CN101874026B - Process for production of furan compound - Google Patents
Process for production of furan compound Download PDFInfo
- Publication number
- CN101874026B CN101874026B CN2008801176329A CN200880117632A CN101874026B CN 101874026 B CN101874026 B CN 101874026B CN 2008801176329 A CN2008801176329 A CN 2008801176329A CN 200880117632 A CN200880117632 A CN 200880117632A CN 101874026 B CN101874026 B CN 101874026B
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- China
- Prior art keywords
- furfural
- compound
- catalyzer
- reaction
- quality
- 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.)
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- -1 furan compound Chemical class 0.000 title claims abstract description 249
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 238000000034 method Methods 0.000 title abstract description 66
- 230000008569 process Effects 0.000 title abstract description 8
- 238000004519 manufacturing process Methods 0.000 title description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N Furaldehyde Natural products O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 490
- 229910052751 metal Inorganic materials 0.000 claims abstract description 80
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 220
- 150000002240 furans Chemical class 0.000 claims description 54
- 238000002360 preparation method Methods 0.000 claims description 25
- 229910052697 platinum Inorganic materials 0.000 claims description 24
- 239000005864 Sulphur Substances 0.000 claims description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 17
- WVHJBVPYIIBODU-UHFFFAOYSA-N 2-methyl-3h-furan-2-carbaldehyde Chemical compound O=CC1(C)CC=CO1 WVHJBVPYIIBODU-UHFFFAOYSA-N 0.000 claims description 2
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims description 2
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 85
- 230000000694 effects Effects 0.000 abstract description 50
- 239000002184 metal Substances 0.000 abstract description 40
- 229910052735 hafnium Inorganic materials 0.000 abstract description 9
- 230000006866 deterioration Effects 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 74
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 59
- 230000009466 transformation Effects 0.000 description 55
- 238000009835 boiling Methods 0.000 description 54
- 239000012535 impurity Substances 0.000 description 50
- 239000007789 gas Substances 0.000 description 47
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 45
- 150000001875 compounds Chemical class 0.000 description 42
- 239000001257 hydrogen Substances 0.000 description 42
- 229910052739 hydrogen Inorganic materials 0.000 description 42
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 40
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 36
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 36
- 229910052763 palladium Inorganic materials 0.000 description 35
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 26
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 24
- 229910052700 potassium Inorganic materials 0.000 description 24
- 239000002253 acid Substances 0.000 description 22
- 229910052757 nitrogen Inorganic materials 0.000 description 21
- 239000001273 butane Substances 0.000 description 20
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 20
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 20
- 239000001294 propane Substances 0.000 description 20
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 20
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 20
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 20
- 239000000203 mixture Substances 0.000 description 18
- 239000012071 phase Substances 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 16
- 150000002431 hydrogen Chemical group 0.000 description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 239000006227 byproduct Substances 0.000 description 15
- 238000004821 distillation Methods 0.000 description 15
- 239000007791 liquid phase Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 15
- 239000000654 additive Substances 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 150000002500 ions Chemical group 0.000 description 13
- 230000009467 reduction Effects 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000002829 reductive effect Effects 0.000 description 12
- 230000008929 regeneration Effects 0.000 description 11
- 238000011069 regeneration method Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000002594 sorbent Substances 0.000 description 10
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 241000196324 Embryophyta Species 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 8
- 230000006324 decarbonylation Effects 0.000 description 8
- 238000006606 decarbonylation reaction Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000969 carrier Substances 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000002309 gasification Methods 0.000 description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 5
- 150000002823 nitrates Chemical class 0.000 description 5
- 229910017464 nitrogen compound Inorganic materials 0.000 description 5
- 150000002830 nitrogen compounds Chemical class 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 150000003016 phosphoric acids Chemical class 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000010970 precious metal Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000012808 vapor phase Substances 0.000 description 4
- 108091064702 1 family Proteins 0.000 description 3
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 229960001866 silicon dioxide Drugs 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 2
- IHCCAYCGZOLTEU-UHFFFAOYSA-N 3-furoic acid Chemical compound OC(=O)C=1C=COC=1 IHCCAYCGZOLTEU-UHFFFAOYSA-N 0.000 description 2
- ASHGTJPOSUFTGB-UHFFFAOYSA-N 3-methoxyphenol Chemical compound COC1=CC=CC(O)=C1 ASHGTJPOSUFTGB-UHFFFAOYSA-N 0.000 description 2
- KJRRQXYWFQKJIP-UHFFFAOYSA-N 3-methylfuran Chemical compound CC=1C=COC=1 KJRRQXYWFQKJIP-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- FVIGODVHAVLZOO-UHFFFAOYSA-N Dixanthogen Chemical compound CCOC(=S)SSC(=S)OCC FVIGODVHAVLZOO-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 2
- 229910013553 LiNO Inorganic materials 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 229910006501 ZrSiO Inorganic materials 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- NDYQTSSLBWQIHF-UHFFFAOYSA-N 1-(furan-3-yl)-2-methylprop-2-en-1-one Chemical compound CC(=C)C(=O)C=1C=COC=1 NDYQTSSLBWQIHF-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- JKTCBAGSMQIFNL-UHFFFAOYSA-N 2,3-dihydrofuran Chemical compound C1CC=CO1 JKTCBAGSMQIFNL-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- LXZFMKLKTRIZDJ-UHFFFAOYSA-N 2-(furan-2-yl)prop-2-enoic acid Chemical compound OC(=O)C(=C)C1=CC=CO1 LXZFMKLKTRIZDJ-UHFFFAOYSA-N 0.000 description 1
- UYLKDZXJEKFFHJ-UHFFFAOYSA-N 2-(furan-2-ylmethylsulfanylmethyl)furan Chemical compound C=1C=COC=1CSCC1=CC=CO1 UYLKDZXJEKFFHJ-UHFFFAOYSA-N 0.000 description 1
- GBGPVUAOTCNZPT-UHFFFAOYSA-N 2-Methylcumarone Chemical compound C1=CC=C2OC(C)=CC2=C1 GBGPVUAOTCNZPT-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- KEFJLCGVTHRGAH-UHFFFAOYSA-N 2-acetyl-5-methylfuran Chemical compound CC(=O)C1=CC=C(C)O1 KEFJLCGVTHRGAH-UHFFFAOYSA-N 0.000 description 1
- IEMMBWWQXVXBEU-UHFFFAOYSA-N 2-acetylfuran Chemical compound CC(=O)C1=CC=CO1 IEMMBWWQXVXBEU-UHFFFAOYSA-N 0.000 description 1
- QQBUHYQVKJQAOB-UHFFFAOYSA-N 2-ethenylfuran Chemical class C=CC1=CC=CO1 QQBUHYQVKJQAOB-UHFFFAOYSA-N 0.000 description 1
- OFTKFKYVSBNYEC-UHFFFAOYSA-N 2-furoyl chloride Chemical compound ClC(=O)C1=CC=CO1 OFTKFKYVSBNYEC-UHFFFAOYSA-N 0.000 description 1
- QXSXKNKKQRKGJB-UHFFFAOYSA-N 2-methyl-5-prop-1-enylfuran Chemical class CC=CC1=CC=C(C)O1 QXSXKNKKQRKGJB-UHFFFAOYSA-N 0.000 description 1
- HRNSWROQIADGLJ-UHFFFAOYSA-N 4-(furan-3-yl)butan-2-one Chemical compound CC(=O)CCC=1C=COC=1 HRNSWROQIADGLJ-UHFFFAOYSA-N 0.000 description 1
- OUDFNZMQXZILJD-UHFFFAOYSA-N 5-methyl-2-furaldehyde Chemical compound CC1=CC=C(C=O)O1 OUDFNZMQXZILJD-UHFFFAOYSA-N 0.000 description 1
- ROWKJAVDOGWPAT-UHFFFAOYSA-N Acetoin Chemical compound CC(O)C(C)=O ROWKJAVDOGWPAT-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229910019589 Cr—Fe Inorganic materials 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- SRBFZHDQGSBBOR-LECHCGJUSA-N alpha-D-xylose Chemical compound O[C@@H]1CO[C@H](O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-LECHCGJUSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 125000004852 dihydrofuranyl group Chemical group O1C(CC=C1)* 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000002228 disulfide group Chemical group 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- STJIISDMSMJQQK-UHFFFAOYSA-N furan-3-ylmethanol Chemical compound OCC=1C=COC=1 STJIISDMSMJQQK-UHFFFAOYSA-N 0.000 description 1
- 125000002425 furfuryl group Chemical group C(C1=CC=CO1)* 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical group COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000001020 rhythmical effect Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 125000005190 thiohydroxy group Chemical group 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 238000009156 water cure Methods 0.000 description 1
- 229960003487 xylose Drugs 0.000 description 1
Classifications
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
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- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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- B01J23/56—Platinum group metals
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- 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
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
- C07D307/08—Preparation of tetrahydrofuran
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- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
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- 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
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- 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
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- C07—ORGANIC CHEMISTRY
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- 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
- C07D307/36—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 only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
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- C07D—HETEROCYCLIC COMPOUNDS
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- 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
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- Furan Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Disclosed is a process for producing a furan compound from a furfural compound, in which the deterioration in the activity of a catalyst over time can be prevented and the furfural compound can be converted steadily and, therefore, the furan compound can be produced with a high degree of efficiency. The process for producing a furan compound comprises the step of decarbonylating a furfural compound (a starting material) in the presence of a catalyst containing at least one element selected from Zr and Hf and at least one metal element selected from the metal elements belonging to Groups 8, 9 and 10.
Description
Technical field
The present invention relates to method by furfural compound furan compound.
Background technology
Furans is the useful as intermediates chemical, can be as the raw material of preparation THF, pyrroles, thiophene etc., and its de-carbonyl reaction by furfural prepares.Furfural is not to derive from the raw material of oil but utilize the piperylene as hemicellulose components contained in the plant to prepare usually; Therefore; Derive and the furans that obtains also is classified as the chemical in plant material source by it, rather than the chemical in petroleum source.
The method that is prepared furans by furfural is known traditionally (patent documentation 1 etc.); As the method that obtains chemical effectively from the raw material of plant origin; Particularly carry out (patent documentation 2, non-patent literature 1) to the research and development that utilize the de-carbonyl reaction that uses catalyzer to prepare the method for furans.As preparing the method for furans through decarbonylation base (decarbonylation) reaction from furfural, divide from big aspect, known have two kinds of methods.A kind of method (patent documentation 3 etc.) that is to use the such oxide catalyst of Zn-Cr-Mn, Zn-Cr-Fe composite oxides, another kind is to use the method for the catalyzer that supports precious metal.Even, therefore proposed the method for utilizing a kind of method in back, preparing furans through liquid phase reaction (patent documentation 4,6, non-patent literature 2) because catalyzer also can show activity under lower temperature of reaction in a kind of method in back.In addition, identical with preceding a kind of method, in a kind of method in back, also proposed to utilize gas phase circulation reaction (patent documentation 2, non-patent literature 1, patent documentation 5) to prepare the method for furans.
Particularly; Liquid phase reaction adopts following method to carry out: in the liquid of furfural compound or to the furfural compound dissolution in solvent etc. and add catalyzer in the solution that obtains; Carry out de-carbonyl reaction, and reclaim the furan compound that produces and gasify because of de-carbonyl reaction.
On the other hand, gas phase circulation reaction adopts following method to carry out: the gas shape raw material through the furfural compound that will gasify in advance feeds in the catalyzer and carries out de-carbonyl reaction, and reclaims the furan compound that obtains because of de-carbonyl reaction.If the furfural compound heats under high density or liquid state for a long time; Then can generate the polymkeric substance of paste-like etc., thereby, can think and compare with liquid phase reaction; Use the furfural compound that gasifies to carry out the reaction efficiency height of the gas phase circulation reaction of instantaneous reaction, be suitable for industrial preparation.
Patent documentation 1: USP the 2nd, 337, No. 027 communique
Patent documentation 2: USP the 4th, 780, No. 552 communiques
Patent documentation 3: USP the 2nd, 374, No. 149 communiques
Patent documentation 4: USP the 3rd, 257, No. 417 communiques
Patent documentation 5: USP the 3rd, 223, No. 714 communiques
Patent documentation 6: Japan special table 2003-528868 communique
Non-patent literature 1:Tianranqi Huagong 2002,27,9
Non-patent literature 2:Biomass, 16 (1988), 89
Summary of the invention
The problem that invention will solve
On the other hand, there is following problems in the method for preparing furan compound with a step at the de-carbonyl reaction that utilizes the furfural compound in the presence of the catalyzer: when reacting continuously, activity of such catalysts significantly reduces in time.But the reason that activity of such catalysts significantly reduces in time is not very clear.
For example; Aspect liquid phase reaction; That long-time heating generates because of high density furfural compound is carried out in some cases, with the irrelevant paste-like polymkeric substance of catalyst reaction etc. can physical property ground attached on the catalyzer; Thereby hinder the dispersion of catalyzer, or hinder de-carbonyl reaction as target.
In addition; When gas phase circulation reaction; Only the furfural compound of gasification contacts with catalyzer, thereby the furan compound of furfural compound, generation forms tamper (コ one Network) sometimes and accumulate on catalyzer, thus the capping site; But be not easy to get into the catalyst layer this point from the polymkeric substance of furfural compound, it is superior to liquid phase reaction.
If catalyst activity reduces in time, then furfural conversion of compounds rate reduces, and the amount of the furan compound of unit time preparation reduces, thereby the efficient of industrial technology reduces.In addition, the Separation and Recovery, discarded or problem such as recycle that also has unreacted furfural compound.
Under the situation that catalyst activity significantly reduces in time, stably prepare furan compound in order to keep furfural conversion of compounds rate, must remedy through the amount or the temporary transient temperature of reaction that improves of temporary transient increase catalyzer.And if the increase frequency of the replacing of catalyzer or manipulation of regeneration, then the operation of industrial technology will become the difficulty.For this reason, in order to stablize and to prepare furan compound efficiently, need the active catalyzer that reduces still less.
In the past, many active catalyzer that is inhibited or technology that relate to the catalyst regeneration of inactivation of reducing that relate to had been proposed.
For example, for liquid phase reaction, utilize in the past Pd, the such metal of Pt are supported on the carbon and the catalyzer that obtains reacts; In addition, for gas phase circulation reaction, utilize Pd, the such metal of Pt are supported on the alumina supporter and the catalyzer that obtains reacts.But so far, catalyst life is still insufficient, might not satisfy the requirement of the economy aspect in the industrial implementation.
In addition, when catalyst activity reduces, need wait through calcination process in some cases and regenerate.For the carriers such as the activated carbon that proposes under liquid phase, carrying out the de-carbonyl reaction of furfural compound, silicon-dioxide; When utilizing calcination process to regenerate; The burning of carrier can take place under the manipulation of regeneration condition; Or cause the clinkering (シ Application タ リ Application グ) of carrying metal, the micropore obturation of carrier, be difficult to obtain original activity.
Therefore; The object of the present invention is to provide a kind of furan compound preparation method, said furan compound preparation method can suppress catalyst activity and reduce in time from furfural compound furan compound the time; Stably transform the furfural compound, thereby prepare furan compound efficiently.
The method of dealing with problems
The inventor etc. further investigate the catalyzer that is used for de-carbonyl reaction through the furfural compound and prepares furan compound; The result finds: if contain at least a kind of element that is selected among Zr, the Hf and be selected from least a kind of metallic element in 8,9,10 families catalyzer in the presence of; React the de-carbonyl reaction that carries out the furfural compound through the gas phase circulation, then can in long-time, efficiently and stably obtain furan compound; Thereby the present invention below having accomplished.
The present invention relates to the preparation method of furan compound; This preparation method is included under the existence of the catalyzer that comprises the a kind of element that is selected among Zr, the Hf and be selected from a kind of metallic element in 8,9,10 families at least at least, makes the furfural compound carry out the step of de-carbonyl reaction through gas phase circulation reaction.Wherein, the furfural compound is meant: with the raw material integral body that comprises the furfural compound is benchmark (100 quality %), contains the furfural compound that preferred 95 quality % are above, more preferably 98 quality % are above, preferred especially 99 quality % are above.Through using such catalyzer to carry out the de-carbonyl reaction of furfural compound; Catalyst activity reduces few in time; Therefore can keep high furfural compound ratio transformation and high furan compound selection rate for a long time, can stablize and prepare furan compound efficiently.In addition; Amount attached to the tamper on the catalyzer reduces; Thereby catalyzer can long-time continuous use; This not only can reduce the frequency of catalyst regeneration or replacing, and when utilizing roasting to carry out catalyst regeneration, can also prevent because of activeconstituents clinkering or the inaccessible catalyst degradation that causes of micropore.
In the present invention, at least a kind of metallic element that is selected from 8,9,10 families is preferably Pd or Pt, is preferably Pd especially.Contain the catalyzer of the metallic element of such optimal way through use, can more effectively carry out de-carbonyl reaction.
In addition; The inventor etc. cause in the de-carbonyl reaction of furan compound that to the furfural compound is converted into the factor that catalyst activity reduces in time furthers investigate; The result finds: the impurity that is comprised in the furfural compound of plant origin causes that catalyst activity reduces in time, thereby has accomplished the present invention.
Below shown in the present invention relates to: carry out de-carbonyl reaction through supplying with the furfural compound that contained impurity level is controlled in below the specified amount, thus the method that leaping property ground prolongs catalyst life.
Remove impurity contained in the furfural compound etc. through separating in advance; With Control of Impurities below specified amount; Then such furfural compound is offered the de-carbonyl reaction step, the activity of such catalysts that can suppress to use in the de-carbonyl reaction step reduces, and does not rely on the kind of catalyzer.So, can keep activity of such catalysts for a long time, efficiently and stably prepare furan compound.
The 2nd invention is that the preparation method of furan compound, this preparation method are characterised in that, is that furfural compound below the 6.0ppm offers the de-carbonyl reaction step with sulphur concentration.Through removing or reducing sulphur or sulfocompound as impurity, provide sulphur concentration to be controlled in the furfural compound below the prescribed value, can keep catalyst activity for a long time, efficiently and stably prepare furan compound.
The step of in the present invention, preferably carrying out de-carbonyl reaction comprises following step: the gas shape raw material of the furfural compound of gasification is contacted with said catalyzer carry out the step of de-carbonyl reaction.Furfural raw materials of compound through making gasification contacts with catalyzer, can more effectively carry out de-carbonyl reaction.
The effect of invention
In the present invention; Through using special catalyst to carry out the de-carbonyl reaction of furfural raw materials of compound; It is few that catalyst activity reduces in time, can keep high furfural compound ratio transformation and high furan compound selection rate for a long time, stable and prepare furan compound efficiently.In addition, reduce, thereby catalyzer can long-time continuous use, can reduce the frequency of catalyst regeneration or replacing attached to the amount of the tamper on the catalyzer.
Through the furfural compound is carried out purifying, thereby the furfural compound that impurity is controlled in below the specified amount offers the de-carbonyl reaction step, and the activity of such catalysts that can suppress to use in the de-carbonyl reaction reduces, and the kind of this inhibition and catalyzer has nothing to do.Thereby can keep activity of such catalysts for a long time, efficiently and stably prepare furan compound.
Embodiment
Below, the present invention is elaborated.
The present invention is the preparation method of furan compound, and this preparation method is included under the existence of special catalyst and makes the furfural compound carry out the step of de-carbonyl reaction.Below, at first furfural compound and furan compound are described.
< furfural compound >
Raw material furfural compound as using among the furan compound preparation method of the present invention does not have particular restriction, can use known furfural compound.The furfural compound is meant the represented compound of formula (1).
[Chemical formula 1]
In the above-mentioned general formula (1), R
1, R
2, R
3Can be mutually the same also can be different, for example can enumerate out: various functional groups such as hydrogen, optional aliphatic alkyl with functional group, optional aromatic hydrocarbyl with functional group, hydroxyl, aldehyde radical, can enumerate out particularly-H ,-CH
2OH ,-CH
3,-CHO etc.As the object lesson of furfural compound, can enumerate hydroxymethyl furfural, 2-methyl furfural, 3-methyl furfural, furans dicarbaldehyde, furfural as preferred example, this wherein preferred especially furfural.
< furan compound >
The furan compound that utilizes furan compound preparation method of the present invention to obtain does not have particular restriction, and it is known furan compound.Furan compound is meant formula (2)～(6) represented compound.
[Chemical formula 2]
[chemical formula 3]
[chemical formula 4]
[chemical formula 5]
[chemical formula 6]
R
4, R
5, R
6Can be mutually the same also can be different, for example can enumerate out: various functional groups such as hydrogen, optional aliphatic alkyl with functional group, optional aromatic hydrocarbyl with functional group, hydroxyl, can enumerate out particularly-H ,-CH
2OH ,-CH
3,-CHO etc.As the object lesson of furan compound, can enumerate out 2-methyl furan, 3-methyl furan, furans, dihydrofuran-, furfuryl alcohol, THF, tetrahydrofurfuryl alcohol, preferred especially furans.
< furfural raw materials of compound >
In the present invention, in the presence of special catalyst, make furfural compound generation de-carbonyl reaction.Wherein, The furfural compound is meant: whole with the raw material (the following raw material that also abbreviates as) that comprises the furfural compound as benchmark (100 quality %), comprise the furfural compound that preferred 95 quality % are above, more preferably 98 quality % are above, preferred especially 99 quality % are above.
Preparing method for raw material does not have particular restriction, can be through the plant origin raw material being carried out hot-water cure or acid hydrolysis obtains.
In the present invention, comprise at least a kind of element that is selected among Zr, the Hf and be selected from least a kind of metallic element in 8,9,10 families catalyzer in the presence of, the de-carbonyl reaction that carries out the furfural raw materials of compound obtains furan compound.Through using such catalyzer; From furfural compound furan compound the time; Can suppress catalyst activity and reduce in time, keep high furfural compound ratio transformation and high furan compound selection rate for a long time, thus stable and prepare furan compound efficiently.
The purity of furfural compound in the definition of above-mentioned furfural raw materials of compound record; Through removing impurity contained in the furfural compound; Activity of such catalysts of the present invention reduces in time can access further inhibition, thereby can more stablize and prepare efficiently furan compound.In the contained impurity of furfural raw materials of compound,, then can obtain high effect if reduce sulphur or sulphur compound, nitrogen compound and various acid.
Particularly; For gas phase circulation reaction; When use comprises at least a kind of element that is selected among Zr, the Hf and is selected from the catalyzer of at least a kind of metallic element in 8,9,10 families, can reduce furfural compound, furan compound and on catalyzer, form tamper, these impurity possibly directly accumulated on catalyzer or the capping site; Therefore through reducing these impurity, can stablize and prepare efficiently furan compound for more time.
Form for sulphur contained in the furfural compound or sulphur compound does not have particular restriction, aspect valency, can enumerate out S
0, S
2-Perhaps S
6+(SO
x) the sulphur composition.More specifically, can enumerate out: amino acid such as halfcystine comprise this amino acid whose protein; Compound with sulfydryl, thiohydroxy, thioether group, disulfide group has the aromatic cycle compound of S, sulfuric acid, sulfonic acid and their salt in the skeleton; Sulfurous acid and sulphite, perhaps complex salts.The contained sulphur or the amount of sulphur compound in the furfural compound with the densitometer of sulphur, are generally below the 6.0ppm, are preferably below the 5.0ppm, more preferably below the 3.0ppm, be preferably below the 2.0ppm especially.Offer the de-carbonyl reaction step through these sulfur-bearing compositions are controlled in the furfural compound of counting below the 6.0ppm with sulphur concentration, catalyst activity reduces significantly in time and reduces.If leading to continuous reaction with 10 hours vapor phase stream is example, furfural conversion of compounds rate remains on more than 9 one-tenth of initial stage, therefore can prepare furan compound efficiently.Do not have particular restriction for sulphur contained in the furfural compound or sulphur compound quantitative analysis method,, can adopt burning-absorption-ion chromatography to analyze as an example.
Form for nitrogen compound contained in the furfural compound does not have particular restriction, aspect valency, can enumerate out N
3-Perhaps N
5+, N
3+Nitrogen component.More specifically, said nitrogen compound is ammonia, amine and its esters, and each seed amino acid, protein have the aromatic cycle compound of N, nitric acid and nitrate salt, nitrous acid and nitrite, perhaps complex salts in the skeleton.The amount of contained nitrogen compound in the furfural compound with the densitometer of nitrogen-atoms, is generally below the 4.0ppm, is preferably below the 3.0ppm, more preferably below the 2.0ppm.Offer the de-carbonyl reaction step through these nitrogen containing components being controlled at the furfural compound of counting below the 4.0ppm with the concentration of nitrogen, catalyst activity reduces significantly in time and reduces.If leading to continuous reaction with 10 hours vapor phase stream is example, furfural conversion of compounds rate remains on more than 9 one-tenth of initial stage, therefore can prepare furan compound efficiently.Nitrogen compound quantitative analysis method for contained in the furfural compound does not have particular restriction, as an example, can adopt the analysis of combustion decomposition-chemoluminescence method.
Form for sour composition contained in the furfural compound does not have particular restriction, can enumerate out mineral acids such as sulfuric acid, sulfonic acid, nitric acid, and the organic acid (for example furans sulfonic acid, furancarboxylic acid) with sulfo group, carboxyl.The amount of contained sour composition is represented with acid number in the furfural compound, is generally below the 0.12mgKOH/g, is preferably below the 0.1mgKOH/g, is preferably below the 0.08mgKOH/g especially.Furfural compound through these sour compositions are controlled in below the 0.12mgKOH/g offers the de-carbonyl reaction step, and catalyst activity reduces significantly in time and reduces.If leading to continuous reaction with 10 hours vapor phase stream is example, furfural conversion of compounds rate remains on more than 9 one-tenth of initial stage, therefore can prepare furan compound efficiently.Measuring method for acid number does not have particular restriction, can adopt neutralization titration.As concrete example, can through with the furfural compound with alcohol dilution after, use the potassium hydroxide aqueous solution of 0.01N to carry out titration, measure acid number thus.
The furfural compound that does not contain these impurity is normally water white.Therefore; The tone of furfural compound; If (Yellowness Index: yellowness index) value is that the number of benchmark calculates, and then is generally below 500, is preferably below 300, more preferably below 100, be preferably below 50 especially to adopt YI with APHI (American Public Healty Association) standard color solution.These tones can wait through the transmission measurement of using colour-difference meter and analyze and calculate.
Can think and contain the reasons are as follows of these impurity in the furfural compound.Usually; Compare with the organic cpds in oil source; The organic cpds of plant origin does not generally contain S composition, N composition; But, can comprise in the plant as the raw material of furfural compound much by the material that the sulfo-of plant is thanked, nitrogen metabolism etc. produces, might sneak into wherein via the preparatory phase of furfural compound so derive from these impurity.In addition, coarse raw materials normally with mineral acids such as sulfuric acid as catalyzer, the dehydration through glucose, fructose or wood sugar or the decomposition of piperylene obtain, and have sulfate radical or sulfonic compound so might sneak in this process.
On the other hand, the furfural compound has carbonyl, therefore, if contact with oxygen, then oxidation and generate carboxylic acid inevitably.Quantitative acid is the acid in the catalyst component source in the preparation process of coarse raw materials, sneaked into and the carboxylic acid that generates because of the oxidation of carbonyl through the acid number evaluation.
Through using these impurity to be controlled in the furfural compound below the specified amount, can in de-carbonyl reaction, keep activity of such catalysts for a long time.On the contrary, if in the raw material that the de-carbonyl reaction step is supplied with, comprise these above impurity of specified amount, the activity of such catalysts of then using in the de-carbonyl reaction significantly reduces in time.Its reason is still indeterminate, but as a kind of reason, can think that these impurity are poisoned active site.In addition, contained acid is considered to promote the polymerization of furfural compound in the raw material, therefore, can infer that the existence of acid has promoted the generation of tamper on the catalyzer, has quickened the coating of active site.
Method for from the furfural compound, removing impurity does not have particular restriction, can remove to wait through the absorption of distillation purifying or impurity and remove.Example goes out the condition when through underpressure distillation the about 400g of furfural raw material being carried out purifying.The ヴ イ グ リ ユ ウ pipe that uses internal diameter 18mm, height 245mm is seated in the furfural raw material in the 1L flask as rectifying tower, to carrying out the nitrogen displacement in the system, through oil bath the furfural raw material in the flask is heated, then to carrying out underpressure distillation in the system then.The temperature that makes the furfural raw material is that 75 ℃, vapour temperature are that 55 ℃, system internal pressure are 1.2 * 10
3Pa removes about 13 quality % of total amount with the form of starting fraction, removes about 25 quality % of total amount with the form of residue at the bottom of the still, can access the furfural behind the purifying of about 250g.
As the low boiling point component beyond the furfural compound of from the furfural compound, removing, can enumerate out usually easily from hanging down the compound more than 5 ℃ as boiling point fractionation by distillation the furfural compound of principal constituent, that boiling point likens to the furfural compound of principal constituent.If with the furfural of 162 ℃ of boiling points example as the furfural compound; Then can enumerate out: nitric acid, isobutyric aldehyde, 1; 3-pentadienal, 2-(1-propenyl)-5-methyl-furans, boiling point are that 54-55 ℃ 2,3 dihydro furan, the furfuryl group methyl disulfide that boiling point is 60-61 ℃, the 2-methyl furan that boiling point is 63-66 ℃, 2-cyclopentenes-1-ketone that boiling point is 64-65 ℃, the 2-furyl methyl ketone that boiling point is 67 ℃, the butyraldehyde that boiling point is 75 ℃, the 1-furfuryl group pyrroles that boiling point is 76-78 ℃, the 3-furyl alcohol that boiling point is 79-80 ℃, 3-hydroxyl-2-butanone that boiling point is 90-91 ℃, the thiocyanic acid chaff ester that boiling point is 90-92 ℃, the 2-vinyl furans that boiling point is 97-100 ℃, the furtural dimethyl-hydrazone that boiling point is 98 ℃, 2-ethanoyl-5-methyl furan that boiling point is 100-101 ℃, the formic acid that boiling point is 101 ℃, the 3-methoxyphenol that boiling point is 113-115 ℃, the acetic acid that boiling point is 117-118 ℃, the difurfuryl dithioether that boiling point is 112-115 ℃, 3-amylene-2-ketone that boiling point is 121-124 ℃, the 3-furancarboxylic acid that boiling point is 120-122 ℃, the difurfuryl sulfide that boiling point is 135-143 ℃, the furylamine that boiling point is 145-146 ℃, the 2-cyanic acid furans that boiling point is 146-148 ℃, the 2-furyl thiomethyl alcohol that boiling point is 155 ℃, the boiling points such as isocyanic acid chaff ester that boiling point is 157-158 ℃ are the compound below 158 ℃.Total mass with contained low boiling point component is benchmark (100 quality %), and the ratio of the low boiling point component of removal is generally more than the 30 quality %, is preferably more than the 50 quality %, more preferably more than the 75 quality %, further is preferably more than the 90 quality %.
If the quality with the furfural compound is benchmark (100 quality %), then be generally 0.01 quality % above and below the 50 quality %, to be preferably 0.05 quality % above and below the 40 quality %, more preferably 0.1 quality % is above and below the 30 quality %.
As the high boiling point composition beyond the furfural compound of from the furfural compound, removing, can enumerate out usually: easily from as fractionation by distillation the furfural compound of principal constituent, boiling point likens the high compound more than 5 ℃ of boiling point into the furfural compound of principal constituent to.If with the furfural of 162 ℃ of boiling points example as the furfural compound; Then can enumerate out: boiling point is that 173-174 ℃ 2 furoyl chloride, 3-(2-furyl) propyl alcohol that boiling point is 181-182 ℃, the phenol that boiling point is 182 ℃, the 5 methyl furfural that boiling point is 187 ℃, the 2-methyl cumarone that boiling point is 197-198 ℃, 4-(2-furyl)-1-butylene-4-alcohol, the boiling point that boiling point is 204-205 ℃ are 230-232 ℃ pyromucic acid, the 4-methoxyphenol that boiling point is 243 ℃, 1-(2-furyl) vinylformic acid, anti-form-1-(2-furyl) propenal, 4-(2-furyl)-3-butene-2-ketone, two (2-furyl) methane, the 3-ethyl-2 that boiling point is 286 ℃, and the boiling points such as polymkeric substance of 5-dimethyl furan, 2-methoxyl group-4-ethylphenol, methoxy-ethylene base phenol, 1-(3-furyl)-3-butanone, 1-(3-furyl)-2-methyl-propenal, ethylphenol, two (2-furyl) Ketene dimethyl, sulfuric acid, uronic acid, halfcystine, furfural are the compound more than 167 ℃.Total quality with contained high boiling point composition is benchmark (100 quality %), the high boiling point components in proportions of removal be generally 30 quality % above, be preferably 50 quality % above, more preferably 75 quality % above, further be preferably more than the 90 quality %.If the quality with the furfural compound is benchmark (100 quality %), then be generally 0.1 quality % above and below the 50 quality %, to be preferably 0.5 quality % above and below the 30 quality %.
Furfural compound through these low boiling point components, high boiling point composition are fully removed from raw material offers the de-carbonyl reaction step; Can suppress catalyst activity reduces in time; Stably the furfural compound is converted into furan compound, thereby prepares furan compound efficiently.On the contrary, if the removal of these low boiling point components, high boiling point composition is insufficient, then in de-carbonyl reaction, activity of such catalysts reduces in time, can't stably the furfural compound be converted into furan compound.
Can also remove impurity through adsorbing to separate.Sorbent material for this moment does not have particular restriction; Can preferably use activated carbon or porous materials such as ion exchange resin, ion exchanged zeolite or silicon-dioxide; Perhaps metal, precious metal maybe are supported on this metal, precious metal on the such carrier of silicon-dioxide, aluminum oxide, zeolite or activated carbon and the sorbent material that obtains.Sorbent material can also use multiple simultaneously.Method as absorption is removed can add sorbent material in raw material, through after certain treatment time, adopt to filter to wait and separate; Also can be in advance sorbent material be packed in pillar etc., make raw material then from wherein passing through.In addition, can also enumerate out as preferable methods: when distillation purifying, filling raw material and sorbent material, on one side absorption remove impurity, obtain purified furfural compound through distillation on one side.As the sorbent material of this moment, except the above-mentioned material of enumerating, can also preferred use removing alkali metal hydroxide, Na such as the effective NaOH of disacidify composition
2CO
3Deng alkaline carbonate etc.And, preferably after using sorbent material to remove impurity, further carry out distillation purifying, remove not the impurity removed through absorption or the impurity in sorbent material source.In addition, can also behind distillation purifying, adsorb and remove.
Following example is sent as an envoy to aluminum oxide loading Pd (2 quality %Pd/Al
2O
3, all the ratio of Pd is 2 quality % in the catalyzer) condition when coming purifying furfural compound as sorbent material.With the H of this aluminum oxide loading Pd (21g) at 200 ℃, 100ml/ minute
2Air-flow kept 1.5 hours down, carried out heat drying and reduction.Then, the temperature that makes the aluminum oxide loading Pd is 130 ℃, the N at 100ml/ minute
2Speed with about 1.5ml/ minute under the air-flow drips coarse raw materials.Spend about 5 hours and drip the coarse raw materials of about 400ml, thereby can obtain the purified furfural compound of about 380ml.
Condition for preserving when having reduced the furfural compound of impurity through purifying etc. does not have particular restriction, preferably in the atmosphere of blocking-up oxygen, light, preserves.Preserving oxygen concn in the atmosphere is generally below 20%, is preferably below 10%, more preferably below 5%, be preferably below 1% especially.
< de-carbonyl reaction catalyzer >
In the present invention, comprise at least a kind of element that is selected among Zr, the Hf and be selected from least a kind of metallic element in 8,9,10 families catalyzer in the presence of, carry out the de-carbonyl reaction of furfural compound, obtain furan compound.
Be selected from least a kind of element among Zr, the Hf and preferably be added on to support in the carrier that is selected from least a kind of metallic element in 8,9,10 families or load on and support on the carrier that is selected from least a kind of metallic element in 8,9,10 families, perhaps constitute part or all of this carrier components.As supporting the carrier that is selected from least a kind of metallic element in 8,9,10 families, the preferred use comprises the material that is selected from least a kind of element among Zr, the Hf.
Form for being selected from least a kind of element among Zr, the Hf does not have particular restriction, can enumerate out the form of phosphoric acid salt, vitriol, oxyhydroxide, oxyhydroxide (moisture acidulants), oxide compound, composite oxides.As phosphoric acid salt, vitriol, can enumerate out Zr
3(PO
4)
4, ZrP
2O
7, Zr (SO
4)
24H
2O etc.As oxyhydroxide, oxyhydroxide, oxide compound, can enumerate out ZrO (OH)
2, ZrO
2, HfO
2In addition, can enumerate out ZrSiO
4, ZrO
2-SiO
2, ZrO
2-TiO
2, ZrO
2-Al
2O
3Deng composite oxides.This wherein preferably lists: ZrSiO
4Deng multielement oxide (multiple acidulants), ZrO
2-SiO
2, ZrO
2-TiO
2, ZrO
2-Al
2O
3Deng composite oxides and ZrO
2, HfO
2Etc. single oxide, more preferably list ZrO
2, HfO
2Etc. single oxide, especially preferably list ZrO
2For ZrO
2Crystal formation do not have particular restriction, be generally oblique system, metastable isometric system, isometric system or amorphous, be preferably oblique system, metastable isometric system or isometric system, more preferably oblique system or metastable isometric system are preferably oblique system especially.
With regard to the surface acid alkalescence that contains the carrier that is selected from least a kind of element among Zr, the Hf, if with Hammett function H
0Represent, then usually its highest strength of acid for more than-3, be preferably more than 1.5, more preferably more than 3.3, further be preferably more than 4.0, be preferably more than 6.8 point of maximum intensity H especially
0, max be generally more than 0 and 15 below, be preferably more than 5 and below 10.
Compare with in liquid phase reaction, using, the catalyzer that comprises at least a kind of element that is selected among Zr, the Hf and be selected from least a kind of metallic element in 8,9,10 families can be brought into play effect in gas phase circulation reaction.Contain the catalyzer that is selected from least a kind of element among Zr, the Hf and have surface acid alkalescence (though weak); Therefore; With carbonyl reaction, Tishchenko reacts, the Cannizaro reaction and cause in the liquid phase reaction that has high density furfural compound, produces by products such as ester dipolymer.In addition; In some cases, that long-time heating generates because of high density furfural compound is carried out, with the irrelevant paste-like polymkeric substance of catalyst reaction etc. can physical property ground attached on the catalyzer, thereby hinder the dispersion of catalyzer; Or obstruction is as the de-carbonyl reaction of target; And, compare with the catalyzer that constitutes by non-polar carriers such as carbon, its degree contain the catalyzer that is selected from least a kind of element among Zr, the Hf such, by having in the catalyzer that the polar carrier constitutes more very.
Therefore, contain the surperficial soda acid characteristic of the catalyzer that is selected from least a kind of element among Zr, the Hf, particularly in gas phase circulation reaction long-time and stable be preferred when preparing furan compound effectively.
As supporting the carrier that is selected from least a kind of metallic element in 8,9,10 families; Except above-mentioned comprising is selected from the phosphoric acid salt, vitriol, oxyhydroxide, oxyhydroxide, oxide compound, composite oxides of at least a kind of element among Zr, the Hf, can also enumerate out: SiO
2, TiO
2, Al
2O
3, MgO, SiO
2-Al
2O
3, MgO-Al
2O
3Etc. single oxide compound or composite oxides, porous oxides such as zeolite have the oxide compound or the gac of mesopore.When these carriers do not contain at least a kind of element that is selected among Zr, the Hf; Can with these carriers with after the compound physical that comprises Zr, Hf element is mixed; Perhaps, use as supporting the carrier that is selected from least a kind of metallic element in 8,9,10 families with after being selected from least a kind of element among Zr, the Hf and adding in these carriers or be supported on these carriers.
Surface-area to carrier does not have particular restriction, is generally 1m
2Above and the 1000m of/g
2Below/the g, be preferably 10m
2Above and the 500m of/g
2Below/the g, 20m more preferably
2Above and the 200m of/g
2Below/the g.Micropore volume to carrier does not have particular restriction, be generally 0.1ml/g above and below the 5ml/g, to be preferably 0.2ml/g above and below the 3ml/g.If the surface-area of carrier or micropore volume are little, then the furfural compound can not must be carried out the recovery of unreacted furfural compound etc. by abundant conversion, because of rather than effectively.If the surface-area of carrier or micropore volume are excessive, then be selected from least a kind of element among Zr, the Hf and suppress the effect that catalyst activity reduces in time and diminish, thereby and it is not preferred.
As adding in the carrier or be supported on the method on the carrier with being selected from least a kind of element among Zr, the Hf; The following method of preferred employing: when supporting at least a kind of metallic element that is selected from 8,9,10 families, add the liquid that is dissolved with the compound that is selected from least a kind of element among Zr, the Hf simultaneously.In addition, also can be supported on the carrier at least a kind of metallic element in will being selected from 8,9,10 families after, add the liquid be dissolved with the compound that is selected from least a kind of element among Zr, the Hf again.In addition; At least a kind of metallic element in being selected from 8,9,10 families or supported to add or support in the material of these metallic elements and comprise the material that is selected from least a kind of element among Zr, the Hf; Perhaps mix, so also can access the target catalyzer through methods such as physical mixed.
The compound that uses during as at least a kind of element being selected from interpolation among Zr, the Hf can be enumerated out metal alkoxide, subnitrate or subsulphate, preferred subnitrate.After interpolation is selected from least a kind of element among Zr, the Hf, can then carry out following operation: the removing of moisture or liquid component, the dry or roasting in oxygen-containing gas.
Preferably comprising these reasons that are selected from the catalyzer of at least a kind of element among Zr, the Hf is: these compositions are inactive to furfural compound or furan compound, and the catalytic furfural compound of at least a kind of metallic element that therefore is difficult in being selected from 8,9,10 families causes side reaction in the conversion of furan compound.The furan compound selectivity that comprises these catalyzer that are selected from least a kind of element among Zr, the Hf is generally more than 90%, can obtain the yield of furan compound to greatest extent.
In addition, comprise soda acid character or soda acid two meta functions that these surfaces that are selected from the material of at least a kind of element among Zr, the Hf have appropriateness, therefore, can avoid the excessive absorption or the reaction of furfural compound and furan compound.In addition, from identical reason, can also avoid undesirable reactions such as these compound polymerizations, therefore can prevent the situation that has tamper to accumulate at catalyst surface because of polymerization etc.The result is that for the de-carbonyl reaction of furfural compound, effectively catalyst activity is put long-time continuous action.If leading to continuous reaction with 10 hours vapor phase stream is example, furfural conversion of compounds rate remains on more than 9 one-tenths of initial stage, so can be efficiently and stably prepare furan compound.
With the catalyzer total mass is benchmark (100 quality %); The amount that is selected from least a kind of element among Zr, the Hf in the catalyzer is generally more than the 0.001 quality % and below the 90 quality %; Be preferably more than the 1 quality % and below the 85 quality %; More preferably more than the 5 quality % and below the 85 quality %, be preferably especially more than the 10 quality % and below the 75 quality %.
If it is very few to be selected from the amount of at least a kind of element among Zr, the Hf, then suppress the effect that catalyst activity reduces in time and diminish, therefore not preferred.In addition, if it is too much to be selected from the amount of at least a kind of element among Zr, the Hf, then the furfural compound can not must be carried out the recovery of unreacted furfural compound etc. by abundant conversion, because of rather than effectively.
At least a kind of metallic element for being selected from 8,9,10 families does not have particular restriction, preferably enumerates out: Ni, Ru, Ir, Pd, Pt, more preferably Ru, Ir, Pd, Pt, further preferred Pd, Pt, preferred especially Pd.At least a kind of metallic element through these being selected from 8,9,10 families is used as catalyst component, can highly selective the furfural compound be converted into furan compound, thereby prepare furan compound effectively.These metallic elements are supported on such as on the above-mentioned carrier usually, thereby use with the form of carrying metal catalyzer.
The content that is selected from least a kind of metallic element in 8,9,10 families is relevant with the kind of metal, carrier; Cannot treat different things as the same; But with the catalyzer total mass is benchmark (100 quality %), its content be generally 0.01 quality % above and below the 100 quality %, be preferably 0.05 quality % above and below the 50 quality %, more preferably 0.1 quality % above and below the 20 quality %, to be preferably 0.5 quality % especially above and below the 5 quality %.If it is few to be selected from the content of at least a kind of metallic element in 8,9,10 families; Then the furfural compound can not must be carried out the recovery of unreacted furfural compound etc. by abundant conversion, because of rather than effectively; Moreover, it also is inefficient the catalyzer after using, reclaiming connection metal.On the other hand,, then be selected from least a kind of element among Zr, the Hf and suppress the effect that catalyst activity reduces in time and diminish if it is too much to be selected from the content of at least a kind of metallic element in 8,9,10 families, thus and it is not preferred.
Be selected from the catalyzer of at least a kind of metallic element in 8,9,10 families having supported these, can contain and be useful on the composition that improves catalyst performance or stability (below be referred to as modified additive).As modified additive, can enumerate out: 1 family's metal or their ion, 2 family's metals or their ion, 6 family's metals or their ion, 13 family's metals or their ion.Preferred 1 family's metal or their ion, 2 family's metals or their ion, 6 family's metals or their ion, more preferably 1 family's metal or their ion.Particularly, be metal or the ion of Cs, Rb, K, Na, Li, be preferably metal or the ion of K, Na especially.These metals or ion can make up multiple use.According to the kind that is selected from least a kind of metallic element in 8,9,10 families, contain these modified additives in the catalyzer through making, can further improve life of catalyst, thereby more effectively prepare furan compound.
When using these modified additives, at least a kind of metallic element that is selected from 8,9,10 families that can obtain unusual effect is Ni, Ru, Ir, Pd, Pt, and more preferably Pd, Pt are preferably Pd especially.
There is not particular restriction for the form of these modified additives in catalyzer; Can enumerate out: metal itself, carboxylate salt, carbonate, phosphoric acid salt, nitrate salt, vitriol or oxyhydroxide, oxide compound, composite oxides, preferred carbonate, nitrate salt or oxyhydroxide, oxide compound, composite oxides.These modified additives can join in the above-mentioned carrier in advance carry out compoundization, perhaps also can be supported at least a kind of metallic element in will being selected from 8,9,10 families on the carrier to add afterwards again.In addition, can also carry out compoundization or alloying etc. with at least a kind of metallic element that is selected from 8,9,10 families.When preferably at least a kind of metallic element in will being selected from 8,9,10 families is supported on the above-mentioned carrier, adds these modified additives simultaneously and carry out compoundization.
Modified additive as when supporting at least a kind of metallic element that is selected from 8,9,10 families, adding is specially Cs (CH
3COO), Rb (CH
3COO), K (CH
3COO), Na (CH
3COO), Li (CH
3COO), CsNO
3, RbNO
3, KNO
3, NaNO
3, LiNO
3, Cs
2CO
3, Rb
2CO
3, K
2CO
3, Na
2CO
3, Li
2CO
3, CsOH, RbOH, KOH, NaOH, LiOH, more preferably CsNO
3, KNO
3, NaNO
3, LiNO
3, Cs
2CO
3, K
2CO
3, Na
2CO
3, Li
2CO
3, CsOH, KOH, NaOH, LiOH, further preferred KNO
3, NaNO
3, K
2CO
3, Na
2CO
3, KOH, NaOH.
The content of these modified additives is relevant with the kind of metal, carrier; Thereby cannot treat different things as the same; But the catalyzer total mass is made as 100 quality %, its content be generally 0.01 quality % above and below the 50 quality %, be preferably 0.05 quality % above and below the 20 quality %, more preferably 0.1 quality % above and below the 10 quality %, to be preferably 0.5 quality % especially above and below the 5 quality %.
If the content of modified additive is very few, then suppress the effect that catalyst activity reduces in time and diminish, thereby not preferred.In addition, if the amount of modified additive is too much, then the furfural compound can not must be carried out the recovery of unreacted furfural compound etc. by abundant conversion, because of rather than effectively.
At least a kind of metallic element for being selected from 8,9,10 families is supported on the method on the carrier; Do not have particular restriction, can enumerate out ion exchange method, impregnation and support method, filling perforation (pore filling) method, wet impregnation method (incipient-wetness), spraying just and support method etc.Carrier can carry out roasting in advance in the oxygen-containing gas atmosphere.Maturing temperature be generally more than 200 ℃ and below 1200 ℃, be preferably more than 300 ℃ and below 1000 ℃, more preferably more than 400 ℃ and below 800 ℃, be preferably more than 500 ℃ especially and below 700 ℃.
When at least a kind of metallic element in will being selected from 8,9,10 families adopts that ion exchange method or impregnation support etc. and is supported on the carrier; As employed raw metal, usually use water miscible salt or their acidic solutions such as the muriate that is selected from least a kind of metallic element in 8,9,10 families or nitrate salt.Preferably nitrate, amine complex nitrate salt, amine complex nitro-compound etc. do not contain the water-soluble material of halogen element.
To be selected from after at least a kind of metal ingredient in 8,9,10 families is supported on the carrier, and adopt filtration, centrifugal dewatering or drying to remove moisture, liquid component adopting ion exchange method, impregnation to support method.Then, be employed in preferably that air is medium to carry out roasting.Maturing temperature be generally more than 200 ℃ and below 1000 ℃, be preferably more than 250 ℃ and below 800 ℃, more preferably more than 300 ℃ and below 600 ℃.Also preferably be packed in the pipe, carry out roasting while feed oxygen-containing gas.
And; Catalyzer is reacted with reductive agent in liquid phase; Perhaps be loaded into it in pipe and feed hydrogeneous, pure gas and under the reducing gas air-flow, handle, can at least a kind the metal ingredient that be selected from 8,9,10 families be reduced and deactivated catalyst thus.As the reductive reductive agent that is used for liquid phase, can enumerate out Superlysoform, hydrazine, azanol, pyruvic alcohol, ethanol, formic acid, oxalic acid, hydrogen, preferably enumerate out Superlysoform, hydrazine.As reducing gas, can enumerate out hydrogen, ammonia, carbon monoxide, nitrogen protoxide, preferably enumerate out hydrogen.Temperature when using reducing gas to handle, be generally more than 100 ℃ and below 900 ℃, be preferably more than 150 ℃ and below 570 ℃, be preferably more than 200 ℃ especially and below 500 ℃.These reduction are handled also and can be carried out before the de-carbonyl reaction of furfural compound being about to be used for.In addition, can also in the same reactor drum of the de-carbonyl reaction that carries out the furfural compound, carry out.
< de-carbonyl reaction >
Reaction formation for the de-carbonyl reaction among the present invention does not have particular restriction, can implement any type of reaction in rhythmic reaction, the continuous flow reaction, the preferred continuous flow reaction formation that adopts in the industry.In addition, the reaction formation of de-carbonyl reaction all can be implemented in liquid phase reaction, gas phase circulation reaction, reacts but gas furfural raw materials of compound and solid catalyst etc. are contacted.Its reason is: because the furfural compound concentrations of unit volume diminishes, thereby the condensation, polymerization etc. that can suppress the furfural compound cause dysgenic side reaction etc. to the yield of furan compound.In addition, gas phase circulation reaction also have can be through reactor drum design being made catalyzer replacing or the regeneration easy advantage that becomes.For example; Through making reactor drum is fixed-bed type, can regenerate through roasting etc., and need not from reactor drum, to take out catalyzer; Through being set up in parallel a plurality of fixed-bed reactor in advance; When the catalyzer of a reactor drum being regenerated or change, other reactor drum still can carry out the de-carbonyl reaction of furfural compound, therefore can prepare furan compound continuously.
When adopting gas phase circulation reaction, in the fixed bed tube-type reactor that is filled with catalyzer, supply with the gas that contains the furfural compound usually continuously, react through the catalyzer that gas is passed in the reactor drum, thereby obtain furan compound.Preferably in the gasifier that is provided with in advance, make the furfural compound become gas.Method for gasification does not have particular restriction, can enumerate out: in the furfural compound of liquid state, blast the method for (gas bubbling) hydrogen or non-active gas etc., or the method for employing spraying gasification etc.As required with non-active gas etc. as blasting under the situation of gas or gas-entrained (entrained gas), gas-entrained purity such as employed non-active gas be generally 95vol% above, be preferably 99vol% above, more preferably 99.9vol% above, be preferably more than the 99.99vol% especially.
In the de-carbonyl reaction of the furfural compound that has used the catalyzer that comprises at least a kind of element that is selected among Zr, the Hf and be selected from least a kind of metallic element in 8,9,10 families of the present invention, preferred coexistence has hydrogen as reaction initiator.Amount to the hydrogen carried secretly does not have particular restriction, with the molar ratio computing of furfural compound, its amount be generally more than 0.01 and below 4, be preferably 0.02 or more and below 2, more preferably more than 0.04 and 1 following, be preferably more than 0.06 especially and below 0.5.If the amount of hydrogen is few, then the furfural raw materials of compound can't transform fully, must carry out the recovery of unreacted furfural compound etc., because of rather than effectively.If the amount of hydrogen is too much, then the hydrogenation degradation production of furfural compound increases, and the furan compound that generates can progressively take place preferably not react, and the result causes the yield of furan compound to reduce, thereby not preferred.The purity of the hydrogen that use this moment is generally more than 99%, is preferably more than 99.9%, more preferably more than 99.99%, be preferably more than 99.999% especially.In addition, look catalyzer and decide all right water entrainment steam.
With respect to the precious metal 1mol that bears catalyst activity, the feed rate of furfural compound be generally 0.0001mol/h above and below the 50000mol/h, to be preferably 0.001mol/h above and below the 10000mol/h, more preferably 0.01mol/h is above and below the 5000mol/h.With respect to catalyst weight 1g, the feed rate of furfural compound be generally 1mmol/h above and below the 3000mmol/h, to be preferably 10mmol/h above and below the 1500mmol/h, more preferably 20mmol/h is above and below the 500mmol/h.
Residence time be generally more than 0.001 second and below 10 seconds, be preferably more than 0.01 second and below 5 seconds, more preferably more than 0.05 second and below 2 seconds, be preferably more than 0.1 second especially and below 1 second.When catalyst metal amount or catalytic amount with respect to the feed rate of furfural compound after a little while or the residence time in short-term, the furfural raw materials of compound can't transform fully, must carry out the recovery of unreacted furfural compound etc., because of rather than effectively.In addition, when catalyst metal amount or catalytic amount with respect to the feed rate of furfural compound for a long time or residence time when long, the furan compound that generates in some cases progressively reacts, the result makes the yield of furan compound reduce.But, when carrying out long successive reaction, can reduce catalyst activity sometimes and predict, and load the catalyzer of excess quantity in advance.Temperature of reaction be generally more than 170 ℃ and below 450 ℃, be preferably more than 180 ℃ and below 380 ℃, more preferably more than 200 ℃ and below 340 ℃, be preferably more than 230 ℃ especially and below 300 ℃.If temperature of reaction is low, then the furfural raw materials of compound can't transform fully, must carry out the recovery of unreacted furfural compound etc., because of rather than effectively.In addition, if temperature of reaction is too high, the furan compound that then generates progressively reacts, and the result causes the yield of furan compound to reduce, and is therefore not preferred.When reaction pressure is represented with absolute pressure, be generally 0.01MPa above and below the 3MPa, to be preferably 0.05MPa above and below the 2MPa, more preferably 0.1MPa is above and below the 1MPa.If reaction pressure is low, then when the furan compound that separate to generate, the loss that produces furan compound sometimes.
Carrying out under the liquid reactive situation; With the furfural compound and the catalyzer that comprises at least a kind of element that is selected among Zr, the Hf and be selected from least a kind of metallic element in 8,9,10 families be encased in the reactor drum; Under agitation under suitable temperature, react; When the boiling point of the furan compound that generates hangs down, can from gas phase, collect furan compound.With regard to temperature of reaction, be generally more than 120 ℃ and below 250 ℃, be preferably more than 140 ℃ and below 230 ℃, be preferably more than 155 ℃ and below 220 ℃ and carry out especially.When reaction pressure is represented with absolute pressure, be generally 0.1MPa above and below the 1MPa, to be preferably 0.15MPa above and below the 0.6MPa, more preferably 0.2MPa is above and below the 0.3MPa.Can use high bp polar solvent such as gamma-butyrolactone, N-Methyl pyrrolidone, triglyme or tetraethylene glycol dimethyl ether, also can make fluid additives such as water.Can also use alkaline additives such as salt of wormwood, yellow soda ash, lime acetate aptly.As required, can carry out the removing (パ one ジ removes) of by product or the interpolation or the replacing of catalyzer.In addition, can also adopt aptly and supply with the furfural compound continuously.
When the furfural compound that impurity reduced supplies to the de-carbonyl reaction device continuously; The purification devices that preferably will be used to reduce impurity is connected with the de-carbonyl reaction device; The furfural compound is carried out distillation purifying or adsorb removing purifying, and it is supplied to the de-carbonyl reaction device continuously.When adopting distillation purifying, not only getting rid of high boiling impurity is effectively, and it also is effective removing and being supplied to the de-carbonyl reaction device behind the lower boiling impurity.
Can after separating, carry out purifying through operations such as distillations with the furan compound of gained and the carbon monoxide that generates as by product or by product and as the hydrogen that reaction initiator imports.Isolated hydrogen can cycling and reutilization, also can be used for other purposes effectively with carbon monoxide.
In addition; In the method for the invention; When particularly comprising the catalyzer of special metals such as Pt in use; Furfural compound under the situation of hydrogen is arranged in the conversion reaction of furan compound in coexistence, the furan compound of furfural compound or generation is hydrogenated, hydrogenation is decomposed, thereby generates ethane, ethene, propane, propylene, butane, butylene, propyl alcohol, butanols, THF, 2-methyl furan, 2-methyltetrahydrofuran.Therefore, method of the present invention also is useful as the method from the said ethane of furfural compound, ethene, propane, propylene, butane, butylene, propyl alcohol, butanols, THF, 2-methyl furan, 2-methyltetrahydrofuran.
The catalyzer of the application of the invention can obtain the few furan compound of foreign matter content with fabulous selection rate.The purity of gained furan compound is generally more than 99%.For catalyzer of the present invention, owing to avoided the polyreaction on the catalyst surface etc., so the ratio of the contained by product that generates because of polyreaction etc. also becomes extremely low in the gained furan compound.The gained furan compound is water white, if (Yellowness Index: yellowness index) value be a benchmark, and the form of employing number is calculated, and then is below 50 with the YI of APHI (American Public Healty Association) standard color solution.
Because foreign matter content is few in the furan compound of gained of the present invention, so it is useful as various resin raw materials or additive.In addition, based on identical reason, it also is useful as derived prods synthetic midbody, and can carry out with the furan compound efficiently is the building-up reactions of raw material.For example; If the gained furan compound is the furan compound of general formula (2); The hydrogenation through using catalyzer to carry out then can be converted into the furan compound of general formula (6), and can be converted into the furan compound of general formula (3)～(5) through the partially hydrogenated reaction.In addition, through combined, can also be converted into 1, lactone such as glycolss such as 4-butyleneglycol, gamma-butyrolactone with hydration (water with) etc.
The catalyzer of the application of the invention from furfural compound furan compound the time, reduces attached to the amount of the tamper on the catalyzer, and therefore catalyzer use continuously for a long time, can reduce and regenerate or the frequency of catalyst changeout more.Catalyst regeneration process or manipulation of regeneration during for catalyst deactivation do not have particular restriction.For example, can remove impurity or tamper that catalyst surface adheres to, catalyst performance is recovered through in oxygen-containing gas, implementing pyroprocessing.In addition, also can clean, remove impurity or tamper that catalyst surface adheres to, and carry out drying catalyst performance is recovered through utilizing organic solvents such as alcohol.After having removed impurity or tamper, be supplied to before the de-carbonyl reaction of furfural compound once more, reduction identical in the time of can implementing with Preparation of Catalyst is handled.That is, preferably through make its in liquid phase with reductive agent reaction, perhaps through it is seated in the pipe, and feed hydrogeneous or pure gas, in the reducing gas air-flow, handle, reduce the metal of undertaking catalytic activity.Above-mentioned a series of manipulation of regeneration also can be in the reactor drum that carries out de-carbonyl reaction, be filled with under the state of catalyzer and carrying out.In this case, a plurality of reactor drums that carry out de-carbonyl reaction preferably are set in advance.During the catalyzer that in to a reactor drum, loads carries out regenerated, utilize the catalyzer that loads in other reactor drum to carry out the de-carbonyl reaction of furfural compound, can prepare furan compound continuously thus.
Embodiment
Below explain more specifically that through embodiments of the invention but the present invention only otherwise break away from its purport, just do not receive the qualification of these embodiment.Need to prove; Furfural compound purity in the furfural raw materials of compound is estimated by the peak area ratio of GC; The mensuration of sulphur concentration, nitrogen concentration adopts burning-absorption-ion chromatography respectively, and (combustion unit: Mitsubishi chemical Co., Ltd makes, test portion combustion unit, QF-02; Analytical equipment: Japanese Dionex manufactured, chromatography of ions DX-500), (Mitsubishi chemical Co., Ltd makes combustion decomposition-chemoluminescence method, and the trace nitrogen analytical equipment TN-10) carries out.In addition, the determination of acid value of furfural raw materials of compound carries out as follows: with the furfural raw materials of compound with alcohol dilution after, use the potassium hydroxide aqueous solution of 0.01N to carry out titration.
(embodiment 1)
< furfural transformation efficiency over time: ZIRCONIUM DIOXIDE 99.5 supports 1 quality %Pd catalyzer >
With commercially available particulate state ZIRCONIUM DIOXIDE 99.5 (surface-area: 99m
2/ g, PV:0.35ml/g) pulverize, sieve into particle diameter 500 μ m～1000 μ m, in the air draught of about 100ml/min in 600 ℃ of roastings 6 hours.Among the ZIRCONIUM DIOXIDE 99.5 5.00g after this roasting, use with zero(ppm) water 0.50g palladium nitrate solution ([Pd (NO
3)
4]
2-) (Pd:9.98 quality %, HNO
3: dilution and the solution that obtains adopts just wet impregnation method that Pd is contained and is immersed in the above-mentioned ZIRCONIUM DIOXIDE 99.5 18.8 quality %).After removing moisture through hot water bath, in the nitrogen gas stream of about 30ml/min in 120 ℃ of dryings 6 hours.Again in the air draught of about 50ml/min in 500 ℃ of roastings 4 hours, obtain ZIRCONIUM DIOXIDE 99.5 and support 1 quality %Pd catalyzer (1 quality %Pd/ZrO
2).
As the raw material of de-carbonyl reaction, use commercial reagent furfural A, and it is not carried out purifying especially.At this moment, the furfural purity in the furfural raw material is more than 99%, and with regard to impurity concentration, sulphur concentration is that 23.1ppm, nitrogen concentration are 4.9ppm.The ZIRCONIUM DIOXIDE 99.5 that adopts aforesaid method to obtain is supported 1 quality %Pd catalyzer 1.00g be filled in the glass reaction tubes of internal diameter 8mm, under the condition of circulation 10Nml/min hydrogen, heat up with 13 ℃/min.After the temperature of catalyst layer arrives 260 ℃, in the hydrogen stream of this temperature, kept about 10 minutes.Then, the composition with circulated gases changes to hydrogen 0.84Nml/min, nitrogen 32.0Nml/min.The raw material furfural is gasified through the gasifier that is heated to 170 ℃, supply with, begin reaction with the flow velocity of 36.22mmol/h.At this moment, W/F is 28g
CatH/mol
Furfural, be 4mol with respect to the supply furfural of carrying metal amount
Furfural/ hg
Pd, the ratio of hydrogen/furfural is 0.06.Reaction pressure is expressed as 0.1MPa with absolute pressure.The part that distillates gas of autoreaction pipe outlet in the future imports among the GC, and furans, carbon monoxide and other product are carried out quantitative analysis.Obtain furfural transformation efficiency and furans selection rate through following formula.
Furfural transformation efficiency (%)=[1-{ reaction back furfural residual volume (mol)/furfural feed rate (mol) }] * 100
Furans selection rate (%)={ furans yield (%)/furfural transformation efficiency (%) } * 100
=[{ furans growing amount (mol)/furfural inlet amount (mol) } * 100 (%)/furfural transformation efficiencys (%)] * 100
Using ZIRCONIUM DIOXIDE 99.5 to support under the situation of 1 quality %Pd catalyzer, the furfural transformation efficiency of reaction beginning after 1.1 hours is 99%, and the furfural transformation efficiency of reaction beginning after 6.3 hours is 93%.6.3 hour reaction in the MV of furans selection rate be 98%.React after 6.3 hours, stop the supply of furfural, under the gas flow of hydrogen 0.84Nml/min, nitrogen 32.0Nml/min, cool the temperature to room temperature.From reaction tubes, take out catalyzer and measure its weight, because the adhering to of the stifled basic thing that the impurity of furfural raw material sources and reaction are produced, observing weight has increased 0.04g.
(comparative example 1)
< furfural transformation efficiency over time: aluminum oxide supports 1 quality % palladium catalyst >
Except using aluminum oxide to support 1 quality %Pd catalyzer (1 quality %Pd/Al
2O
3) as beyond the catalyzer, likewise react with embodiment 1.Aluminum oxide supports 1 quality %Pd Preparation of catalysts and supports the same method of 1 quality %Pd catalyzer and carry out according to the ZIRCONIUM DIOXIDE 99.5 for preparing with embodiment 1, and difference is: with commercially available particulate state γ-Al
2O
3(surface-area: 174m
2/ g, PV:0.37ml/g) pulverize, sieve into particle diameter 500 μ m～1000 μ m, use it as alumina supporter.
Using aluminum oxide to support under the situation of 1 quality %Pd catalyzer, the furfural transformation efficiency of reaction beginning after 1.1 hours is 91%, and the furfural transformation efficiency of reaction beginning after 6.3 hours is reduced to 65%.6.3 hour reaction in the MV of furans selection rate be 98%.In addition, implement 6.3 hours reaction after because the adhering to of the tamper that the impurity of furfural raw material sources and reaction produce, the weight of catalyzer has increased 0.17g.
(embodiment 2)
< furfural transformation efficiency over time: ZIRCONIUM DIOXIDE 99.5 supports 1 quality %Pd-1 quality %K catalyzer >
With commercially available particulate state ZIRCONIUM DIOXIDE 99.5 (surface-area: 99m
2/ g, PV:0.35ml/g) pulverize, sieve into particle diameter 500 μ m～1000 μ m, in the air draught of about 100ml/h in 600 ℃ of roastings 6 hours.Among the ZIRCONIUM DIOXIDE 99.5 5.00g after this roasting, use with zero(ppm) water 0.50g palladium nitrate solution ([Pd (NO
3)
4]
2-) (Pd:9.98 quality %, HNO
3: 18.8 quality %) and the KNO of 0.13g
3The solution that dilutes, dissolves and obtain adopts just wet impregnation method that Pd, K are contained and is immersed in the above-mentioned ZIRCONIUM DIOXIDE 99.5.After removing moisture through hot water bath, in the nitrogen gas stream of about 30ml/min, in 120 ℃ of dryings 6 hours.Again in the air draught of about 50ml/min in 500 ℃ of roastings 4 hours, then, in 450 ℃, the hydrogen stream of about 75ml/min, carry out reduction in 2 hours, obtain ZIRCONIUM DIOXIDE 99.5 and support 1 quality %Pd-1 quality %K catalyzer (1 quality %Pd-1 quality %K/ZrO
2).
Except using the above-mentioned ZIRCONIUM DIOXIDE 99.5 of 0.75g to support 1 quality %Pd-1 quality %K catalyzer, likewise react with embodiment 1 as the catalyzer.At this moment, W/F is 21g
CatH/mol
Furfural, be 5mol with respect to the supply furfural of carrying metal amount
Furfural/ hg
Pd, the ratio of hydrogen/furfural is 0.06.Reaction pressure is expressed as 0.1MPa with absolute pressure.
Using ZIRCONIUM DIOXIDE 99.5 to support under the situation of 1 quality %Pd-1 quality %K catalyzer, the furfural transformation efficiency of reaction beginning after 1.1 hours is 100%, and the furfural transformation efficiency of reaction beginning after 6.3 hours is 96%.6.3 hour reaction in, the MV of furans selection rate is 99%.React after 6.3 hours, stop the supply of furfural, in the gas flow of hydrogen 0.84Nml/min, nitrogen 32.0Nml/min, cool the temperature to room temperature.From reaction tubes, take out catalyzer and measure its weight, owing to the impurity of furfural raw material sources and adhering to of the tamper that reacts generation, observing weight has increased 0.03g.
(comparative example 2)
< furfural transformation efficiency over time: aluminum oxide supports 1 quality %Pd-1 quality %K catalyzer >
Except the aluminum oxide that uses 1.00g supports 1 quality %Pd-1 quality %K catalyzer (1 quality %Pd-1 quality %K/Al
2O
3) as beyond the catalyzer, likewise react with embodiment 2.Aluminum oxide supports 1 quality %Pd-1 quality %K Preparation of catalysts and supports the same method of 1 quality %Pd-1 quality %K catalyzer and carry out according to the ZIRCONIUM DIOXIDE 99.5 for preparing with embodiment 2, and difference is: with commercially available particulate state γ-Al
2O
3(surface-area: 174m
2/ g, PV:0.37ml/g) pulverize, sieve into particle diameter 500 μ m～1000 μ m, and with this as alumina supporter.At this moment, W/F is 28g
CatH/mol
Furfural, be 4mol with respect to the supply furfural of carrying metal amount
Furfural/ hg
Pd, the ratio of hydrogen/furfural is 0.06.Reaction pressure is expressed as 0.1MPa with absolute pressure.
Using aluminum oxide to support under the situation of 1 quality %Pd-1 quality %K catalyzer, the furfural transformation efficiency of reaction beginning after 1.1 hours is 100%, and the furfural transformation efficiency of reaction beginning after 6.3 hours is reduced to 89%.6.3 hour reaction in, the MV of furans selection rate is 98%.In addition, implement 6.3 hours reaction after because the adhering to of the tamper that the impurity of furfural raw material sources and reaction produce, the weight of catalyzer has increased 0.11g.
(comparative example 3)
< furfural transformation efficiency over time: silica supported 1 quality %Pd-1 quality %K catalyzer >
Except using silica supported 1 quality %Pd-1 quality %K catalyzer (the 1 quality %Pd-1 quality %K/SiO of 0.75g
2) as beyond the catalyzer, likewise react with embodiment 2.Silica supported 1 quality %Pd-1 quality %K Preparation of catalysts supports the same method of 1 quality %Pd-1 quality %K catalyzer and carries out according to the ZIRCONIUM DIOXIDE 99.5 for preparing with embodiment 2, and difference is: use Cariact Q-50 (surface-area: 79m
2/ g, PV:1.01ml/g, particle diameter: 0.85mm～1.70mm) as silica supports.At this moment, W/F is 21g
CatH/mol
Furfural, be 5mol with respect to the supply furfural of carrying metal amount
Furfural/ hg
Pd, the ratio of hydrogen/furfural is 0.06.Reaction pressure is expressed as 0.1MPa with absolute pressure.
Under the situation of using silica supported 1 quality %Pd-1 quality %K catalyzer, the furfural transformation efficiency of reaction beginning after 1.1 hours is 85%, and the furfural transformation efficiency of reaction beginning after 6.3 hours is reduced to 52%.6.3 hour reaction in, the MV of furans selection rate is 98%.In addition, implement 6.3 hours reaction after because the adhering to of the tamper that the impurity of furfural raw material sources and reaction produce, the weight of catalyzer has increased 0.05g.
(embodiment 3)
< furfural transformation efficiency over time: ZIRCONIUM DIOXIDE 99.5 supports 1 quality %Pd catalyzer >
For the catalyzer that likewise prepares with embodiment 1, in 450 ℃, the hydrogen stream of about 75ml/min, carry out 2 hours reduction, obtain ZIRCONIUM DIOXIDE 99.5 and support 1 quality %Pd catalyzer (1 quality %Pd/ZrO
2).
As the raw material of de-carbonyl reaction, use commercial reagent furfural B is carried out distillation purifying and the material that obtains.At this moment, the furfural purity of furfural raw material is more than 99%, and with regard to impurity concentration, sulphur concentration is 1.3ppm, and nitrogen concentration is 1.5ppm, and acid number is 0.072mgKOH/g.Above-mentioned ZIRCONIUM DIOXIDE 99.5 is supported 1 quality %Pd catalyzer 0.75g be filled in the glass reaction tubes of internal diameter 8mm, under the condition of circulation 10Nml/min hydrogen, heat up with 14 ℃/min.After the temperature of treating catalyst layer reaches 275 ℃, in the hydrogen stream of this temperature, kept about 10 minutes.Then, the composition with the gas that circulates changes to hydrogen 6.6Nml/min, nitrogen 26.3Nml/min.The raw material furfural is gasified through the gasifier that is heated to 170 ℃, supply with, begin reaction with the flow velocity of 36.22mmol/h.At this moment, W/F is 21g
CatH/mol
Furfural, be 5mol with respect to the supply furfural of carrying metal amount
Furfural/ hg
Pd, the ratio of hydrogen/furfural is 0.5.Reaction pressure is expressed as 0.1MPa with absolute pressure.
When support 1 quality %Pd catalyzer at ZIRCONIUM DIOXIDE 99.5 on, making furfural raw material successive reaction carry out the decarbonylation base, the furfural transformation efficiency of reaction beginning after 2 hours is 100%, and the furans selection rate is 96%.The furfural transformation efficiency of reaction beginning after 50 hours is 62%, and the furans selection rate is 97%.After the reaction in 64 hours, stop the supply of furfural, in the gas flow of hydrogen 6.6Nml/min, nitrogen 26.3Nml/min, cool the temperature to room temperature.From reaction tubes, take out catalyzer and measure its weight, owing to the impurity of furfural raw material sources and adhering to of the tamper that reacts generation, observing weight has increased 0.04g.
(comparative example 4)
< furfural transformation efficiency over time: aluminum oxide supports 1 quality %Pd catalyzer >
Except the aluminum oxide that uses 1.00g supports 1 quality %Pd catalyzer (1 quality %Pd/Al
2O
3) as beyond the catalyzer, likewise react with embodiment 3.Aluminum oxide supports 1 quality %Pd catalyzer and prepares by following method.
With commercially available spherical gama-alumina (surface-area: 231m
2/ g, PV:0.55ml/g) in air draught in 300 ℃ of roastings 3 hours.Make the about 10g of this aluminum oxide that about 1 week of moisture absorption in the moisture eliminator of water is being housed through roasting.For the about 13g of the aluminum oxide after the moisture absorption (being about 10g during drying), use four ammino palladium (II) nitrate salt ([Pd (NH
3)
4] (NO
3)
2) 0.3g be dissolved among the zero(ppm) water 10g and solution, adopt the impregnation method that Pd is contained and be immersed in the above-mentioned aluminum oxide.After removing moisture with rotatory evaporator, in the air draught of about 100ml/min in 120 ℃ of dryings 3 hours.Again in the air draught of about 100ml/min in 520 ℃ of roastings 2 hours, obtain aluminum oxide and support 1 quality %Pd catalyzer.
In this reaction, W/F is 28g
CatH/mol
Furfural, be 4mol with respect to the supply furfural of carrying metal amount
Furfural/ hg
Pd, the ratio of hydrogen/furfural is 0.5.Reaction pressure is expressed as 0.1MPa with absolute pressure.
When support 1 quality %Pd catalyzer at aluminum oxide on, making furfural raw material successive reaction carry out the decarbonylation base, the reaction beginning furfural transformation efficiency after 2 hours is 93%, the furans selection rate is 97%.The furfural transformation efficiency of reaction beginning after 50 hours is reduced to 44%, and the furans selection rate is 97%.In addition, implement 63 hours reaction after because the adhering to of the tamper that the impurity of furfural raw material sources and reaction produce, the weight of catalyzer has increased 0.25g.
(embodiment 4)
< furfural transformation efficiency over time: ZIRCONIUM DIOXIDE 99.5 supports 2 quality %Pt catalyzer >
With commercially available particulate state ZIRCONIUM DIOXIDE 99.5 (surface-area: 99m
2/ g, PV:0.35ml/g) pulverize, sieve into particle diameter 500 μ m～1000 μ m, in the air draught of about 100ml/min in 600 ℃ of roastings 6 hours.Among the ZIRCONIUM DIOXIDE 99.5 5.00g after this roasting, use with zero(ppm) water 1.93g platinum nitrate solution ([Pt (NO
3)
4]
2-) (Pt:5.17 quality %) dilution and the solution that obtains adopts just wet impregnation method that Pt is contained and is immersed in the above-mentioned ZIRCONIUM DIOXIDE 99.5.After removing moisture through hot water bath, in the nitrogen gas stream of about 30ml/min in 120 ℃ of dryings 6 hours.Again in the air draught of about 50ml/min in 500 ℃ of roastings 4 hours, in 450 ℃, the hydrogen stream of about 75ml/min, carry out 2 hours reduction then, obtain ZIRCONIUM DIOXIDE 99.5 and support 2 quality %Pt catalyzer (2 quality %Pt/ZrO
2).
Except having used above-mentioned ZIRCONIUM DIOXIDE 99.5 to support the 2 quality %Pt catalyzer 1.00g, likewise react with embodiment 3.At this moment, W/F is 28g
CatH/mol
Furfural, be 2mol with respect to the supply furfural of carrying metal amount
Furfural/ hg
Pt, the ratio of hydrogen/furfural is 0.5.Reaction pressure is expressed as 0.1MPa with absolute pressure.
When support 2 quality %Pt catalyzer at ZIRCONIUM DIOXIDE 99.5 on, making furfural raw material successive reaction carry out the decarbonylation base, the reaction beginning furfural transformation efficiency after 2 hours is 73%, the furans selection rate is 85%.Main by product is propane, propylene, butane, butylene etc., and propane, propylene, butane, butylene shared ratio in resultant adds up to 11%.The furfural transformation efficiency of reaction beginning after 50 hours is 79%, and the furans selection rate is 94%.Main by product is propane, propylene, butane, butylene etc., and propane, propylene, butane, butylene shared ratio in resultant adds up to 4%.After the reaction in 64 hours, stop the supply of furfural, in the gas flow of hydrogen 6.6Nml/min, nitrogen 26.3Nml/min, cool the temperature to room temperature.From reaction tubes, take out catalyzer and measure its weight, because the adhering to of the tamper that the impurity of furfural raw material sources and reaction are produced, observing weight has increased 0.05g.
(comparative example 5)
< furfural transformation efficiency over time: aluminum oxide supports 2 quality %Pt catalyzer >
Except the aluminum oxide that uses 1.00g supports 2 quality %Pt catalyzer (2 quality %Pt/Al
2O
3) as beyond the catalyzer, likewise react with embodiment 3.Aluminum oxide supports 2 quality %Pt Preparation of catalysts and supports the same method of 2 quality %Pt catalyzer and carry out according to the ZIRCONIUM DIOXIDE 99.5 for preparing with embodiment 4, and different is: with commercially available particulate state γ-Al
2O
3(surface-area: 174m
2/ g, PV:0.37ml/g) pulverize, sieve into particle diameter 500 μ m～1000 μ m, and with this as alumina supporter.At this moment, W/F is 28g
CatH/mol
Furfural, be 2mol with respect to the supply furfural of carrying metal amount
Furfural/ hg
Pt, the ratio of hydrogen/furfural is 0.5.Reaction pressure is expressed as 0.1MPa with absolute pressure.
When support 2 quality %Pt catalyzer at aluminum oxide on, making furfural raw material successive reaction carry out the decarbonylation base, the furfural transformation efficiency of reaction beginning after 2 hours is 99%, and the furans selection rate is 95%.Main by product is propane, propylene, butane, butylene etc., and propane, propylene, butane, butylene proportion in resultant adds up to 4%.The furfural transformation efficiency of reaction beginning after 50 hours is reduced to 92%, and the furans selection rate is 96%.Main by product is propane, propylene, butane, butylene etc., and propane, propylene, butane, butylene proportion in resultant adds up to 3%.In addition, implement 50 hours reaction after because the adhering to of the tamper that the impurity of furfural raw material sources and reaction produce, the weight of catalyzer has increased 0.18g.
(embodiment 5)
< long duration test: ZIRCONIUM DIOXIDE 99.5 supports 1 quality %Pd-1 quality %K catalyzer >
As the raw material of the de-carbonyl reaction of furfural, use commercial reagent furfural B is carried out distillation purifying and the material that obtains.At this moment, the furfural purity of furfural raw material is more than 99%, and with regard to impurity concentration, sulphur concentration is 1.3ppm, and nitrogen concentration is 1.5ppm, and acid number is 0.072mgKOH/g.The ZIRCONIUM DIOXIDE 99.5 of the method preparation of adopting embodiment 2 is supported 1 quality %Pd-1 quality %K catalyzer 0.30g be filled in the glass reaction tubes of internal diameter 8mm, under the condition of circulation 10Nml/min hydrogen, heat up with 14 ℃/min.After the temperature of treating catalyst layer arrives 285 ℃, in the hydrogen stream of this temperature, kept about 10 minutes.Then, the composition with the gas that circulates changes to hydrogen 2.2Nml/min, nitrogen 39.6Nml/min.The raw material furfural is gasified through the gasifier that is heated to 170 ℃, supply with, begin reaction with the flow velocity of 12.07mmol/h.At this moment, W/F is 25g
CatH/mol
Furfural, be 4mol with respect to the supply furfural of carrying metal amount
Furfural/ hg
Pd, the ratio of hydrogen/furfural is 0.5.Reaction pressure is expressed as 0.1MPa with absolute pressure.
When support 1 quality %Pd-1 quality %K catalyzer at ZIRCONIUM DIOXIDE 99.5 on, making furfural raw material successive reaction carry out the decarbonylation base, the furfural transformation efficiency of reaction beginning after 10 hours is 100%, and the furans selection rate is 98%.The furfural transformation efficiency of reaction beginning after 50 hours is 96%, and the furans selection rate is 98%.The furfural transformation efficiency of reaction beginning after 100 hours is 94%, and the furans selection rate is 98%.The furfural transformation efficiency of reaction beginning after 150 hours is 94%, and the furans selection rate is 98%.The furfural transformation efficiency of reaction beginning after 200 hours is 94%, and the furans selection rate is 98%.After the reaction beginning 70 hours, do not observe the furfural transformation efficiency over time, the furans selection rate over time.React after 200 hours, stop the supply of furfural, in the gas flow of hydrogen 2.2Nml/min, nitrogen 39.6Nml/min, cool the temperature to room temperature.From reaction tubes, take out catalyzer and measure its weight, owing to the impurity of furfural raw material sources and adhering to of the tamper that reacts generation, observing weight has increased 0.02g.
(embodiment 6)
< long duration test: ZIRCONIUM DIOXIDE 99.5 supports 2 quality %Pt catalyzer >
As the raw material of the de-carbonyl reaction of furfural, use commercial reagent furfural B is carried out distillation purifying and the material that obtains.At this moment, the furfural purity of furfural raw material is more than 99%, and with regard to impurity concentration, sulphur concentration is 1.3ppm, and nitrogen concentration is 1.5ppm, and acid number is 0.072mgKOH/g.Except using ZIRCONIUM DIOXIDE 99.5 to support 2 quality %Pt catalyzer (2 quality %Pt/ZrO by the method preparation of embodiment 4
2) 0.50g is as beyond the catalyzer, likewise react with embodiment 5.At this moment, W/F is 41g
CatH/mol
Furfural, be 1.2mol with respect to the supply furfural of carrying metal amount
Furfural/ hg
Pt, the ratio of hydrogen/furfural is 0.5.Reaction pressure is expressed as 0.1MPa with absolute pressure.
When support 2 quality %Pt catalyzer at ZIRCONIUM DIOXIDE 99.5 on, making furfural raw material successive reaction carry out the decarbonylation base, the furfural transformation efficiency of reaction beginning after 10 hours is 81%, and the furans selection rate is 89%.Main by product is propane, propylene, butane, butylene etc., and propane, propylene, butane, butylene proportion in resultant adds up to 9%.The furfural transformation efficiency of reaction beginning after 50 hours is 80%, and the furans selection rate is 92%.Main by product is propane, propylene, butane, butylene etc., and propane, propylene, butane, butylene proportion in resultant adds up to 7%.The furfural transformation efficiency of reaction beginning after 98 hours is 84%, and the furans selection rate is 93%.Main by product is propane, propylene, butane, butylene etc., and propane, propylene, butane, butylene proportion in resultant adds up to 5%.The furfural transformation efficiency of reaction beginning after 150 hours is 86%, and the furans selection rate is 94%.Main by product is propane, propylene, butane, butylene etc., and propane, propylene, butane, butylene proportion in resultant adds up to 5%.The furfural transformation efficiency of reaction beginning after 200 hours is 83%, and the furans selection rate is 94%.Main by product is propane, propylene, butane, butylene etc., and propane, propylene, butane, butylene proportion in resultant adds up to 5%.By back 120 hours of reaction beginning, the furfural transformation efficiency improved in time, and the ratio of by product reduces with the reaction times process, and the furans selection rate improves.After the reaction beginning 120 hours, do not observe basically the furfural transformation efficiency over time, the furans selection rate over time.React after 200 hours, stop the supply of furfural, in the gas flow of hydrogen 2.2Nml/min, nitrogen 39.6Nml/min, cool the temperature to room temperature.From reaction tubes, take out catalyzer and measure its weight, owing to the impurity of furfural raw material sources and adhering to of the tamper that reacts generation, observing weight has increased 0.03g.
(comparative example 6)
The identical catalyzer 1.00g that in the flask of 200ml, uses among filling and the embodiment 1, with embodiment 1 in the identical furfural 60.0g that uses, and make the nitrogen 32.0Nml that circulates in the flask.Use oil bath that flask is heated, liquidus temperature is controlled at 150 ℃, the liquid phase de-carbonyl reaction of beginning furfural.The concentration of the furans that nitrogen is carried secretly out carry out through the time quantitative, obtain the formation speed of furans, the formation speed of furans is below the 10mmol/h as a result.The furans concentration of reaction beginning after 6.3 hours is furans concentration 9 one-tenth below of reaction beginning after 1.1 hours, and can know: catalyst activity reduces in time.
[table 1]
| Catalyzer | 1.1 the transformation efficiency after hour (%) | 6.3 the transformation efficiency after hour (%) | Furans selection rate (%) | Catalyst weight increases (%) | |
| Embodiment 1 | 1 quality %Pd/ZrO 2 | 99 | ?93 | 98 | 0.04 |
| Comparative example 1 | 1 quality %Pd/Al 2O 3 | 91 | ?65 | 98 | 0.17 |
| Embodiment 2 | 1 quality %Pd-1 quality %K/ZrO 2 | 100 | ?96 | 99 | 0.03 |
| Comparative example 2 | 1 quality %Pd-1 quality %K/Al 2O 3 | 100 | ?89 | 98 | 0.11 |
| Comparative example 3 | 1 quality %Pd-1 quality %K/SiO 2 | 85 | ?52 | 98 | 0.05 |
Embodiment 1 is compared and can know with comparative example 1: compare with the situation of using the catalyzer that does not contain Zr; When use contains the catalyzer of Zr; Catalyst activity reduction in time is less; Therefore can keep high furfural transformation efficiency and high furans selection rate, can stablize and prepare furan compound efficiently.Can know in addition: compare with the catalyzer that does not contain Zr, use when containing the catalyzer of Zr, after the reaction of having implemented certain hour, the impurity of furfural raw material sources lacked with the adhering to of tamper that reaction produces.
Embodiment 2 is compared and can know with comparative example 2,3: compare with the situation of using the catalyzer that does not contain Zr; When use contains the catalyzer of Zr; Catalyst activity reduction in time is less; Can keep high furfural transformation efficiency and high furans selection rate, thereby can stablize and prepare furan compound efficiently.Can know in addition: compare with the catalyzer that does not contain Zr, use when containing the catalyzer of Zr, after the reaction of having implemented certain hour, the impurity of furfural raw material sources lacked with the adhering to of tamper that reaction produces.
[table 2]
| Catalyzer | Yield after 2 hours (%) (selection rate (%)) | Yield after 50 hours (%) (selection rate (%)) | Catalyst weight increases (g) (reaction times) | |
| Embodiment 3 | 1 quality %Pd/ZrO 2 | 100(96) | 62(97) | 0.04(64h) |
| Comparative example 4 | 1 quality %Pd/Al 2O 3 | 93(97) | 44(97) | 0.25(63h) |
| Embodiment 4 | 2 quality %Pt/ZrO 2 | 73(85) | 79(94) | 0.05(64h) |
| Comparative example 5 | 2 quality %Pt/Al 2O 3 | 99(95) | 92(96) | 0.18(50h) |
Embodiment 3 is compared and can know with comparative example 4: compare with the situation of using the catalyzer that does not contain Zr; When use contains the catalyzer of Zr; Catalyst activity reduction in time is less; Can keep high furfural transformation efficiency and high furans selection rate, thereby can stablize and prepare furan compound efficiently.Can know in addition: compare with the catalyzer that does not contain Zr, use when containing the catalyzer of Zr, after the reaction of having implemented certain hour, the impurity of furfural raw material sources lacked with the adhering to of tamper that reaction produces.。
Embodiment 4 is compared and can know with comparative example 5: compare with the situation of using the catalyzer that does not contain Zr; When use contains the catalyzer of Zr; Catalyst activity reduction in time is less; Can keep high furfural transformation efficiency and high furans selection rate, thereby can stablize and prepare furan compound efficiently.Can know in addition: compare with the catalyzer that does not contain Zr, use when containing the catalyzer of Zr, after the reaction of having implemented certain hour, the impurity of furfural raw material sources lacked with the adhering to of tamper that reaction produces.
Result by embodiment 5 and embodiment 6 can know: when use contained the catalyzer of Zr, catalyst activity reduction in time was less, can keep high furfural transformation efficiency and high furans selection rate for a long time, therefore can stablize and prepared furan compound efficiently.
Embodiment 1 is compared and can know with comparative example 6: using ZIRCONIUM DIOXIDE 99.5 to support under the situation of 1 quality %Pd catalyzer, and carrying out the reacting phase ratio in liquid phase, the reaction efficiency that reacts with the gas phase circulation style is high.In addition, catalyst activity reduction in time is less, can stablize and prepares furan compound efficiently.
More than; Think so far tool practicality with us and preferred embodiment combine; Describe the present invention, but the present invention does not receive the qualification of disclosed embodiment in the present specification, is construed as: do not violate can the Accessory Right claim and the scope of the purport of the description in its entirety invention of reading or design in; Can change aptly, be accompanied by this change and the preparation method of the furan compound that produces is also contained in the technical scope of the present invention.
Japanese patent application that the application proposed based on November 30th, 2007 (the special 2007-311127 of hope) and the Japanese patent application (the special 2007-311149 of hope) that proposed on November 30th, 2007, its content is incorporated this paper in this form with reference.
Industrial applicibility
In the present invention; Carry out the de-carbonyl reaction of furfural raw materials of compound through using specific catalyst; Catalyst activity reduction in time is less; Therefore can keep high furfural compound ratio transformation and high furan compound selection rate for a long time, can stablize and prepare furan compound efficiently.In addition, the amount that is attached to the tamper of catalyzer reduces, thereby, but the catalyzer long-time continuous use, can reduce the regeneration or the frequency of catalyst changeout more.
Claims (3)
1. the preparation method of a furan compound; This preparation method comprise the steps: comprise Zr be selected from least a kind of metallic element among Pd and the Pt catalyzer in the presence of; Make the furfural compound carry out de-carbonyl reaction through gas phase circulation reaction; Said furfural compound is hydroxymethyl furfural, 2-methyl furfural, 3-methyl furfural, furans dicarbaldehyde or furfural, wherein
Said catalyzer is that Zr adds to and supports in the carrier that is selected from least a kind of metallic element among Pd, the Pt or Zr loads on and supports on the carrier that is selected from least a kind of metallic element among Pd, the Pt and catalyzer that obtains or Zr constitute the part of this carrier components or the catalyzer that all obtains.
2. the preparation method of furan compound according to claim 1 wherein, comprises at least a kind of element in 1,2,6,13 family's elements that is selected from more than the 0.01 quality % and below the 50 quality % in the said catalyzer, is 100 quality % with the catalyzer total mass.
3. the preparation method of furan compound according to claim 1 and 2, the sulphur concentration in the wherein said furfural compound is below the 6.0ppm.
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| JP311149/07 | 2007-11-30 | ||
| JP2007311149 | 2007-11-30 | ||
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| WO2010080290A1 (en) * | 2008-12-18 | 2010-07-15 | E. I. Du Pont De Nemours And Company | Vapor phase decarbonylation process |
| CN101967133B (en) * | 2010-09-10 | 2013-01-23 | 西南化工研究设计院 | Process for preparing furan through decarbonylation of furfural |
| UA116630C2 (en) | 2012-07-03 | 2018-04-25 | Ксілеко, Інк. | METHOD OF CONVERTING SUGAR TO FURFURYL ALCOHOL |
| CN107011290B (en) * | 2012-10-18 | 2019-07-26 | 三菱化学株式会社 | The manufacturing method of tetrahydrofuran |
| RU2689115C2 (en) | 2014-03-31 | 2019-05-24 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. | Method of producing furan and derivatives thereof |
| JP6575126B2 (en) * | 2014-05-08 | 2019-09-18 | 三菱ケミカル株式会社 | Method for producing furfural and method for producing furan |
| WO2016158706A1 (en) | 2015-03-27 | 2016-10-06 | 三菱化学株式会社 | Method for producing furan compound and furfural composition |
| CN108467374A (en) * | 2018-02-11 | 2018-08-31 | 浙江大学 | The method that furfural hydrogenation reaction prepares biological furans is carried out in fixed bed reactors |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4780552A (en) * | 1986-09-23 | 1988-10-25 | Basf Aktiengesellschaft | Preparation of furan by decarbonylation of furfural |
| CN1095397C (en) * | 2000-11-09 | 2002-12-04 | 中国科学院兰州化学物理研究所 | Catalyst for preparing furan by gas-phase decarbonylation of furaldehyde |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US3007941A (en) * | 1959-12-31 | 1961-11-07 | Du Pont | Decarbonylation of furfural |
| JPS5841828A (en) * | 1981-09-04 | 1983-03-11 | Sumitomo Chem Co Ltd | Decarbonylating method of organic acid halide |
| DE10211101A1 (en) * | 2002-03-14 | 2003-09-25 | Basf Ag | Catalysts and processes for the production of amines |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4780552A (en) * | 1986-09-23 | 1988-10-25 | Basf Aktiengesellschaft | Preparation of furan by decarbonylation of furfural |
| CN1095397C (en) * | 2000-11-09 | 2002-12-04 | 中国科学院兰州化学物理研究所 | Catalyst for preparing furan by gas-phase decarbonylation of furaldehyde |
Non-Patent Citations (3)
| Title |
|---|
| 石军 等.糠醛制呋喃用Pd/C催化剂的制备研究.《郑州工业大学学报》.1998,第19卷(第3期),第96-99页. * |
| 胡艳平 等.糠醛气相脱羰Pd-Ni/γ-Al2O3催化剂的再生.《长春工业大学学报(自然科学版)》.2005,第26卷(第2期),第92-95页. * |
| 郑洪岩 等.糠醛脱羰制呋喃催化技术的研究进展.《精细与专用化学品》.2005,第13卷(第12期),第7-9,27页. * |
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