JPH03141273A - Purification of lactones - Google Patents
Purification of lactonesInfo
- Publication number
- JPH03141273A JPH03141273A JP1274999A JP27499989A JPH03141273A JP H03141273 A JPH03141273 A JP H03141273A JP 1274999 A JP1274999 A JP 1274999A JP 27499989 A JP27499989 A JP 27499989A JP H03141273 A JPH03141273 A JP H03141273A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- lactones
- ruthenium
- column
- catalyst
- 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
- 150000002596 lactones Chemical class 0.000 title claims abstract description 41
- 238000000746 purification Methods 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 28
- 238000004821 distillation Methods 0.000 claims abstract description 24
- -1 dicarboxylic acid ester Chemical class 0.000 claims abstract description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920000570 polyether Polymers 0.000 claims abstract description 8
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 7
- 239000007791 liquid phase Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 26
- 150000002170 ethers Chemical class 0.000 claims description 7
- 239000007788 liquid Substances 0.000 abstract description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 8
- 150000001991 dicarboxylic acids Chemical class 0.000 abstract description 6
- 239000004721 Polyphenylene oxide Substances 0.000 abstract 1
- 150000003951 lactams Chemical class 0.000 abstract 1
- 239000012264 purified product Substances 0.000 abstract 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 18
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 16
- 239000002253 acid Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000005984 hydrogenation reaction Methods 0.000 description 10
- 238000000354 decomposition reaction Methods 0.000 description 8
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 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 6
- 241001550224 Apha Species 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 238000004040 coloring Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000003304 ruthenium compounds Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229940014800 succinic anhydride Drugs 0.000 description 3
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 3
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- UAXNXOMKCGKNCI-UHFFFAOYSA-N 1-diphenylphosphanylethyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)C(C)P(C=1C=CC=CC=1)C1=CC=CC=C1 UAXNXOMKCGKNCI-UHFFFAOYSA-N 0.000 description 1
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 description 1
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- CLRJSTYUENQJNT-UHFFFAOYSA-N C1(=CC=CC=C1)C(P(O)=O)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)C(P(O)=O)C1=CC=CC=C1 CLRJSTYUENQJNT-UHFFFAOYSA-N 0.000 description 1
- AXKPBIUQVYVDHP-UHFFFAOYSA-N CCc1cccc(c1CC)P(O)=O Chemical compound CCc1cccc(c1CC)P(O)=O AXKPBIUQVYVDHP-UHFFFAOYSA-N 0.000 description 1
- YUXIBTJKHLUKBD-UHFFFAOYSA-N Dibutyl succinate Chemical compound CCCCOC(=O)CCC(=O)OCCCC YUXIBTJKHLUKBD-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical compound C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910021603 Ruthenium iodide Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- ROZSPJBPUVWBHW-UHFFFAOYSA-N [Ru]=O Chemical class [Ru]=O ROZSPJBPUVWBHW-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000000998 batch distillation Methods 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- XYZMOVWWVXBHDP-UHFFFAOYSA-N cyclohexyl isocyanide Chemical compound [C-]#[N+]C1CCCCC1 XYZMOVWWVXBHDP-UHFFFAOYSA-N 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- IEPRKVQEAMIZSS-AATRIKPKSA-N diethyl fumarate Chemical compound CCOC(=O)\C=C\C(=O)OCC IEPRKVQEAMIZSS-AATRIKPKSA-N 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- HASCQPSFPAKVEK-UHFFFAOYSA-N dimethyl(phenyl)phosphine Chemical compound CP(C)C1=CC=CC=C1 HASCQPSFPAKVEK-UHFFFAOYSA-N 0.000 description 1
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical compound [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 1
- WUOIAOOSKMHJOV-UHFFFAOYSA-N ethyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(CC)C1=CC=CC=C1 WUOIAOOSKMHJOV-UHFFFAOYSA-N 0.000 description 1
- VMDTXBZDEOAFQF-UHFFFAOYSA-N formaldehyde;ruthenium Chemical compound [Ru].O=C VMDTXBZDEOAFQF-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 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
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- MBABOKRGFJTBAE-UHFFFAOYSA-N methyl methanesulfonate Chemical compound COS(C)(=O)=O MBABOKRGFJTBAE-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229960003753 nitric oxide Drugs 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- SWMBQMGPRYJSCI-UHFFFAOYSA-N octylphosphane Chemical compound CCCCCCCCP SWMBQMGPRYJSCI-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 150000004714 phosphonium salts Chemical class 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
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- JDNQPKBFOBQRBN-UHFFFAOYSA-N ruthenium monohydride Chemical compound [RuH] JDNQPKBFOBQRBN-UHFFFAOYSA-N 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 description 1
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 description 1
- WYRXRHOISWEUST-UHFFFAOYSA-K ruthenium(3+);tribromide Chemical compound [Br-].[Br-].[Br-].[Ru+3] WYRXRHOISWEUST-UHFFFAOYSA-K 0.000 description 1
- VDRDGQXTSLSKKY-UHFFFAOYSA-K ruthenium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ru+3] VDRDGQXTSLSKKY-UHFFFAOYSA-K 0.000 description 1
- LJZVDOUZSMHXJH-UHFFFAOYSA-K ruthenium(3+);triiodide Chemical compound [Ru+3].[I-].[I-].[I-] LJZVDOUZSMHXJH-UHFFFAOYSA-K 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Pyrane Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Furan Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はラクトン類の精製法に間するものである。詳し
くは、シ゛カルボン酸、ジカルボン散策水物又はジカル
ボン酸エステルをルテニウム触媒の存在下液相で水素化
することにより得られる粗ラクトン類を精製する方法に
間するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for purifying lactones. Specifically, the present invention relates to a method for purifying crude lactones obtained by hydrogenating dicarboxylic acids, dicarboxylic acids, or dicarboxylic acid esters in a liquid phase in the presence of a ruthenium catalyst.
（従来の技術）
ジカルボン酸、ジカルボン酸無水物又はジカルボン酸エ
ステル、あるいはこれ等の混合物を水素化してラクトン
類を製造する方法は古くから検討され、これまでに多数
提案されている０例えば触媒としてニッケル系触媒く特
公昭４３−６９４７号公報）、コバルト系触媒（特開昭
５１−９５０５７号公？１）、銅−クロム系触媒（特公
昭３８−２０１１９号公報）、銅−亜鉛系触媒（特公昭
４２−１４４６３号公報）等を使用して、固定床又は懸
濁液相により水素化反応を行なう方法が知られている。(Prior Art) Methods for producing lactones by hydrogenating dicarboxylic acids, dicarboxylic acid anhydrides, dicarboxylic acid esters, or mixtures thereof have been studied for a long time, and many proposals have been made so far. Nickel-based catalysts (Japanese Patent Publication No. 43-6947), cobalt-based catalysts (JP-A-51-95057-1), copper-chromium catalysts (Japanese Patent Publication No. 38-20119), copper-zinc catalysts (Japanese Patent Publication No. 38-20119) A method is known in which the hydrogenation reaction is carried out in a fixed bed or suspension phase using, for example, Japanese Patent Publication No. 42-14463.
一方、均一系のルテニウム系触媒を使用して上記の水素
化反応を行なう方法も知られ、例えば米国特許３９５７
８２７号には、［ＲｕＸｎ（ＰＲ＋Ｒｉａ）ｘＬｙ］型
のルテニウム系触媒を使用し４０〜４００ ｐｓｉの加
圧下で水素化してラクトン類を製造する方法が記載され
、また米国特許４４８５２４６号には、同様の触媒によ
る水素化反応を有機アミンの存在下で行なうことが記載
されている。On the other hand, methods of carrying out the above hydrogenation reaction using a homogeneous ruthenium-based catalyst are also known, for example, in US Pat.
No. 827 describes a method for producing lactones by hydrogenation using a [RuXn(PR+Ria)xLy] type ruthenium-based catalyst under pressure of 40 to 400 psi, and U.S. Pat. It is described that the catalytic hydrogenation reaction is carried out in the presence of an organic amine.
（発明が解決しようとする課題）
しかしながら、上記のニッケル系触媒、コバルト系触媒
、銅−クロム系触媒、銅−亜鉛系触媒等の固体触媒を使
用する従来の方法は、反応条件が数十気圧以上の苛酷な
条件の採用は避けられないという問題点があった。一方
、上記均一系のルテニウム系触媒を使用する方法は、比
較的温和な条件下で水素化反応が進行するという特徴が
ある半面、触媒活性がやや低水準であるうえ、触媒寿命
が短かく、またハロゲンを使用しているため反応装置の
［蝕が生ずるという問題がある。(Problem to be Solved by the Invention) However, in conventional methods using solid catalysts such as the above-mentioned nickel-based catalysts, cobalt-based catalysts, copper-chromium-based catalysts, copper-zinc-based catalysts, etc., the reaction conditions are several tens of atmospheres. There was a problem in that the adoption of the above harsh conditions was unavoidable. On the other hand, the method using the homogeneous ruthenium-based catalyst has the characteristic that the hydrogenation reaction proceeds under relatively mild conditions, but the catalyst activity is at a rather low level and the catalyst life is short. Furthermore, since halogen is used, there is a problem of corrosion of the reactor.
そこで本出願人は、先に溶媒を用い、ルテニウム、有機
ホスフィン及びｐＫａ値が２より小さい酸の共役塩基を
含有するルテニウム触媒の存在下液相で水素化する方法
を提案した（特開平１−２５７７１号公報）、この方法
では高活性なルテニウム触媒を使用するので、温和な条
件下で収率よくラクトン類を製造することができる。Therefore, the applicant proposed a method of hydrogenation in a liquid phase using a solvent in the presence of a ruthenium catalyst containing ruthenium, an organic phosphine, and a conjugated base of an acid with a pKa value of less than 2 (Japanese Patent Application Laid-Open No. 1999-1-1910). Since this method uses a highly active ruthenium catalyst, lactones can be produced in good yield under mild conditions.
しかし、その後の検討により、水素化反応の溶媒として
好適なエーテル類又はポリエーテル類、あるいはこれ等
の混合物を使用すると、粗ラクトン類を蒸留により精製
する際に不純物が生成して溶媒を着色し、これが製品の
品位を低下する原因となることが判明した。However, subsequent studies revealed that if ethers, polyethers, or mixtures thereof, which are suitable as solvents for hydrogenation reactions, are used, impurities will be produced when crude lactones are purified by distillation, and the solvent will be colored. It was found that this caused the quality of the product to deteriorate.
ラクトン類は極めて高品位を要求される製品で＆るので
、微量でも不純物が混入することは、商業的にラクトン
類を製造する場合に極めて不利であり、この問題を解決
することがラクトン類を製造する場合の大きな課題であ
った。Since lactones are products that require extremely high quality, the contamination of even a small amount of impurities is extremely disadvantageous when commercially producing lactones. This was a major issue in manufacturing.
本発明は、ルテニウム触媒を使用してラクトン類を製造
する方法における上述の問題点を解決し、高純度のラク
トン類を工業的有利に得ることを目的とするものである
。The present invention aims to solve the above-mentioned problems in the method of producing lactones using a ruthenium catalyst, and to obtain highly purified lactones with industrial advantage.
（課題を解決するための手段）
本発明者等は上記の目的を達成するために検討中のとこ
ろ、粗ラクトン類を蒸留した場合に生成する不純物が、
溶媒に使用したエーテル類、ポリエーテル類が微量分解
することに起因することを確かめ、この知見に基づいて
更に検討を重ねた結果、粗ラクトン類を蒸留して精製す
る際に、特定の蒸留条件を選ぶときは、溶媒の分解が抑
制されて着色が抑制され高品位のラクトン類を得ること
ができることを見出し本発明を達成した。即ち、本発明
の要旨は、ジカルボン酸、ジカルボン酸無水物又はジカ
ルボン酸エステルを、溶媒としてエーテル類又はポリエ
ーテル類を使用しルテニウム触媒の存在下液相で水素化
して得られる反応生成物から触媒を分離した粗ラクトン
類を蒸留することにより精製するにあたり、蒸留塔の塔
底温度を１５０℃以下とし、かつ缶出液の滞留時間を６
時間以下に保持することを特徴とするラクトン類の精製
法に存する。(Means for Solving the Problems) In order to achieve the above object, the present inventors are currently considering that impurities generated when crude lactones are distilled are
We confirmed that this was due to the slight decomposition of the ethers and polyethers used in the solvent, and based on this knowledge, we conducted further studies and found that certain distillation conditions were required when distilling and purifying crude lactones. The present invention was achieved by discovering that when selecting lactones, decomposition of the solvent is suppressed, coloring is suppressed, and high-quality lactones can be obtained. That is, the gist of the present invention is to obtain a catalyst from a reaction product obtained by hydrogenating dicarboxylic acid, dicarboxylic acid anhydride, or dicarboxylic acid ester in a liquid phase in the presence of a ruthenium catalyst using ethers or polyethers as a solvent. In purifying the separated crude lactones by distillation, the bottom temperature of the distillation column is set to 150°C or lower, and the residence time of the bottoms is set to 6.
The present invention relates to a method for purifying lactones, which is characterized by maintaining the lactones for a period of time or less.
本発明の詳細な説明するに、本発明におけるラクトン類
の原料物質としては、炭素数３〜７の飽和又は不飽和の
ジカルボン酸、それ等の無水物、あるいはそれ等のジカ
ルボン酸のエステル、あるいはこれ等の混合物が挙げら
れ、エステルとしては低級アルキルエステルが好ましい
。具体的には例えば、マレイン酸、フマール酸、コハク
酸、無水マレイン酸、無水コハク酸、マレイン酸ジメチ
ル、フマール酸ジエチル、コハク酸−ジ−ｎ−ブチル等
が使用される。To explain the present invention in detail, raw materials for the lactones in the present invention include saturated or unsaturated dicarboxylic acids having 3 to 7 carbon atoms, anhydrides thereof, esters of such dicarboxylic acids, or Mixtures of these may be mentioned, and lower alkyl esters are preferred as the esters. Specifically, for example, maleic acid, fumaric acid, succinic acid, maleic anhydride, succinic anhydride, dimethyl maleate, diethyl fumarate, di-n-butyl succinate, etc. are used.
また、ルテニウム触媒としては、例えば（イ）ルテニウ
ム、（ロ）有機ホスフィン及びくハ）ｐＫａが２より小
さい酸の兵役塩基を含有するルテニウム系触媒が挙げら
れ、場合によりこれに更に（ニ）中性配位子を含有させ
た触媒が好適に使用される。Examples of the ruthenium catalyst include (a) ruthenium, (b) organic phosphine, and c) a ruthenium-based catalyst containing a military base of an acid having a pKa of less than 2. A catalyst containing a functional ligand is preferably used.
更に、溶媒であるエーテル類又はポリエーテル類として
は、例えばジエチルエーテル、アニソール、テトラヒド
ロフラン、エチレングリコールジメチルエーテル、ジオ
キサン等のエーテル類；トリプライム（トリエチレング
リコールジメチルエーテル）、テトラグライム（テトラ
エチレングリコールジメチルエーテル）、１８−クラウ
ン−６等のポリエーテル類等が挙げられ、これ等は単独
で又は混合物として使用される。Furthermore, examples of ethers or polyethers that are solvents include ethers such as diethyl ether, anisole, tetrahydrofuran, ethylene glycol dimethyl ether, and dioxane; triprime (triethylene glycol dimethyl ether), tetraglyme (tetraethylene glycol dimethyl ether), Examples include polyethers such as 18-crown-6, which may be used alone or as a mixture.
ラクトン類の製造は、反応容器に前記原料物質、触媒成
分及び溶媒を仕込み、これに水素を導入して水素化する
ことにより実施される。水素は窒素あるいは二酸化炭素
等の反応に不活性なガスで希釈されたものであってもよ
い。反応温度は通常５０〜２５０℃、好ましくは１００
〜２００℃である。水素分圧は特に限られないが、工業
的実施上は通常０．１〜１００に８／Ｃｌ１２、好まし
くは１０〜５０ ｋｇ／ｃｍ２である０反応は回分方式
及び連続方式の何れも実施することができ、回分方式の
場合の所要反応時間は通常１〜２０時間である。The production of lactones is carried out by charging the raw material, catalyst component, and solvent into a reaction vessel, and hydrogenating the mixture by introducing hydrogen therein. Hydrogen may be diluted with a gas inert to the reaction, such as nitrogen or carbon dioxide. The reaction temperature is usually 50 to 250°C, preferably 100°C.
~200°C. The hydrogen partial pressure is not particularly limited, but in industrial practice it is usually 0.1 to 100 to 8/Cl12, preferably 10 to 50 kg/cm2.The reaction can be carried out either batchwise or continuously. In the case of a batch method, the required reaction time is usually 1 to 20 hours.
上記の水素化反応により得られる反応生成物を、通常の
蒸留塔を用いて蒸留し、塔頂から粗ラクトン類を留出さ
せて、触媒を含む残留液（触媒液）から分離する。この
ようにして得られた粗ラクトン類は、主要成分の一つと
してラクトン類を含み、更に溶媒、未反応原料、水素化
反応による生成水、その他側反応生成物であるプロピオ
ン酸等の有機酸、軽沸点生成物、高沸点生成物等を含有
している液状物である。The reaction product obtained by the above hydrogenation reaction is distilled using a conventional distillation column, and the crude lactones are distilled off from the top of the column and separated from the residual liquid (catalyst liquid) containing the catalyst. The crude lactones obtained in this way contain lactones as one of the main components, and also include a solvent, unreacted raw materials, water produced by the hydrogenation reaction, and organic acids such as propionic acid, which are the reaction products on the other side. It is a liquid material containing , light boiling point products, high boiling point products, etc.
本発明の方法では、この粗ラクトン類を蒸留して精製す
る際に、蒸留塔の塔底温度を１５０℃以下、好ましくは
１３０℃以下とし、かっ缶出液の蒸留塔内における滞留
時間を６時間以下、好ましくは３時間以下、特に好まし
くは１時間以下に保持することが必要である。なお、塔
底温度の下限は蒸留可能であればよく通常２０℃程度以
上である。また缶出液の滞留時間の下限は、実用上３０
分間程度である。In the method of the present invention, when distilling and purifying the crude lactones, the bottom temperature of the distillation column is set to 150°C or lower, preferably 130°C or lower, and the residence time of the bottom solution in the distillation column is 6. It is necessary to hold the temperature at most 3 hours, preferably at most 3 hours, particularly preferably at most 1 hour. Note that the lower limit of the bottom temperature is generally about 20° C. or higher as long as distillation is possible. In addition, the lower limit of the residence time of bottoms liquid is practically 30
It takes about a minute.
塔底温度を１５０℃以下に調整するには、主として塔頂
の減圧度を調整すればよい０例えば、塔頂の減圧度を３
０〜１０ ｍｍＨｇとすることにより塔底温度は１３０
〜１５０℃に保持される。また、蒸留塔内における缶出
液の滞留時間の調整は、熱交換器の伝熱面積、塔の熱媒
体と塔底液の温度差を適切に調整することにより達成さ
れる。In order to adjust the bottom temperature to 150°C or less, it is sufficient to mainly adjust the degree of vacuum at the top of the column.For example, if the degree of vacuum at the top of the column is adjusted to 3
By setting the temperature to 0 to 10 mmHg, the bottom temperature of the column can be reduced to 130 mmHg.
It is maintained at ~150°C. Further, the residence time of the bottoms in the distillation column can be adjusted by appropriately adjusting the heat transfer area of the heat exchanger and the temperature difference between the heat medium of the column and the bottom liquid.
以上に述べた本発明の方法によって、粗ラクトン類に含
まれる溶媒の分解を無視し得る程度に抑制して、溶媒の
着色を阻止し、高品位のラクトン類を得ることができる
。By the method of the present invention described above, it is possible to suppress the decomposition of the solvent contained in crude lactones to a negligible extent, prevent coloring of the solvent, and obtain high-quality lactones.
なお、本発明における射水（イ）ルテニウム、（ロ）有
機ホスフィン及び（ハ）ρにａ値が２より小さい酸の共
役塩基を含有し、更に場合により中性配位子を含有して
いてもよいルテニウム触媒の具体例を詳記すれば以下の
通りである。In addition, even if Imizu (a) ruthenium, (b) organic phosphine, and (c) ρ in the present invention contain a conjugate base of an acid with an a value of less than 2, and further contain a neutral ligand in some cases, Specific examples of good ruthenium catalysts are as follows.
（イ）ルテニウム：
ルテニウムとしては、金属ルテニウム及びルテニウム化
合物の何れも使用することができる。ルテニウム化合物
としては、ルテニウムの酸化物、ハロゲン化物、水酸化
物、無機酸塩、有機酸塩又は錯化合物が使用され、具体
的には例えば、二酸化ルテニウム、四酸化ルテニウム、
三水酸化ルテニウム、塩化ルテニウム、臭化ルテニウム
、ヨウ化ルテニウム、硝酸ルテニウム、酢酸ルテニウム
トリス（アセチルアセトン）ルテニウム、ヘキサクロロ
ルテニウム酸ナトリウム、テトラカルボニルルテニウム
酸ジカリウム、ペンタカルポニルルデニウム、シクロペ
ンタジェニルジ力ルポニルルテニウム、ジブロモトリカ
ルボニルルテニウム、クロロトリス（トリフェニルホス
フィン）ヒドリドルテニウム、ビス（トリーｎ−ブチル
ホスフィン）トリカルボニルルテニウム、ドデカカルボ
ニルトリルテニウム、テトラヒドリトデ力力ルポニルテ
トラルテニウム、オクタデカカルボニルへキサルテニウ
ム酸ジセシウム、ウンデカカルボニルヒドリドトリルテ
ニウム酸テトラフェニルホスホニウム等が挙げられる。(a) Ruthenium: As ruthenium, both metal ruthenium and ruthenium compounds can be used. As the ruthenium compound, ruthenium oxides, halides, hydroxides, inorganic acid salts, organic acid salts, or complex compounds are used, and specifically, for example, ruthenium dioxide, ruthenium tetroxide,
Ruthenium trihydroxide, ruthenium chloride, ruthenium bromide, ruthenium iodide, ruthenium nitrate, ruthenium acetate, tris(acetylacetone)ruthenium, sodium hexachlororuthenate, dipotassium tetracarbonylruthenate, pentacarponylrudenium, cyclopentagenyl diruponyl Ruthenium, dibromotricarbonylruthenium, chlorotris(triphenylphosphine)hydridoruthenium, bis(tri-n-butylphosphine)tricarbonylruthenium, dodecacarbonyltriruthenium, tetrahydritideluponyltetraruthenium, dicesium octadecacarbonylhexarthenate, Examples include undecacarbonylhydridotriruthenate tetraphenylphosphonium.
これ等の金属ルテニウム及びルテニウム化合物の使用量
は、反応溶Ｍｌリットル中のルテニウムとしてｏ、ｏｏ
ｏｔ −ｉｏｏミリモル、好ましくは０．００１〜１０
ミリモルである。The amount of these metal ruthenium and ruthenium compounds used is o, oo as ruthenium per liter of reaction solution.
ot -ioo mmol, preferably 0.001-10
Millimoles.
（ロ）有機ホスフィン：
有機ホスフィンは、主触媒である（イ）のルテニウムの
電子状態を制御したり、ルテニウムの活性状態を安定化
するのに寄与するものと考えられる。(b) Organic phosphine: The organic phosphine is thought to contribute to controlling the electronic state of ruthenium (a), which is the main catalyst, and to stabilizing the active state of ruthenium.
有機ホスフィンの具体例としては、トリー〇−オクチル
ホスフィン、トリーｎ−ブチルホスフィン、ジメチル−
〇−オクチルホスフィン等のトリアルキルホスフィン類
、トリシクロへキシルホスフィンのようなトリシクロア
ルキルホスフィン類、トリフェニルホスフィンのような
トリアリールホスフィン類、ジメチルフェニルホスフィ
ンのようなアルキルアリールホスフィン類、１．２−ビ
ス（ジフェニルホスフィノ）エタンのような多官能性ホ
スフィン類が挙げられる。有機ホスフィンの使用量は通
常、ルテニウム１モルに対して、０．１−１０００モル
程度、好ましくは１−ｔｏｏモルである。また、有機ホ
スフィンは、それ自体単独で、あるいはルテニウム触媒
との複合体の形で、反応系に供給することができる。Specific examples of organic phosphine include tri-octylphosphine, tri-n-butylphosphine, dimethyl-
〇- Trialkylphosphines such as octylphosphine, tricycloalkylphosphines such as tricyclohexylphosphine, triarylphosphines such as triphenylphosphine, alkylarylphosphine such as dimethylphenylphosphine, 1.2- Examples include polyfunctional phosphines such as bis(diphenylphosphino)ethane. The amount of organic phosphine used is usually about 0.1-1000 mol, preferably 1-too mol, per 1 mol of ruthenium. Further, the organic phosphine can be supplied to the reaction system either alone or in the form of a complex with a ruthenium catalyst.
（ハ）ｐＫａ値が２より小さい酸の共役塩基：ｐ Ｋ
ａ １ｇが２より小さい酸の共役塩基は、ルテニウム触
媒の付加的促進剤として作用し、触媒：ｌｉＩ製中又は
反応系中において、ｐにａｍが２より小さい酸の兵役塩
基を生成するものであればよく、その供給形態としては
、ｐＫａ値が２より小さいブレンステッド酸又はその各
種の塩等が用いられる。具体的には例えば、硫酸、亜硫
酸、硝酸、亜硝酸、過塩素酸、燐酸、ホウフッ化水素酸
、ヘキサフルオロ燐酸、タングステン酸、燐モリブデン
酸、燐タングステン酸、シリコンタングステン酸、ポリ
ケイ酸、フルオロスルホン酸等の無機酸類、トリクロロ
酢酸、ジクロロ酢酸、トリフルオロ酢酸、メタンスルホ
ン酸、トリフルオロメタンスルホン酸、ラウリルスルホ
ン酸、ベンゼンスルホン酸、ｐ−）ルエンスルホン酸等
の有８１９．あるいはこれ等の酸のアンモニウム塩、ホ
スホニウム塩が挙げられる。(c) Conjugate base of acid with pKa value smaller than 2: pK
The conjugate base of an acid in which 1g is less than 2 acts as an additional promoter for the ruthenium catalyst and forms a conjugate base of an acid in which p and am are less than 2 in the preparation of the catalyst:liI or in the reaction system. As the supply form, a Brønsted acid having a pKa value of less than 2 or various salts thereof is used. Specifically, for example, sulfuric acid, sulfite, nitric acid, nitrous acid, perchloric acid, phosphoric acid, fluoroboric acid, hexafluorophosphoric acid, tungstic acid, phosphomolybdic acid, phosphotungstic acid, silicon tungstic acid, polysilicic acid, fluorosulfone Inorganic acids such as trichloroacetic acid, dichloroacetic acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, laurylsulfonic acid, benzenesulfonic acid, p-)luenesulfonic acid, etc. Alternatively, ammonium salts and phosphonium salts of these acids may be mentioned.
また、これ等の酸の兵役塩基が反応系で生成すると考え
られる酸誘導体、例えば酸ハロゲン化物、酸真水物、エ
ステル、酸アミド等の形で添加しても同様の効果が得ら
れる。これ等の酸又はその塩の使用量は、ルテニウム１
モルに対して０，０１〜１０００モル、好ましくは０．
１〜１００モル、更に好ましくは０．５〜２０モルの範
囲である。The same effect can also be obtained by adding acid derivatives that are thought to be produced in the reaction system, such as acid halides, fresh acid hydrates, esters, and acid amides. The amount of these acids or their salts used is ruthenium 1
0.01 to 1000 mol, preferably 0.01 to 1000 mol.
The amount is in the range of 1 to 100 mol, more preferably 0.5 to 20 mol.
上記（イ）、（ロ）及び（ハ）の成分の外に、場合によ
り含イｆすることができる（二）中性配位子としては、
水素、エチレン、プロピレン、ブテン、シクロペンテン
、シクロヘキセン、ブタジェン、シクロペンタジェン、
シクロオクタジエン、ツルボナシエン等のオレフィン類
、−酸化炭素、ジエチルエーテル、アニソール、ジオキ
サン、テトラヒドロフラン、アセトン、アセトフェノン
、ヘンシフエノン、シクロヘキサノン、プロピオン酸、
カフ゛ロン酸、酪酸、安息香酸、酢酸エチル、酢酸アリ
ル、安息香酸ヘンシル、ステアリン酸ヘンシル等の含酸
素化合物、酸化窒素、アセトニトリル、プロピオニトリ
ル、ヘンジニトリル、シクロヘキシルイソニトリル、ブ
チルアミン、アニリン、トルイジン、トリエチルアミン
、ピロール、ピリジン、Ｎ−メチルホルムアミド、アセ
トアミド、１．１，３．３−テトラメチル尿素、Ｎ−メ
チルピロリドン、カプロラクタム、ニトロメタン等の含
窒素化合物、二硫化炭嚢、ｎ−ブチルメルカプタン、チ
オフェノール、ジメチルスルフィト、ジメチルジスルフ
ィド、チオフェン、ジメチルスルホキシド、ジフェニル
スルホキシド等の含硫黄化合物、トリブチルホスフィン
オキシト、エチルジフェニルホスフィンオキシト、トリ
フェニルホスフィンオキシト、ジエチルフェニルホスフ
ィネート、ジフェニルメチルホスフィネート、ジフェニ
ルエチルホスフィネート、０．０−ジメチルメチルホス
ホノチオレート、トリエチルホスファイト、トリフェニ
ルホスファイト、トリエチルホスフェート、トリフェニ
ルホスフェート、ヘキサメチルホスホリックトリアミド
等の有機ホスフィン以外の含燐化合物が挙げられる。In addition to the above components (a), (b), and (c), (f) neutral ligands that may optionally be included include:
Hydrogen, ethylene, propylene, butene, cyclopentene, cyclohexene, butadiene, cyclopentadiene,
Olefins such as cyclooctadiene and turbonasien, carbon oxide, diethyl ether, anisole, dioxane, tetrahydrofuran, acetone, acetophenone, hensifenone, cyclohexanone, propionic acid,
Oxygenated compounds such as capfuronic acid, butyric acid, benzoic acid, ethyl acetate, allyl acetate, hensyl benzoate, hensyl stearate, nitrogen oxide, acetonitrile, propionitrile, hendinitrile, cyclohexylisonitrile, butylamine, aniline, toluidine, triethylamine, Pyrrole, pyridine, N-methylformamide, acetamide, 1.1,3.3-tetramethylurea, N-methylpyrrolidone, caprolactam, nitrogen-containing compounds such as nitromethane, charcoal disulfide, n-butylmercaptan, thiophenol, Sulfur-containing compounds such as dimethyl sulfite, dimethyl disulfide, thiophene, dimethyl sulfoxide, diphenyl sulfoxide, tributylphosphine oxyto, ethyldiphenylphosphine oxyto, triphenylphosphine oxyto, diethylphenylphosphinate, diphenylmethylphosphinate, diphenylethylphosph Examples include phosphorus-containing compounds other than organic phosphines, such as phosphonate, 0.0-dimethylmethylphosphonothiolate, triethyl phosphite, triphenyl phosphite, triethyl phosphate, triphenyl phosphate, and hexamethylphosphoric triamide.
（実施例）
以下本発明を実施例及び比較例について更に詳細に説明
するが、本発明はその要旨を超えない限りこれ等の実施
例に限定されるものではない。(Examples) The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples unless the gist thereof is exceeded.
実施例１
触媒液の調！！：
ルテニウムアセチルアセトナ−） １．９９ ｇ（Ｒｕ
：５ミリモル）、トリオクチルホスフィン１８．５ ｇ
（５０ミリモル）及びｐ−）ルエンスルホン酸８．４
ｇ（４４ミリモル）を、トリグライム（トリエチレング
リコールジメチルエーテル溶媒）３．２ ｋｇに溶解し
、アルゴン雰囲気下２００℃で２時間加熱処理して触媒
液を調製した。Example 1 Preparation of catalyst liquid! ! : Ruthenium acetylacetoner) 1.99 g (Ru
: 5 mmol), trioctylphosphine 18.5 g
(50 mmol) and p-)luenesulfonic acid 8.4
g (44 mmol) was dissolved in 3.2 kg of triglyme (triethylene glycol dimethyl ether solvent) and heated at 200° C. for 2 hours in an argon atmosphere to prepare a catalyst solution.
水素化反応：
反応器（５１５Ｉ１１１０１加圧釜）にＥ記触媒液及び
無水コハク酸４００ ｇ（４，０モル）を仕込み、室温
で水素を４０電圧で圧入し、２０５℃に加熱して４時間
水素化反応を行なった。反応後、生成物をガスクロマト
グラフィーにより分析した結果、無水コハク酸の転化率
は９１．４％であり、γ−ブチロラクトンの選択率は９
０．２％、収率は８２．４％であった。Hydrogenation reaction: Charge E catalyst solution and 400 g (4.0 mol) of succinic anhydride into a reactor (515I11101 pressure cooker), pressurize hydrogen at 40°C at room temperature, heat to 205°C, and heat hydrogen for 4 hours. A chemical reaction was carried out. After the reaction, the product was analyzed by gas chromatography, and the conversion rate of succinic anhydride was 91.4%, and the selectivity of γ-butyrolactone was 9.
The yield was 82.4%.
粗ラクトンの採取：
上記反応生成物１．５ ｋｇを、３０段の蒸留塔を用い
、塔頂減圧度３０〜１０ ｍｍＨ３、塔底温度１３０〜
１５０℃、還流比ｌＯで回分蒸留して、塔頂からγ−ブ
チロラクトン４５重量％、水９．０重量％及び溶媒４３
重量％を含む粗ラクトンを留出させ採取した。残留液は
、触媒、溶媒及び未反応原料等を含有する触媒液である
。Collection of crude lactone: 1.5 kg of the above reaction product was collected in a 30-stage distillation column at a top vacuum of 30-10 mmH3 and a bottom temperature of 130-130 mmH3.
Batch distillation was carried out at 150°C and a reflux ratio of 1O, and from the top of the column 45% by weight of γ-butyrolactone, 9.0% by weight of water and 43% of solvent were collected.
Crude lactone containing % by weight was distilled and collected. The residual liquid is a catalyst liquid containing a catalyst, a solvent, unreacted raw materials, and the like.
粗ラクトンの精！１：
上記に採取した粗ラクトンを、ガラスオルダーショー実
段数３５段、塔頂減圧度２０ ｍｒａＨｇ、塔底温度１
３０℃、缶出液滞留時間３時間で運転する蒸留塔に供給
して蒸留し、塔頂からγ−ブチロラクトン及び水を留出
させると共に、溶媒及び高沸点物質を含む缶出液を塔底
から抜き出した。Crude lactone spirit! 1: The crude lactone collected above was heated to 35 glass plates, a vacuum at the top of the column 20 mraHg, and a temperature at the bottom of the column 1.
The bottoms are fed to a distillation column operated at 30°C and with a residence time of 3 hours for distillation, γ-butyrolactone and water are distilled from the top of the column, and the bottoms containing solvent and high-boiling substances are distilled from the bottom of the column. I pulled it out.
上記留出液及び缶出液の夫々に含まれるジエチレングリ
コールモノメチルエーテル（トリプライムの分解物）を
ガスクロマトグラフィーにより分析し、蒸留塔に供給し
た溶媒（トリプライム）の分解率（分解物のモル数／供
給物のモル数）を求め、分解率を後記の表１に示した。The diethylene glycol monomethyl ether (decomposed product of Triprime) contained in each of the above distillate and bottoms was analyzed by gas chromatography, and the decomposition rate (number of moles of the decomposed product) of the solvent (Triprime) supplied to the distillation column was determined. /number of moles of feed) was determined, and the decomposition rate is shown in Table 1 below.
また、缶出液の着色度を下記の測定法により測定し、表
１にＡＰＨＡＩＩｍを示した。In addition, the degree of coloration of the bottoms was measured by the following measuring method, and APHAIIm is shown in Table 1.
着色度の測定（硫酸着色法）
硫Ｍ着色試験法には、センサンド法、イーストマン法、
積木法等があるが、何れも微細な条件が異なるのみで主
たる操作は同じであり、センサント法が一般に広く用い
られている０本実施例においても以下に記載するセンサ
ンド法を採用した。Measurement of degree of coloration (sulfuric acid coloring method) Sulfur M coloring test methods include Sensand method, Eastman method,
Although there are building block methods and the like, the main operations are the same except for the minute conditions, and the Sensand method is generally widely used. In this example, the Sensand method described below was also adopted.
［測定法］
洗浄し乾燥した３００■１の共栓付平底フラスコに、試
料１００ ｍｌを入れる。試料を攪拌しなから３０”Ｃ
以下の室温で９８重量％の濃硫酸８１を２５１ビユレツ
トにて２１７分の速度で加える。フラスコに栓をして９
８±２℃の水浴中に２時間浸しておく。ついで水で室温
まで冷却した後、試料１００ ｍｌを内径２５１、高さ
２７０ ａｍの平底のガラス製比色管に移し、同様な比
色管にて同量のＡＰＨＡ色標準液と目視により比較し、
同色のＡＰＨＡ［を測定値とする。[Measurement method] Place 100 ml of the sample into a washed and dried 300 x 1 flat-bottomed flask with a stopper. 30"C without stirring the sample.
At room temperature, 98% by weight concentrated sulfuric acid 81 is added at a rate of 217 minutes at 251 barrels. Stopper the flask 9
Soak in a water bath at 8±2°C for 2 hours. After cooling to room temperature with water, 100 ml of the sample was transferred to a flat-bottom glass colorimeter tube with an inner diameter of 251 mm and a height of 270 am, and visually compared with the same amount of APHA color standard solution in the same colorimeter tube. ,
APHA of the same color is the measured value.
ＡＰＨＡ色原液の組成は次の通りである。The composition of the APHA color stock solution is as follows.
塩化白金酸カリウム（Ｋ２ＰｔＣｌｅ） １．２
４５ ｇ塩化コバルト （ＣＯＣｌ２ ・６Ｈ２０
） １．０００８９８％濃硫酸
１００ ｍ１以上を１０００ ｍｌ容のメスフラ
スコに入れ、蒸留水を加えて溶解し、蒸留水にて正確に
１０００ ｍｌとする。この液がＡＰＨＡ色原液であり
、以下蒸留水にて比例希釈して低いＡＰＨＡ色標準液を
得る。Potassium chloroplatinate (K2PtCle) 1.2
45 g cobalt chloride (COCl2 ・6H20
) 1.000898% concentrated sulfuric acid
Pour 100 ml or more into a 1000 ml volumetric flask, add distilled water to dissolve, and make up to exactly 1000 ml with distilled water. This solution is an APHA color stock solution, and is then proportionally diluted with distilled water to obtain a low APHA color standard solution.
実施例１〜６及び比較例１〜２
実施例１の方法で蒸留採取した粗ラクトンを、表１に示
す条件で運転する実施例１の蒸留塔に供給して蒸留を行
ない、塔頂からγ−ブチロラクトン及び水を留出させ、
溶媒及び高沸点物質を含む缶出液を塔底から抜き出した
。実施例１の方法で測定した溶媒の分解率及び缶出液の
着色度を表１に示した。Examples 1 to 6 and Comparative Examples 1 to 2 The crude lactone collected by distillation by the method of Example 1 was fed to the distillation column of Example 1 operated under the conditions shown in Table 1, and distilled. - distilling off butyrolactone and water;
The bottoms containing solvent and high-boiling substances were withdrawn from the bottom of the column. The decomposition rate of the solvent and the degree of coloration of the bottoms measured by the method of Example 1 are shown in Table 1.
表１
実施例７
実施例１の方法で蒸留採取した粗ラクトン（γ−ブチロ
ラクトン４５重量％、水９．０重量％及び溶媒４３重量
％を含む）を、実段数３０段、塔頂減圧度３０〜１０
ｖ＋＋Ｈｇ、塔底温度９０〜１２０℃、還流比ｔｏで運
転する蒸留塔に供給して蒸留し、塔頂から水を留出させ
た。Table 1 Example 7 Crude lactone (containing 45% by weight of γ-butyrolactone, 9.0% by weight of water, and 43% by weight of solvent) collected by distillation by the method of Example 1 was prepared using a column with 30 plates and a column top vacuum of 30%. ~10
The mixture was supplied to a distillation column operated at v++Hg, a bottom temperature of 90 to 120° C., and a reflux ratio to for distillation, and water was distilled from the top of the column.
残留液（γ−ブチロラクトン３３重量％及び溶媒６７重
量％からなる）をガラスオルダーショー実段数３５段、
塔頂減圧度２０ ｍｍＨｇ、塔底温度１２５℃、缶出液
滞留時開３時間で運転する蒸留塔に供給して蒸留し、塔
頂からγ−ブチロラクトンを留出させると共に、溶媒か
らなる缶出液を塔底から抜き出した。The residual liquid (consisting of 33% by weight of γ-butyrolactone and 67% by weight of solvent) was passed through a glass plate with 35 plates.
Distillation is carried out by supplying the distillation column to a distillation column that operates at a vacuum level of 20 mmHg at the top, a bottom temperature of 125°C, and is open for 3 hours when the bottoms are retained. γ-butyrolactone is distilled from the top of the column, and the bottoms consisting of the solvent are distilled. The liquid was taken out from the bottom of the tower.
上記留出液及び缶出液について、実施例１と同一の方法
で測定した溶媒の分解率を表２に示した。Table 2 shows the solvent decomposition rates of the above distillate and bottoms measured in the same manner as in Example 1.
また缶出液の着色度を表２に示した。Table 2 also shows the degree of coloring of the bottoms.
実施例８及び比較例３
実施例７において、粗ラクトン中の水を蒸留により留出
させた残留液（γ−ブチロラクトン３３重量％及び溶媒
６７重量％からなる）を、表２に示す条件で運転する実
施例７の蒸留塔に供給して蒸留を行ない、塔頂からγ−
ブチロラクトン及び水を留出させ、溶媒及び高沸点物質
を含む缶出液を塔底から抜き出した。実施例１の方法で
測定した溶媒の分解率及び缶出液の着色度を表２に示し
た。Example 8 and Comparative Example 3 In Example 7, the residual liquid obtained by distilling off the water in the crude lactone (consisting of 33% by weight of γ-butyrolactone and 67% by weight of solvent) was operated under the conditions shown in Table 2. The γ-
Butyrolactone and water were distilled off, and the bottoms containing solvent and high-boiling substances were extracted from the bottom of the column. The decomposition rate of the solvent and the degree of coloration of the bottoms measured by the method of Example 1 are shown in Table 2.
表２
（発明の効果）
本発明方法によれば、ジカルボン酸、ジカルボン酸無水
物及び／又はジカルボン酸エステルからなる原料をエー
テル類及びポリエーテル類から選ばれた溶媒を用い、ル
テニウム触媒の存在下液相で水素化して得られる反応生
成物から触媒を分離した粗ラクトン類を蒸留することに
より精製する際に、特定の蒸留条件を選ぶことにより、
前記の実施例に示すように、高品位のラクトン類を得る
ことができ、工業的にラクトン類を製造する場合の価値
は大きい。Table 2 (Effects of the invention) According to the method of the present invention, a raw material consisting of dicarboxylic acid, dicarboxylic acid anhydride and/or dicarboxylic acid ester is used in a solvent selected from ethers and polyethers in the presence of a ruthenium catalyst. By selecting specific distillation conditions when purifying crude lactones by distilling the catalyst from the reaction product obtained by hydrogenation in the liquid phase,
As shown in the examples above, high-quality lactones can be obtained and are of great value in the industrial production of lactones.
Claims (1)
ン酸エステルを、溶媒としてエーテル類又はポリエーテ
ル類を使用しルテニウム触媒の存在下液相で水素化して
得られる反応生成物から触媒を分離した粗ラクトン類を
蒸留することにより精製するにあたり、蒸留塔の塔底温
度を１５０℃以下とし、かつ缶出液の滞留時間を６時間
以下に保持することを特徴とするラクトン類の精製法。(1) Crude lactone obtained by separating the catalyst from the reaction product obtained by hydrogenating dicarboxylic acid, dicarboxylic acid anhydride, or dicarboxylic acid ester in the liquid phase in the presence of a ruthenium catalyst using ethers or polyethers as a solvent. 1. A method for purifying lactones, which comprises keeping the temperature at the bottom of a distillation column at 150° C. or lower and maintaining the residence time of the bottoms at 6 hours or less.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1274999A JPH07121928B2 (en) | 1989-10-24 | 1989-10-24 | Lactone purification method |
| US07/582,158 US5047561A (en) | 1989-09-27 | 1990-09-14 | Process for producing a lactone |
| EP90118196A EP0420062B1 (en) | 1989-09-27 | 1990-09-21 | Process for producing a lactone |
| DE69017570T DE69017570T2 (en) | 1989-09-27 | 1990-09-21 | Process for the preparation of a lactone. |
| BR909004837A BR9004837A (en) | 1989-09-27 | 1990-09-26 | PROCESS FOR THE PRODUCTION OF A LACTONE |
| KR1019900015317A KR0145318B1 (en) | 1989-09-27 | 1990-09-26 | Process for producing a lactone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1274999A JPH07121928B2 (en) | 1989-10-24 | 1989-10-24 | Lactone purification method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03141273A true JPH03141273A (en) | 1991-06-17 |
| JPH07121928B2 JPH07121928B2 (en) | 1995-12-25 |
Family
ID=17549484
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1274999A Expired - Lifetime JPH07121928B2 (en) | 1989-09-27 | 1989-10-24 | Lactone purification method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07121928B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7427684B2 (en) | 2003-10-30 | 2008-09-23 | Davy Process Technology Limited | Process for the production of lactams |
| US7709689B2 (en) | 2002-05-02 | 2010-05-04 | Davy Process Technololgy Limited | Homogenous process for the hydrogenation of carboxylic acids and derivatives thereof |
-
1989
- 1989-10-24 JP JP1274999A patent/JPH07121928B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7709689B2 (en) | 2002-05-02 | 2010-05-04 | Davy Process Technololgy Limited | Homogenous process for the hydrogenation of carboxylic acids and derivatives thereof |
| US9636671B2 (en) | 2002-05-02 | 2017-05-02 | Davy Process Technology Limited | Homogeneous process for the hydrogenation of carboxylic acids and derivatives thereof |
| US7427684B2 (en) | 2003-10-30 | 2008-09-23 | Davy Process Technology Limited | Process for the production of lactams |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07121928B2 (en) | 1995-12-25 |
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