US20010009964A1 - Catalyst for preparing lactone and a method for preparing lactone - Google Patents
Catalyst for preparing lactone and a method for preparing lactone Download PDFInfo
- Publication number
- US20010009964A1 US20010009964A1 US09/737,894 US73789400A US2001009964A1 US 20010009964 A1 US20010009964 A1 US 20010009964A1 US 73789400 A US73789400 A US 73789400A US 2001009964 A1 US2001009964 A1 US 2001009964A1
- Authority
- US
- United States
- Prior art keywords
- catalyst
- copper
- zinc
- lactone
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- 150000002596 lactones Chemical class 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 150000002009 diols Chemical class 0.000 claims abstract description 17
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 150000003752 zinc compounds Chemical class 0.000 claims abstract description 9
- 230000003213 activating effect Effects 0.000 claims abstract description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 54
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 38
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 32
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 19
- 239000011787 zinc oxide Substances 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052788 barium Inorganic materials 0.000 claims description 9
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 8
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 4
- UNVGBIALRHLALK-UHFFFAOYSA-N 1,5-Hexanediol Chemical compound CC(O)CCCCO UNVGBIALRHLALK-UHFFFAOYSA-N 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 4
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 claims description 4
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 4
- -1 δ-butyrolactone Chemical compound 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011667 zinc carbonate Substances 0.000 claims description 3
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 3
- 229940058015 1,3-butylene glycol Drugs 0.000 claims description 2
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 claims description 2
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052790 beryllium Inorganic materials 0.000 claims description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 2
- GSCLMSFRWBPUSK-UHFFFAOYSA-N beta-Butyrolactone Chemical compound CC1CC(=O)O1 GSCLMSFRWBPUSK-UHFFFAOYSA-N 0.000 claims description 2
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 claims description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 2
- 229910000009 copper(II) carbonate Inorganic materials 0.000 claims description 2
- 229910000153 copper(II) phosphate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 2
- GQDHEYWVLBJKBA-UHFFFAOYSA-H copper(ii) phosphate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GQDHEYWVLBJKBA-UHFFFAOYSA-H 0.000 claims description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 2
- 239000011646 cupric carbonate Substances 0.000 claims description 2
- 235000019854 cupric carbonate Nutrition 0.000 claims description 2
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- SXCBDZAEHILGLM-UHFFFAOYSA-N heptane-1,7-diol Chemical compound OCCCCCCCO SXCBDZAEHILGLM-UHFFFAOYSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229960000380 propiolactone Drugs 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 235000004416 zinc carbonate Nutrition 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 2
- 229940007718 zinc hydroxide Drugs 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 2
- 229960000314 zinc acetate Drugs 0.000 claims 1
- 235000013904 zinc acetate Nutrition 0.000 claims 1
- 229940043825 zinc carbonate Drugs 0.000 claims 1
- 229960001939 zinc chloride Drugs 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 229960004643 cupric oxide Drugs 0.000 description 13
- 239000005751 Copper oxide Substances 0.000 description 12
- 229910000431 copper oxide Inorganic materials 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 239000010949 copper Substances 0.000 description 9
- 239000012018 catalyst precursor Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(i) oxide Chemical compound [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- OBKXEAXTFZPCHS-UHFFFAOYSA-N 4-phenylbutyric acid Chemical compound OC(=O)CCCC1=CC=CC=C1 OBKXEAXTFZPCHS-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DGAODIKUWGRDBO-UHFFFAOYSA-N butanethioic s-acid Chemical compound CCCC(O)=S DGAODIKUWGRDBO-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000008194 pharmaceutical composition Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
Definitions
- the present invention relates to a catalyst for preparing a lactone, which is prepared by supporting a cupric compound, a zinc compound and at least one alkaline earth metal compound on the supporter.
- the present invention also relates to a method for preparing a lactone, which comprises a dehydrocyclization reaction of a diol under a gas phase in the presence of the aforementioned catalyst after activating said catalyst.
- Lactone such as ⁇ -butyrolactone
- ⁇ -butyrolactone may be used as a herbicide, used in the pharmaceutical composition, or used for preparing an intermediate; this intermediate is used to prepare pyrrolidone (such as N-methylpyrrolidone, 2-pyrrolidone and N-vinylpyrrolidone), piperidine, phenylbutyric acid and thiobutyric acid.
- pyrrolidone such as N-methylpyrrolidone, 2-pyrrolidone and N-vinylpyrrolidone
- piperidine such as N-methylpyrrolidone, 2-pyrrolidone and N-vinylpyrrolidone
- phenylbutyric acid such as phenylbutyric acid
- thiobutyric acid such as N-methylpyrrolidone, 2-pyrrolidone and N-vinylpyrrolidone
- ⁇ -butyrolactone was produced by a dehydrocyclization reaction with 1,4-butanediol, where a hydrogen by-product was generated as a raw material and as fuel.
- This method for preparing ⁇ -butyrolactone through the dehydrocyclization reaction of 1,4-butanediol is disclosed in Japanese Patent Unexamined Publication No. Sho-58-13575, wherein the dehydrocyclization reaction is carried out under liquid phase using a platinum/lead catalyst; however, the activity of said catalyst is low and the selectivity of ⁇ -butyrolactone is also low.
- Sho-61-246173 describes that ⁇ -butyrolactone is obtained by passing 1,4-butanediol vapor through a copper/chromium/zinc catalyst; however, this method may generate many tetrahydrofuran and butanol by-products, and the selectivity and yield of ⁇ -butyrolactone is usually low.
- the method disclosed in Japanese Patent Unexamined Publication No. Hei-3-232874 describes that ⁇ -butyrolactone is produced by passing 1,4-butanediol vapor through a copper/chromium/maniganese or barium catalyst; the method disclosed in U.S. Pat. No.
- the present inventors have deeply studied the above defects of the traditional technique and found more effective catalyst for preparing a lactone in the catalyst supporting a cupric compound, a zinc compound and at least one alkaline earth metal compound.
- the process for preparing lactone through the dehydrocyclization reaction of diol using the above catalyst under gas phase may increase the activity and lifetime of catalyst, while the selectivity may be up to 99 mol % or more; therefore the beneficial economic effect of industrial processes may be substantially increased.
- the present invention relates to a catalyst for preparing a lactone, which is prepared by supporting a cupric compound, a zinc compound and at least one alkaline earth metal compound on the supporter.
- the present invention also relates to a method for preparing a lactone, which comprises a dehydrocyclization reaction of a diol under a gas phase in the presence of the aforementioned catalyst after activating said catalyst.
- the catalyst for preparing lactone of the present invention is quite economic because of its high activity, long lifetime and high selectivity of products.
- the catalyst of the present invention used for preparing a lactone is prepared by supporting a cupric compound, a zinc compound and at least one alkaline earth metal compound on the supporter.
- the suitable materials for the supporter used in the catalyst of the present invention are silica, alumina, or their mixture, more preferably the mixture of silica and alumina.
- the zinc compound used in the catalyst of the present invention may be various zinc salts, of which the example are zinc nitrate (Zn(NO 3 ) 2 .6H 2 O), zinc carbonate (ZnCO 3 ), zinc acetate (Zn(CH 3 COO) 2 .2H 2 O), zinc chloride (ZnCl 2 ), zinc hydroxide (Zn(OH) 2 ), zinc sulfate (ZnSO 4 .7H 2 O), etc.
- the alkaline earth metal compound used in the catalyst of the present invention is at least one selected from a metal compound consisting of beryllium, magnesium, calcium, strontium and barium, and more preferably at least one selected from a metal compound consisting of magnesium, calcium and barium, which comprises their carbonate, hydroxide, silicate, phosphate, etc.
- the catalyst of the present invention used for preparing a lactone is prepared according to the following method.
- the supporter is immersed in the above aqueous cupric salt and zinc salt solutions, and the value of pH is adjusted between 8 and 11 using ammonia water, while the hydroxides of copper and zinc are precipitated on the supporter.
- the precipitate is washed with water and dried.
- the precipitate is immersed in the above aqueous salts solution selected from one or two alkaline earth metal compound(s) consisting of magnesium, calcium and barium, and then calcined for 3 to 5 hours at 400 to 500° C. If it is necessary, a mold-aid agent such as graphite may be added, and a predeterminate shape is molded by a molding machine.
- each metal component exists in the form of oxide. Therefore, before the dehydrogenation reaction of diol, the catalyst must be reduced and be activated at a temperature ranging from 180 to 250° C. for 6 to 20 hours with hydrogen gas wherein the ratio of hydrogen gas to nitrogen gas starts between 1:20 and 1:10 by volume, then gradually adjusts to all hydrogen gas.
- the ratio of copper (II) oxide to zinc oxide is usually 6:1 to 1:2 by weight, preferably 5:1 to 1:1.
- the alkaline earth metal compounds selected from a group consisting of magnesium, calcium and barium is used, its amount is preferably 0.01 to 10 wt %, more preferably 0.05 to 5 wt %, based on the total weight of copper (II) oxide and zinc oxide in terms of oxides.
- the example of the lactone used in the method for preparing lactone of the present invention includes, for instance, ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -butyrolactone, ⁇ -caprolactone, ⁇ -caprolactone, ⁇ -hydroxyoctylic acid lactone, ⁇ -hydroxynonylic acid lactone, ⁇ -hydroxydecylic acid lactone, ⁇ -hydroxydecylic acid lactone, etc.
- the reaction temperature usually ranges from 160 to 280° C., preferably 180 to 250° C.. If the reaction temperature is too low, the conversion of 1,4-butylene glycol may be decreased. Although the higher temperature may increase the conversion of 1,4-butylene glycol, the selectivity of ⁇ -butyrolactone may be substantially decreased.
- the reaction pressure usually ranges from 0 to 10 atm., preferably from 1 to 5 atm.
- the higher reaction pressure may easily carry out an undesired reaction, decreasing the yield.
- the hydrogen gas is needed as a carrier gas. If the hydrogen gas do not exist in the reaction system, the lifetime of catalyst may be shortened. The amount of hydrogen gas must at least maintain the reaction system in gas phase.
- the molar ratio of hydrogen gas to 1,4-butylene glycol used in the present invention ranges from (12 to 1): 1, preferably from (8 to 1.5):1.
- aqueous copper nitrate solution 350 g was slowly poured into 40 wt % of aqueous zinc nitrate solution (220 g) and the powder of silica (10 g) wherein the BET surface area was 185 m 2 /g (said surface area was measured according to the Brunner-Emmett-Teller Method), and the mixture was stirred vigorously. Subsequently, 25 wt % of ammonia water was added to maintain the pH value of the mixed aqueous solution at 10 while the mixture was still stirred. The precipitate was filtered and separated, washed with water, and placed into a oven to dry at 100° C.
- This catalyst precursor was moved to a tubular high-temperature furnace ,heated to 450° C., and calcined for 4 hours.
- the component of this catalyst was at a copper oxide/zinc oxide ratio of 3:1.
- the catalyst precursor prepared by Example 1 was immersed in 1.5 wt % of aqueous barium hydroxide solution. Then, this catalyst was moved to a tubular high-temperature furnace, heated to 450° C., and calcined for 4 hours. The component of this catalyst was 55 wt % of copper oxide, 22 wt % of zinc oxide and 1.2 wt % of barium oxide.
- the catalyst precursor prepared by Example 1 was immersed in 1.0 wt % of aqueous calcium hydroxide solution. Then, this catalyst was moved to a tubular high-temperature furnace, heated to 450° C., and calcined for 4 hours. The component of this catalyst was 53 wt % of copper oxide, 24 wt % of zinc oxide and 0.81 wt % of calcium oxide.
- the catalyst precursor prepared by Example 1 was immersed in 1.0 wt % of aqueous magnesium hydroxide solution. Then, this catalyst was moved to a tubular high-temperature furnace heated to 450° C., and calcined for 4 hours. The component of this catalyst was 49 wt % of copper oxide, 26 wt % of zinc oxide and 0.52 wt % of magnesium oxide.
- the catalyst precursor prepared by Example 1 was immersed in 1.5 wt % of aqueous barium hydroxide solution and 0.3 wt % of aqueous calcium hydroxide solution. Then, this catalyst was moved to a tubular high-temperature furnace, heated to 450° C., and calcined for 4 hours. The component of this catalyst was 55 wt % of copper oxide, 22 wt % of zinc oxide, 1.2 wt % of barium oxide and 0.14 wt % of calcium oxide.
- the catalyst precursor prepared by Example 1 was immersed in 1.0 wt % of aqueous magnesium hydroxide solution and 0.2 wt % of aqueous barium hydroxide solution. Then, this catalyst was moved to a tubular high-temperature furnace, heated to 450° C., and calcined for 4 hours. The component of this catalyst was 49 wt % of copper oxide, 26 wt % of zinc oxide, 0.52 wt % of magnesium oxide and 0.1 wt % of barium oxide.
Abstract
Description
- The present invention relates to a catalyst for preparing a lactone, which is prepared by supporting a cupric compound, a zinc compound and at least one alkaline earth metal compound on the supporter. The present invention also relates to a method for preparing a lactone, which comprises a dehydrocyclization reaction of a diol under a gas phase in the presence of the aforementioned catalyst after activating said catalyst.
- Lactone, such as γ-butyrolactone, may be used as a herbicide, used in the pharmaceutical composition, or used for preparing an intermediate; this intermediate is used to prepare pyrrolidone (such as N-methylpyrrolidone, 2-pyrrolidone and N-vinylpyrrolidone), piperidine, phenylbutyric acid and thiobutyric acid. Thus, developing an economic method for preparing γ-butyrolactone is a common industrial requirement.
- Previously, γ-butyrolactone was commonly produced by a hydrogenation reaction with maleic anhydride or maleic acid ester under liquid phase or gas phase. However, this is an undesirable industrial process because the process needs a lot of hydrogen gas and its catalyst has a short lifetime.
- Recently, γ-butyrolactone was produced by a dehydrocyclization reaction with 1,4-butanediol, where a hydrogen by-product was generated as a raw material and as fuel. This method for preparing γ-butyrolactone through the dehydrocyclization reaction of 1,4-butanediol is disclosed in Japanese Patent Unexamined Publication No. Sho-58-13575, wherein the dehydrocyclization reaction is carried out under liquid phase using a platinum/lead catalyst; however, the activity of said catalyst is low and the selectivity of γ-butyrolactone is also low. The method disclosed in Japanese Patent Unexamined Publication No. Sho-61-246173 describes that γ-butyrolactone is obtained by passing 1,4-butanediol vapor through a copper/chromium/zinc catalyst; however, this method may generate many tetrahydrofuran and butanol by-products, and the selectivity and yield of γ-butyrolactone is usually low. The method disclosed in Japanese Patent Unexamined Publication No. Hei-3-232874 describes that γ-butyrolactone is produced by passing 1,4-butanediol vapor through a copper/chromium/maniganese or barium catalyst; the method disclosed in U.S. Pat. No. 5,110,954 describes that γ-butyrolactone is obtained by adding 1,4-butanediol into the solution of copper/chromium catalyst; and the method disclosed in Japanese Patent Unexamined Publication No. Hei-2-255668 describes that γ-butyrolactone is produced by passing 1,4-butanediol vapor through a copper/zinc/alkali metal catalyst. However, the activity of these catalysts may decay quickly, and the conversion of 1,4-butylene glycol may become lower after reacting over a long period. Therefore, it is undesirable as an industrial process.
- The present inventors have deeply studied the above defects of the traditional technique and found more effective catalyst for preparing a lactone in the catalyst supporting a cupric compound, a zinc compound and at least one alkaline earth metal compound. The process for preparing lactone through the dehydrocyclization reaction of diol using the above catalyst under gas phase may increase the activity and lifetime of catalyst, while the selectivity may be up to 99 mol % or more; therefore the beneficial economic effect of industrial processes may be substantially increased. We have hereby accomplished the present invention.
- The present invention relates to a catalyst for preparing a lactone, which is prepared by supporting a cupric compound, a zinc compound and at least one alkaline earth metal compound on the supporter. The present invention also relates to a method for preparing a lactone, which comprises a dehydrocyclization reaction of a diol under a gas phase in the presence of the aforementioned catalyst after activating said catalyst. The catalyst for preparing lactone of the present invention is quite economic because of its high activity, long lifetime and high selectivity of products.
- The catalyst of the present invention used for preparing a lactone is prepared by supporting a cupric compound, a zinc compound and at least one alkaline earth metal compound on the supporter. The suitable materials for the supporter used in the catalyst of the present invention are silica, alumina, or their mixture, more preferably the mixture of silica and alumina.
- In the catalyst of the present invention used for preparing lactone, the cupric compound may be various cupric salts, of which the examples are copper (II) nitrate (Cu(NO3)2.3H2O), copper (II) carbonate (Cu2(OH)2CO3), copper (II) acetate (Cu(CH3COO)2), copper (II) chloride (CuCl2.2H2O), copper (II) hydroxide (Cu(OH)2), copper (II) phosphate (Cu3(PO4)2.3H2O), copper (II) sulfate (CuSO4.5H2O), etc. The zinc compound used in the catalyst of the present invention may be various zinc salts, of which the example are zinc nitrate (Zn(NO3)2.6H2O), zinc carbonate (ZnCO3), zinc acetate (Zn(CH3COO)2.2H2O), zinc chloride (ZnCl2), zinc hydroxide (Zn(OH)2), zinc sulfate (ZnSO4.7H2O), etc. The alkaline earth metal compound used in the catalyst of the present invention is at least one selected from a metal compound consisting of beryllium, magnesium, calcium, strontium and barium, and more preferably at least one selected from a metal compound consisting of magnesium, calcium and barium, which comprises their carbonate, hydroxide, silicate, phosphate, etc.
- The catalyst of the present invention used for preparing a lactone is prepared according to the following method. The supporter is immersed in the above aqueous cupric salt and zinc salt solutions, and the value of pH is adjusted between 8 and 11 using ammonia water, while the hydroxides of copper and zinc are precipitated on the supporter. The precipitate is washed with water and dried. The precipitate is immersed in the above aqueous salts solution selected from one or two alkaline earth metal compound(s) consisting of magnesium, calcium and barium, and then calcined for 3 to 5 hours at 400 to 500° C. If it is necessary, a mold-aid agent such as graphite may be added, and a predeterminate shape is molded by a molding machine. In such resultant catalyst, each metal component exists in the form of oxide. Therefore, before the dehydrogenation reaction of diol, the catalyst must be reduced and be activated at a temperature ranging from 180 to 250° C. for 6 to 20 hours with hydrogen gas wherein the ratio of hydrogen gas to nitrogen gas starts between 1:20 and 1:10 by volume, then gradually adjusts to all hydrogen gas.
- In the catalyst of the present invention used for preparing lactone, the ratio of copper (II) oxide to zinc oxide is usually 6:1 to 1:2 by weight, preferably 5:1 to 1:1. When any one of the alkaline earth metal compounds selected from a group consisting of magnesium, calcium and barium is used, its amount is preferably 0.01 to 10 wt %, more preferably 0.05 to 5 wt %, based on the total weight of copper (II) oxide and zinc oxide in terms of oxides. When any two of the alkaline earth metal compounds selected from a group consisting of magnesium, calcium and barium is used, their amounts are preferably 0.5 to 20 wt %, more preferably 1 to 10 wt %, based on the total weight of copper (II) oxide and zinc oxide in terms of oxides. The amount of support is preferably 0.5 to 20 wt %, more preferably 1 to 10 wt %, based on the total weight of copper (I) oxide and zinc oxide in terms of silica.
- The present invention also relates to a method for preparing a lactone, which comprises a dehydrocyclization reaction of a diol under a gas phase in the presence of the aforementioned catalyst after activating said catalyst.
- The example of the lactone used in the method for preparing lactone of the present invention includes, for instance, β-propiolactone, β-butyrolactone, γ-butyrolactone, γ-valerolactone, δ-butyrolactone, γ-caprolactone, ε-caprolactone, δ-hydroxyoctylic acid lactone, δ-hydroxynonylic acid lactone, γ-hydroxydecylic acid lactone, δ-hydroxydecylic acid lactone, etc.
- The example of the diol used in the method for preparing lactone of the present invention includes for instance, 1,3-propylene glycol, 2-methyl-1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,4-petanediol, 1,5-hexanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, etc.
- In the dehydrocyclization reaction of the method for preparing lactone such as γ-butyrolactone used in the present invention, the reaction temperature usually ranges from 160 to 280° C., preferably 180 to 250° C.. If the reaction temperature is too low, the conversion of 1,4-butylene glycol may be decreased. Although the higher temperature may increase the conversion of 1,4-butylene glycol, the selectivity of γ-butyrolactone may be substantially decreased.
- In the dehydrocyclization reaction of the method for preparing lactone such as γ-butyrolactone used in the present invention, the reaction pressure usually ranges from 0 to 10 atm., preferably from 1 to 5 atm. However, the higher reaction pressure may easily carry out an undesired reaction, decreasing the yield.
- In the dehydrocyclization reaction of the method for preparing lactone such as γ-butyrolactone used in the present invention, the hydrogen gas is needed as a carrier gas. If the hydrogen gas do not exist in the reaction system, the lifetime of catalyst may be shortened. The amount of hydrogen gas must at least maintain the reaction system in gas phase. In generally, the molar ratio of hydrogen gas to 1,4-butylene glycol used in the present invention ranges from (12 to 1): 1, preferably from (8 to 1.5):1.
- In the dehydrocyclization reaction of the method for preparing lactone such as γ-butyrolactone used in the present invention, if the gas hourly space velocity of 1,4-butylene glycol is too low, the retention time of gas in the catalyst bed is also too long so that the product may be decomposed, resulting in the decreasing selectivity of γ-butyrolactone. If the gas hourly space velocity of 1,4-butylene glycol is too high, the retention time of gas in the catalyst bed is also too short so that the conversion of 1,4-butylene glycol decreases. In general, the gas hourly space velocity of 1,4-butylene glycol ranges from 10 to 20,000 hr−1, preferably 30 to 9,000 hr−1.
- In the dehydrocyclization reaction of the method for preparing lactone such as γ-butyrolactone used in the present invention, the catalyst bed may be a fixed bed or a fluid bed.
- The present invention will be further described in the following Examples and Comparative Examples. However, the scope of the present invention is not restricted by such Examples.
- In a given time after the dehydrocyclization reaction, the product was collected by condensation. The component of the efflux from the outlet was analyzed by HP-6890 gas chromatograph. The conversion of diol and the selectivity of lactone were calculated according to the following equation (1) and (2), and the yield of lactone is also obtained:
- A commercially available copper-chromium catalyst (30 ml) (wherein copper oxide was 42 wt %, chromium oxide was 28 wt %, and a diameter was 5 mm) was packed in the stainless steel reactor having an inside diameter of 23.5 mm. After the temperature was elevated to 150° C. with nitrogen gas, the mixed gas of 10 vol % hydrogen gas was passed into the reactor, then the catalytic reduction reaction was initiated. The temperature and the concentration of hydrogen gas were gradually elevated until the reduction temperature of catalyst was 200° C. and the concentration of hydrogen gas was 100 vol %. When the temperature of catalyst bed was confirmed to be the same as that of the heating equipment, the reduction reaction was terminated.
- Subsequently, the temperature of the reactor was elevated to 210° C. 1,4-butylene glycol was pumped into the reactor using a quantitative pump, and the gas hourly space velocity of 1,4-butylene glycol was maintained at 4500 hr−1. After the dehydrogenation reaction was carried out at a hydrogen gas/1,4-butylene glycol ratio of 5 mole:1 mole, the product was collected and analyzed. The results are shown in Table 1.
- The same steps as in Reference Example 1 were repeated, but a commercially available copper-zinc catalyst (G-66) was used, wherein the component was 60 wt % of copper oxide and 30 wt % of zinc oxide. The results are shown in Table 1.
- The same steps as in Reference Example 1 were repeated, but a copper/chromium/zinc catalyst which was prepared by the method of Japanese Patent Unexamined Publication No. Hei-61-246173 was used, wherein the component was 35 wt % of copper oxide, 4.5 wt % of zinc oxide and 60 wt % of chromium oxide. The results are shown in Table 1.
- The same steps as in Reference Example 1 were repeated, but a commercially available copper-zinc catalyst (G-66) which was immersed in 0.5 wt % of aqueous sodium hydroxide solution and then dried was used, wherein the component was 60 wt % of copper oxide, 30 wt % of zinc oxide and 0.12 wt % of sodium hydroxide. The results are shown in Table 1.
TABLE 1 Reference Example 1 2 3 4 Reaction Temperature (° C.) 210 210 210 210 Reaction Pressure (atm) 1 1 1 1 Gas Hourly Space Velocity of 4500 4500 4500 4500 1,4-Butylene Glycol (h−1) Molar Ratio of Hydrogen Gas to 5/1 5/1 5/1 5/1 1,4-Butylene Glycol Conversion of 1,4-Butylene Glycol 72.50 91.50 81.30 97.20 (mol %) Selectivity of γ-Butyrolactone 88.30 92.50 90.50 95.30 (mol %) Yield of γ-Butyrolactone (mol %) 64.02 84.64 73.82 92.63 - 60 wt % of aqueous copper nitrate solution (350 g) was slowly poured into 40 wt % of aqueous zinc nitrate solution (220 g) and the powder of silica (10 g) wherein the BET surface area was 185 m2/g (said surface area was measured according to the Brunner-Emmett-Teller Method), and the mixture was stirred vigorously. Subsequently, 25 wt % of ammonia water was added to maintain the pH value of the mixed aqueous solution at 10 while the mixture was still stirred. The precipitate was filtered and separated, washed with water, and placed into a oven to dry at 100° C. for 12 hours, after which time a catalyst precursor was obtained. This catalyst precursor was moved to a tubular high-temperature furnace ,heated to 450° C., and calcined for 4 hours. The component of this catalyst was at a copper oxide/zinc oxide ratio of 3:1.
- 1.0 wt % of graphite was added to the above catalyst, then that catalyst was extruded to a roundly-granular catalyst having a diameter of 5 mm. The same steps as in Reference Example 1 were repeated with this catalyst (30 ml). The results are shown in Table 2.
- The same steps as in Example 1 were repeated, but the ratio by weight of copper oxide to zinc oxide, the temperature of dehydrogenation, and the molar ratio of hydrogen gas to 1,4-butylene glycol are all shown in Table 2. The results of Table 2 are as follows.
TABLE 2 Example 1 2 3 4 5 6 7 Ratio by Weight of Cupric Oxide to 3/1 5/1 1/2 5/1 3/1 5/1 3/1 Zinc Oxide Reaction Temperature (° C.) 210 210 210 210 210 230 230 Reaction Pressure (atm) 1 1 1 1 1 1 1 Gas Hourly Space Velocity of BOD (hr−1) 4500 4500 4500 4500 4500 4500 4500 Molar Ratio of Hydrogen Gas to BOD 5/1 5/1 5/1 2/1 2/1 5/1 5/1 Conversion of BOD (mol %) 97.30 98.50 92.10 95.30 93.50 98.10 97.20 Selectivity of γ-Butyrolactone (mol %) 96.10 97.40 90.50 97.10 96.50 91.50 90.30 Yield of γ-Butyrolactone (mol %) 93.50 95.94 83.35 92.53 90.22 89.76 87.77 - The catalyst precursor prepared by Example 1 was immersed in 1.5 wt % of aqueous barium hydroxide solution. Then, this catalyst was moved to a tubular high-temperature furnace, heated to 450° C., and calcined for 4 hours. The component of this catalyst was 55 wt % of copper oxide, 22 wt % of zinc oxide and 1.2 wt % of barium oxide.
- The same steps as in Reference Example 1 were carried out with this catalyst. The results are shown in Table 3.
- The catalyst precursor prepared by Example 1 was immersed in 1.0 wt % of aqueous calcium hydroxide solution. Then, this catalyst was moved to a tubular high-temperature furnace, heated to 450° C., and calcined for 4 hours. The component of this catalyst was 53 wt % of copper oxide, 24 wt % of zinc oxide and 0.81 wt % of calcium oxide.
- The same steps as in Reference Example 1 were carried out with this catalyst. The results are shown in Table 3.
- The catalyst precursor prepared by Example 1 was immersed in 1.0 wt % of aqueous magnesium hydroxide solution. Then, this catalyst was moved to a tubular high-temperature furnace heated to 450° C., and calcined for 4 hours. The component of this catalyst was 49 wt % of copper oxide, 26 wt % of zinc oxide and 0.52 wt % of magnesium oxide.
- The same steps as in Reference Example 1 were carried out with this catalyst. The results are shown in Table 3.
- The catalyst precursor prepared by Example 1 was immersed in 1.5 wt % of aqueous barium hydroxide solution and 0.3 wt % of aqueous calcium hydroxide solution. Then, this catalyst was moved to a tubular high-temperature furnace, heated to 450° C., and calcined for 4 hours. The component of this catalyst was 55 wt % of copper oxide, 22 wt % of zinc oxide, 1.2 wt % of barium oxide and 0.14 wt % of calcium oxide.
- The same steps as in Reference Example 1 were carried out with this catalyst. The results are shown in Table 3.
- The catalyst precursor prepared by Example I was immersed in 1.0 wt % of aqueous calcium hydroxide solution and 0.4 wt % of aqueous magnesium hydroxide solution. Then, this catalyst was moved to a tubular high-temperature furnace, heated to 450° C., and calcined for 4 hours. The component of this catalyst was 53 wt % of copper oxide, 24 wt % of zinc oxide, 0.81 wt % of calcium oxide and 0.16 wt % of magnesium oxide.
- The same steps as in Reference Example 1 were carried out with this catalyst. The results are shown in Table 3.
- The catalyst precursor prepared by Example 1 was immersed in 1.0 wt % of aqueous magnesium hydroxide solution and 0.2 wt % of aqueous barium hydroxide solution. Then, this catalyst was moved to a tubular high-temperature furnace, heated to 450° C., and calcined for 4 hours. The component of this catalyst was 49 wt % of copper oxide, 26 wt % of zinc oxide, 0.52 wt % of magnesium oxide and 0.1 wt % of barium oxide.
- The same steps as in Reference Example 1 were carried out with this catalyst. The results are shown in Table 3.
TABLE 3 Example 8 9 10 11 12 13 Reaction Temperature (° C.) 210 210 210 210 210 210 Reaction Pressure (atm) 1 1 1 1 1 1 Gas Hourly Space Velocity of BOD (hr−1) 4500 4500 4500 4500 4500 4500 Molar Ratio of Hydrogen Gas to BOD 5/1 5/1 5/1 5/1 5/1 5/1 Conversion of BOD (mol %) 99.50 99.20 99.60 99.90 99.50 99.80 Selectivity of γ-Butyrolactone (mol %) 99.10 98.60 98.10 99.80 99.10 99.30 Yield of γ-Butyrolactone (mol %) 98.60 97.81 97.70 99.70 98.60 99.10
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JP2874016B2 (en) | 1990-02-09 | 1999-03-24 | 東燃株式会社 | Production method of γ-butyrolactone |
US5110954A (en) | 1990-07-11 | 1992-05-05 | E. I. Du Pont De Nemours And Company | Dehydrogenation of diols |
JP3232874B2 (en) | 1994-05-31 | 2001-11-26 | 松下電器産業株式会社 | FF type heater |
-
2000
- 2000-01-14 TW TW089100512A patent/TW496771B/en not_active IP Right Cessation
- 2000-12-14 JP JP2000380525A patent/JP3763738B2/en not_active Expired - Lifetime
- 2000-12-15 US US09/737,894 patent/US6323347B2/en not_active Expired - Lifetime
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US10246649B2 (en) * | 2011-07-29 | 2019-04-02 | Saudi Arabian Oil Company | Process for reducing the total acid number in refinery feedstocks |
CN103980241A (en) * | 2014-04-23 | 2014-08-13 | 迈奇化学股份有限公司 | Delta-valerolactone production method |
CN103980241B (en) * | 2014-04-23 | 2015-10-21 | 迈奇化学股份有限公司 | A kind of production method of δ-valerolactone |
CN113443960A (en) * | 2021-06-30 | 2021-09-28 | 凯瑞环保科技股份有限公司 | Preparation method of 1,4 butanediol |
CN116272984A (en) * | 2023-03-01 | 2023-06-23 | 陕西延长石油(集团)有限责任公司 | Catalyst for preparing gamma-butyrolactone by catalyzing 1, 4-butanediol to dehydrogenate, and preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
JP2001219067A (en) | 2001-08-14 |
JP3763738B2 (en) | 2006-04-05 |
US6323347B2 (en) | 2001-11-27 |
TW496771B (en) | 2002-08-01 |
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