CN113908841A - 一种Cu基催化剂在糠醇氢解制备戊二醇中的应用 - Google Patents
一种Cu基催化剂在糠醇氢解制备戊二醇中的应用 Download PDFInfo
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- CN113908841A CN113908841A CN202111180328.2A CN202111180328A CN113908841A CN 113908841 A CN113908841 A CN 113908841A CN 202111180328 A CN202111180328 A CN 202111180328A CN 113908841 A CN113908841 A CN 113908841A
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- catalyst
- pentanediol
- furfuryl alcohol
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- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000007327 hydrogenolysis reaction Methods 0.000 title abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 11
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 8
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052790 beryllium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 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
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 239000002243 precursor Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000002028 Biomass Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000010949 copper Substances 0.000 description 31
- 238000001354 calcination Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 10
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000012266 salt solution Substances 0.000 description 9
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052802 copper Chemical class 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 238000004451 qualitative analysis Methods 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- RFVVBBUVWAIIBT-UHFFFAOYSA-N beryllium nitrate Chemical compound [Be+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O RFVVBBUVWAIIBT-UHFFFAOYSA-N 0.000 description 2
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000004448 titration Methods 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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical class [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical class [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002477 CuCr2O4 Inorganic materials 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 229910002339 La(NO3)3 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical class [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- 229910016978 MnOx Inorganic materials 0.000 description 1
- 239000005822 Propiconazole Substances 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical class [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical class [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- MOXBWFCVRDSGQZ-UHFFFAOYSA-N barium(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MOXBWFCVRDSGQZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical class [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- ICSSIKVYVJQJND-UHFFFAOYSA-N calcium nitrate tetrahydrate Chemical compound O.O.O.O.[Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ICSSIKVYVJQJND-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical class [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical class [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000000474 nursing effect Effects 0.000 description 1
- 150000002972 pentoses Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- STJLVHWMYQXCPB-UHFFFAOYSA-N propiconazole Chemical compound O1C(CCC)COC1(C=1C(=CC(Cl)=CC=1)Cl)CN1N=CN=C1 STJLVHWMYQXCPB-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical class [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- CBRVNNFPYLQDQN-UHFFFAOYSA-N zirconium(4+) tetranitrate hexahydrate Chemical compound O.O.O.O.O.O.[N+](=O)([O-])[O-].[Zr+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] CBRVNNFPYLQDQN-UHFFFAOYSA-N 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本申请公开了一种复合强碱性氧化物负载Cu催化剂催化糠醇开环氢解制备戊二醇的方法。催化剂是由La2O3‑MO复合氧化物载体负载活性组分Cu构成。其优异性体现在:1.本发明所涉及的催化剂制备方法简单、产物易分离、可循环多次使用、成本低廉。2.本发明所涉及的催化剂的载体具有超强碱性,有助于反应物糠醇的吸附及后续氢解开环的发生。3.本发明是以廉价可再生生物质资源衍生的糠醇替代化石原料生产戊二醇,原料来源广泛且成本低廉,反应条件温和、工艺简单。4.本发明糠醇的转化率≥95%,所制得的戊二醇的选择性≥90%,并且催化剂可循环使用多次并保持良好的催化性能。
Description
技术领域
本发明涉及一种糠醇开环氢解制备戊二醇的方法,具体涉及在一种复合强碱性载体上负载Cu催化剂使糠醇开环氢解制备戊二醇的方法。
背景技术
随着化石能源的日益消耗,生物质作为唯一可再生的碳资源受到越来越广泛的关注,其中糠醛作为一种重要的生物质基平台化合物,主要通过无定形结构的半纤维素降解为五碳糖如木糖等,进一步催化脱水制得。近年来,采用糠醛及其衍生物糠醇和四氢糠醇为原料,通过进一步选择性开环氢解制备戊二醇受到了越来越多的关注。戊二醇是一种重要的化工原料,其中1,2-戊二醇是合成杀菌剂丙环唑的重要中间体,也是生产聚酯纤维、表面活性剂、护理用品的重要原料,1,5-戊二醇作为一种重要的端基二元醇,是合成聚氨酯弹性体、聚酯、医药中间体的重要单体。目前,已有文献和专利报道了由糠醛(糠醇、四氢糠醇)制备戊二醇的方法。早在1931年,Adkins等人报道了以CuCr2O4为催化剂,在175℃,10-15MPaH2下,以糠醇为原料制备戊二醇,糠醇的转化率为100%,1,2-戊二醇的收率为40%,1,5-戊二醇的收率为30%(J.Am.Chem. Soc.,1931,53,1091-1095)。但该催化剂中含有有毒金属Cr,会对环境造成污染限制了其在工业上的应用。此后,Tomishige课题组在2009年首次报道以四氢糠醇为原料,在水相体系中,以Rh-ReOx/SiO2为催化剂,在120℃,8MPa H2的条件下反应24h,四氢糠醇的转化率为96.2%,高选择性(77.1%)获得1, 5-戊二醇单一二醇产物(Chem Commun.,2009,106,2035-2037)。随后,该课题组又报道了以糠醛为原料在Rh-Ir-ReOx/SiO2催化剂下,先在40℃,8MPa H2下反应4h,再在100℃下反应24h,糠醛的转化率为100%,1,5-戊二醇的选择性为71.1%(Cata.Sci.Technol.,2104,4,2535-2549)。此外,贵金属Ru基或 Pt基催化剂:Ru/MnOx(Green Chem.2012,14:3402-3409)、Pt/CeO2(Catal.Commun. 2017,101:129-133)、Pt/Co2AlO4(Chem.Commun.2011,47:3924-3926)、Pt/HT (ACS Sustain.Chem.Eng.2014,2:2243-2247)也用于催化糠醛或糠醇氢解,在 120-180℃,1-2MPa H2条件下可以获得约16%-73%不等的1,2-戊二醇。虽然贵金属催化剂可以高选择性地获得1,2或1,5-戊二醇,但催化剂制备成本高昂、回收复杂限制其在工业上的应用。非贵金属催化剂Cu-Mg3AlO4.5(Catal.Sci. Technol.,2016,6,668-671)、Cu1.8Mg1.2Al(ACS Sustain.Chem.Eng.2020,8: 5217-5228)、Cu-Al2O3(Chin.J.Catal.2018,39,319-326)、Cu0.25Co0.75Al(ACS Sustain.Chem.Eng.2020,8:5217-5228)也被报道用于催化糠醇制备戊二醇,在 140-160℃,4-6MPa H2条件下,获得57.7%-80%收率不等的戊二醇。目前Cu基催化剂主要以MgAl水滑石载体为主,因此开发其他强碱性载体负载Cu催化剂用于温和条件下制备戊二醇具有重要的研究意义。
发明内容
本发明所要解决的技术问题是针对现有的糠醇开环氢解制备戊二醇工艺中,贵金属Rh,Ir基催化剂等成本昂贵,负载Cu基催化剂效率不高等问题,提供一种新的强碱性载体负载Cu催化剂高效催化转化糠醇为戊二醇,包括1,2- 戊二醇和1,5-戊二醇,如下式1所示。该催化剂能够在温和的条件下催化反应发生,具有催化剂制备成本低廉,反应后易于分离,可循环利用,且反应后不产生多聚物等优点。
式1.糠醇催化转化为戊二醇
为达到以上目的,本发明采取的技术方案如下:本方案涉及一种强碱性载体负载Cu催化剂在糠醇催化转化制备戊二醇中的应用,其特征在于:所述的催化剂组成为Cu/La2O3-MO,其中载体为La2O3和MO的复合氧化物,M为Be、 Mg、Ca、Sr、Ba、Ce、Zr等金属的任意一种二种以上,其中MO与La2O3中金属M与La的摩尔比为1-10,金属Cu的负载量为2-30wt%。所述戊二醇为1, 2-戊二醇和1,5-戊二醇中的一种或两种。所述的强碱性载体负载Cu催化剂采用共沉淀法制备,具体实施方法如下:
步骤1,称取铍、镁、钙、锶、钡、铈、锆中的任意一种或两种以上有机盐,溶于水中,金属有机盐的摩尔浓度为0.05-2mol/L,称取镧和铜的有机盐加入上述溶液,室温下超声溶解,得金属盐溶液A。
上述的方法,其中,各金属的有机盐包括:硝酸盐、氯化盐、硫酸盐、磷酸盐、碳酸盐、醋酸盐中的一种或多种组合。
步骤2,称取1-5g NaOH、KOH、Ca(OH)2、Ba(OH)2固体和1-5g Na2CO3、 NaHCO3、K2CO3、KHCO3中一种或两种固体溶解于水中,其中,固体碱的摩尔浓度为1-5mol/L,室温下超声溶解,得碱溶液B。
步骤3,在20-60℃下,将金属盐溶液A慢慢滴加于碱溶液B中,滴定结束时保持溶液最终的pH值在9-12之间。所得的混合物转移至水热釜中,一定温度下水热一定时间。冷却后,所得的沉淀抽滤,去离子水洗涤至pH=7,置于 60-100℃烘箱中干燥24h。充分研磨后置于管式炉中在400-800℃下空气氛围下加热4-8h,然后在H2氛围下400-800℃下加热还原4-8h。
上述的方法,其中,水热温度为20-150℃,水热时间为2-48h。
步骤4,上述所制备的催化剂用于糠醇开环氢解制备戊二醇中,将糠醇,催化剂,溶剂加入到高压反应釜中,将反应釜密封。通入N2置换反应釜中的空气,向反应釜中通入H2,将反应釜的温度升高至特定温度,反应一定时间得到反应溶液。反应结束后,待反应釜冷却后释放H2,通过简单过滤催化剂得到反应液。以气质联用仪和气相色谱进行定性和定量分析,然后计算反应的转化率、产物的选择性和收率。
上述的方法,其中,溶剂为水、乙醇、甲醇、异丙醇、四氢呋喃、丙酮中的一种或多种组合。
上述的方法,其中,所述原料的质量分数为2-50%。
上述的方法,其中,反应温度为100-200℃,氢气压力为2.0-8.0MPa,反应时间为2-28h。
综上所述,通过上述方法,本发明与现有技术相比,有以下优点和有益效果:
1.本发明所涉及的催化剂制备方法简单、回收方便、产物易分离、可循环多次使用、成本低廉。
2.本发明所涉及的催化剂的载体具有超强碱性,有助于反应物糠醇的吸附,开环的发生。
3.本发明是以廉价可再生生物质资源衍生的糠醇替代化石原料生产戊二醇,原料来源广泛且成本低廉,反应条件温和、工艺简单。
4.本发明糠醇的转化率≥95%,所制得的戊二醇的选择性≥90%,并且催化剂可循环使用多次并保持良好的催化性能。
具体实施方式
下面结合实施例对本发明的具体实施方式做进一步详细介绍。
在下列实施实例中,糠醇的转化率以及产物戊二醇的选择性由下式来定义。
分析液相产物组成所采用仪器为岛津QP-2010 Ultra GC-MS仪器,色谱柱为 Rtx-5Sil MS(30m×0.25m×0.25μm)。
实施例1
配置金属盐溶液A:将6.53g六水合硝酸钡、1.62g三水合硝酸铜、3.80g 六水合硝酸镧、50ml去离子水加入到烧杯中,室温下超声15min使其完全溶解。配置碱溶液B:将2.81gKOH、2.07g K2CO3、50ml去离子水加入到烧杯中,室温下超声15min使其完全溶解。将碱溶液B转移到三口烧瓶中,金属盐溶液 A转移至滴液漏斗中,慢慢滴加溶液A至溶液B中,滴定结束保持PH≥10.5。将所得悬浊液抽滤后,置于100℃烘箱中干燥24h。充分研磨后,置于管式炉中在500℃下煅烧5h,空气流速为200ml/min。然后在高纯H2氛围中程序升温加热至500℃,维持5h,H2流速为200ml/min。待完全冷却后,使用3∶1比例的N2和空气老化备用。
将0.3g所制备Cu/La2O3-BaO催化剂加入反应釜中,加入3g糠醇和27g 乙醇。将反应釜密封,通入H2置换反应釜中的空气;向反应釜中通入4MPa H2,将反应釜的温度升温至140℃,反应24h。反应结束后冷却,释放H2,开釜得到反应液,用气质联用仪和气相色谱进行定性和定量分析,产物分布见表1。
实施例2
操作同实施例1,只是以10.853g六水合硝酸铈替代硝酸钡盐,煅烧还原后即得本发明所提供活性催化剂2Cu/La2O3-CeO2。
实施例3
操作同实施例1,只是以10.733g硝酸锆替代硝酸钡盐,煅烧还原后即得本发明所提供活性催化剂3Cu/La2O3-ZrO2。
实施例4
操作同实施例1,只是以6.41g六水合硝酸镁替代硝酸钡盐,煅烧还原后即得本发明所提供活性催化剂4Cu/La2O3-MgO。
实施例5
操作同实施例1,只是以4.35g硝酸钙(四水)替代硝酸钡盐,煅烧还原后即得本发明所提供活性催化剂5Cu/La2O3-CaO。
实施例6
操作同实施例1,只是以5.291g硝酸锶替代硝酸钡盐,煅烧还原后即得本发明所提供活性催化剂6Cu/La2O3-SrO。
实施例7
操作同实施例1,只是以3.33g硝酸铍替代硝酸钡盐,煅烧还原后即得本发明所提供活性催化剂6Cu/La2O3-BeO。
实施例8
操作同实施例1,只是以0.70g六水合硝酸铈和5.46g六水合硝酸镁替代硝酸钡盐,煅烧还原后即得本发明所提供活性催化剂8Cu/La2O3-MgO-CeO2。
实施例9
操作同实施例1,只是以0.94g六水合硝酸锆和5.46g六水合硝酸镁替代硝酸钡盐,煅烧还原后即得本发明所提供活性催化剂9Cu/La2O3-MgO-ZrO2。
实施例10
操作同实施例1,只是以1.502g SiO2替代硝酸钡盐,煅烧还原后即得本发明所提供活性催化剂9Cu/La2O3-SiO2。
表1不同载体负载金属Cu的催化剂对糠醇开环氢解的催化结果
由以上结果可知,强碱性复合载体La2O3-BaO、La2O3-MgO、La2O3-CaO、 La2O3-SrO、La2O3-BeO、La2O3-SiO2负载金属Cu的催化剂在糠醇开环氢解制备戊二醇中具有优异的催化性能,而La2O3-CeO2、La2O3-ZrO2、La2O3-MgO-CeO2、 La2O3-MgO-ZrO2等载体负载金属Cu的催化剂催化性能较差。
实施例11
操作同实施例4,只是配置金属盐溶液A时加入0.38g Cu(NO3)2·3H2O、 5.02g Mg(NO3)2·6H2O、2.94g La(NO3)3·6H2O,煅烧还原后即得本发明所提供活性催化剂11 5%Cu/La2O3-MgO,产物分布见表2。
实施例12
操作同实施例4,只是配置金属盐溶液A时加入1.51g Cu(NO3)2·3H2O、 4.24g Mg(NO3)2·6H2O、2.49g La(NO3)3·6H2O,煅烧还原后即得本发明所提供活性催化剂12 20%Cu/La2O3-MgO,产物分布见表2。
实施例13
操作同实施例4,只是配置金属盐溶液A时加入1.88g Cu(NO3)2·3H2O、 4.10g Mg(NO3)2·6H2O、2.30g La(NO3)3·6H2O,煅烧还原后即得本发明所提供活性催化剂13 25%Cu/La2O3-MgO,产物分布见表2。
实施例14
操作同实施例4,只是配置金属盐溶液A时加入2.27g Cu(NO3)2·3H2O、 3.85g Mg(NO3)2·6H2O、2.17g La(NO3)3·6H2O,煅烧还原后即得本发明所提供活性催化剂14 30%Cu/La2O3-MgO,产物分布见表2。
实施例15
操作同实施例4,只是配置金属盐溶液A时加入3.02g Cu(NO3)2·3H2O、 3.26g Mg(NO3)2·6H2O、1.82g La(NO3)3·6H2O,煅烧还原后即得本发明所提供活性催化剂15 40%Cu/La2O3-MgO,产物分布见表2。
表2不同负载量Cu基催化剂对糠醇开环氢解的催化结果
由以上结果可知,金属Cu的负载量直接影响产物戊二醇的整体收率,当 Cu的负载量过高,过度氢解的产物戊醇的选择性会增加,当Cu的负载量过低时,反应的转化率较低,影响反应发生的速率。
实施例16
反应在100ml高压反应釜中进行,加入3g糠醇和27g乙醇,0.3g活性催化剂4。将反应釜密封,通入H2置换反应釜中的空气;向反应釜中通入4-8MPa H2,反应温度在140-200℃,反应8-24h。反应结束后冷却,释放H2,开釜得到反应液,用气质联用仪和气相色谱进行定性和定量分析,产物分布见表3。
表3糠醇在不同反应条件下开环氢解的反应性能
从表3结果看出,反应温度、H2压力、反应时间对糠醇开环氢解都有很大的影响,温度升高、H2压力增大有利于糠醇的转化,但过高的温度、H2压力过高导致副产物的增加,其中戊二醇会过度氢解生成戊醇,导致戊二醇的选择性降低。因此,适当的温度和H2压力下才能控制糠醇开环氢解反应的进行。
以上所述的实施例仅用于说明本发明的技术思想及特点,其目的在于使本领域内的技术人员能够了解本发明的内容并据以实施,不能仅以本实施例来限定本发明的专利范围,即凡依本发明所揭示的精神所作的同等变化或修饰,仍落在本发明的专利范围内。
Claims (6)
1.一种复合强碱性氧化物负载Cu催化剂催化糠醇开环氢解制戊二醇的体系,其特征在于:所述的催化剂组成为Cu/La2O3-MO,其中载体为La2O3和MO的复合氧化物,M为Be、Mg、Ca、Sr、Ba、Ce、Zr等金属的任意一种或二种以上,其中MO与La2O3中金属M与La的摩尔比为1-10,金属Cu的负载量为2-30wt%。
2.根据权利要求1所述的应用,其特征在于:所述戊二醇为1,2-戊二醇和1,5-戊二醇中的任意一种或两种组合。
3.根据权利要求1所述的应用,其特征在于:所述的强碱性载体负载Cu催化剂采用共沉淀法制备。
4.根据权利要求3所述的应用,其特征在于:共沉淀制备方法所述的金属盐前驱体为硝酸盐、氯化盐、硫酸盐、磷酸盐、碳酸盐、醋酸盐中的一种或多种组合。
5.根据权利要求1所述的应用,其特征在于:将糠醇,催化剂,溶剂加入到高压反应釜中,将反应釜密封。通入N2置换反应釜中的空气,向反应釜中通入H2,将反应釜的温度升高至特定温度,反应一定时间得到反应溶液。反应结束后,待反应釜冷却后释放H2,通过简单过滤催化剂得到反应液。
6.根据权利要求5所述的应用,其特征在于:所述溶剂为水、乙醇、甲醇、异丙醇、四氢呋喃、丙酮中的一种或多种组合。所述糠醇原料的质量分数为2-50%。所述反应温度为100-200℃,氢气压力为2.0-8.0MPa,反应时间为2-28h。
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CN114380660B (zh) * | 2022-01-29 | 2023-08-11 | 中国科学院广州能源研究所 | 一种5-羟甲基糠醛开环氢解制备2-己醇的方法 |
CN118022792A (zh) * | 2024-04-09 | 2024-05-14 | 广东以色列理工学院 | 用于糠醇催化转化为1,2-戊二醇的催化剂、制备方法及应用 |
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