CN1210526A - 由二烷氧基丁烯制备四氢呋喃 - Google Patents
由二烷氧基丁烯制备四氢呋喃 Download PDFInfo
- Publication number
- CN1210526A CN1210526A CN97192054A CN97192054A CN1210526A CN 1210526 A CN1210526 A CN 1210526A CN 97192054 A CN97192054 A CN 97192054A CN 97192054 A CN97192054 A CN 97192054A CN 1210526 A CN1210526 A CN 1210526A
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- CN
- China
- Prior art keywords
- formula
- catalyst
- butyleneglycol
- catalyzer
- butylene
- 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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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 title claims abstract description 76
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title abstract 3
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 15
- 238000005649 metathesis reaction Methods 0.000 claims abstract description 14
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 46
- 150000001875 compounds Chemical class 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000005984 hydrogenation reaction Methods 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 13
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- -1 1,4-dibutoxy butylene Chemical group 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 7
- 229910052702 rhenium Inorganic materials 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 150000002431 hydrogen Chemical group 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical class CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims 1
- 150000003304 ruthenium compounds Chemical class 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 14
- OZCRKDNRAAKDAN-UHFFFAOYSA-N but-1-ene-1,4-diol Chemical compound O[CH][CH]CCO OZCRKDNRAAKDAN-UHFFFAOYSA-N 0.000 abstract 2
- 125000006732 (C1-C15) alkyl group Chemical group 0.000 abstract 1
- 125000003710 aryl alkyl group Chemical group 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 16
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 229910021536 Zeolite Inorganic materials 0.000 description 11
- 239000010457 zeolite Substances 0.000 description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 10
- 150000002739 metals Chemical class 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000011964 heteropoly acid Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002841 Lewis acid Substances 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000002638 heterogeneous catalyst Substances 0.000 description 4
- 150000007517 lewis acids Chemical class 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229960001866 silicon dioxide Drugs 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000007600 charging Methods 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 229910000765 intermetallic Inorganic materials 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 230000017105 transposition Effects 0.000 description 3
- IFTGEZOPUAJVMG-UHFFFAOYSA-N 1,1-dibromobut-1-ene Chemical compound CCC=C(Br)Br IFTGEZOPUAJVMG-UHFFFAOYSA-N 0.000 description 2
- OBXQRJAQMQQZMY-UHFFFAOYSA-N 4-butoxybutan-1-ol Chemical class CCCCOCCCCO OBXQRJAQMQQZMY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000001149 thermolysis Methods 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- MLRCQIICAYVJHD-UHFFFAOYSA-N 1-but-1-enoxybut-1-ene Chemical compound CCC=COC=CCC MLRCQIICAYVJHD-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- JKTCBAGSMQIFNL-UHFFFAOYSA-N 2,3-dihydrofuran Chemical compound C1CC=CO1 JKTCBAGSMQIFNL-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- VHFCHIFMOIOXSV-UHFFFAOYSA-L [Cu].[Ba].[Cr](=O)(O)O Chemical compound [Cu].[Ba].[Cr](=O)(O)O VHFCHIFMOIOXSV-UHFFFAOYSA-L 0.000 description 1
- SHPBBNULESVQRH-UHFFFAOYSA-N [O-2].[O-2].[Ti+4].[Zr+4] Chemical compound [O-2].[O-2].[Ti+4].[Zr+4] SHPBBNULESVQRH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229940000488 arsenic acid Drugs 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 229910052676 chabazite Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium 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
- 239000000470 constituent Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002084 enol ethers Chemical class 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010285 flame spraying Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 125000001145 hydrido group Chemical group *[H] 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- LVIYYTJTOKJJOC-UHFFFAOYSA-N nickel phthalocyanine Chemical compound [Ni+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 LVIYYTJTOKJJOC-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- FXADMRZICBQPQY-UHFFFAOYSA-N orthotelluric acid Chemical compound O[Te](O)(O)(O)(O)O FXADMRZICBQPQY-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
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Abstract
描述了一种制备四氢呋喃的方法,该法包括,在20—300℃、1—300巴下、在催化剂或催化剂组合物存在下,使式Ⅰ和 /或Ⅱ的1,4-丁二醇二醚与水和氢反应,式中R可为相同的可不同的,为C1-C15烷基或环烷基、C6-C12芳基或C7-C15芳烷基,催化剂或催化剂组合物具有有加氢能力以及有酸性中心或碱性中心的成分,还描述了一种通过易位作用来制备式Ⅰ的1,4-丁二醇二醚的新方法。
Description
本发明涉及一种在催化剂或催化剂组合物存在下,通过二烷氧基丁烯与水和氢反应来制备四氢呋喃的方法,该催化剂有加氢能力且有酸性或碱性中心。
在工业上,通过1,4-丁二醇环化来大规模制备四氢呋喃(Weissermel,Arpe工业有机化学,第4版,VCH出版社Weinheim,1994,111页)。另一制备四氢呋喃的可能方法是二氢呋喃加氢(EP-A524216)。
在这些情况下,前体原料是乙炔、丙烯或环氧丙烷、顺酐或丁二烯。因为丁二烯很容易得到,所以现在优先寻找由丁二烯出发的新方法,以便以更简单的方式和更低的费用来制备四氢呋喃,特别是减少反应步骤的数目。
以丁二烯原料为基础的中间体是二烷氧基丁烯,它们可为1,4-二烷氧基-2-丁烯(顺式的和反式的)和1,4-二烷氧基-1-丁烯。
它们可用以下通式表示
RO-CH2-CH=CH-CH2-OR Ⅰ和 RO-CH2-CH2-CH=CH-OR Ⅱ式中,R为相同的或不同的C1-C15烷基或环烷基,C6-C12芳基或C7-C15芳烷基。
式Ⅰ和Ⅱ的1,4-丁二醇二醚可用各种方法制备,例如通过二溴丁烯与2当量的醇反应,通过醇氧化加成到丁二烯上(SU-A 1046238或EP-A 462 031)或通过醇加成到乙烯基环氧乙烷上(WO-A 8902 883)。
同样与本发明有关的另一方法包括,使醇加成到丁二烯上,生成单烷氧基丁烯(如WO95/19334公开的),然后后者易位成二烷氧基-2-丁烯和2-丁烯。
我们发现,当式Ⅰ和/或式Ⅱ的1,4-丁二醇二醚在20-300℃、1-300巴下,在以下催化剂或催化剂组合物存在下与水和氢反应时,可用很少的步骤从丁二烯出发制得很好产率的四氢呋喃,
RO-CH2-CH=CH-CH2-OR Ⅰ
RO-CH2-CH2-CH=CH-OR Ⅱ
式中,R可相同或不同,为C1-C15烷基或环烷基、C6-C12芳基或C7-C15芳烷基。催化剂含有具备加氢能力以及有酸性或碱性中心的组分。
消去的醇可用来制备原料化合物Ⅰ和Ⅱ也是可能的。
有关设想的单个步骤的以下信息可在文献中得到:
虽然二烷氧基-2-丁烯异构成相应的二烷氧基-1-丁烯未描述过。但是,双三甲基甲硅烷基2-丁烯醚用氢化镍异构成双三甲基甲硅烷基1-丁烯醚(C.Malange et al.四面体通讯,36)1995(1133-1136)被认为是与此类似的。
二烷氧基-1-丁烯水解成相应的醇和醛醚并不知道,文献中只有简单烯醇醚酸催化水解的例子(如下Okuyama et al.,美国化学协会杂志,89(1967)5826-5831)。
描述了醛醚用阮内镍作为催化剂(仅在α位烷基化的化合物用作烷氧基化合物)加氢成相应的4-烷氧基丁醇,随后在酸性催化剂上环化成四氢呋喃(THF)(EP18164B1)。但是,在这种情况下,醚组分不仅作为醇被消去,而且也作为相应的脱水产物如烯烃被消去,它们在环化过程可再利用,但有一定困难。由于经济原因,再利用是优选的。如果生成烯烃,则THF不是主要产物,而1,4-丁二醇是主要产物,并只有在水消去后才生成THF。
根据上述现有技术,令人吃惊的是,有可能由式Ⅰ和Ⅱ的二烷氧基丁二烯以一步或最多两步高选择性地制备THF,同时得到醇组分(因此有循环的可能性和形成一种循环工艺)。
反应可按一步或两步进行。
在一步法中,式Ⅰ和/或Ⅱ的化合物在气相或液相中、在水和氢以及催化剂存在下反应,得到THF和醇。该催化剂有加氢能力并有Brnsted酸和/或Lewis酸或碱中心,或者为加有Brnsted酸和/或Lewis酸或碱的适合催化剂。
前体和中间体中的R基团可为不同的,但优选为相同的。优选使用的基团是那些在消去作用后能得到伯醇的基因。
在两步法中,或Ⅰ和/或Ⅱ的化合物在水和氢以及加氢催化剂存在下反应,制得1,4-丁二醇单醚,后者带有中间纯化或不用中间纯化、在酸性或碱性催化剂上转化成THF和醇。
一步法或两步法可间歇进行,优选连续进行。
以下的方法特点适用于一步法和两步法中的第一步:
水与式Ⅰ和/或Ⅱ的1,4-丁二醇二醚的摩尔比为100∶1、优选50∶1、特别是10∶1。
主要由氢决定的反应压力为1-300、优选1-200、特别是1-100巴,反应温度为20-300、优选40-270、特别是80-200℃。
特别适用于本发明的催化剂是那些能使酮类或醛类与氢催化加氢生成醇类的催化剂。通常,它们含有周期表第Ⅰ、Ⅱ、Ⅵ-Ⅷ副族或第Ⅲ-Ⅴ主族中的一种或多种元素或其化合物。催化剂可为均相溶液(例子在以下文献中:H.Kropf,有机化学方法(Houben-Weyl),卷Ⅳ/IC,Georg Thieme出版社,斯图加特,1980,45-67页)或非均相催化剂。
优选的均相催化剂的例子是铑、钌、铱、钯、铂和钴与膦或亚磷酸盐配体的络合物,其制备方法例如在(A-A727641,H.Brunner in Hartley:金属-碳键的化学;卷5,110-124页,JohnWiley & Sons,New York 1989和Toth等人,无机化学学报(Inorg.Chim Acta)42,(1980)153以及它们所引的文献中描述。此外,适合的金属络合物还在WO95-193344公开。
Ru络合物是特别优选的。可提到的例子是HRuCl(CO)(TPP)3和H2Ru(CO)(TPP)3(TPP=三苯基膦)。
非均相催化剂可固定使用或移动使用,例如在流化床反应器中或在悬浮中使用。其例子例如在Houben-Weyl,有机化学方法,卷Ⅳ/IC16-26页中描述。
这些加氢催化剂中优选的是那些含有一种或多种第Ⅰb、Ⅱb、Ⅵb、Ⅶb和Ⅷ族元素,特别是铜、铬、铼、钴、铑、镍、钯、钌、铱和铂或其化合物的催化剂。
在本发明方法中使用的催化剂例如可为所谓的沉淀催化剂的那些催化剂。这类催化剂可用以下步骤来制备:通过加入碱金属和/或碱土金属的氢氧化物和/或碳酸盐,使催化活性组分从其盐溶液中、特别是从硝酸盐和/或乙酸盐溶液中沉淀出来,如作为微溶的氢氧化物、氧化物水合物、碱式盐或碳酸盐沉淀出来;随后干燥沉淀物;然后通过在300-700、特别是400-600℃下焙烧,将它们转化成相应的氧化物、混合氧化物和混合价氧化物;后者在50-700、特别是100-400℃下用氢或含氢气体进行处理,还原成相应的金属和/或低氧化态的氧化化合物,并转化成实际的催化活性形式。通常,这一还原过程一直进行到不再生成水为止。在含载体材料的沉淀催化剂的制备中,催化活性组分的沉淀可在相关载体材料存在下进行。但是,催化活性组分也可优选在载体材料从相关盐溶液中沉淀的同时沉淀、优选用于本发明方法的加氢催化剂是那些沉积在载体材料上的催化加氢的金属或金属化合物的催化剂。除了含催化活性组分外,上述的沉淀的催化剂另外还含有这样一种也适用于本发明方法的载体材料,它们中有催化加氢活性的组分例如通过浸渍法已涂布到载体材料上。
将催化活性金属涂布到载体上的方法通常并不重要,可用各种方法来完成。例如可用以下步骤将催化活性金属涂布到载体上、用相关元素的盐或氧化物的溶液或悬浮液浸渍;干燥;然后用还原剂、优选用氢或复杂氢化物将金属化合物还原成相关的金属或低氧化态的化合物。将催化活性金属涂布到载体上的另一可能的方法包括以下步骤:用易于进行热分解的盐溶液如硝酸盐溶液或用易于进行热分解的络合化合物的溶液如催化活性金属的羰基络合物或氢化络合物的溶液浸渍载体;将经浸渍的载体在300-600℃下加热,以便使吸附的金属化合物热分解,这一热分解优选在保护性气氛下进行。适合的保护气的例子是氮、二氧化碳、氢或惰性气体。
催化活性金属也可通过气相沉积法或火焰喷涂法沉积在催化剂载体上。对于本发明方法的成功来说,催化活性金属在这些负载催化剂上的含量原则上并不重要。对于熟练的技术人员来说,在这些负载催化剂中较高的催化活性金属含量比较低的含量可得到更高的空时转化率,这一点是不言而喻的。通常,按整个催化剂计,所用的负载催化剂含有0.1-90、优选0.5-40%(重量)催化活性金属。因为所述的含量是基于包括载体材料在内的整个催化剂,但是不同的载体材料可能有不同的比重和比表面,含量在这一范围上下波动也是可能的,对本发明的方法没有不良影响。当然,将多种催化活性金属涂布到特定载体材料上也是可能的。此外,例如用DE-A2519817、EP-A1477219和EP-A285420的方法将催化活性金属涂布到载体上是可能的。在这些专利公开的催化剂中,催化活性金属作为热处理和/或还原上述金属的盐或络合物浸渍得到的浸渍物生成的合金存在。
沉淀催化剂和负载催化剂的活化也可在反应开始时用存在的氢原位进行,但这些催化剂优选在使用前单独活化。
通常铝的氧化物,二氧化钛锆,二氧化硅,铝氧土如蒙脱土,硅酸盐如硅酸镁或硅酸铝,沸石如ZSM-5或ZSM-10沸石以及活性炭可用作载体材料。优选的载体材料是氧化铝、二氧化钛、二氧化硅、二氧化锆和活性炭。当然,使用不同载体材料的混合物作为本发明的催化剂载体也是可能的。
可提到的用于本发明方法的非均相催化剂的例子如下: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、镁/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、亚铬酸钡铜以及在DE-A3932332、US-A3449445、EP-A44444、EP-A147219、DE-A3904083、DE-A2321101、WEP-A415202、DE-A2366264和EP-A100406中公开的催化剂。
特别优选的催化剂含有金属铜、钌或铼中至少一种。
对于气相反应,可将Brnsted酸和/或Lewis酸或碱涂布到催化剂上;而对于液相反应,它们也可为均相溶液形式。Brnsted酸和/或Lewis酸是优选的。优选使用的酸或碱如下。
如果反应分两步进行,第一步的流出物—若适宜,除去催化剂后—可直接分离或优选蒸馏分离成醇组分、若适宜过量水、和4-烷氧基丁醇,后者再用于在气相或液相中释放THF。
生成THF和醇的环化可在均相的或非均相的碱性催化剂上、优选在均相的或非均相的酸性催化剂进行。
碱性催化剂的例子是碱金属的或碱土金属的氧化物或氢氧化物或含有这些碱性组分的载体材料,例如浸渍的或喷涂的或碱性离子交换的。
酸性催化剂的例子是H型沸石、酸性离子交换剂、杂多酸、酸性的和超强酸性的金属氧化物—如果适当,它们可用硫酸盐或磷酸盐掺杂,以及无机酸或有机酸。
适用的沸石的例子为丝光沸石类,或小孔的毛沸石或菱沸石,八面沸石如Y-、X-或L-沸石。这类八面沸石还包括八面沸石型的“超稳”沸石,即脱铝的沸石。
特别优选的沸石是那些五元环结构(pentasil structure)的沸石,如ZSM-5、ZSM-11和ZSM-10。它们有SiO2四面体构成的五元环形式的共同的基本结构单元。它们有高的SiO2/Al2O3比,其孔径介于A型沸石和X或Y型沸石之间。
同样适用的酸性催化剂是杂多酸,如无机多酸,与同多酸不同,它们有至少两个不同的中心原子。可提到的例子是磷钨酸H3PW12O40·xH2O和磷钼酸H3PMo12O40·xH2O。原则上也可使用在EP-A158229中提到的催化剂和催化剂组合物。
优选的杂多酸是钼或钨与磷酸、碲酸、硒酸、砷酸、硅酸的杂多酸,特别是与磷酸的杂多酸。
杂多酸的质子可部分地被金属离子替代,在这种情况下,碱金属离子和碱土金属离子是优选的。
酸性离子交换剂如带磺基的交联聚苯乙烯或酸性金属氧化物如SiO2、Al2O3、ZrO2、TiO2、SuO2、TiO2等或单个氧化物的组合物也是适用的。氧化物也可用无机酸如硫酸处理,以提高酸强度。
无机酸如硫酸和磷酸以及有机酸如磺酸也适用作酸性催化剂。
如果反应以两步进行,本发明第二反应步骤中的温度保持在30-300、优选40-280、特别是60-250℃。
取决于所选的体系,反应压力可能稍有下降或升高。通常,反应压力为0.1-10、优选0.5-5、特别是0.8-4巴。
反应产物可通过惰性气流优选从均相反应混合物中除去。
反应产物THF和醇用传统的方法分离,优选用蒸馏法分离。
完成本发明方法的另一可能的方法是一步法和两步法的组合。在这种情况下,在一步法条件下未完全转化成THF和醇的4-烷氧基丁醇在本发明的条件下、在第二步中完全被转化是可能的。
此外,本发明还涉及单独制备式Ⅲ的1,4-丁二醇单醚
HO-CH2-CH2-CH2-CH2-OR Ⅲ,式中,R有式Ⅰ和Ⅱ所示的含义,在这种场合下,式Ⅰ和/或Ⅱ的1,4-丁二醇二醚如权利要求1所要求的那样与水和氢在加氢催化剂存下、在20-300℃、1-300巴下反应。
适合的加氢催化剂是能进一步催化生成四氢呋喃的反应而又没有酸性或碱性中心的上述所有催化剂。式Ⅲ的丁二醇单醚是有价值的中间体,在合成活性物质和塑料中用作C4基本单元。
此外,本发明还涉及一种用易位法制备式Ⅰ原料的新方法,其中式Ⅳ的2-丁醇醚
CH3-CH=CH-CH2-OR Ⅳ,R有式Ⅰ和Ⅱ所述的含义,在易位催化剂存在下转化成丁烯和式Ⅰ的1,4-丁二醇二醚
RO-CH2-CH=CH-CH2-OR Ⅰ,式中R有上述式Ⅰ给出的含义,条件是两个R有相同含义。
适合的易位催化剂是过渡金属、特别是元素周期表第Ⅳ、Ⅵ、Ⅶ和Ⅷ副族金属的均相化合物和非均相化合物,以及含有这些化合物的均相催化剂和非均相催化剂。这样的催化剂的例子在文献有描述(如G.W.Parshall,S.D.Ⅲd,均相催化,第2版,1992,Wiley,217页往后;R.L.Banks,催化,卷,100页往后;R.H.Grubbls,无机化学进展,卷24,1页往后)。
优选的催化剂为Grubbs在WO93、20111中公开的通式为RuX2(=CHR)(PR′3)2的钌化合物,式中X为卤素,R为氢、烷基或芳基,R′为烷基。式〔Ru(η6-arene)X2〕2/(PR3)/N2CHR′化合物的混合物也是适用且优选的,其作为易位催化剂的适用性在Neols的化学协会杂志,化学通讯,1995,1127页往后中描述,式中arene例如为苯、均三甲苯或异丙苯,X为卤素,R为烷基和R′为氢、烷基、芳基或三甲基甲硅烷基。
络合物RuCl2(=CHPh)(PCy3)2(Cy=环己基)以及基于商购的化合物〔Ru(η6-对异丙苯)Cl2〕2/PCy3/N2CHSiMe3的催化剂体系是特别优选的。也可使用其反应产物、即络合物〔Ru(η6-对异丙苯)(PCy3)Cl2〕代替组分Ru(η6-对异丙苯)Cl2和PCy3。
US5342985(DE3940196A)和化学协会杂志,化学通讯(1979)330-331页描述了在非均相Re化合物作为易位催化剂存在下,通过消去乙烯,由相应的烯丙基醚合成1,4-二烷氧基丁烯。
所以,令人吃惊的是,在Ru化合物存在下,原则上不容易易位反应(与烯丙基醚相比)的1-烷氧基-2-丁烯不会异构成1-烷氧基-1-丁烯,相反,却通过消去2-丁烯,选择性生成了1,4-二烷氧基丁烯。
因为与使用二溴丁烯相比,易位反应是在工业上和环境上有利的替代方法,使用通过易位作用制备的丁二醇二醚作为本发明制备四氢呋喃的前体是优选的。
用以下实施例详细地说明本发明的方法,但决不是对本发明的限制。用气相色谱法进行分析。在实施例中使用的二丁氧基丁烯的纯度为约98%。
实施例1
将200ml铜/活性炭催化剂(按CuO计,铜含量为约10%;在4mm活性炭小球上;铜作为氨化物涂布)装入200ml管式反应器中,然后在约180℃下、氢气流中活化。在氢气流中(40l/h),在1巴、230℃下将两种进料通过催化剂段,进料为10%(重量)二丁氧基-2-丁烯于正丁醇中的溶液(11g/h)和11g/h水,每种进料为气态。反应流出物呈两相。每小时间隔取样,并用气相色谱分析。有机相含有(按无水计算)95-98%正丁醇和约0.8%THF。水相含(按无水计算)95%正丁醇和约0.5%THF。
实施例2
将200ml铼/活性炭催化剂(Re含量约6%(重量),4mm活性炭小球,Re作为Re2O7涂布)在300℃下活化,如在实施例1中那样。然后在220℃下用25l/h氢气载气流使约12g/h二丁氧基-2-丁烯和约11g/h水通过催化剂。流出物含有59%丁醇和30%THF。
实施例3(两步法制备)
a)将5g二丁氧基-2-丁烯、5g水、0.1g HRuCl(CO)(TPP)3和0.05g TPP(三苯基膦)装入72ml金属高压釜中,然后注入50巴氢气。在搅拌下将高压釜加热到150℃,2小时后冷却。残压为40巴。将反应的两相流出物用13g甲醇均质化,以便分析。发现有约80%4-丁氧基丁醇和约17%丁醇。
b)将10g粉末Al2O3和18g 4-丁氧基丁醇送入蒸馏设备的底部,并加热到175℃。在这一温度下蒸出反应产物。以产物蒸出速率连续补充新鲜的4-丁氧基丁醇。蒸馏物含有约3%前体、52%丁醇和45%THF。
实施例4(通过易位作用制备二烷氧基丁烯)
在氩气氛下,在玻璃容器中将41mg RuCl2(=CHPh)(PCy3)2(Cy=环己基)与8.0g 1-丁氧基-2-丁烯混合,并将混合物在室温下搅拌。反应中生成的丁烯可通过计泡计排出。12小时后,用气相色谱(GC/MS联用)分析反应混合物。除了原料化合物外,还鉴定出1-丁氧基-2-丁烯(E和Z异构体为51.6和18.6%(面积))和二丁基醚(4.2%(面积)、1,4-二丁氧基-2-丁烯)E和Z异构体为4.78和17.1%(面积))和2-丁烯(2.9%(面积))。1,4-二丁氧基-1-丁烯(0.7%(面积))为次要组分。
实施例5
步骤为实施例4中所述的,但使用〔Ru(η6-对异丙苯)(PCy3)Cl2〕/N2CHSiMe3作为催化剂。在60℃下12小时后,用气相色谱柱测出1,4-二丁氧基丁烯(1.9和3.0%(面积))。
Claims (11)
1.一种制备四氢呋喃的方法,该法包括,在20-300℃、1-300巴下,在催化剂或催化剂组合物存在下,使式Ⅰ和/或Ⅱ的1,4-丁二醇二醚
RO-CH2-CH=CH-CH2-OR Ⅰ
RO-CH2-CH2-CH=CH-OR Ⅱ,与水和氢反应,式中,R为相同的或不同的,为C1-C15烷基或环烷基、C6-C12芳基或C7-C15芳烷基,催化剂或催化剂组合物含有有加氢能力且有酸性中心或碱性中心的成分。
2.根据权利要求1的方法,其中使用含有周期表第Ⅰ、Ⅱ或Ⅵ、Ⅶ、Ⅷ副族或Ⅲ、Ⅳ、Ⅴ主族元素中一种或多种元素或其化合物作为加氢组分的催化剂。
3.根据权利要求1的方法,其中使用含有铼、铜或钌中一种或多种元素或其化合物作为加氢组分的催化剂。
4.根据权利要求1的方法,其中反应按两步进行:
a)在第一步中、在加氢催化剂存在下,使式Ⅰ和/或Ⅱ的丁二醇二醚与水和氢反应,得到相应的1,4-丁二醇单醚,以及
b)在40-280℃下、在酸性催化剂或碱性催化剂存在下,使后者环化,生成四氢呋喃。
5.一种制备式Ⅰ的1,4-丁二醇二醚的方法,
RO-CH2-CH=CH-CH2-OR Ⅰ该法包括,在易位催化剂存在下,使式Ⅳ的2-丁醇醚反应,生成丁烯和相应的1,4-丁二醇二醚,
CH3-CH=CH-CH2-OR Ⅳ式中,R为C1-C15烷基或环烷基、C6-C12芳基或C7-C15芳烷基。
6.根据权利要求1的方法,其中用权利要求5的方法制备的1,4-丁二醇二醚用作前体。
7.根据权利要求5的方法,其中使用含有钌或钌化合物的催化剂。
8.根据权利要求5的方法,其中式RuCl2(=CHR)(PR′3)2的化合物用作易位催化剂,式中R为氢、烷基或芳基,R'为烷基。
9.根据权利要求5的方法,其中式〔RuX2(η6-对异丙苯)PCy3〕/N2CHR′的化合物用作易位催化剂,式中X为卤素,Cy为环己基,R′为氢、烷基、芳基或三甲基甲硅烷基。
10.根据权利要求5的方法,其中在易位催化剂存在下,将1-丁氧基-2-丁烯转化成2-丁烯和1,4-二丁氧基丁烯。
11.一种制备式Ⅲ的1,4-丁二醇单醚的方法,
HO-CH2-CH2-CH2-CH2-OR Ⅲ式中,R有权利要求1中所述的含义,该法包括,在加氢催化剂存在下,在20-300℃、1-300巴下,使权利要求1所示的式Ⅰ和/或Ⅱ的1,4-丁二醇二醚与水和氢反应。
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US7538060B2 (en) * | 2007-02-14 | 2009-05-26 | Eastman Chemical Company | Palladium-copper chromite hydrogenation catalysts |
US20080194398A1 (en) * | 2007-02-14 | 2008-08-14 | Eastman Chemical Company | Ruthenium-copper chromite hydrogenation catalysts |
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US2251835A (en) * | 1939-05-05 | 1941-08-05 | Gen Aniline & Film Corp | Production of tetrahydrofurane from 1,4-butylene glycol |
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