JP3911582B2 - Catalyst for alkoxylation of complex oxide - Google Patents
Catalyst for alkoxylation of complex oxide Download PDFInfo
- Publication number
- JP3911582B2 JP3911582B2 JP28157397A JP28157397A JP3911582B2 JP 3911582 B2 JP3911582 B2 JP 3911582B2 JP 28157397 A JP28157397 A JP 28157397A JP 28157397 A JP28157397 A JP 28157397A JP 3911582 B2 JP3911582 B2 JP 3911582B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- catalyst
- oxide
- mol
- alkoxylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003054 catalyst Substances 0.000 title claims description 55
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 229910044991 metal oxide Inorganic materials 0.000 claims description 16
- 150000004706 metal oxides Chemical class 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 11
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 11
- 150000002602 lanthanoids Chemical class 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 125000002947 alkylene group Chemical group 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 10
- 230000000737 periodic effect Effects 0.000 claims description 10
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052712 strontium Inorganic materials 0.000 claims description 5
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 239000007864 aqueous solution Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 239000006227 byproduct Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000009826 distribution Methods 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000011572 manganese Substances 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- -1 alkylphenols Chemical class 0.000 description 4
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 4
- 239000001639 calcium acetate Substances 0.000 description 4
- 235000011092 calcium acetate Nutrition 0.000 description 4
- 229960005147 calcium acetate Drugs 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 150000003138 primary alcohols Chemical class 0.000 description 4
- 150000003333 secondary alcohols Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 235000011118 potassium hydroxide Nutrition 0.000 description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ACUZDYFTRHEKOS-SNVBAGLBSA-N 2-Decanol Natural products CCCCCCCC[C@@H](C)O ACUZDYFTRHEKOS-SNVBAGLBSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical class FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- ACUZDYFTRHEKOS-UHFFFAOYSA-N decan-2-ol Chemical compound CCCCCCCCC(C)O ACUZDYFTRHEKOS-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- XSWSEQPWKOWORN-UHFFFAOYSA-N dodecan-2-ol Chemical compound CCCCCCCCCCC(C)O XSWSEQPWKOWORN-UHFFFAOYSA-N 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229940044658 gallium nitrate Drugs 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- OHZZTXYKLXZFSZ-UHFFFAOYSA-I manganese(3+) 5,10,15-tris(1-methylpyridin-1-ium-4-yl)-20-(1-methylpyridin-4-ylidene)porphyrin-22-ide pentachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mn+3].C1=CN(C)C=CC1=C1C(C=C2)=NC2=C(C=2C=C[N+](C)=CC=2)C([N-]2)=CC=C2C(C=2C=C[N+](C)=CC=2)=C(C=C2)N=C2C(C=2C=C[N+](C)=CC=2)=C2N=C1C=C2 OHZZTXYKLXZFSZ-UHFFFAOYSA-I 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- HKUFIYBZNQSHQS-UHFFFAOYSA-N n-octadecyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCC HKUFIYBZNQSHQS-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 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 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- 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
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、アルコキシル化触媒に関する。詳しくは、特定の金属酸化物からなるアルコキシル化触媒、および該触媒を用いて行う、副生成物が少なく、重合度分布が狭い、アルコキシレートの製造方法に関する。
【０００２】
【従来の技術】
高級アルコール、アルキルフェノール、脂肪酸、アルキルアミン等の活性水素含有化合物は、アルキレンオキサイドとの付加重合により、疎水基の構造と親水基の構造を自由に組み合わせることができるので、家庭用洗剤および工業用界面活性剤、さらにアニオン界面活性剤の原料として広範な用途に利用されている。これらの活性水素を持つ化合物とアルキレンオキサイドから得られるアルコキシレートを製造するためには、従来より触媒として、苛性ソーダ、苛性カリ、トリエチルアミン等の塩基性触媒や三弗化ホウ素コンプレックス（エーテラート等）や五塩化アンチモン等の酸性触媒が用いられている。
【０００３】
【発明が解決しようとする課題】
しかしながら、これらの公知の触媒には以下のような欠点がある。
【０００４】
すなわち、塩基性触媒を用いた場合は、副生成物が少なく、重合度が高いものが容易に得られるが、重合度分布が広くなり、高級アルコール等の活性水素含有化合物の未反応物からアルキレンオキサイドの重合度の高いものまで含む混合物となる。未反応物が多いと重合物の臭気が強く、重合物の石油エーテル可溶分等の値が高くなるので、洗浄用の界面活性剤としての使用には問題があり、また、アルキレンオキサイドの重合度が高いものが多いと、疎水性と親水性のバランスが崩れるので、界面活性剤としての性能の低下等が問題となる。
【０００５】
一方、酸性触媒を用いた場合は、高級アルコール等の活性水素含有化合物の未反応物は少なくなるが、ポリアルキレングリコールやジオキサン、ジオキソラン等の望ましくない副生成物が多く生成する。また、酸性触媒は、金属に対する腐食性が強いので、使用する装置が限定され、工業用触媒として不具合な点を有する。
【０００６】
重合度分布が狭く、副生成物が少なくなる触媒としては、ハロゲン化物（特開昭６０−２９３７０号、特開平２−２２７４２６号公報）、複合金属酸化物（特開平１−１６４４３７号、特開平２−７１８４１号、特開平６−３２２０９８号、特開平７−２２７５４０号公報）、ポリフィリン（特公平５−１４７３４号公報）等が提案されている。
【０００７】
しかし、これらの触媒には次のような問題点がある。
【０００８】
例えば、ハロゲン化物の触媒は、金属に対する腐食性があるので、装置が限定され、またポリフィリンは、触媒活性が低いため、反応時間が非常に長くなり、いずれも工業的には有利であるとはいえない。
【０００９】
一方、複合酸化物の触媒では、アルコキシレートの重合度の分布は狭いものの、触媒を除去するための濾過行程に時間を要し、工業的には問題があったので、最近では、より高く活性化して触媒添加量を減らすことにより、濾過行程の効率化が図られている。
【００１０】
本発明は上記に鑑みてなされたものであり、濾過行程の効率が向上し、なおかつアルコキシレートの重合度の分布が狭く、副生成物が少なくなる高い触媒活性を持ったアルコキシル化触媒、およびその触媒を用いるアルコキシレートの製造方法を提供することを目的とする。
【００１１】
【課題を解決するための手段】
上記の課題を解決するために、請求項１の複合酸化物系アルコキシル化用触媒は、亜族方式周期律表の第３Ａ族、３Ｂ族、５Ａ族、７Ａ族、８族およびランタノイド類から選ばれた元素を含有する岩塩型構造をとる金属酸化物を含有してなり、活性水素原子含有化合物にアルキレンオキサイドを付加し、アルコキシレートを製造する際に用いる、複合酸化物系アルコキシル化触媒であって、岩塩型構造をとる金属酸化物の金属元素が、カルシウム、ストロンチウム、バリウム、マンガンからなる群から選ばれた一種又は二種以上であり、亜族方式周期律表の第３Ａ族、３Ｂ族、５Ａ族、７Ａ族、８族およびランタノイド類から選ばれた元素として、アルミニウム、ガリウム、インジウム、マンガン、及びプラセオジウムからなる群から選ばれた一種又は二種以上を含有してなり、亜族方式周期律表の第３Ａ族、３Ｂ族、５Ａ族、７Ａ族、８族及びランタノイド類から選ばれた元素の含有量が、前記岩塩型構造をとる金属酸化物の金属元素１．０に対し、０．００１〜０．５の割合（但し組成比）であるものとする。
【００１２】
請求項２の製造方法においては、活性水素原子含有化合物にアルキレンオキサイドを付加し、アルコキシレートを製造するに際し、上記のうちいずれかの複合酸化物系アルコキシル化用触媒を用いる。
【００１３】
【発明の実施の形態】
本発明の複合酸化物系アルコキシル化用触媒は、岩塩型構造をとる金属酸化物が、亜族方式周期律表の第３Ａ族、３Ｂ族、５Ａ族、７Ａ族、８族およびランタノイド類から選ばれた元素を、一種又は二種以上含有してなる複合酸化物である。
【００１４】
岩塩型構造をとる金属酸化物の金属元素の例としては、カルシウム、ストロンチウム、バリウム、マンガン、鉄、ニッケル、コバルト等が挙げられる。このうち好ましいものとしては、触媒活性、濾過性の点から、カルシウム、ストロンチウム、マンガンが挙げられる。
【００１５】
岩塩型構造をとる金属酸化物に含有される、亜族方式周期律表の第３Ａ族、３Ｂ族、５Ａ族、７Ａ族、８族およびランタノイド類としては、スカンジウム、イットリウム、アルミニウム、ガリウム、インジウム、マンガン、ニッケル、プラセオジウム等が挙げられる。触媒活性、濾過性の点からは、アルミニウム、ガリウム、インジウム、マンガン、プラセオジウムが好ましく、特にインジウムが好ましい。
【００１６】
本発明の触媒において，亜族方式周期律表の第３Ａ族、３Ｂ族、７Ａ族、８族およびランタノイド類元素の含有量は、組成比で、金属酸化物の金属元素１．０に対して０．００１〜０．５０の割合が好ましく、０．０１〜０．３の割合が特に好ましい。
【００１７】
上記した本発明の触媒の製造方法は、特に限定されず、公知の金属酸化物の調整法により製造することができる。
【００１８】
たとえば、金属の硝酸塩、硫酸塩、炭酸塩、酢酸塩、乳酸塩、塩化物、水酸化物、酸化物等の化合物を含む混合水溶液または水分散液に沈殿剤を添加し、得られた沈殿物を水洗・乾燥し、窒素気流中または空気中で、５００〜１，５００℃、好ましくは６００〜１，２００℃で焼成する方法（共沈殿法）、あるいは金属酸化物に、硝酸塩等の水溶液を含浸して、乾燥後、窒素気流中または空気中で、５００〜１，５００℃、好ましくは６００〜１，２００℃で焼成する方法（含浸法）等が挙げられる。
【００１９】
本発明の製造方法においては、活性水素原子含有化合物にアルキレンオキサイドを付加してアルコキシレートを製造するに際し、上記複合酸化物系アルコキシル化用触媒を用いる。
【００２０】
上記活性水素含有化合物としては、アルコール類、多価アルコール類、フェノール類、カルボン酸類、アミン類およびそれらの混合物等が挙げられる。
【００２１】
アルコール類としては、炭素数２〜３０の飽和または不飽和の直鎖もしくは分枝構造のアルキル基を有する１級アルコールや２級アルコール、アリールアルキルアルコール等が挙げられる。具体的には、１級アルコールとしては、ｎ−オクタノール、ｎ−デカノール、ｎ−ドデカノール、オレイルアルコール、２−エチルヘキサノール等、２級アルコールとしては、２−デカノール、２−ドデカノール等である。
【００２２】
多価アルコール類としては、エチレングリコール、プロピレングリコール、ジエチレングリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトール、ソルビトール等が挙げられる。
【００２３】
フェノール類としては、フェノール、オクチルフェノール、ノニルフェノール等が挙げられる。
【００２４】
カルボン酸類としては、炭素数１〜３０の飽和または不飽和の直鎖もしくは分枝構造のアルキル基を有する脂肪酸等が挙げられる。具体的には、酢酸、プロピオン酸、ラウリン酸、ステアリン酸、オレイン酸等が挙げられる。
【００２５】
アミン類としては、炭素数１〜３０の飽和または不飽和のアルキル基を有する１級または２級アミン等が挙げられる。具体的には、オクチルアミン、ラウリルアミン、ステアリルアミン、ジステアリルアミン等が挙げられる。
【００２６】
これらの活性水素原子含有化合物の中では、炭素数８〜２２の飽和または不飽和の直鎖もしくは分枝構造のアルキル基を有する１級アルコールおよび２級アルコール類が好ましく、特に好ましいのは炭素数１０〜１８の直鎖もしくは分枝構造の飽和の１、２級アルコールである。
【００２７】
本発明で用いられるアルキレンオキサイドは、活性水素を持つ化合物と反応してアルコキシレートを生成し得るものであればどのようなものでも良いが、エチレンオキサイドやプロピレンオキサイド等のオキシラン環を持つものが好ましく、特に好ましいのはエチレンオキサイドである。
【００２８】
本発明の製造方法によるアルコキシレートの製造は、オートクレーブ等の圧力反応器で、通常の操作手順および反応条件で容易に行うことができる。
【００２９】
触媒の使用量は、活性水素含有化合物に対して、好ましくは０．０１〜２０重量％、特に好ましくは０．１〜５重量％である。
【００３０】
反応温度は、好ましくは８０〜２３０℃、特に好ましくは１２０〜１８０℃である。
【００３１】
反応後、触媒は反応生成物中に分散して懸濁状態をなしているが、濾過、遠心分離等の通常の方法で除去することができる。
【００３２】
なお、触媒を濾過で除去して得られたアルコキシレートは、中性であるので、酸やアルカリ等で中和する必要はない。
【００３３】
【実施例】
以下に本発明を実施例により詳細に説明するが、本発明はこれらの実施例によって限定されるものではない。
【００３４】
［実施例１］
微粉末の酸化カルシウム５６ｇ（１モル）に、１０％酢酸アルミニウム水溶液を２０４ｇ（０．１モル）、イオン交換水を５００ｇ加え、１時間撹拌した。１０５℃で徐々に水を蒸発させ、次いで１１０℃で１０時間乾燥後、得られた固形物を細かく粉砕し、窒素気流下、８００℃で５時間焼成して、ＣａＯ−Ａｌ2 Ｏ3 触媒（金属元素の組成比；Ｃａ：Ａｌ＝１．０：０．１）を得た。
【００３５】
［実施例２］
１０％酢酸カルシウム水溶液１，５８０ｇ（１モル）に、１０％硝酸インジウム水溶液を６０２ｇ（０．２モル）加え、１時間撹拌した後、１０５℃で徐々に水を蒸発させて乾燥した。その後得られた固形物を細かく粉砕し、窒素気流下、１，０００℃で８時間焼成して、ＣａＯ−Ｉｎ2 Ｏ3 触媒（金属元素の組成比；Ｃａ：Ｉｎ＝１．０：０．２）を得た。
【００３６】
［実施例３］
微粉末の炭酸ストロンチウム１４８ｇ（１モル）に、１０％硝酸プラセオジウム水溶液１６４ｇ（０．０５モル）とイオン交換水５００ｇを加え、１時間撹拌した後、１０５℃で徐々に水を蒸発させて乾燥した。その後得られた固形物を細かく粉砕し、窒素気流下、１，０００℃で１２時間焼成して、ＢａＯ−Ｐｒ2 Ｏ3 触媒（金属元素の組成比；Ｓｒ：Ｐｒ＝１．０：０．０５）を得た。
【００３７】
［実施例４］
１０％硝酸カルシウム水溶液１，６４１ｇ（１モル）に、１０％硝酸ガリウム水溶液を４２８ｇ（０．１モル）加え、３０分間撹拌した後、２時間かけて２０％炭酸カリウム水溶液６９１ｇ（１モル）を滴下し、１時間静置した。その後、母液を濾過で除き、沈殿物をイオン交換水で３回洗浄した。１０５℃で徐々に水を蒸発させ、次いで、１１０℃で１０時間乾燥した後、得られた固形物を細かく粉砕し、窒素気流下、８００℃で７時間焼成して、ＣａＯ−Ｇａ2 Ｏ3 触媒（金属元素の組成比；Ｃａ：Ｇａ＝１．０：０．１）を得た。
【００３８】
［実施例５］
１０％酢酸バリウム水溶液２，５５５ｇ（１モル）に、１０％硝酸インジウム水溶液を３０１ｇ（０．１モル）加え、３０分間撹拌した後、２時間かけて２０％炭酸ナトリウム水溶液５３０ｇ（１モル）を滴下し、１時間静置した。その後、母液を濾過で除き、沈殿物をイオン交換水で３回洗浄した。１０５℃で徐々に水を蒸発させ、次いで１１０℃で１０時間乾燥した後、得られた固形物を細かく粉砕し、窒素気流下、１，０００℃で１０時間焼成して、ＢａＯ−Ｉｎ2 Ｏ3 触媒（金属元素の組成比；Ｂａ：Ｉｎ＝１．０：０．１）を得た。
【００３９】
［実施例６］
１０％酢酸カルシウム水溶液１，５８２ｇ（１モル）に、１０％酢酸マンガン水溶液を３４８ｇ（０．１５モル）加え、１時間撹拌した後、１０５℃で徐々に水を蒸発させて乾燥した。その後得られた固形物を細かく粉砕し、窒素気流下、８００℃で７時間焼成して、ＣａＯ−ＭｎＯ2 触媒（金属元素の組成比；Ｃａ：Ｍｎ＝１．０：０．１５）を得た。
【００４０】
［実施例７］
微粉末の炭酸マンガン１１５ｇ（１モル）に、１０％硝酸インジウム水溶液を３０１ｇ（０．１モル）加え、１時間撹拌した後、１０５℃で徐々に水を蒸発させて乾燥した。その後、得られた固形物を細かく粉砕し、窒素気流下、９００℃で７時間焼成して、ＭｎＯ2 −Ｉｎ2 Ｏ3 触媒（金属元素の組成比；Ｍｎ：Ｉｎ＝１．０：０．１）を得た。
【００４１】
［比較例１］
１０％酢酸カルシウム水溶液１，５８２ｇ（１モル）を１時間撹拌後、１０５℃で水を徐々に蒸発させ、次いで、１１０℃で１０時間乾燥後、得られた固形物を細かく粉砕し、窒素気流下、６００℃で５時間焼成して、ＣａＯ触媒を得た。
【００４２】
［比較例２］
炭酸ストロンチウム１４８ｇ（１モル）に、イオン交換水５００ｇを加え、１時間撹拌した後、１０５℃で水を徐々に蒸発させた。次いで、１１０℃で１０時間乾燥した後、得られた固形物を細かく粉砕し、窒素気流下、８００℃で５時間焼成して、ＢａＯ触媒を得た。
【００４３】
［比較例３］
粉末の酸化マグネシウム４０ｇ（１モル）に、１０％硫酸チタン水溶液を３８４ｇ（０．１モル）、イオン交換水を５００ｇ加え、１時間撹拌した後、１０５℃で徐々に水を蒸発させ、次いで、１１０℃で１０時間乾燥した後、得られた固形物を細かく粉砕し、窒素気流下、１０００℃で１２時間焼成して、ＭｇＯ−ＴｉＯ2 触媒（金属元素の組成比；Ｍｇ：Ｔｉ＝１．０：０．１）を得た。
【００４４】
［比較例４］
１０％酢酸カルシウム水溶液１，５８２ｇ（１モル）に、１０％硝酸亜鉛水溶液を１８９ｇ（０．１モル）加え、３０分撹拌した後、２時間かけて２０％炭酸ナトリウム水溶液５３０ｇ（１モル）を滴下し、１時間静置した。その後、母液を濾過で除き、沈殿物をイオン交換水で３回洗浄した。１０５℃で徐々に水を蒸発させ、次いで１１０℃で１０時間乾燥した後、得られた固形物を細かく粉砕し、窒素気流下、１，０００℃で５時間焼成して、ＣａＯ−ＺｎＯ触媒（金属元素の組成比；Ｃａ：Ｚｎ＝１．０：０．１）を得た。
【００４５】
［反応実施例１〜７および反応比較例１〜４］
１リットルのオートクレーブにラウリルアルコールを１８８ｇ（１モル）と実施例１〜７および比較例１〜４で得られた複合酸化物系の触媒を１．９ｇ（原料アルコールに対して１．０重量％）仕込み、オートクレーブ内を窒素で置換した後、撹拌しながら１８０℃まで昇温し、同温度でエチレンオキサイド１３２ｇ（３モル）を圧力２〜５ｋｇ／ｃｍ2 （０．２〜０．５ＭＰａ）に保ちながら導入し、反応を行った。同温度で１〜２時間熟成した後、８０℃に冷却し、触媒を通常の方法で濾過により除去した。
【００４６】
反応実施例および反応比較例の反応性、副生成物量、濾過性、付加モル数分布の比較を表１および図１に示す。
【００４７】
エチレンオキサイドの付加反応速度は、通常使用されているアルカリ触媒であるＫＯＨを用いた場合の付加反応速度と比較して、同程度であれば○、やや遅い場合は△、かなり遅い場合は×とした。
【００４８】
副生成物としては、ポリエチレングリコール（ＰＥＧ）の量をガスクロマトグラフィーで測定した。また、エチレンオキサイド付加モル数（分子量分布）は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定した。
【００４９】
濾過性は、内径９．５ｍｍの桐山ロートを設置できる濾過器を用い、グラスファイバー濾紙（保留粒子：０．８ミクロン）を使用して減圧下（７６ｃｍＨｇ（１．３３ｋＰａ））で行った時の濾過時間を比較した。
【００５０】
【表１】
［反応比較例５］
触媒としてＫＯＨ触媒（対アルコール０．３重量％）を用いて、反応実施例１〜７と同様の反応を行い、エチレンオキサイド付加モル数（分子量分布）を、ＧＰＣにより測定した。結果を図１に併せ示す。
【００５２】
【発明の効果】
請求項１のアルコキシル化触媒は、重合度分布が狭く、しかも未反応原料や副生成物が少ないアルコキシレートが製造でき、中和工程が省略できるので、産業上大きな価値がある。
【００５３】
特に、岩塩型構造をとる金属酸化物の金属元素が、カルシウム、ストロンチウム、バリウム、マンガンからなる群から選ばれた一種又は二種以上であることにより、上記に加えて触媒の活性が高いため、製造時間の面でも従来のものと比較して遜色がない。
【００５４】
さらに、亜族方式周期律表の第３Ａ族、３Ｂ族、５Ａ族、７Ａ族、８族およびランタノイド類から選ばれた元素として、アルミニウム、ガリウム、インジウム、マンガン、プラセオジウムからなる群から選ばれた一種又は二種以上を含有することから、未反応原料や副生成物がほとんどなく、また触媒の活性が高いことにより製造時間が短縮できる上に、反応物から容易に触媒を除去できるため、濾過行程での効率が向上する。
【００５５】
また、亜族方式周期律表の第３Ａ族、３Ｂ族、５Ａ族、７Ａ族、８族及びランタノイド類から選ばれた元素の含有量が、前記岩塩型構造をとる金属酸化物の金属元素１．０に対し、０．００１〜０．５の割合（但し組成比）であることによっても、未反応原料や副生成物がほとんどなく、触媒の活性が高いため、製造時間の面で有利である。
【００５６】
請求項２の製造方法によれば、上記したような、重合度分布が狭く、未反応原料や副生成物が少ないアルコキシレートが容易に効率よく製造できる。
【図面の簡単な説明】
【図１】 実施例及び比較例の触媒を用いた結果得られたポリエチレンオキサイドの、エチレンオキサイド付加モル数分布を示すグラフである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an alkoxylation catalyst. Specifically, the present invention relates to an alkoxylation catalyst comprising a specific metal oxide, and a method for producing an alkoxylate, which is carried out by using the catalyst and has few by-products and has a narrow polymerization degree distribution.
[0002]
[Prior art]
Active hydrogen-containing compounds such as higher alcohols, alkylphenols, fatty acids, and alkylamines can be combined freely with the structure of hydrophobic groups and hydrophilic groups by addition polymerization with alkylene oxide. It is used in a wide range of applications as a raw material for activators and anionic surfactants. In order to produce alkoxylates obtained from these active hydrogen-containing compounds and alkylene oxides, conventional catalysts such as caustic soda, caustic potash, triethylamine, boron trifluoride complexes (such as etherate) and pentachloride have been used as catalysts. An acidic catalyst such as antimony is used.
[0003]
[Problems to be solved by the invention]
However, these known catalysts have the following disadvantages.
[0004]
That is, when a basic catalyst is used, a by-product with a low degree of by-products and a high degree of polymerization can be easily obtained. A mixture containing even a high degree of polymerization of oxide. If there are many unreacted substances, the odor of the polymer is strong and the value of the petroleum ether soluble matter of the polymer is high, so there is a problem in use as a surfactant for washing, and the polymerization of alkylene oxide If the degree is high, the balance between hydrophobicity and hydrophilicity is lost, so that the performance as a surfactant deteriorates.
[0005]
On the other hand, when an acidic catalyst is used, an unreacted product of an active hydrogen-containing compound such as a higher alcohol is reduced, but many undesirable by-products such as polyalkylene glycol, dioxane and dioxolane are generated. Moreover, since an acidic catalyst has strong corrosiveness with respect to a metal, the apparatus to be used is limited and has a fault as an industrial catalyst.
[0006]
Examples of the catalyst having a narrow polymerization degree distribution and less by-products include halides (Japanese Patent Laid-Open Nos. 60-29370 and 2-227426) and composite metal oxides (Japanese Patent Laid-Open No. 1-164437 and Japanese Patent Laid-Open No. No. 2-71841, JP-A-6-322098, JP-A-7-227540), and polyphyrin (Japanese Patent Publication No. 5-14734) have been proposed.
[0007]
However, these catalysts have the following problems.
[0008]
For example, halide catalysts are corrosive to metals, so the equipment is limited, and polyphyrins have low catalytic activity, resulting in very long reaction times, both of which are industrially advantageous. I can't say that.
[0009]
On the other hand, in the composite oxide catalyst, although the distribution of the degree of polymerization of the alkoxylate is narrow, it took time for the filtration process to remove the catalyst, and there was an industrial problem. The efficiency of the filtration process is improved by reducing the catalyst addition amount.
[0010]
The present invention has been made in view of the above, and an alkoxylation catalyst having a high catalytic activity in which the efficiency of the filtration process is improved, the distribution of the degree of polymerization of the alkoxylate is narrow, and by-products are reduced, and its It aims at providing the manufacturing method of the alkoxylate using a catalyst.
[0011]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the composite oxide alkoxylation catalyst according to
[0012]
In the production method of
[0013]
DETAILED DESCRIPTION OF THE INVENTION
In the composite oxide-based alkoxylation catalyst of the present invention, the metal oxide having a rock salt structure is selected from Group 3A, Group 3B, Group 5A, Group 7A, Group 8 and Lanthanoids of the Subgroup Periodic Table Or a composite oxide containing one or more of these elements.
[0014]
Examples of the metal element of the metal oxide having a rock salt structure include calcium, strontium, barium, manganese, iron, nickel, cobalt and the like. Among these, calcium, strontium, and manganese are preferable from the viewpoint of catalytic activity and filterability.
[0015]
The group 3A, 3B, 5A, 7A, 8 and lanthanoids contained in the metal oxide having a rock salt structure include scandium, yttrium, aluminum, gallium and indium. , Manganese, nickel, praseodymium and the like. From the viewpoint of catalytic activity and filterability, aluminum, gallium, indium, manganese and praseodymium are preferable, and indium is particularly preferable.
[0016]
In the catalyst of the present invention, the contents of Group 3A, Group 3B, Group 7A, Group 8, and lanthanoid elements in the subgroup periodic table are in composition ratio with respect to metal element 1.0 of the metal oxide. A ratio of 0.001 to 0.50 is preferable, and a ratio of 0.01 to 0.3 is particularly preferable.
[0017]
The method for producing the catalyst of the present invention described above is not particularly limited, and can be produced by a known method for adjusting a metal oxide.
[0018]
For example, a precipitate obtained by adding a precipitant to a mixed aqueous solution or aqueous dispersion containing a compound such as metal nitrate, sulfate, carbonate, acetate, lactate, chloride, hydroxide, oxide, etc. Is washed with water and dried, and calcined at 500 to 1,500 ° C., preferably 600 to 1,200 ° C. in a nitrogen stream or air (coprecipitation method), or an aqueous solution such as nitrate is added to the metal oxide Examples of the method include impregnation and drying, followed by firing in a nitrogen stream or in air at 500 to 1,500 ° C., preferably 600 to 1,200 ° C. (impregnation method).
[0019]
In the production method of the present invention, when the alkoxylate is produced by adding an alkylene oxide to an active hydrogen atom-containing compound, the above-mentioned composite oxide-based alkoxylation catalyst is used.
[0020]
Examples of the active hydrogen-containing compound include alcohols, polyhydric alcohols, phenols, carboxylic acids, amines, and mixtures thereof.
[0021]
Examples of alcohols include primary alcohols, secondary alcohols, and arylalkyl alcohols having a saturated or unsaturated linear or branched alkyl group having 2 to 30 carbon atoms. Specific examples of the primary alcohol include n-octanol, n-decanol, n-dodecanol, oleyl alcohol, and 2-ethylhexanol. Examples of the secondary alcohol include 2-decanol and 2-dodecanol.
[0022]
Examples of the polyhydric alcohols include ethylene glycol, propylene glycol, diethylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol and the like.
[0023]
Examples of phenols include phenol, octylphenol, nonylphenol and the like.
[0024]
Examples of the carboxylic acids include fatty acids having a saturated or unsaturated linear or branched alkyl group having 1 to 30 carbon atoms. Specific examples include acetic acid, propionic acid, lauric acid, stearic acid, oleic acid and the like.
[0025]
Examples of amines include primary or secondary amines having a saturated or unsaturated alkyl group having 1 to 30 carbon atoms. Specific examples include octylamine, laurylamine, stearylamine, distearylamine and the like.
[0026]
Among these active hydrogen atom-containing compounds, primary alcohols and secondary alcohols having a saturated or unsaturated linear or branched alkyl group having 8 to 22 carbon atoms are preferable, and carbon number is particularly preferable. It is a saturated primary or secondary alcohol having 10 to 18 linear or branched structures.
[0027]
The alkylene oxide used in the present invention may be any alkylene oxide that can react with a compound having active hydrogen to produce an alkoxylate, but preferably has an oxirane ring such as ethylene oxide or propylene oxide. Particularly preferred is ethylene oxide.
[0028]
Production of the alkoxylate by the production method of the present invention can be easily carried out in a pressure reactor such as an autoclave under ordinary operating procedures and reaction conditions.
[0029]
The amount of the catalyst used is preferably 0.01 to 20% by weight, particularly preferably 0.1 to 5% by weight, based on the active hydrogen-containing compound.
[0030]
The reaction temperature is preferably 80 to 230 ° C, particularly preferably 120 to 180 ° C.
[0031]
After the reaction, the catalyst is dispersed in the reaction product to form a suspended state, but can be removed by a usual method such as filtration or centrifugation.
[0032]
In addition, since the alkoxylate obtained by removing the catalyst by filtration is neutral, it is not necessary to neutralize with an acid or alkali.
[0033]
【Example】
EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
[0034]
[Example 1]
To 56 g (1 mol) of finely powdered calcium oxide, 204 g (0.1 mol) of 10% aluminum acetate aqueous solution and 500 g of ion-exchanged water were added and stirred for 1 hour. After gradually evaporating water at 105 ° C. and then drying at 110 ° C. for 10 hours, the obtained solid was finely pulverized and calcined at 800 ° C. for 5 hours in a nitrogen stream to obtain a CaO—Al 2 O 3 catalyst ( Metal element composition ratio; Ca: Al = 1.0: 0.1) was obtained.
[0035]
[Example 2]
To 1,580 g (1 mol) of 10% calcium acetate aqueous solution, 602 g (0.2 mol) of 10% indium nitrate aqueous solution was added and stirred for 1 hour, and then water was gradually evaporated at 105 ° C. to dry. Thereafter, the obtained solid was finely pulverized and calcined at 1,000 ° C. for 8 hours under a nitrogen stream, and a CaO—In 2 O 3 catalyst (composition ratio of metal elements; Ca: In = 1.0: 0. 2) was obtained.
[0036]
[Example 3]
To 148 g (1 mol) of fine powder strontium carbonate, 164 g (0.05 mol) of 10% praseodymium nitrate solution and 500 g of ion-exchanged water were added and stirred for 1 hour, and then water was gradually evaporated and dried at 105 ° C. . Thereafter, the obtained solid was finely pulverized and calcined at 1,000 ° C. for 12 hours in a nitrogen stream, and BaO—Pr 2 O 3 catalyst (composition ratio of metal elements; Sr: Pr = 1.0: 0. 05).
[0037]
[Example 4]
To 1,641 g (1 mol) of 10% calcium nitrate aqueous solution, 428 g (0.1 mol) of 10% gallium nitrate aqueous solution was added and stirred for 30 minutes, and then 691 g (1 mol) of 20% potassium carbonate aqueous solution was added over 2 hours. The solution was dropped and allowed to stand for 1 hour. Thereafter, the mother liquor was removed by filtration, and the precipitate was washed three times with ion exchange water. After gradually evaporating water at 105 ° C. and then drying at 110 ° C. for 10 hours, the obtained solid was finely pulverized and calcined at 800 ° C. for 7 hours in a nitrogen stream to obtain CaO—Ga 2 O 3. A catalyst (composition ratio of metal elements; Ca: Ga = 1.0: 0.1) was obtained.
[0038]
[Example 5]
To 2,555 g (1 mol) of 10% barium acetate aqueous solution, 301 g (0.1 mol) of 10% indium nitrate aqueous solution was added and stirred for 30 minutes, and then 530 g (1 mol) of 20% sodium carbonate aqueous solution was added over 2 hours. The solution was dropped and allowed to stand for 1 hour. Thereafter, the mother liquor was removed by filtration, and the precipitate was washed three times with ion exchange water. After gradually evaporating water at 105 ° C. and then drying at 110 ° C. for 10 hours, the obtained solid was finely pulverized and calcined at 1,000 ° C. for 10 hours in a nitrogen stream, and BaO—In 2 O 3 catalysts (composition ratio of metal elements; Ba: In = 1.0: 0.1) were obtained.
[0039]
[Example 6]
348 g (0.15 mol) of 10% manganese acetate aqueous solution was added to 1,582 g (1 mol) of 10% calcium acetate aqueous solution and stirred for 1 hour, and then water was gradually evaporated at 105 ° C. to dry. Thereafter, the obtained solid was finely pulverized and calcined at 800 ° C. for 7 hours under a nitrogen stream to obtain a CaO—MnO 2 catalyst (composition ratio of metal elements; Ca: Mn = 1.0: 0.15). It was.
[0040]
[Example 7]
To 115 g (1 mol) of fine powdered manganese carbonate, 301 g (0.1 mol) of 10% indium nitrate aqueous solution was added and stirred for 1 hour, and then water was gradually evaporated at 105 ° C. to dry. Thereafter, the obtained solid was finely pulverized and calcined at 900 ° C. for 7 hours under a nitrogen stream, and MnO 2 —In 2 O 3 catalyst (composition ratio of metal elements; Mn: In = 1.0: 0.1 )
[0041]
[Comparative Example 1]
After stirring 1582 g (1 mol) of 10% calcium acetate aqueous solution for 1 hour, water was gradually evaporated at 105 ° C., and then dried at 110 ° C. for 10 hours. Then, it was calcined at 600 ° C. for 5 hours to obtain a CaO catalyst.
[0042]
[Comparative Example 2]
To 148 g (1 mol) of strontium carbonate, 500 g of ion-exchanged water was added and stirred for 1 hour, and then water was gradually evaporated at 105 ° C. Subsequently, after drying at 110 degreeC for 10 hours, the obtained solid substance was grind | pulverized finely and it baked at 800 degreeC under nitrogen stream for 5 hours, and obtained the BaO catalyst.
[0043]
[Comparative Example 3]
To 40 g (1 mol) of powdered magnesium oxide, 384 g (0.1 mol) of a 10% titanium sulfate aqueous solution and 500 g of ion-exchanged water were added and stirred for 1 hour, and then water was gradually evaporated at 105 ° C. After drying at 110 ° C. for 10 hours, the obtained solid was finely pulverized and calcined at 1000 ° C. for 12 hours in a nitrogen stream, and MgO—TiO 2 catalyst (composition ratio of metal elements; Mg: Ti = 1. 0: 0.1) was obtained.
[0044]
[Comparative Example 4]
189 g (0.1 mol) of 10% zinc nitrate aqueous solution was added to 1,582 g (1 mol) of 10% calcium acetate aqueous solution, stirred for 30 minutes, and then 530 g (1 mol) of 20% sodium carbonate aqueous solution was added over 2 hours. The solution was dropped and allowed to stand for 1 hour. Thereafter, the mother liquor was removed by filtration, and the precipitate was washed three times with ion exchange water. After gradually evaporating water at 105 ° C. and then drying at 110 ° C. for 10 hours, the obtained solid was finely pulverized and calcined at 1,000 ° C. for 5 hours in a nitrogen stream to obtain a CaO—ZnO catalyst ( A composition ratio of metal elements; Ca: Zn = 1.0: 0.1) was obtained.
[0045]
[Reaction Examples 1 to 7 and Reaction Comparative Examples 1 to 4]
In a 1 liter autoclave, 188 g (1 mol) of lauryl alcohol and 1.9 g of the composite oxide catalyst obtained in Examples 1 to 7 and Comparative Examples 1 to 4 (1.0% by weight based on the raw material alcohol) ) After charging and replacing the inside of the autoclave with nitrogen, the temperature was raised to 180 ° C. with stirring, and 132 g (3 mol) of ethylene oxide was adjusted to a pressure of 2 to 5 kg / cm 2 (0.2 to 0.5 MPa) at the same temperature. The reaction was carried out while maintaining the reaction. After aging at the same temperature for 1 to 2 hours, the mixture was cooled to 80 ° C., and the catalyst was removed by filtration in the usual manner.
[0046]
Table 1 and FIG. 1 show a comparison of the reactivity, the amount of by-products, the filterability, and the added mole number distribution of the reaction examples and the reaction comparative examples.
[0047]
The addition reaction rate of ethylene oxide is approximately the same as the addition reaction rate when using KOH, which is a commonly used alkali catalyst, △ if it is the same, △ if it is somewhat slow, and × if it is quite slow. did.
[0048]
As a by-product, the amount of polyethylene glycol (PEG) was measured by gas chromatography. The number of moles of ethylene oxide added (molecular weight distribution) was measured by gel permeation chromatography (GPC).
[0049]
The filterability is obtained when a filter capable of setting a 9.5 mm inner diameter Kiriyama funnel is used and glass fiber filter paper (retained particles: 0.8 micron) is used under reduced pressure (76 cmHg (1.33 kPa)). The filtration times were compared.
[0050]
[Table 1]
[Reaction Comparative Example 5]
The same reaction as in Reaction Examples 1 to 7 was performed using a KOH catalyst (0.3% by weight of alcohol) as a catalyst, and the number of moles of ethylene oxide added (molecular weight distribution) was measured by GPC. The results are also shown in FIG.
[0052]
【The invention's effect】
The alkoxylation catalyst according to
[0053]
In particular, since the metal element of the metal oxide having a rock salt structure is one or more selected from the group consisting of calcium, strontium, barium, and manganese , the activity of the catalyst is high in addition to the above, In terms of manufacturing time, it is not inferior to the conventional one.
[0054]
Furthermore, as an element selected from Group 3A, 3B, 5A, 7A, 8 and lanthanoids of the subgroup periodic table, it was selected from the group consisting of aluminum, gallium, indium, manganese and praseodymium. Since it contains one or two or more, there are almost no unreacted raw materials or by-products, and the catalyst activity is high, so that the production time can be shortened and the catalyst can be easily removed from the reaction product. Efficiency in the process is improved.
[0055]
In addition, the content of an element selected from Group 3A, Group 3B, Group 5A, Group 7A, Group 8 and lanthanoids in the subgroup periodic table is a
[0056]
According to the production method of
[Brief description of the drawings]
FIG. 1 is a graph showing the ethylene oxide addition mole number distribution of polyethylene oxide obtained as a result of using the catalysts of Examples and Comparative Examples.
Claims (2)
前記岩塩型構造をとる金属酸化物の金属元素が、カルシウム、ストロンチウム、バリウム、マンガンからなる群から選ばれた一種又は二種以上であり、
前記亜族方式周期律表の第３Ａ族、３Ｂ族、５Ａ族、７Ａ族、８族およびランタノイド類から選ばれた元素として、アルミニウム、ガリウム、インジウム、マンガン、及びプラセオジウムからなる群から選ばれた一種又は二種以上を含有してなり、
前記亜族方式周期律表の第３Ａ族、３Ｂ族、５Ａ族、７Ａ族、８族及びランタノイド類から選ばれた元素の含有量が、前記岩塩型構造をとる金属酸化物の金属元素１．０に対し、０．００１〜０．５の割合（但し組成比）である ことを特徴とする複合酸化物系アルコキシル化用触媒。 It contains a metal oxide having a rock salt structure containing an element selected from Group 3A, 3B, 5A, 7A, 8 and lanthanoids of the subgroup periodic table, and an active hydrogen atom A complex oxide-based alkoxylation catalyst used in the production of an alkoxylate by adding alkylene oxide to a containing compound,
The metal element of the metal oxide having the rock salt structure is one or more selected from the group consisting of calcium, strontium, barium and manganese,
The element selected from Group 3A, 3B, 5A, 7A, 8 and lanthanoids of the subgroup periodic table was selected from the group consisting of aluminum, gallium, indium, manganese, and praseodymium. Containing one or more,
In the subgroup periodic table, the content of an element selected from Group 3A, Group 3B, Group 5A, Group 7A, Group 8 and lanthanoid is a metal element of a metal oxide having the rock salt structure. A composite oxide alkoxylation catalyst , characterized in that the ratio is 0.001 to 0.5 (composition ratio) to 0 .
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| US6504061B1 (en) | 1998-06-10 | 2003-01-07 | Lion Corporation | Alkoxylation catalyst and method for producing the same, and method for producing alkylene oxide adduct using the catalyst |
| EP1123915B1 (en) | 2000-02-10 | 2004-07-28 | Nippon Shokubai Co., Ltd. | Process for producing alpha, beta-unsaturated carboxylic acid esters and catalyst for use in such process |
| JP4607704B2 (en) * | 2005-08-23 | 2011-01-05 | 第一工業製薬株式会社 | Catalyst for alkoxylation and process for producing alkoxylate |
| JP5112950B2 (en) * | 2007-05-22 | 2013-01-09 | 第一工業製薬株式会社 | Method for producing alkylene oxide adduct |
| CN115715979B (en) * | 2021-08-26 | 2024-07-12 | 中国石油化工股份有限公司 | Oxidation catalyst, preparation method thereof and application of oxidation catalyst in preparation of 2, 5-furandicarboxylic acid |
-
1997
- 1997-10-15 JP JP28157397A patent/JP3911582B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11114417A (en) | 1999-04-27 |
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