技术进行。
实施例1
本实施例提供一种锆基和铪基天然高分子杂化催化剂(Zr-LS)的制备方法与在糠醇转移氢化反应中的应用,同时提供铁基天然高分子杂化催化剂(Fe-LS)和钴基天然高分子杂化催化剂(Co-LS)的应用对照例。
(1)Zr-LS的制备:
将5g木质素磺酸钠溶于50g水中,将5g ZrCl4溶于15g水中。在室温下搅拌混合后,置于100ml水热釜中于120℃烘箱中水热反应8h。离心分离后用水洗涤至滤液至中性并呈无色透明。置于50℃烘箱中干燥12h,得到Zr-LS催化剂。
(2)Hf-LS的制备:
将(1)中的ZrCl4替换成HfCl4,重复(1)的制备过程,得到Hf-LS催化剂。
(3)Fe-LS的制备:
将(1)中的ZrCl4替换成FeCl3,重复(1)的制备过程,得到Fe-LS催化剂。
(4)Co-LS的制备:
将(1)中的ZrCl4替换成CoCl2,重复(1)的制备过程,得到Co-LS催化剂。
(5)催化剂在糠醇转移氢化反应中的应用:
空白对照:称取1mmol糠醛、10mL异丙醇置于25ml的后壁耐压瓶中密封,置于80℃的油浴锅中反应1h后,冷却至室温,过滤得到液体混合物,取样进行气相分析。所用分析仪器为岛津Shimadzu Nexis GC-2030,汽化室温度:280℃;检测器温度:280℃;40℃,保留2min,30℃/min的速率升高到280℃,保留5min;柱压力:150kPa;分流比:50。得到糠醛的转化率为0%,糠醇的选择性为0%。
催化应用:取四个25ml的厚壁耐压瓶,在每个耐压瓶中分别加入1mmol糠醛和10mL异丙醇,然后在四个耐压瓶中分别加入200mg的Zr-LS催化剂、Hf-LS催化剂、Fe-LS催化剂和Co-LS催化剂。密封四个耐压瓶,置于80℃的油浴锅中反应1h后,过滤得到液体混合物,取样进行气相分析,得到的糠醛转化率和糠醇选择性如表1所示。可见,与铁基和钴基天然高分子杂化催化剂相比,锆基和铪基天然高分子杂化催化剂对糠醇转移氢化反应具有更高的催化效率。
表1不同催化剂下所得的糠醛转化率和糠醇选择性
实施例2
本实施例提供一种锆基天然高分子杂化催化剂(Zr-AL)的制备方法与在糠醇转移氢化反应中的应用
(1)Zr-AL的制备:
将5g碱性木质素溶于50g水中,将5g ZrCl4溶于15g水中。在室温下搅拌混合后,置于100ml水热釜中于120℃烘箱中水热反应8h。离心分离后用水洗涤至滤液至中性并呈无色透明。置于50℃烘箱中干燥12h,得到Zr-AL催化剂。
(2)催化剂在糠醇转移氢化反应中的应用:
向25ml的厚壁耐压瓶中加入1mmol糠醛、10mL异丙醇和200mg的Zr-AL催化剂。密封耐压瓶,置于80℃的油浴锅中反应1h后,过滤得到液体混合物,取样进行气相分析,检测方法同实施例1,得到的糠醛转化率为48%,糠醇选择性为81%。
实施例3
本实施例提供一种锆基天然高分子杂化催化剂(Zr-LS)在糠醇转移氢化反应中的应用。
向25ml的厚壁耐压瓶中加入1mmol糠醛、10mL异丙醇和200mg实施例1中制备的Zr-LS催化剂。密封耐压瓶,置于100℃的油浴锅中反应1h后,过滤得到液体混合物,取样进行气相分析,检测方法同实施例1,得到的糠醛转化率为99%,糠醇选择性为95%。
实施例4
本实施例提供一种锆基天然高分子杂化催化剂(Zr-LS)在5-羟甲基糠醛转移氢化反应中的应用。
向25ml的厚壁耐压瓶中加入1mmol的5-羟甲基糠醛、10mL异丙醇和200mg实施例1中制备的Zr-LS催化剂。密封耐压瓶,置于80℃的油浴锅中反应5h后,过滤得到液体混合物,取样进行气相分析,检测方法同实施例1,得到的5-羟甲基糠醛转化率为60%,2,5-呋喃二甲醇选择性为96%。
实施例5
本实施例提供一种锆基天然高分子杂化催化剂(Zr-LS)在肉桂醛转移氢化反应中的应用。
向25ml的厚壁耐压瓶中加入1mmol肉桂醛、10mL异丙醇和200mg实施例1中制备的Zr-LS催化剂。密封耐压瓶,置于80℃的油浴锅中反应3h后,过滤得到液体混合物,取样进行气相分析,检测方法同实施例1,得到的肉桂醛转化率为95%,肉桂醇选择性为98%。
实施例6
本实施例提供一种锆基天然高分子杂化催化剂(Zr-LS)在乙酰丙酸乙酯转移氢化反应中的应用。
向25ml的厚壁耐压瓶中加入1mmol的乙酰丙酸乙酯、10mL异丙醇和200mg实施例1中制备的Zr-LS催化剂。密封耐压瓶,置于130℃的油浴锅中反应7h后,过滤得到液体混合物,取样进行气相分析,检测方法同实施例1,得到的乙酰丙酸乙酯的转化率为69%,γ-戊内酯选择性为85%。
实施例7
本实施例提供一种锆基天然高分子杂化催化剂(Zr-LS)在苯甲醛转移氢化反应中的应用。
向25ml的厚壁耐压瓶中加入1mmol苯甲醛、10mL异丙醇和200mg实施例1中制备的Zr-LS催化剂。密封耐压瓶,置于80℃的油浴锅中反应2h后,过滤得到液体混合物,取样进行气相分析,检测方法同实施例1,得到的苯甲醛的转化率为99%,苯甲醇选择性为99%。
实施例8
本实施例提供一种锆基天然高分子杂化催化剂(Zr-LS)在苯乙醛转移氢化反应中的应用。
向25ml的厚壁耐压瓶中加入1mmol的苯乙醛、10mL异丙醇和200mg实施例1中制备的Zr-LS催化剂。密封耐压瓶,置于80℃的油浴锅中反应2h后,过滤得到液体混合物,取样进行气相分析,检测方法同实施例1,得到的苯乙醛的转化率为91%,苯乙醇选择性为96%。
实施例9
本实施例提供一种锆基天然高分子杂化催化剂(Zr-LS)在正己醛转移氢化反应中的应用。
向25ml的厚壁耐压瓶中加入1mmol的正己醛、10mL异丙醇和200mg实施例1中制备的Zr-LS催化剂。密封耐压瓶,置于80℃的油浴锅中反应100min后,过滤得到液体混合物,取样进行气相分析,检测方法同实施例1,得到的正己醛的转化率为93%,正己醇选择性为91%。
实施例10
本实施例提供一种锆基天然高分子杂化催化剂(Zr-LS)在环己基甲醛转移氢化反应中的应用。
向25ml的厚壁耐压瓶中加入1mmol的环己基甲醛、10mL异丙醇和200mg实施例1中制备的Zr-LS催化剂。密封耐压瓶,置于80℃的油浴锅中反应100min后,过滤得到液体混合物,取样进行气相分析,检测方法同实施例1,得到环己基甲醛的转化率为95%,环己基甲醇选择性为94%。
实施例11
本实施例提供一种锆基天然高分子杂化催化剂(Zr-LS)在环己酮转移氢化反应中的应用。
向25ml的厚壁耐压瓶中加入1mmol的环己酮、10mL异丙醇和200mg实施例1中制备的Zr-LS催化剂。密封耐压瓶,置于80℃的油浴锅中反应5h后,过滤得到液体混合物,取样进行气相分析,检测方法同实施例1,得到环己酮的转化率为96%,环己醇选择性为100%。
实施例12
本实施例提供一种锆基天然高分子杂化催化剂(Zr-LS)的制备方法和应用
将实施例1中(1)的木质素磺酸钠质量改为1g,ZrCl4质量改为10g,重复实施例1中(1)的制备过程和应用过程,得到的糠醛转化率为67%,糠醇选择性为80%。
实施例13
本实施例提供一种锆基天然高分子杂化催化剂(Zr-LS)的制备方法和应用
将实施例1中(1)的木质素磺酸钠质量改为10g,ZrCl4质量改为1g,重复实施例1中(1)的制备过程和应用过程,得到的糠醛转化率为84%,糠醇选择性为84%。
实施例14
本实施例提供一种锆基天然高分子杂化催化剂(Zr-LS)的制备方法和应用
将实施例1中(1)的水热温度改为25℃,重复实施例1中(1)的制备过程和应用过程,得到的糠醛转化率为55%,糠醇选择性为87%。
实施例15
本实施例提供一种锆基天然高分子杂化催化剂(Zr-LS)的制备方法和应用
将实施例1中(1)的水热温度改为160℃,重复实施例1中(1)的制备过程和应用过程,得到的糠醛转化率为85%,糠醇选择性为92%。
实施例16
本实施例提供一种锆基天然高分子杂化催化剂(Zr-LS)的制备方法和应用
将实施例1中(1)的水热时间改为2h,重复实施例1中(1)的制备过程和应用过程,得到的糠醛转化率为84%,糠醇选择性为90%。
实施例17
本实施例提供一种锆基天然高分子杂化催化剂(Zr-LS)的制备方法和应用
将实施例1中(1)的水热时间改为20h,重复实施例1中(1)的制备过程和应用过程,得到的糠醛转化率为87%,糠醇选择性为93%。
实施例18
本实施例提供一种锆基天然高分子杂化催化剂(Zr-LS)的制备方法和应用
将实施例1中(1)的氯化锆改为二氯氧锆,重复实施例1中(1)的制备过程和应用过程,得到的糠醛转化率为89%,糠醇选择性为96%。
上述实施例为本发明较优的实施方式,但本发明的实施方式并不受限于上述实施例,其它的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应等效的置换方式,都包含在本发明的保护范围之内。
Claims (10)
1.一种过渡金属天然高分子杂化催化剂的制备方法,其特征在于,包括以下步骤:
将木质素和金属盐分别溶于水中,得到均一的木质素溶液和金属盐溶液,然后将两种溶液混合,得到均一的悬浊液,进行水热反应,反应后分离出沉淀,洗涤沉淀至滤液无色透明并呈中性后,干燥沉淀,即得过渡金属天然高分子杂化催化剂;
所述金属盐为第VB族的过渡金属盐。
2.根据权利要求1所述的过渡金属天然高分子杂化催化剂的制备方法,其特征在于:所述的过渡金属盐为锆盐或铪盐。
3.根据权利要求1所述的过渡金属天然高分子杂化催化剂的制备方法,其特征在于:所述的木质素为木质素磺酸钠、木质素磺酸钙、碱性木质素或磺化木质素。
4.根据权利要求1所述的过渡金属天然高分子杂化催化剂的制备方法,其特征在于:所述的过渡金属盐为硫酸盐、硝酸盐或氯化物。
5.根据权利要求1所述的过渡金属天然高分子杂化催化剂的制备方法,其特征在于:所述的悬浊液中,木质素与金属盐的质量比为10:1~1:10。
6.根据权利要求1所述过渡金属天然高分子杂化催化剂的制备方法,其特征在于:所述的水热反应的温度为25~160℃。
7.根据权利要求1~6任一项所述的过渡金属天然高分子杂化催化剂的制备方法,其特征在于:
所述的木质素溶液的浓度为5~50wt.%;
所述的金属盐溶液的浓度为5~50wt.%。
8.一种过渡金属天然高分子杂化催化剂,其特征在于:由权利要求1~7任一项所述方法制备而得。
9.权利要求8所述的过渡金属天然高分子杂化催化剂的应用,其特征在于:将所述的催化剂用于醛类、酮类或乙酰丙酸酯类与醇类有机物的转移氢化反应。
10.根据权利要求9所述的过渡金属天然高分子杂化催化剂的应用,其特征在于,所述的转移氢化反应包括以下步骤:将醛类、酮类或乙酰丙酸酯类与催化剂和醇类有机物混合,在50~200℃下反应0.1~20h,过滤分离,得到产物。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810318748.4A CN108554451B (zh) | 2018-04-11 | 2018-04-11 | 一种过渡金属天然高分子杂化催化剂及其制备方法与应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810318748.4A CN108554451B (zh) | 2018-04-11 | 2018-04-11 | 一种过渡金属天然高分子杂化催化剂及其制备方法与应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108554451A true CN108554451A (zh) | 2018-09-21 |
CN108554451B CN108554451B (zh) | 2020-08-18 |
Family
ID=63534779
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810318748.4A Expired - Fee Related CN108554451B (zh) | 2018-04-11 | 2018-04-11 | 一种过渡金属天然高分子杂化催化剂及其制备方法与应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108554451B (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109761938A (zh) * | 2018-12-15 | 2019-05-17 | 华南理工大学 | 一种催化5-羟甲基糠醛一步还原醚化的方法 |
CN110639617A (zh) * | 2019-10-11 | 2020-01-03 | 江南大学 | 有机-金属催化剂的合成方法及其在mpv反应中的应用 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104530444A (zh) * | 2014-11-21 | 2015-04-22 | 东北林业大学 | 一种提高工业木质素活性的改性方法 |
CN104828895A (zh) * | 2015-04-28 | 2015-08-12 | 台州学院 | 一种采用氧化锆改性的酶解木质素的水处理方法 |
CN106243141A (zh) * | 2016-08-01 | 2016-12-21 | 常州聚博节能科技有限公司 | 无机杂化羟甲基木质素及其制备方法 |
-
2018
- 2018-04-11 CN CN201810318748.4A patent/CN108554451B/zh not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104530444A (zh) * | 2014-11-21 | 2015-04-22 | 东北林业大学 | 一种提高工业木质素活性的改性方法 |
CN104828895A (zh) * | 2015-04-28 | 2015-08-12 | 台州学院 | 一种采用氧化锆改性的酶解木质素的水处理方法 |
CN106243141A (zh) * | 2016-08-01 | 2016-12-21 | 常州聚博节能科技有限公司 | 无机杂化羟甲基木质素及其制备方法 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109761938A (zh) * | 2018-12-15 | 2019-05-17 | 华南理工大学 | 一种催化5-羟甲基糠醛一步还原醚化的方法 |
CN110639617A (zh) * | 2019-10-11 | 2020-01-03 | 江南大学 | 有机-金属催化剂的合成方法及其在mpv反应中的应用 |
CN110639617B (zh) * | 2019-10-11 | 2020-12-01 | 江南大学 | 有机-金属催化剂的合成方法及其在mpv反应中的应用 |
Also Published As
Publication number | Publication date |
---|---|
CN108554451B (zh) | 2020-08-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Kang et al. | Recent advances in carbon-based sulfonated catalyst: preparation and application | |
US10807938B2 (en) | Method for preparing maleate by selective catalytic oxidation of lignin | |
CN112044450B (zh) | 一种酸碱双功能生物质碳基催化剂及其制备方法 | |
CN101348487A (zh) | 一种多磺酸基功能化离子液体的制备方法 | |
CN104447239B (zh) | 甲醇为原始反应物料连续生产聚甲氧基二甲醚的方法 | |
CN103012334A (zh) | 一种温和条件下高选择性制备γ-戊内酯的方法 | |
CN108276364A (zh) | 一种多孔的六偏磷酸锆催化剂的制备及应用 | |
CN108745333A (zh) | 一种多孔碳气凝胶催化剂及其制备方法与应用 | |
CN108554451A (zh) | 一种过渡金属天然高分子杂化催化剂及其制备方法与应用 | |
CN103694203B (zh) | 纤维素基磺酸催化剂催化果糖制备5-羟甲基糠醛的方法 | |
CN109761938A (zh) | 一种催化5-羟甲基糠醛一步还原醚化的方法 | |
CN103193623B (zh) | 一种由生产木糖的废渣一步催化制备乙酰丙酸的方法 | |
CN113333001A (zh) | 一种木质素衍生碳基固体酸催化剂的制备方法及其应用 | |
CN107413382B (zh) | 一种合成生物柴油酸碱双中心固体催化剂及其制备方法 | |
CN106268940A (zh) | 木聚糖基碳基固体酸及由其催化合成苯并呫吨类化合物的方法 | |
CN103157509A (zh) | 一种由甘蔗渣制备炭基固体磺酸的方法 | |
CN102850304B (zh) | 一种复合钙钛矿一步水解木聚糖制备糠醛的方法 | |
CN114920648B (zh) | 一种3-(3-氧-2-戊基)环戊基丙二酸二甲酯的合成方法及催化剂 | |
CN109692690B (zh) | 一种用于生产左旋葡萄糖酮的催化剂及制备方法 | |
CN102824907B (zh) | 一种制备dns酸及其盐的催化剂及其制备方法 | |
CN109836403B (zh) | 以木质素磺酸基-醛型树脂为催化剂将生物质糖类化合物转化为5-羟甲基糠醛的方法 | |
CN110479309A (zh) | 一种以木素为原料的纳米球形碳基固体酸及其制备方法和应用 | |
CN110156581A (zh) | 一种一步光催化木质素解聚及胺化合成含氮芳香化合物的方法 | |
CN110227547A (zh) | 一种木质素磺酸催化剂的制备方法及其应用 | |
CN108479801B (zh) | 一种用于合成乙酰丙酸酯的催化剂及其应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200818 |