CN1058493C - r-丁内酯的制备方法 - Google Patents
r-丁内酯的制备方法 Download PDFInfo
- Publication number
- CN1058493C CN1058493C CN94194193A CN94194193A CN1058493C CN 1058493 C CN1058493 C CN 1058493C CN 94194193 A CN94194193 A CN 94194193A CN 94194193 A CN94194193 A CN 94194193A CN 1058493 C CN1058493 C CN 1058493C
- Authority
- CN
- China
- Prior art keywords
- dihydrofuran
- hydrogenation catalyst
- catalyst
- butyrolactone
- hydrogen
- 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.)
- Expired - Fee Related
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- 238000000034 method Methods 0.000 title claims abstract description 66
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 54
- JKTCBAGSMQIFNL-UHFFFAOYSA-N 2,3-dihydrofuran Chemical compound C1CC=CO1 JKTCBAGSMQIFNL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007789 gas Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 18
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 18
- 229910052702 rhenium Inorganic materials 0.000 claims description 17
- 229910052802 copper Inorganic materials 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 15
- 239000012159 carrier gas Substances 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 230000000737 periodic effect Effects 0.000 claims description 5
- 230000002829 reductive effect Effects 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 3
- 239000008246 gaseous mixture Substances 0.000 claims 1
- ARGCQEVBJHPOGB-UHFFFAOYSA-N 2,5-dihydrofuran Chemical compound C1OCC=C1 ARGCQEVBJHPOGB-UHFFFAOYSA-N 0.000 abstract description 20
- 238000002360 preparation method Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 3
- 125000004852 dihydrofuranyl group Chemical group O1C(CC=C1)* 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 41
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 21
- 239000000463 material Substances 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- 239000007787 solid Substances 0.000 description 17
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 150000002739 metals Chemical class 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 230000009466 transformation Effects 0.000 description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 150000002240 furans Chemical class 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 229960001866 silicon dioxide Drugs 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 229910000765 intermetallic Inorganic materials 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- LEHBURLTIWGHEM-UHFFFAOYSA-N pyridinium chlorochromate Chemical compound [O-][Cr](Cl)(=O)=O.C1=CC=[NH+]C=C1 LEHBURLTIWGHEM-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 238000006424 Flood reaction Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 238000004176 ammonification Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229930188620 butyrolactone Natural products 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229940116318 copper carbonate Drugs 0.000 description 2
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000007792 gaseous phase Substances 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 2
- 229910052622 kaolinite Inorganic materials 0.000 description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 235000012245 magnesium oxide Nutrition 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000000391 magnesium silicate Substances 0.000 description 2
- 229910052919 magnesium silicate Inorganic materials 0.000 description 2
- 235000019792 magnesium silicate Nutrition 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000001149 thermolysis Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 230000001131 transforming effect Effects 0.000 description 2
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 2
- JNODDICFTDYODH-UHFFFAOYSA-N 2-hydroxytetrahydrofuran Chemical compound OC1CCCO1 JNODDICFTDYODH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229920001800 Shellac Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 229910001038 basic metal oxide Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009904 heterogeneous catalytic hydrogenation reaction Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229960000869 magnesium oxide Drugs 0.000 description 1
- 229940091250 magnesium supplement Drugs 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910003449 rhenium oxide Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000004208 shellac Substances 0.000 description 1
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 description 1
- 229940113147 shellac Drugs 0.000 description 1
- 235000013874 shellac Nutrition 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D315/00—Heterocyclic compounds containing rings having one oxygen atom as the only ring hetero atom according to more than one of groups C07D303/00 - C07D313/00
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Furan Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
r-丁内酯的制备方法,在该法中让2,5-二氢呋喃或2,3-二氢呋喃或这两种二氢呋喃的混合物,在气相里,在水的存在下,在有附加氢或没有附加氢存在下,在较高的温度下,在一种氢化催化剂的作用下进行转化。
Description
本发明涉及一种制备r-丁内酯的方法。
Havel et al.(J.Org.Chem.41,513(1976))通过用三重态氧氧化2,3-二氢呋喃制得r-丁内酯。在该反应中r-丁内酯的产率仅为1.4%。Piancatelli etal.(Tetrahedron Lett.39,3483(1977))借助氯铬酸吡啶鎓氧化2,3-二氢呋喃。这种贵重的氧化剂氯铬酸吡啶鎓在该反应中以化学计量被消耗,所以这种办法由于经济上不合算,决不可能用于工业化。
r-丁内酯到目前为止还不可能由2,5-二氢呋喃出发直接得到。Alper et al.(J.Mol.Cat.72,143(1992))描述了用氧通过氯化钴(II)催化氧化反应,使2,5-二氢呋喃变成2-丁烯-4-羟酸内酯,见结构式I它的C-C双键在生成r-丁内酯之前,必须在下一步反应中进行氢化。因此该方法也是不经济的。
按EP-A 24 770文献,2,5-二氢呋喃在液相与水反应,在铂/钯/氧化铝催化剂作用下生成4-羟基丁醛。r-丁内酯在该反应中没有被发现。
r-丁内酯是一种需求很大的化学试剂,例如作为聚丙烯腈、酯酸纤维、聚苯乙烯、虫胶和树脂等的溶剂,另外作为制备重要经济产品的原料,如:吡咯烷酮、N-甲基吡咯烷酮和聚乙烯基吡咯烷酮。
本发明的任务是找到一种方法,该法从经济角度能实现由2,5-二氢呋喃或2,3-二氢呋喃出发制备出r-丁内酯。尤其应该找到一种途径,由2,5-二氢呋喃直接地,一步法制备出r-丁内酯。
因此,我们发现了一种制备r-丁内酯的方法,其特征是,让2,5-二氢呋喃或2,3-二氢呋喃或这两种二氢呋喃的混合物,在气相,在水的存在下和在有附加氢或无附加氢的条件下,在较高的温度下,在氢化催化剂上进行反应。
虽然对于本发明所述方法的基本反应的化学反应机理还不清楚,但是可以推测,该反应可按如下反应模式进行。推测2,5-二氢呋喃II首先在氧化催化剂上按反应式(1)异构化成为2,3-二氢呋喃III。随后,可将水加到2,3-二氢呋喃上(2),这里生成2-羟基四氢呋喃其结构式为IV,它与它的开链异构体4-羟基丁醛V处于平衡状态。2-羟基四氢呋喃IV然后由氢化催化剂,猜想按反应式(3)脱氢,生成r-丁内酯VI。使用的氢化催化剂因 而作为脱氢催化剂起作用。由于本发明所用的催化剂通常在工业上作为氢化催化剂使用,尽管在本报告范围内这些催化剂具有脱氢作用,但在本发明所述的方法中继续称作“氢化催化剂”。应该说,前面所叙述的反应机理,仅仅是为了解释在本发明所述的方法中,在催化剂上进行的化学过程,对于单一过程没有作进一步研究。对于该反应机理的建议基本上是以如下观察为依据的:在本发明所述的方法中,不仅2,5-二氢呋喃,而且2,3-二氢呋喃也可以被采用,本发明所述的方法可以在不存在氢的情况下进行,而且所发现的副反应也支持了以上的反应机理。
在本发明所述的方法中,2,5-二氢呋喃或2,3-二氢呋喃或这两种化合物的混合物,最好是2,5-二氢呋喃单一的,在气相与水反应,二氢呋喃/水的摩尔比通常为2∶1-1∶100,优选为1∶1-1∶50和更优选为1∶1-1∶10,在一种氢化催化剂存在下,在压力通常为50-5000千帕(0.50-50bar),优选为80-4000千帕(0.8-40bar)和更优选为100-1000千帕(1-10bar)情况下,在温度为100-350℃,优选为130-330℃和更优选为170-320℃条件下进行反应,生成r-丁内酯。
作为氢化催化剂,在本发明所述的方法中,实际上所有的适于氢化羰基的多相催化剂都可以被采用。例如,在文献Houben-Weyl,Methoden der OrganischenChemie Band IV,1C,S.16-26,Thieme-Vetlag,Stuttgart,1980所报导的。氢化催化剂在本发明所述的方法中可以配置在反应器中的固定床上或者流动的如在一个流化床上。
在本发明所述的方法中,最好使用多相氢化催化剂,该种催化剂含有元素周期表中Ib、VIb、VIIb和VIIIb族的一种或多种元素。这些催化剂出于催化活性和选择性的要求,还可以另外含有一种或多种选自元素周期表中Ia、IIa、IIIa、IVa和Va族的元素。优选的催化剂是这样的,它含有作为催化活性的组分,如:铜、铬、铼、钴、镍、铑、钌、铱、钯、铁或铂或者这些元素中的多种元素的混合物,以及任选地,作为其他的影响催化活性的选择性的组分,如:铟、锡或锑。特别优选的是在本发明所述的方法中使用含有铼和/或铜的氢化催化剂。
作为可用于本发明所述的方法中的多相催化剂,不仅所谓的沉淀催化剂,而且传统的载体催化剂也可以被采用,后者是通过把催化活性组分施放到一种载体材料上而制备的。
沉淀催化剂可以按下法制备:首先将催化活性的组分从它们的盐溶液中,尤其是从它的硝酸盐和/或醋酸盐的溶液中,通过加入碱金属和/或碱土金属氢氧化物溶液和/或碳酸盐溶液,例如作为难溶的氢氧化物、氧化物水合物、碱性盐或碳酸盐沉降出来,得到的沉淀物随后进行干燥,并随后通过煅烧,通常在300-700℃,尤其在400-600℃煅烧转变成相应的氧化物、混合氧化物和/或混合价的氧化物,它们通过用氢或含氢的气体,通常在50-700℃,尤其100-400℃进行处理,还原成相应的金属和/或较低氧化价的氧化物,并且转化成它们的真正的催化活性的形式。为此目的可使用其它适宜的还原剂,如:肼取代氢,当然最好是用氢气。在这里,通常还原反应进行到实际上不再消耗氢气为止。在制备含一种载体材料的沉淀催化剂时,催化活性组分的沉淀可以在有关的载体材料存在的情况下进行。但催化活性组分与载体材料同时从相关的盐溶液中被沉降出来则更为有利。合适的载体材料,例如:铝和钛的氧化物、锌氧化物、二氧化锆、二氧化硅、泥质土例如:高岭石、硅酸盐,如硅酸镁或硅酸铝或沸石,如ZSM-5-沸石或ZSM-10-沸石。也可以使用这些载体材料的混合物。如需要,可将干燥过的沉淀物在煅烧之前,与定形助剂,如:石墨、滑石或硬脂精,和/或与发泡剂,如:纤维素、甲基纤维素、淀粉、蜡、石蜡和/或聚亚烷基二醇进行掺合,并且压制或挤出成催化剂的成品形状,如:片剂、球形、环状或条状形状。
在本发明所述的方法中,最好采用如下的氢化催化剂,它含有沉积在一种载体材料上的能催化氢化反应的金属或金属化合物。除了上述的沉淀催化剂(该催化剂除了催化活性组分之外,还另外含有一个载体材料,)之外,通常如下这种载体催化剂特别适合于本发明所述的方法,在载体催化剂中,催化活性组分例如通过浸渍被施用上去的。
催化活性金属被施用到载体上的方式通常不是关键性的,可以用各种方式方法来达到。催化活性金属可以通过以下方法被施用到一种载体材料上去;例如通用用相关元素的盐或氧化物的溶液或悬浮液进行浸渍,然后干燥和随后借助一种还原剂,例如用氢、含氢的气体或肼,最好用含氢的气体,将金属化合物还原成相应的金属或较低氧化价的化合物。沉积在载体材料上的金属化合物的还原反应可以在与前面关于沉淀催化剂所描述的相同条件下进行。将催化活性金属施用到载体上去的另一种可能性是:载体用容易热分解的盐溶液进行浸渍,例如:用硝酸盐或容易热分解的配合物,例如:催化活性金属的羰基络合物或氢化配合物,并且对浸渍的载体在300-600℃进行加热,以便使吸附的金属化合物达到热分解。这个热分解最好在保护气体的气氛中进行。适合的保护气体是,如:氮气、二氧化碳、氢气或稀有气体。另外,催化活性金属还可以通过蒸发或火焰喷涂被沉积到催化剂载体上去。在这种情况下,作为载体材料也可以用金属线网或金属箔。
载体催化剂中的催化活性金属的含量,原则上讲,对于本发明所述方法的成功不是关键性的。对于本领域技术人员来讲,载体催化剂中具有较高的催化活性金属含量时,比起较低含量时产生较高的时空转化率。通常载体催化剂的催化活性金属占催化剂总量的0.1-90%重量,优选的为0.5-40%重量。由于这些含量数据是与催化剂总量有关。其中包括载体材料,然而不同的载体材料具有不同的比重和比表面积,所以这些数据也可以低于或高于给定的范围,而对本发明所述方法的结果不产生不利的影响。这些当然也适用于在各自的载体材料上的多种催化活性金属。催化活性金属例如还可以按文献DE-A 25 19 817,EP-A 147 219和EP-A 285 420的方法施用到载体上去。在上述文献所述的催化剂里,催化活性金属是作为合金存在的,它们是通过热处理和/或还原上述金属的盐或配合物产生的,上述金属的盐或配合物,例如通过使之浸渍法而沉积在载体上。
作为载体材料,通常可以用铝和钛氧化物、锌氧化物、二氧化锆、二氧化硅、泥质土例如:高岭石、硅酸盐如硅酸镁或硅酸铝、沸石如ZSM-5-沸石或ZSM-10-沸石、以及活性炭。优选的载体材料是铝氧化物、钛二氧化物、二氧化硅、二氧化锆或活性炭。当然也可以利用各种载体材料的混合物作为在本发明方法中所用的氢化催化剂的载体。
作为在本发明方法中所采用的氢化催化剂举例如下:铂/活性炭、钯/活性炭、钯/氧化铝、钴/活性炭、钴/二氧化硅、钴/氧化铝、铁/活性炭上、锰/活性炭、铼/活性炭、铼/二氧化硅、铼/锡/活性炭、铼/钯/活性炭、铜/活性炭、铜/二氧化硅、铜/氧化铝、亚铬酸铜(kupferchromit)以及按着DE-A 392 332、US-A 3 449445、EP-A 44 444、EP-A 147 219、DE-A 39 04 083、DE-A 23 21 101、EP-A 415 202、DE-A 23 66 264和EP-A 100 406所述的催化剂。
特别优选的催化剂包含至少铜或铼金属中的一种金属。含有铜的沉淀催化剂通常含有占催化剂总重量的0.1-90%重量,优选的含有1-80%重量,特别优选的含有5-50%重量的铜,以CuO进行计算。含有铜的、通过载体材料的浸渍或涂布制备的载体催化剂通常可以含有催化剂重量的0.1-30%重量,优选的含有1-30%重量、特别优选的含有3-25%重量的铜,以CuO计算。含有铼的催化剂,在本发明的方法中优先以载体催化剂的形式被采用,以Re计算的铼占据催化剂总重量的0.1-25%重量,优选的占1-20%重量,特别优选的占2-10%重量。
本发明的方法最好是连续进行。在此,例如可以采用管式反应器,在该种反应器中催化剂最好以固定床形式配置,或者采用流化床反应器,在该种反应器中催化剂通过气流被搅动。
离析物(educt)2,5-二氢呋喃和/或2,3-二氢呋喃和水,在它们被通过催化剂之前,可以在一个蒸发器里先进行气化。离析物最好在一个载气流中被气化,在此作为载气可以被采用的例如:稀有气体、氮气、C1-C4烃、最好是甲烷和优选为氢气。载体气流的计量以离析物、产物和在任何形成的副产物,如:1,4-丁二醇、四氢呋喃和丁醇,在反应器中保持气体状态为宜。
离析物气化时所用的载体流最好形成回路,也就是说,在脱离催化床时在载气流中含有的产物,例如在一个气-液-分离器中或在一个冷凝器里被分离出去以后,可以重新用于离析物的气化,充当载气流。如果没有采用气体循环方式或者采用非氢气的其它载气,那么在按反应式(3)进行的反应中,在催化剂上释放出的氢气足够维持氢化催化剂的活性。
在本发明的方法中,催化剂的负荷通常为0.05-5kg二氢呋喃/l催化剂·小时-1,优选的为0.1-3kg二氢呋喃/l催化剂·小时-1。
气体状态的反应器出料可以在产物冷却和冷凝之后,按传统的方式进行处理,例如通过分级蒸馏。将气态的反应器出料直接通入一个蒸馏柱也是可行的。在所述蒸馏过程中,可从产品r-丁内酯中分离任何存在的在反应器出料中含有的副产物,如:1,4-丁二醇、四氢呋喃和/或正丁醇等所需产物。在必要时,在反应器出料中含有的2,5-和/或2,3-二氢呋喃和/或水可以在产物蒸馏时被分离,并在气化之后,重新回到反应器中。
本发明所述的方法,使得由2,5-二氢呋喃和/或2,3-二氢呋喃出发,经济地制备r-丁内酯成为可能。在这里,特别突出的是r-丁内酯可以由2,5-二氢呋喃经一步法产生。
本发明中所用的原料2,5-二氢呋喃可以例如按us-A 5 034 545和us-A 5 082 956的方法通过乙烯基环氧乙烷的异构化进行制备。2,3-二氢呋喃可以由2,5-二氢呋喃经过碱催化的或光化学催化的异构化获得,例如按Pall et al.的方法(Bull.Soc.Chim.France 668(1950))或者Hubert et al.方法(J.Chem.Soc.Perkin I 366(1972))。
实施例
在下列实施例中给出的选择性(产量/转化率·100)是用气相色谱法采用一个内标进行测定的。实施例1
在一个备有外部加热设备的容量160ml的气相反应器中,放置砂砾状的102g铜/二氧化硅催化剂,(铜含量:22%重量,按CuO计算,催化剂的总重量为100;制法:用一种加氨碳酸铜溶液浸渍载体,浸透的载体在120℃干燥,在500℃煅烧),并且在氢气流中,在起始温度150℃和终结温度250℃条件下进行还原。然后用一个预蒸发器,将33ml/小时水和16ml/小时2,5-二氢呋喃在一个18l/小时的氢气流中,在200℃/101.3千帕(1013 mbar)条件下连续蒸发,并通入到温度为210℃的反应器中。反应器出料收集在一个冷却回收器里,并进行分析。在转化率为58%时,得到具有选择性为83%的r-丁内酯。(2,3-二氢呋喃:0.4%;呋喃:4%;四氢呋喃:9%;正丁醇:3%;残余:少量的各种低沸物,如丙醇,不对它们进行分析)。实施例2
按实施例1相同的方法,将15ml/小时2,5-二氢呋喃和32ml/小时水,在220℃通过149g含有铜/镁/二氧化硅的催化剂,(催化剂的组成:铜,以CuO计算:43.0%重量;镁,以MgO计算:18.0%重量;硅酸盐,以SiO2计算:35.0%重量;钡,以BaO计算:1%重量;铬,以Cr2O3计算:0.6%重量;锌,以ZnO计算:0.4%重量;钠,以Na2O计算:0.2%重量;残余主要是碳酸盐;所有的数据都基于催化剂的总重量。制法:金属盐的溶液和硅酸钠(水玻璃)中用碳酸钠进行同时沉淀,得到的沉淀物进行干燥,挤压成条状物,用滑石粉作为模塑助剂,在500℃煅烧,还原反应与实施例1相同)。在转化率为97%时,得到r-丁内酯,其选择性为85%(2,3-二氢呋喃:1.4%;呋喃:3%;四氢呋喃:9%;正丁醇:1%;残余;少量的各种未分析的低沸物)。实施例3
按实施例1同样方法,将19ml/小时2,5-二氢呋喃和11ml/小时水通过142g实施例2所述的催化剂。以99.7%的转化率得到r-丁内酯,其选择性为89%(2,3-二氢呋喃:0.13%;呋喃:3.9%;四氢呋喃:5%;正丁醇:1.7%;残余:少量的各种未分析的低沸物)。实施例4
按实施例1同样方法,将8ml/小时2,5-二氢呋喃和15ml/小时水,在210℃通过85g铜/活性炭催化剂(铜含量:10%重量,以CuO计算,基于催化剂总重量;制法:4mm的活性炭条状物用加氨碳酸铜溶液进行浸渍;在120℃进行干燥。按实施例1的方法进行还原反应)。以98%的转化率,生成r-丁内酯,其选择性为83%(2,3-二氢呋喃:2%;呋喃:4%;四氢呋喃:4%;正丁醇:1%;4-羟基丁醛:5%;1,4-丁二醇:0.2%;残余:少量的各种未分析的低沸物)。实施例5
按实施例1同样的方法,将10ml/小时2,5-二氢呋喃和9ml/小时水,通过73g铼/活性炭催化剂(铼含量:6%重量,以Re计算;制法:4mm的活性炭条状物用七氧化二铼Re2O7水溶液浸渍;在120℃干燥;按实施例1法还原)。以99%的转化率形成r-丁内酯,其选择性为91%(2,3-二氢呋喃:0.5%;呋喃:1%;四氢呋喃;5%;正丁醇:1%;残余:少量的各种未分析的低沸物)。实施例6
按实施例5同样的方法,将14ml/小时2,5-二氢呋喃和24ml/小时水,在220℃通过铼/活性炭催化剂。在完全转化的情况下,生成r-丁内酯,其选择性为87%(呋喃:2.5%;四氢呋喃:9%;正丁醇:1%;残余:各种未分析的低沸物)。实施例7
按实施例1所述同样方式,将16ml/小时2,5-二氢呋喃和30ml/小时的水在230℃通过253g市售亚铬酸铜(Munich,Suedchemie出售,并带有G22含义,厂商提供组成:37%Cu;46%Cr2O3;13%BaO;以类似于实施例1所述方法还原)。以71%转化率得到r-丁内酯,其选择性为67%(2,3-二氢呋喃:8%,呋喃:3%;四氢呋喃:2%;正丁醇:1%;4-羟基丁醛:0.5%;残余:各种未分析的低沸物)。实施例8
按实施例1同样的方法,将10ml/小时2,3-二氢呋喃和8ml/小时水,在220℃,在13l/小时氢载气流中,通过47g实施例5所述的铼/活性炭催化剂(反应器容积:100ml)。在以99.5%转化率,生成r-丁内酯,其选择性为98%(四氢呋喃:0.3%;4-羟基丁醛:0.5%;残余;少量的各种未分析的低沸物)。实施例9
按实施例8同样的方法,将10ml/小时2,3-二氢呋喃和10ml/小时水,在220℃,在13l/小时氢载气流中,通过45g铼/钯/活性炭催化剂(铼含量:3%重量,以Re计算;钯的含量:3%重量,以Pd计算;各自以催化剂总重量为基;制法:4mm的活性炭条状物用PdCl2的盐酸水溶液浸渍,干燥后再将所述载体用七氧化二铼(Re2O7)水溶液浸渍;在120℃干燥和按实施例1法进行还原)。以99.5%的转化率,生成r-丁内酯,其选择性为1%。
载气流由氢气改换成12l/小时氮气时,在完全转化时,得到其选择性为15%的r-丁内酯。
Claims (10)
1.制备γ-丁内酯的方法,其特征是,让2,5-二氢呋喃或2,3-二氢呋喃或者这两种二氢呋喃的混合物,在气相,在水的存在下,以二氢呋喃/水的摩尔比为2∶1-1∶100,以及在有附加氢或没有附加氢的情况下,在较高的温度下,在一种氢化催化剂的作用下进行反应。
2.按权利要求1所述的方法,其特征是,在有附加氢的存在下,进行转化反应。
3.按权利要求1和2所述的方法,其特征是,在有附加氢的存在下进行转化反应,其中氢作为载气。
4.按权利要求1或2的方法,其特征是,转化反应在100-350℃温度下,50-5000千帕压力进行。
5.按权利要求1或2的方法,其特征是,使用一种氢化催化剂,它含有至少一种选自元素周期表的Ib、VIb、VIIb和/或VIIIb族的元素。
6.按权利要求1或2的方法,其特征是,使用一种氢化催化剂,它除了含有至少一种选自元素周期表的Ib、VIb、VIIb和/或VIIIb族的元素之外,还含有至少一种选自元素周期表的IIb、Ia、IIa、IIIa、Va和/或VIa族的元素。
7.按权利要求1或2的方法,其特征是,使用一种含有铼的氢化催化剂。
8.按权利要求1或2的方法,其特征是,使用一种含有铜的氢化催化剂。
9.按权利要求1或2的方法,其特征是,所用的氢化催化剂是载体催化剂。
10.按权利要求1或2的方法,其特征是,在反应开始之前,用氢或含氢的气体混合物对氢化催化剂进行还原。
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DE4339269A DE4339269A1 (de) | 1993-11-18 | 1993-11-18 | Verfahren zur Herstellung von gamma-Butyrolacton |
DEP4339269.5 | 1993-11-18 |
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CN1135213A CN1135213A (zh) | 1996-11-06 |
CN1058493C true CN1058493C (zh) | 2000-11-15 |
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US (1) | US5646307A (zh) |
EP (1) | EP0729462B1 (zh) |
JP (1) | JP3411285B2 (zh) |
KR (1) | KR100326495B1 (zh) |
CN (1) | CN1058493C (zh) |
AT (1) | ATE176908T1 (zh) |
AU (1) | AU8141294A (zh) |
CA (1) | CA2176587C (zh) |
DE (2) | DE4339269A1 (zh) |
ES (1) | ES2128030T3 (zh) |
FI (1) | FI962046A0 (zh) |
RU (1) | RU2138491C1 (zh) |
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DE19636066A1 (de) * | 1996-09-05 | 1998-03-12 | Basf Ag | Verfahren zur Dehydrierung von 1,4-Butandiol zu gamma-Butyrolacton |
JP4483156B2 (ja) * | 2002-03-28 | 2010-06-16 | 三菱化学株式会社 | ガンマブチロラクトンの精製方法 |
KR101103512B1 (ko) * | 2009-11-25 | 2012-01-09 | 에스케이종합화학 주식회사 | 1,4-부탄디올로부터 n-메틸 피롤리돈의 제조방법 |
CN103204835B (zh) * | 2012-01-13 | 2015-07-29 | 中国石油化工股份有限公司 | 一种丁内酯的制备方法 |
CN103288786B (zh) * | 2012-02-29 | 2015-03-18 | 中国石油化工股份有限公司 | 一种四氢呋喃氧化的方法 |
RU2537349C2 (ru) * | 2013-03-29 | 2015-01-10 | Федеральное государственное бюджетное учреждение науки Институт нефтехимии и катализа Российской академии наук | Способ получения 3-алкилдигидрофуран-2(3н)-онов |
WO2021045153A1 (ja) * | 2019-09-06 | 2021-03-11 | 昭和電工株式会社 | ガンマブチロラクトンの製造方法およびn-メチルピロリドンの製造方法 |
CN115779957B (zh) * | 2022-12-10 | 2024-03-19 | 南通格瑞凯泰工程技术有限公司 | 1,4-丁二醇低压脱氢制γ-丁内酯用催化剂及其应用 |
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EP0024770A1 (en) * | 1979-09-04 | 1981-03-11 | Shell Internationale Researchmaatschappij B.V. | Hydrolysis of allyl ethers and ketones thus prepared |
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RO91930B1 (ro) * | 1985-03-14 | 1987-07-01 | Institutul De Cercetari Chimice | Procedeu pentru prepararea y-butirolactonei |
DE3926147A1 (de) * | 1989-08-08 | 1991-02-14 | Basf Ag | Verfahren zur herstellung von 2,5-dihydrofuranen |
US5082956A (en) * | 1990-03-08 | 1992-01-21 | Eastman Kodak Company | Isomerization of epoxyalkenes to 2,5-dihydrofurans |
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1993
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EP0024770A1 (en) * | 1979-09-04 | 1981-03-11 | Shell Internationale Researchmaatschappij B.V. | Hydrolysis of allyl ethers and ketones thus prepared |
Non-Patent Citations (2)
Title |
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CA,VOL,108(16),ABSTRACT NO.133838E 1988.4.1 A.GHITA-DUMINICA ET AL * |
TETRAHEDRON LETTERS 第39期 1977.9.1 G.0IANCATELL ET AL * |
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FI962046A (fi) | 1996-05-14 |
US5646307A (en) | 1997-07-08 |
CA2176587C (en) | 2004-05-25 |
JPH09505067A (ja) | 1997-05-20 |
WO1995014010A1 (de) | 1995-05-26 |
FI962046A0 (fi) | 1996-05-14 |
KR100326495B1 (ko) | 2002-11-27 |
CA2176587A1 (en) | 1995-05-26 |
TW360649B (en) | 1999-06-11 |
JP3411285B2 (ja) | 2003-05-26 |
DE59407851D1 (de) | 1999-04-01 |
RU2138491C1 (ru) | 1999-09-27 |
EP0729462B1 (de) | 1999-02-24 |
AU8141294A (en) | 1995-06-06 |
DE4339269A1 (de) | 1995-05-24 |
CN1135213A (zh) | 1996-11-06 |
ES2128030T3 (es) | 1999-05-01 |
EP0729462A1 (de) | 1996-09-04 |
KR960705801A (ko) | 1996-11-08 |
ATE176908T1 (de) | 1999-03-15 |
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