NL1039092C2 - Process for preparation of catalyst and process for production of alkylene oxide using catalyst prepared by the same. - Google Patents
Process for preparation of catalyst and process for production of alkylene oxide using catalyst prepared by the same. Download PDFInfo
- Publication number
- NL1039092C2 NL1039092C2 NL1039092A NL1039092A NL1039092C2 NL 1039092 C2 NL1039092 C2 NL 1039092C2 NL 1039092 A NL1039092 A NL 1039092A NL 1039092 A NL1039092 A NL 1039092A NL 1039092 C2 NL1039092 C2 NL 1039092C2
- Authority
- NL
- Netherlands
- Prior art keywords
- catalyst
- reaction
- oxygen
- alkylene oxide
- set forth
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims abstract description 76
- 125000002947 alkylene group Chemical group 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 49
- -1 nitrile compound Chemical class 0.000 claims abstract description 49
- 239000001301 oxygen Substances 0.000 claims abstract description 49
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 49
- 239000001257 hydrogen Substances 0.000 claims abstract description 44
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 44
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 36
- 150000001336 alkenes Chemical class 0.000 claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims description 95
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 33
- 239000002243 precursor Substances 0.000 claims description 18
- 229910052763 palladium Inorganic materials 0.000 claims description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 10
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 239000010931 gold Substances 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052762 osmium Inorganic materials 0.000 claims description 4
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 2
- GNKTZDSRQHMHLZ-UHFFFAOYSA-N [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] Chemical compound [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] GNKTZDSRQHMHLZ-UHFFFAOYSA-N 0.000 claims 10
- 125000004432 carbon atom Chemical group C* 0.000 claims 3
- 239000010970 precious metal Substances 0.000 claims 3
- 150000002825 nitriles Chemical class 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 28
- 229910052799 carbon Inorganic materials 0.000 abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 19
- 150000002431 hydrogen Chemical class 0.000 abstract description 18
- 230000003197 catalytic effect Effects 0.000 abstract description 17
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 9
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 9
- 230000007423 decrease Effects 0.000 abstract description 7
- 230000003247 decreasing effect Effects 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 description 35
- 239000007789 gas Substances 0.000 description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 239000010936 titanium Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 7
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 6
- 150000002736 metal compounds Chemical class 0.000 description 6
- 125000004430 oxygen atom Chemical group O* 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 5
- 150000004056 anthraquinones Chemical class 0.000 description 5
- 150000001639 boron compounds Chemical class 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 150000003377 silicon compounds Chemical class 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 150000002941 palladium compounds Chemical class 0.000 description 4
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 150000003609 titanium compounds Chemical class 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 3
- 235000019838 diammonium phosphate Nutrition 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 238000004993 emission spectroscopy Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- NJWSNNWLBMSXQR-UHFFFAOYSA-N 2-hexyloxirane Chemical compound CCCCCCC1CO1 NJWSNNWLBMSXQR-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229930192627 Naphthoquinone Natural products 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- APAJFZPFBHMFQR-UHFFFAOYSA-N anthraflavic acid Chemical compound OC1=CC=C2C(=O)C3=CC(O)=CC=C3C(=O)C2=C1 APAJFZPFBHMFQR-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 2
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 150000001925 cycloalkenes Chemical class 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- 239000012229 microporous material Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 150000002791 naphthoquinones Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- VYXHVRARDIDEHS-QGTKBVGQSA-N (1z,5z)-cycloocta-1,5-diene Chemical compound C\1C\C=C/CC\C=C/1 VYXHVRARDIDEHS-QGTKBVGQSA-N 0.000 description 1
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 1
- YCTDZYMMFQCTEO-FNORWQNLSA-N (E)-3-octene Chemical compound CCCC\C=C\CC YCTDZYMMFQCTEO-FNORWQNLSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- GVRWIAHBVAYKIZ-FNORWQNLSA-N (e)-dec-3-ene Chemical compound CCCCCC\C=C\CC GVRWIAHBVAYKIZ-FNORWQNLSA-N 0.000 description 1
- IICQZTQZQSBHBY-HWKANZROSA-N (e)-non-2-ene Chemical compound CCCCCC\C=C\C IICQZTQZQSBHBY-HWKANZROSA-N 0.000 description 1
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- ZKKZIPCBLBTIJE-UHFFFAOYSA-N 1,3-diethylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3C(=O)C2=C1 ZKKZIPCBLBTIJE-UHFFFAOYSA-N 0.000 description 1
- DVFAVJDEPNXAME-UHFFFAOYSA-N 1,4-dimethylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(C)=CC=C2C DVFAVJDEPNXAME-UHFFFAOYSA-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
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- FXUKGDZKAQHTRY-UHFFFAOYSA-N 1-propan-2-ylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C FXUKGDZKAQHTRY-UHFFFAOYSA-N 0.000 description 1
- GELKGHVAFRCJNA-UHFFFAOYSA-N 2,2-Dimethyloxirane Chemical compound CC1(C)CO1 GELKGHVAFRCJNA-UHFFFAOYSA-N 0.000 description 1
- KIJPZYXCIHZVGP-UHFFFAOYSA-N 2,3-dimethylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=C(C)C(C)=C2 KIJPZYXCIHZVGP-UHFFFAOYSA-N 0.000 description 1
- PQXKWPLDPFFDJP-UHFFFAOYSA-N 2,3-dimethyloxirane Chemical compound CC1OC1C PQXKWPLDPFFDJP-UHFFFAOYSA-N 0.000 description 1
- RATJDSXPVPAWJJ-UHFFFAOYSA-N 2,7-dimethylanthracene-9,10-dione Chemical compound C1=C(C)C=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 RATJDSXPVPAWJJ-UHFFFAOYSA-N 0.000 description 1
- WUKWGUZTPMOXOW-UHFFFAOYSA-N 2-(2-methylbutan-2-yl)anthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(C(C)(C)CC)=CC=C3C(=O)C2=C1 WUKWGUZTPMOXOW-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- OTTZHAVKAVGASB-HYXAFXHYSA-N 2-Heptene Chemical compound CCCC\C=C/C OTTZHAVKAVGASB-HYXAFXHYSA-N 0.000 description 1
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- MCYPCBFOVKMNDW-UHFFFAOYSA-N 2-butan-2-ylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(C(C)CC)=CC=C3C(=O)C2=C1 MCYPCBFOVKMNDW-UHFFFAOYSA-N 0.000 description 1
- QKHUXWLXTLMABH-UHFFFAOYSA-N 2-butyl-3-ethyloxirane Chemical compound CCCCC1OC1CC QKHUXWLXTLMABH-UHFFFAOYSA-N 0.000 description 1
- MAKLMMYWGTWPQM-UHFFFAOYSA-N 2-butylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(CCCC)=CC=C3C(=O)C2=C1 MAKLMMYWGTWPQM-UHFFFAOYSA-N 0.000 description 1
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- SOCDLWOJPVKBHF-UHFFFAOYSA-J titanium(4+) tetraperchlorate Chemical compound [Ti+4].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O SOCDLWOJPVKBHF-UHFFFAOYSA-J 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- PFXVKGRHTBFKDJ-UHFFFAOYSA-N triazanium;[hydroxy(oxido)phosphoryl] phosphate Chemical compound [NH4+].[NH4+].[NH4+].OP([O-])(=O)OP([O-])([O-])=O PFXVKGRHTBFKDJ-UHFFFAOYSA-N 0.000 description 1
- STYCVOUVPXOARC-UHFFFAOYSA-M trimethyl(octyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCC[N+](C)(C)C STYCVOUVPXOARC-UHFFFAOYSA-M 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 229940070710 valerate Drugs 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7088—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0211—Impregnation using a colloidal suspension
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/033—Using Hydrolysis
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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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
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Abstract
In the case where hydrogen and oxygen are continuously provided with olefin such as propylene to produce alkylene oxide, there was a problem that an amount of alkylene oxide produced is gradually decreased with decline of an catalytic ability of a catalyst to be used. In order to solve the problem, disclosed are a process for preparation of a catalyst comprising a step of contacting a catalyst containing titanosilicate and a noble metal with alcohol having a carbon number of 1-12, and a process for production of alkylene oxide comprising reacting hydrogen, oxygen and olefin in the presence of a catalyst which is prepared by the process as described above and a nitrile compound.
Description
PROCESS FOR PREPARATION OF CATALYST AND PROCESS FOR PRODUCTION OF ALKYLENE OXIDE USING CATALYST PREPARED BY THE SAME 5
Technical Field
[0001]
The present invention relates to a process for preparation of catalysts, a process for production of alkylene 10 oxide using the catalysts prepared by the process for preparation, and the like.
Background Art
[0002] 15 For example, Patent Document 1 describes a process for continuous production of propylene oxide by continuously providing hydrogen, oxygen and propylene in the presence of a catalyst containing titanosilicate and noble metals, and acetonitrile.
20
Conventional technology documents [Patent Document]
[0003] [Patent Document 1] JP 2009-274062A (Examples 1-1-1- 25 3)
Summary of the Invention
[0004]
However, there was a problem that the Production 30 method in the Patent Document 1 has a problem that when olefin such as propylene, hydrogen and oxygen are continuously supplied for a long period of time, a production amount of alykylene oxide gradually decreases with decline of a catalytic ability of the catalyst to be used.
35 [0005] 1039092 2
Under these circumstances, the inventors intensively studied to a process for preparation of a catalyst for recovering its catalytic ability and a process for production of alkylene oxide using the catalyst prepared by the process for preparation 5 and, as the result, have found that, in a particular catalyst, a catalytic ability of a catalyst deteriorated by subjecting to a reaction was recovered by contacting the catalyst with a certain compound, which resulted in completion of the present invention.
[0006] 10 That is, the present invention provides <1> A process for preparation of a catalyst, comprising a step of contacting a catalyst containing titanosilicate and a noble metal with alcohol having a carbon number of 1-12.
<2> The process according to <1>, wherein said catalyst 15 has a lower catalytic ability in a reaction than a catalytic ability in a reaction before subjecting to the reaction.
<3> The process according to <2>, wherein a system of said contact does not substantially contain at least one raw material to be subjected to said reaction.
20 [0007] <4> The process according to any one of <1> to <3>, wherein said contact step comprises contacting said catalyst with said alcohol within a temperature range of 25-250°C.
<5> The process according to any one of <1> to <4>, 25 wherein said contact step comprises contacting said catalyst with said alcohol within a time range of 0.5-120 hours.
<6> The process according to any one of <1> to <5>, further comprising a step of substituting said alcohol having a carbon number of 1-12 which is contained in a solid obtained by a 30 separation procedure after said contact step with a nitrile compound such that a content of said alcohol in said solid becomes 10 parts by weight or less relativé to 100 parts by weight of said catalyst.
[0008] 35 <7> The process according to <2> or <3>, wherein said reaction is to obtain alkylene oxide by reacting hydrogen, oxygen 3 and olefin in the presence of a nitrile compound and the catalyst containing titanosilicate and a noble metal.
<8> The process according to <2> or <3>, wherein said reaction is to continuously obtain alkylene oxide by continuously 5 providing hydrogen, oxygen and olefin in the presence of a nitrile compound and the catalyst containing titanosilicate and a noble metal.
[0009] <9> A process for production of alkylene oxide, comprising 10 reacting hydrogen, oxygen and olefin in the presence of a catalyst which is prepared by the process of any one of <1> to <8> and a nitrile compound.
<10> A process for production of alkylene oxide, comprising continuously providing and reacting hydrogen, oxygen and olefin 15 in the presence of a catalyst prepared by the process of any one of <1> to <8> and a nitrile compound.
[0010] <11> The process according to any one of <1> to <8>, wherein said titanosilicate is laminar titanosilicate having a 20 pore of oxygen 12-member ring or more.
<12> The process according to any one of <1> to <8>, wherein said titanosilicate is a Ti-MWW precursor.
<13> The process according to any one of <1> to <8>, wherein said noble metal is at least one selected from the group 25 consisting of palladium, platinum, ruthenium, rhodium, iridium, osmium and gold.
<14> The process according to any one of <1> to <8>, wherein said catalyst contains titanosilicate and a noble metal supported on a support.
30 <15> The process according to <9> or <10>, wherein said reaction is conducted for 1-12 hours.
<16> A process for production of alkylene oxide, comprising (a) a step of reacting hydrogen, oxygen and olefin in the presence of a nitrile compound and a catalyst containing 35 titanosilicate and a noble metal to obtain alkylene oxide, 4 (b) a step of contacting the catalyst used in the step (a) with alcohol having a carbon number of 1-12, and (c) a step of reacting hydrogen, oxygen and olefin in the presence bf a nitrile compound and the catalyst obtained in the 5 step (b) to obtain alkylene oxide.
[0011]
According to the present invention, alkylene oxide may be efficiently produced without lowering an amount of alkylene oxide produced, by recovering a catalytic ability of a catalyst 10 which has been deteriorated as the result of subjecting to a reaction, even in a process for production of alkylene oxide in which hydrogen, oxygen and olefins such as propylene are continuously provided for a long period of time.
[0012] 15 The present invention will be illustrated below in detail.
* The present invention relates to a process for preparation of a catalyst, comprising a step of contacting a catalyst containing titanosilicate and a noble metal 20 (hereinafter, sometimes referred to as "present catalyst") with alcohol having a carbon number of 1-12 (hereinafter, sometimes referred to as "present alcohol")(hereinafter, sometimes referred to as "contact step").
[0013] 25 Titanosilicate contained in the present catalyst is illustrated.
Titanosilicate is porous silicate (Si02) in which a part of a silicon atom (Si) is substituted with a titanium atom (Ti). The titanium atom (Ti) of titanosilicate is contained in a 30 Si02 skeleton, and it may be easily confirmed by a peak at 210-230 nm in a ultraviolet and visible absorption spectrum. In addition, because Ti of Ti02 is usually six-coordination whereas the Ti of titanosilicate is four-coordination, it may be easily confirmed by measuring a coordination number by XAFS analysis of 35 K shell of titanium, and the like.
[0014] 5
Examples of titanosilicate used in the present invention include crystalline titanosilicate, laminar titanosilicate, mesoporous titanosilicate, and the like.
Examples of crystalline titanosilicate includes, 5 according to a framework type code of IZA (International Zeolite Association), TS-2 having a MEL structure, Ti-ZSM-12 having a MTW structure (for example, those described in Zeolites, 15, 236-242 (1995)), Ti-Beta having a BEA structure (for example, those described in Journal of Catalysis, 199, 41-47 (2001)), Ti-MWW 10 having a MWW structure (for example, those described in Chemistry Letters, 744-775 (2000)), Ti-UTD-1 having a DON structure (for example, those described in Zeolites, 15, 519-525 (1995) ) , and the like.
Examples of laminar titanosilicate include those 15 having an expanded interlaminar MWW structure such as a Ti-MWW precursor (for example, those described in JP 2003-327425 A) and <· Ti-YNU-1 (for example, those described in Angewandte Chemie
International Edition 43, 236-240 (2004)), and the like.
Mesoporous titanosilicate means titanosilicate having 20 a regular pore of 2-10 nm, and examples thereof include Ti-MCM-41 (for example, those described in Microporous Materials, 10, 259-271 (1997)), Ti-MCM-48 (for example, those described in Chemical
Communications, 145-146 (1996)), Ti-SBA-15 (for example, those described in Chemistry of Materials, 14, 1657-1664 (2002)), and 25 the like.
In addition, titanosilicate having both characteristics of mesoporous titanosilicate and titanosilicate zeolite such as Ti-MMM-1 (for example, those described in Microporous and Mesoporous Materials, 52, 11-18 (2002)) is 30 exemplified.
[0015]
Crystalline titanosilicate or laminar titanosilicate having a pore of oxygen 12-member ring or more is preferable as titanosilicate used in the present invention. Examples of 35 crystalline titanosililcate having a pore of oxygen 12-member ring or more include Ti-ZSM-12, Ti-Beta, Ti-MWW and Ti-UTD-1.
6
Examples of laminar titanosilicate having a pore of oxygen 12-member ring or more include a Ti-MWW precursor and Ti-YNU-1. In addition, examples of more preferable titanosilicate include Ti-MWW and the Ti-MWW precursor.
5 [0016]
As titanosilicate used in the present invention, those are preferable, prepared by a process comprising using a structure-directing agent, hydrolyzing a titanium compound and a silicon compound, enhancing crystallization, lamination or pore 10 regularity such as by hydrothermal synthesis as necessary, and then removing the structure-directing agent by firing or extraction.
[0017]
The Ti-MWW precursor is transformable to Ti-MWW by 15 firing, and firing temperature is preferably above 200"C and lOOO'C or less, preferably within a range of 300-650'C. A ratio of temperature increase is not limited, but is preferably 30°C/hour -600°C/hour.
Examples of the process for preparation of the Ti-MWW 20 precursor as a process for preparation of titanosilicate used in the present invention include a method comprising mixing a boron compound, a silicon compound and a structure-directing agent in a sealed vessel such as an autoclave, and heating and pressurizing a mixture within a temperature range of 0-250°C, preferably 50-25 200 ”C and a gage pressure at approximately 0-10 MPa, and the like. The Ti-MWW precursor obtained is separated with filtration, and further is washed with water or the like as necessary. Washing may be properly conducted with monitoring an amount of a washing solution, pH of a washing filtrate, or the 30 like.
Examples of preferable titanosilicate include a Ti-MWW precursor obtained by further dehydration synthesis of interlamellar of the Ti-MWW precursor obtained by the process for preparation as described above by firing at 500-800”C to produce 35 Ti-MWW, and again heating and pressurizing it at a temperature 7 range of 0-250”C, preferably 50-200'C and under a gage pressure at approximately 0-10 MPa, and the like.
[0018]
In this context, the structure-directing agent is an 5 agent capable of forming zeolite having a MWW structure, and examples thereof include piperidine, hexamethyleneimine, an N,N,N-trimethyl-l-adamantane ammonium salt (for example, Ν,Ν,Ν-trimethyl-l-adamantane ammonium hydroxide, N,N,N-trimethyl-l-adamantane ammonium iodide, and the like), an octyltrimethyl 10 ammonium salt (for example, octyltrimethyl ammonium hydroxide, octyltrimethyl ammonium bromide, and the like). These compounds may be used solely or in combination of two or more in an arbitrary ratio.
Preferable structure-directing agents are piperidine 15 and hexamethyleneimine.
An amount of the structure-directing agent to be used is, for example, within a range of 0.001 to 100-folds, preferably within a range of 0.1 to 10-folds relative to a total weight of the boron compound and the silicon compound.
20 [0019]
Examples of the titanium compound include titanium alkoxides such as tetra-n-butyl orthotitanate, peroxytitanate salts such as tetra-n-butylammonium peroxytiatnate, titanium halides such as titanium tetrachloride, and other titanium 25 compounds such as titanium acetate, titanium nitrate, titanium sulfate, titanium phosphate, titanium perchlorate and titanium dioxide. Titanium alkoxides are preferable. An amount of the titanium compound to be used may be within a range of 0.001 to 10 parts by weight, preferably within a range of 0.01 to 2 parts by 30 weight in terms of a weight of the titanium compound relative to 1 part by weight of the boron compound, but may.
[0020]
Examples of the silicon compound include tetraalkyl orthosilicates such as tetraethyl orthosilicate, silica, and the 35 like.
Examples of the boron compound include boric acid.
8
The boron compound and the silicon compound may be used at almost in the same amount.
[0021]
Titanosilicate used in the present invention may be 5 silylated with a silylating agent such as 1,1,1,3,3,3-hexamethyldisilazane.
[0022]
The noble metal contained in the present catalyst is illustrated.
10 Examples of the noble metal include noble metals such as palladium, platinum, ruthenium, rhodium, iridium, osmium and gold, and an alloy or mixture thereof. Examples of a preferable noble metal include palladium, platinum and gold. A more preferable noble metal is palladium. As palladium, for example, 15 a palladium colloid may be used (see, for example, JP 2002-294301 A, Example 1, and the like) . As the noble metal as described above, a noble metal compound which is converted to the noble metal by reduction may be used. A preferable noble compound is a palladium compound. Furthermore, when palladium is used as the 20 noble metal, metals other than palladium, such as platinum, gold, rhodium, iridium and osmium may be also used by adding and mixing therewith. Examples of a preferable metal other than palladium include gold and platinum.
Examples of the palladium compound include tetravalent 25 palladium compounds such as sodium hexachloropalladium (IV) tetrahydrate and potassium hexachloropalladium (IV); divalent palladium compounds such as 'palladium chloride (II), palladium bromide (II), palladium acetate (II), palladium acetylacetonate (II), dichlorobis(benzonitrile)palladium (II)/ 30 dichlorobis(acetonitrile)palladium (II), dichloro(bis(diphenylphosphino)ethane)palladium (II) , dichlorobis(triphenylphosphine)palladium (II) , dichlorotetraammine palladium (II), dibromotetraammine palladium (II), dichloro(cycloocta-1,5-diene)palladium (II), and palladium 35 (II) trifluoroacetate.
[0023] 9
As the process for preparation of the noble metal, it has been known a process comprising supporting the noble metal compound on a support, and then reducing it. Conventionally-known procedures such as an impregnation method may be used for 5 supporting the noble metal compound.
Examples of a reducing method in which a reducing gas is used include a method comprising filling a solid support of the noble metal compound in a suitable filling tube, and injecting the reducing gas to the tube, and the like. Examples 10 of the reducing gas include hydrogen, carbon oxide, methane, ethane, propane, butane, ethylene, propylene, butene, butadiene and a mixture of two or more selected therefrom. Among them, hydrogen is preferable reducing gas. In addition, the reducing gas may be diluted with a diluting gas selected from, for 15 example, nitrogen, helium, argon or water vapor (steam), and a mixture of two or more selected therefrom.
[0024]
Here, examples of the support include titanosilicate used in the present invention, oxides such as silica, alumina, 20 titania, zirconia, niobia; hydrates such as of niobic acid, zirconic acid, tungstic acid and titanic acid; carbon; and a mixture thereof. A preferable support other than titanosilicate may be carbon. Examples of a carbon support include activated carbon, carbon black, graphite, carbon nanotube, and the like.
25 [0025]
Examples of the present catalyst include, in addition to one obtained by supporting the noble metal on titanosilicate used in the present invention, a mixture of a support supporting the noble metal and titanosilicate as described above, and the 30 like.
An amount of the noble metal contained in the support supporting the noble metal is, for example, within a range of 0.01-20 parts by weight, and preferably within a range of 0.1-5 parts by weight relative to 100 parts by weight of a total amount 35 of the support and the noble metal.
[0026] ΊΟ
An amount of the noble metal in the present catalyst (minimum) is, for example, 0.00001 parts by weight or more, preferably 0.0001 parts by weight or more, and more preferably 0.001 parts by weight or more relative to 1 part by weight of 5 titanosilicate as described above. An amount of the noble metal (maximum) is, for example, 100 parts by weight or less, preferably 20 parts by weight or less, and more preferably 5 parts by weight or less relative to 1 part by weight of titanosilicate as described above.
10 [0027]
The present catalyst subjected to a contacting step may be the present'catalyst before subjecting to a reaction. A catalyst having a lower catalytic ability in the reaction than that before subjecting to the reaction is preferable.
15 In this context, examples of the reaction include a reaction for obtaining alkylene oxide by reacting hydrogen, oxygen and olefin in the presence of a nitrile compound and a catalyst containing titanosilicate and a noble metal, and the like.
20 A reaction for obtaining alkylene oxide by reacting hydrogen, oxygen and olefin in the presence of the present catalyst and the nitrile compound (hereinafter, often referred to as "the present reaction" is illustrated below.
[0028] 25 Olefin used in the present reaction is a compound having a carbon number of 2-12 and a carbon-carbon double bond, and preferable examples thereof include alkene having a carbon number of 2-12 which may be substituted, cycloalkene having a carbon number of 4-12 which may be substituted, and the like.
30 Examples of a substituent contained in olefin include a hydroxyl group, a halogen atom, a carbonyl group, an alkoxycarboxyl group, a cyano group, a nitro group, and the like.
Examples of alkene having a carbon number of 2-12 include ethylene, propylene, butene, pentene, hexene, heptene, 35 octene, nonene, decene, 2-butene, isobutene, 2-pentene, 2-hexene, 1 1 3-hexene, 4-methyl-l-pentene, 2-heptene, 3-heptene, 2-octene, 3-octene, 2-nonene, 3-nonene, 2-decene, 3-decene, and the like.
Examples of cycloalkene having a carbon number of 4-12 include cyclobutene, cyclopentene, cyclohexene, cycloheptene, 5 cyclooctene, cyclononene, cyclodecene, and the like.
For example, olefin may be preferably alkene without substituent, more preferably alpha-olefin, and most preferably propylene.
[0029] 10 Alkylene oxide is prepared by oxidizing the double bond of the compound having a carbon-carbon double bond as described above to an oxirane ring, and examples thereof include ethylene oxide (oxirane), propylene oxide (methyloxirane), ethyloxirane, butyloxirane, pentyloxirane, hexyloxirane, 15 hexyloxirane, heptyloxirane, octyloxirane, 2,3-dimethyloxirane, 1,1-dimethyloxirane, l-methyl-3-ethyloxirane, l-methyl-3- butyloxirane, 3,4-diethyloxirane, l-methyl-3-propyloxirane, 2-(4-methyl)propyloxirane, l-methyl-3-pentyloxirane, 2-ethyl-3- butyloxirane, l-methyl-3-hexyloxirane, 2-ethyl-3-pentyloxirane, 20 l-methyl-3-heptyloxirane, 2-ethyl-3-heptyloxirane, and the like.
[0030]
The present reaction may be conducted by placing hydrogen, oxygen and olefin together in a batch reactor to react, and may be preferably conducted by continuously providing 25 hydrogen, oxygen and olefin to a flow reactor or a semibatch reactor to continuously react.
[0031]
Examples of the nitrile compound used in the present reaction include alkylnitrile and benzonitrile having a carbon 30 number of 2-4 such as acetonitrile, propionitrile, isobutyronitrile, butyronitrile, and the like, but preferably include acetonitrile, and the like.
[0032]
For example, the lower limit of reaction temperature 35 in the present reaction may be 0'C, preferably 40 "C. For 12 example, the upper limit of reaction temperature in the present reaction may be 200°C, preferably 150*C.
For example, the lower limit of the reaction pressure (gauge pressure) in the present reaction may be under the 5 pressure of 0.1 MPa, preferably under the pressure of 1 MPa, more preferably under the pressure of 20 MPa, and still more preferably under the pressure of 10 MPa.
[0033]
An amount of olefin used in the present reaction may 10 be varied depending upon a kind thereof, a reaction condition, or the like, it is preferably 0.01 parts by weight or more, and more preferably 0.1 parts by weight or more relative to 100 parts by weight of a total amount of solvent in a reaction system of the present reaction. An upper limit of the amount of olefin in the 15 reaction system of the present reaction is preferably 1000 parts by weight and more preferably 100 parts by weight relative to 100 parts by weight of a total amount of solvent in the reaction system of the present reaction.
[0034] 20 In the case where an amount of the present catalyst is represented in terms of an amount of titanosilicate, a lower limit thereof may be, for example, 0.01 part by weight, preferably 0.1 part by weight and more preferably 0.5 part by weight, and an upper limit thereof may be, for example, 20 parts 25 by weight, preferably 10 parts by weight and more preferably 8 parts by weight.
[0035] A buffer may be preferably used in the present reaction, because there is a propensity to prevent a decrease in 30 a catalytic ability of the present catalyst, to further increase a catalytic ability of the present catalyst, and to enhance an efficiency in utilizing oxygen and hydrogen. In this context, a buffer means a salt providing a buffering action against a hydrogen ion concentration in a solution in the reaction system 35 of the present reaction.
13
Examples of an amount of the buffer to be added include, for example, a range of 0.001-100 mmol relative to 1 kg of the solution in the reaction system of the present reaction.
[0036] 5 Examples of the buffer include those consisting of 1) an anion selected from the group consisting of a sulfate ion, a hydrogen sulfate ion, a carbonate ion, a hydrogen carbonate ion, a phosphate ion, a hydrogen phosphate ion, a dihydrogen phosphate ion, a hydrogen pyrophosphate ion, a pyrophosphate ion, a halogen 10 ion, a nitrate ion, a hydroxide ion and a carboxylate ion having a carbon number of 1-10 and 2) a cation selected from the group consisting of ammonium, alkylammonium, alkyl aryl ammonium, an alkali metal cation and an alkaline earth metal salt cation, and the like.
15 [0037]
Examples of a carboxylate ion having a carbon number of 1-10 include an acetate ion, a formate ion, a propionate ion, a butyrate ion, a valerate ion, a caproate ion, a caprylate ion, a caprate ion, a benzoate ion, and the like.
20 Examples of alkylammonium include tetramethylammonium, tetraethylammonium, tetra-n-propylammonium, tetra-n- butylammonium, cetyltrimethylammonium, and the like.
Examples of the alkali metal cation and the alkaline earth metal cation include a lithium cation, a sodium cation, a 25 potassium cation, a rubidium cation, a cesium cation, a magnesium cation, a calcium cation, a strontium cation, a barium cation, and the like.
[0038]
Examples of a preferable buffer include ammonium salts 30 of an inorganic acid such as ammonium sulfate, ammonium hydrogen sulfate, ammonium carbonate, ammonium bicarbonate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate, ammonium hydrogen pyrophosphate, ammonium pyrophosphate, ammonium chloride and ammonium nitrate, or 35 ammonium salts of carboxylic acid having a carbon number of 1-10 14 such as ammonium acetate, and examples of a preferable ammonium salt include ammonium dihydrogen phosphate.
Instead of the buffer as described above, a compound which generates a buffering salt ion such as an ammine complex of 5 noble metals, and the like may be used as a noble metal compound. For example, when Pd tetraammine chloride is used as a noble metal compound such that a part thereof is not reduced, the ammonium ion is generated upon synthesis of the oxiran compound.
[0039] 10 Preferably, a quinoid compound may be added to the solution in the reaction system of the present reaction because there is a propensity to further increase selectivity of alkylene oxide .
Examples of the quinoid compound include a p-quinoid 15 compound and a phenanthraquinone compound of the following formula (1):
[0040] X X ii) R2
Y
20 wherein, R1, R2, R3 and R4 represent a hydrogen atom, or R1 and R2 are bonded at their end together with the carbon atom to which they are bonded to form a naphthalene ring which may be substituted, and R3 and R4 are bonded at their end together with the carbon atom to which they are bonded to form a naphthalene 25 ring which may be substituted, and X and Y represent independently an oxygen atom or an NH group, and the like
[0041]
Examples of the compound of the formula (1) include 15 1) a quinone compound (1A) of the formula (1) , wherein R1, R2, R3 and R4 are a hydrogen atom, and both of X and Y are an oxygen atom, 2) a quinonimine compound (IB) of the formula (1) , 5 wherein R1, R2, R3 and R4 are a hydrogen atom, X is an oxygen atom, and Y is an NH group, 3) a quinondiimine compound (1C) of the formula (1), wherein R1, R2, R3 and R4 are a hydrogen atom, and X and Y are an NH group, and the like.
10 Examples of the quinoid compound of the formula (1) include an anthraquinone compound of the following formula (2):
[0042]
X
R7 I! R5 D05 - R8 R6
Y
15 wherein, X and Y are as defined in the formula (1), and each of R5, R6, R7 and R8 independently represents a hydrogen atom, a hydroxyl group or an alkyl group (for example, an alkyl group having a carbon number of 1-5 such as methyl, ethyl, propyl, butyl and pentyl group).
20 In the formulas (1) and (2), X and Y are preferably an oxygen atom.
[0043]
Examples of the quinoid compound include benzoquinone, naphthoquinone, anthraquinone, an alkyl anthraquinone compound, 25 polyhydroxy anthraquinone, a p-quinoid compound, an o-quinoid compound, and the like.
Examples of the alkylanthraquinone compound include 2-alkylanthraquinone compounds such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, 2-methylanthraquinone, 30 2-butylanthraquinone, 2-t-amylanthraquinone, 2- 16 isopropylanthraquinone, 2-s-butylanthraquinone and 2-s-amylanthraquinone; polyalkylanthraquinone compounds such as 1,3-diethylanthraquinone, 2,3-dimethylanthraquinone, 1,4- dimethylanthraquinone, 2,7-dimethylanthraquinone; and the like.
5 Examples of polyhydroxyanthraquinone include 2,6- dihydroxyanthraquinone, and the like. Examples of the p-quinoid compound as described above include naphthoquinone, 1,4- phenanthraquinone, and the like. Examples of the o-quinoid compound as described above include 1,2-, 3,4- and 9,10- 10 phenanthraquinone, and the like.
Examples of a preferable quinoid compound include anthraquinone, a 2-alkylanthraquinone compound (in the formula (2), X and Y are an oxygen atom, R5 is an alkyl group substituted at the position 2, R6 is hydrogen, and R7 and R8 are a hydrogen 15 atom), and the like.
[0044] . Examples of an amount of the quinoid compound to be used include a range of 0.001-500 mmol/kg per 1 kg of the solution in the reaction system of the present reaction, and the 20 like, and preferably it is a range of 0.01-50 mmol/kg per 1 kg of the solution in the reaction system of the present reaction, and the like.
[0045]
The quinoid compound may be prepared also by oxidizing 25 a dihydro form of the quinoid compound with oxygen or the like in the reaction system of the present reaction. For example, the quinoid compound may be used, which is generated by adding a hydrogenated quinoid compound such as hydroquinone and 9,10-anthracenediol to the reaction system of the present reaction and 30 oxidizing it with oxygen in the reaction system.
[0046]
Examples of the dihydro form of the quinoid compound include a compound of the following formulas (3) and (4), which is a dihydro form of the compound of the formulas (1) and (2) as 35 described above.
17
XH
)?: ·
YH
wherein, R1, R2, R3, R4, x and Y are as defined in connection with the formula (1) as described above.
[0047]
XH
R7 I R5 frY*i .
R8 1 K6
5 YH
wherein, X, Y, R5, R6, R7, R8 are as defined in connection with the formula (2) as described above.
In the formulas (3) and (4), X and Y are preferably an 10 oxygen atom.
Examples of a preferable dihydro form of the quinoid compound include a dihydro form corresponding to the preferable quinoid compound as described above, and the like.
[0048] 15 In the present reaction where olefin is continuously provided to react, an amount of olefin to be provided may be properly selected depending upon a kind of olefin and a reaction scale, a lower limit thereof is preferably 0.01 part by weight or more, more preferably 0.1 part by weight or more, and most 20 preferably 1 part by weight or more relative to 100 parts by weight of a total amount of the solution in the reaction system of the present reaction. On the other hand, an upper limit of an amount of olefin to be provided is preferably 1000 parts by weight or less, more preferably 100 parts by weight or less, and 25 most preferably 50 parts by weight or less.
18
[0049]
In the present reaction where oxygen and hydrogen are continuously provided to react, examples of a ratio of partial pressure of oxygen and hydrogen to be provided include a range of 5 1:50-50:1, and the like, preferably include a range of 1:2-10:1, and the like. Because there is a propensity that a production rate of alkyleneoxide is enhanced where the ratio of partial pressure of oxygen and hydrogen (oxygen/hydrogen) is 50/1 or less, this range is preferable. In addition, because there is a 10 propensity that side production of alkane compounds is decreased and selectivity of alkylene oxide is enhanced in the case where the ratio of partial pressure of oxygen and hydrogen (oxygen/hydrogen) is 1/50 or more, this range is preferable.
[0050] 15 In this context, oxygen and hydrogen may be diluted.
Examples of a gas to be used for dilution include nitrogen, argon, carbon dioxide, methane, ethane, and propane. A concentration of a gas for dilution is not limited, but synthesis of hydrogen peroxide is conducted with diluting oxygen or 20 hydrogen as necessary.
As oxygen, oxygen itself may be used, or a mixed gas of oxygen and the gas used for dilution as described above, such as air may be used. As an oxygen gas, a low-priced oxygen gas produced by a pressure swing method may be used, or a highly pure 25 oxygen gas produced by a low temperature processing, or the like may be used as necessary.
[0051]
Examples of reaction temperature in the present reaction include a range of 0-200°C, and preferably include a 30 range of 40-150°C, and the like.
Reaction temperature of O'C or more is preferable because there is a propensity that a reaction rate is enhanced in that range, and reaction temperature of 200'C or less is also preferable because there is a propensity that a side reaction is 35 suppressed and selectivity of alkylene oxide is enhanced.
[0052] 19
Examples of the reaction pressure in the present reaction include a positive pressure in a range of 0.1-20 MPa in terms of the gauge pressure, and the like, and it may preferably be the positive pressure in a range of 1-10 MPa.
5 [0053]
After completion of the reaction, alkylene oxide may be removed such as by distillation of a reaction product of the present reaction.
[0054] 10 In the case where the present catalyst is continuously used in the present reaction, examples of a reaction time of the present reaction include a range of 1-12 hours.
[0055]
Next, a contact step is illustrated.
15 In a contact step, preferably, the present catalyst and the present alcohol are contacted, for example, at a temperature range of 25-250'C, and the like, preferably at a temperature range of 50-200°C, and the like.
[0056] 20 Examples of the present alcohol include an aliphatic alcohol having a carbon number of 1-12 or an alicyclic alcohol having a carbon number of 5-12, and the like, and include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, cyclopentanol, cyclohexanol, n-octanol, 2- 25 ethylhexanol, benzyl alcohol, and the like, more preferably include methanol, ethanol, isopropanol, t-butanol, and the like.
[0057]
An amount of the present alcohol to be used is an amount of solvents, and may be 1-100 parts by volume relative to 30 1 part by volume of an apparent total volume of the present catalyst whose catalyst ability had been lowered.
[0058]
The contact step is conducted in a reactor such as a batch reactor, a semibatch reactor or a flow reactor.
35 A lower limit of a time required for contact may be, for example, 0.5 hour, and preferably 1 hour or more as a 20 retention time of the present catalyst in the present alcohol. An upper limit of the time required for contact may be, for example, 120 hours, preferably 72 hours or less, and more preferably 24 hours or less.
5 [0059]
In the case where the present catalyst having a lowered catalytic ability is used, it may be subjected to the contact step in a form just as it had been used in the reaction, or may be subjected to the contact step after grinding it. 10 Alternatively, the present catalyst having a lowered catalytic ability may be subjected to the contact step as a mixture with a carrier and a catalyst other than the present catalyst having a lowered catalytic ability (specifically, the present catalyst newly prepared).
15 In the reaction in which hydrogen, oxygen and olefin are reacted in the presence of a nitrile compound and the catalyst containing titanosilicate and a noble compound to obtain alkylene oxide, a catalytic ability may be measured, for example, on the basis of results of the reaction such as an amount of 20 alkylene oxide produced per a unit weight of titanosilicate and unit time (mol-alkylene oxide/g-titanosilicate·hour) , hydrogen-based selectively of alkylene oxide (mol-alkylene oxide produced/mol-hydrogen consumed), and the like.
Embodiments of the contact step include a procedure 25 comprising placing a mixture which contains the present catalyst and the present alcohol in a sealed vessel such as an autoclave, and incubating it in the range of temperature as described above and pressurizing it, for example, a procedure comprising incubating a mixture which contains the present catalyst and the 30 present alcohol in the range of temperature as described above in a vessel such as a glass firing tube under an atmospheric pressure.
[0060]
The contact step may be conducted under inner gas 35 atmosphere such as nitrogen.
21
For example, a pressure applied in the contact step is preferably from the atmospheric pressure to a positive pressure at approximately 0-10 MPa in a gauge pressure.
[0061] 5 Preferably, the contact step further has a step of substituting the present alcohol which is contained in a solid obtained by a separation manipulation with the nitrile compound. An amount of the present alcohol to be used for the present catalyst is decreased by a substitution step as described above, 10 and because there is a propensity to enhance selectivity of alkylene oxide obtained when the present reaction is conducted with the present catalyst, it is preferable.
An amount of the present alcohol contained in the solid as described above is, for example, 10 parts by weight or 15 less, and preferably 1 part by weight or less relative to 100 parts by weight of the catalyst as described above.
Embodiments thereof include, for example, a procedure comprising washing a solid obtained by the separation manipulation such as filtration with a nitrile compound, a method 20 comprising drying a solid, and then washing it with the nitrile compound, and the like.
[0062]
In this context, examples of the nitrile compound include those as described above.
25 An amount of the nitrile compound to be used corresponds to an amount of the solvent, and may be 1-100 parts by volume, or the like, relative to 1 part by volume of an apparent total volume of the present catalyst used for substitution.
30 [0063]
The catalyst after subjecting to the contact step may be subjected again to the present reaction because a catalyst ability thereof has been recovered. In addition, the catalytic ability of the present catalyst which has been deteriorated and 35 lowered by the reaction may be recovered again by subjecting the catalyst to the contact step. In this way, the catalytic ability 22 of the present catalyst may be repeatedly recovered even when the contact step and the present reaction are repeatedly performed.
Example
[0064] 5 The present invention will be illustrated by way of
Examples .
[0065] (Analysis device used in Examples) [Method of Elemental analysis] 10 Contents of Ti(titanium), Si(silicon) and B(boron) were measured according to an alkali fusion-nitric acid dissolution-ICP emission spectroscopy. A content of N(nitrogen) was measured with Sumigraph (Sumika Chemical Analysis Service, Ltd.) according to an oxygen circulation combustion-TCD detection 15 method.
[0066] [Powder X-ray diffractometry (XRD)]
Powder x-ray diffractometric patterns of samples were measured with following device according to following conditions. 20 Device: RINT2500V manufactured by Rigaku
Corporation
Radiation Source: Cu Kd ray
Output: 40 kV-300 mA
Scan field: 20=0.75-20° 25 Scan rate: l°/min.
[0067] [Ultraviolet and Visible absorption spectrometry (UV-Vis)] A sample was ground thoroughly in an agate mortar and was further pelletized (7 mm in a diameter) to prepare a 30 measuring sample. UV-visible absorption spectrum of the measuring sample prepared was measured with following device according to following conditions.
Device: Diffuse Reflectance Accessory (manufactured by HARRICK, Praying Mantis) 35 Accessory: Ultraviolet and visible spectrophotometer 23 (manufactured by JASCO Corporation, V-7100) Pressure: atmospheric pressure
Measurement: reflectance
Data-acquisition time: 0.1 sec.
5 Band width: 2 nm
Measured wavelength: 200-900 nm
Slit height: partially open
Data acquisition-interval: 1 nm
Baseline correction (reference): BaS04 pellet (7 mm in a 10 diameter)
[0068] (Reference Example 1: Preparation of titanosilicate having MWW precursor structure) 899 g of piperidine, 2402 g of pure water, 112 g of 15 TBOT (tetra-n-butylorthotitanate), 565 g of boric acid, and 410 g of fumed silica (cab-o-sil M7D) were agitated in an autoclave at room temperature (about 25°C) under air atmosphere to prepare a gel. The resulting gel was matured for 1.5 hour and placed in a sealed autoclave, and hydrothermal synthesis was performed by 20 increasing temperature of the gel to 160°C over 8 hours with agitating and the temperature was held for 120 hours.
A suspension obtained by hydrothermal synthesis was filtrated, washed with water until a pH of a filtrate becomes around 10. Then, a filter cake was dried at 50°C until no weight 25 decrease of the filter cake is found to prepare 515 g of Solid a. 3750 ml of 2 M nitric acid was added to 75 g of Solid a obtained, and it was refluxed for 20 hours. Then, the resulting mixture was filtrated, washed with water until a pH of a filtrate becomes around neutral, and vacuum-dried at 1.50 °C until no weight 30 decrease of the mixture is found to obtain 61 g of White powder a. As the result of measurement of the X-ray diffraction pattern and UV-visible absorption spectrum of White powder a, it was confirmed that it is a Ti-MWW precursor, that is, it has a pore of oxygen 12-member ring.
35 60 g of White powder a obtained was fired at 530‘C for 6 hours to obtain 54 g of powder. The resulting powder was 24 confirmed to be Ti-MWW, that is, confirmed to have a pore of oxygen 12-member ring by the X-ray diffraction pattern and confirmed to be titanosilicate having Ti of four-coordination by the measurement of UV-visible absorption spectrum. Furthermore, 5 above procedures were performed twice to obtain a total amount of 162 g of Ti-MWW powder.
135 g of the resulting Ti-MWW, 300 g of piperidine and 600 g of pure water were placed in an autoclave under room temperature and air atmosphere, and agitated to prepare a gel. 10 The resulting gel was matured for 1.5 hour, then the autoclave was sealed, and hydrothermal synthesis was performed by increasing temperature of the gel to 160'C over 4 hours with agitating and the temperature was held for 24 hours.
A suspension obtained by such hydrothermal synthesis 15 was filtrated, washed with water until a pH of the filtrate
becomes around 9. Then, a filter cake (Solid b) was vacuum-dried at 150°C until no weight decrease of the filter cake was found to prepare 141 g of White powder b. As the result of measurement of the X-ray diffraction pattern of White powder b, it showed the X-20 ray diffraction pattern similar to that of White powder a (Ti-MWW
precursor) , and it was found that it has a structure having a pore of oxygen 12-member ring. In addition, as the result of the measurement of UV-visible absorption spectrum, it was found that White powder b is titanosilicate (hereinafter, referred this Ti-25 MWW precursor to as "Ti-MWW precursor b". In addition, an Ti content in White powder b measured by IPC emission spectrometry was 1.61 % by weight.
The resulting Ti-MWW precursor b was agitated in 80 g of a 20/80 (weight ratio) mixed solvent of water/acetonitrile 30 containing 0.1 % by weight of hydrogen peroxide for 1 hour, filtrated, washed with 80 g of water, and then subjected to following examples.
[0069] (Reference example 2: Preparation of noble metal-supporting 35 catalyst (Pd/AC catalyst)) 25 6 g of activated carbon (manufactured by Wako Pure Chemical Industries, Ltd.) pre-washed with 2 L of water and 300 mL of water were placed in a 1 L egg plant flask, and agitated at room temperature under air atmosphere. To the suspension 5 agitated, 100 mL of aqueous suspension containing 0.60 mmol of palladium (Pd) colloid was slowly added dropwise at room temperature under air atmosphere. After adding dropwise, the suspension was further agitated for 8 hours at room temperature under air atmosphere. After agitation, water in the suspension 10 was removed with a rotary evaporator, and the suspension was vacuum-dried at 80 °C for 6 hours and fired at 300“C for 6 hours under nitrogen atmosphere to obtain a palladium catalyst supported on activated carbon (Pd/AC catalyst) . A Pd content in the catalyst measured by IPC emission spectrometry was 0.95 % by 15 weight.
[0070] (Example 1) A. First present reaction
Titanosilicate (Ti-MWW precursor b) and the Pd/AC 20 catalyst were placed in a 0.3 L autoclave as a reactor, the autoclave was sealed, and to which, each of a mixed gas of oxygen/hydrogen/nitrogen (3.3/3.6/93.1 (volume ratio)) at 281 L/hour, a solution of water/acetonitrile (30/70 (weight ratio)) containing 0.7 mmol/kg of anthraquinone and 3.0 mmol/kg of 25 diammonium hydrogen phosphate at 90 g/hour and propylene at 36 g/hour was provided.. Then, a continuous reaction in which a solution containing a reaction product (liquid phase) is removed from a reactor through a filter and a gas produced (gas phase) is removed from a reaction mixture (retention time: 60 minutes) was 30 performed. During the reaction, temperature of contents in the reactor was set at 50°C, and a pressure in the reactor was set at 4.0 MPa (gauge pressure). During the reaction, amounts of titanosilicate (Ti-MWW precursor b) and the Pd/AC catalyst to be used were adjusted such that they became 2.28 g and 1.05 g 35 relative to 133 g of a mixed solvent provided to the reactor, 26 respectively. Under this condition, the reaction was continued for 6 hours .
[0071] B. First contact step 5 Providing hydrogen, oxygen, the solution and propylene was stopped, and a nitrogen gas and methanol were provided to the reactor at 240 L/hour and 347 g/hour, respectively, while temperature of the contents in the reactor was adjusted to 70’C and the pressure in the reactor was adjusted to 4.0 MPa (gauge 10 pressure) to perform the first contact step for 90 minutes.
[0072] C. Second present reaction A gas containing oxygen/hydrogen/nitrogen (3.3/3.6/93.1 (volume ratio)) at 281 L/hour, a solution of 15 water/acetonitrile (30/70 (weight ratio)) containing 0.7 mmol/kg of anthraquinone and 3.0 mmol/kg of diammonium hydrogen phosphate at 90 g/hour and propylene at 36 g/hour were provided to a reactor containing the catalyst which had undergone the first contact step of B. Then, a continuous reaction in which a 20 solution containing a reaction product (liquid phase) was removed from a reactor through a filter and a gas produced (gas phase) was removed from a reaction mixture (retention time: 60 minutes) was performed. During the reaction, temperature of the contents in the reactor was set at 50°C, and a pressure in the reactor was 25 set at 4.0 MPa (gauge pressure). Under these conditions, the reaction was continued for 6 hours. After 6 hours, no alcohol was found in the catalyst.
[0073]
The liquid phase and the gas phase contained in the 30 reactor after completion of additional 3 times of procedures similar to those in above steps B and C (30 hours of a total reaction time in the present reaction has passed) were analyzed with a gas chromatography. As the result, a propylene oxide producing activity per unit weight of titanosilicate was 56.1 35 mmol-PO/g-titanosilicate·hour ("PO" herein means propylene oxide) 27 and hydrogen-based selectively (a molar amount of propylene oxide produced/a molar amount of hydrogen consumed) was 75 %.
[0074] (Comparative Example 1) 5 A reaction was performed as that described in "A" of
Example 1 (first present reaction), except that only A (first present reaction) was performed in the experiment in Example 1 for 27 hours. The liquid phase and the gas phase contained in the reactor after performing "A" (first present reaction) for 27 10 hours were analyzed with a gas chromatography. As the result, a propylene oxide producing activity per unit weight of titanosilicate was 38.8 mmol-PO/g-titanosilicate·hour and hydrogen-based selectively was 39 %.
15 Industrial Applicability
[0075]
According to the present invention, alkyleneoxide may be efficiently produced without decreasing an amount of alkyleneoxide produced, by recovering a catalytic ability of a 20 catalyst which is deteriorated by being subjected to a reaction, even in a process for producing alkyleneoxide in which olefin such as propylene, hydrogen and oxygen are continuously provided for a long period of time.
1039092
Claims (16)
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| JP2010228386A JP2012081390A (en) | 2010-10-08 | 2010-10-08 | Method for preparing catalyst, and method for manufacturing alkylene oxide using the prepared catalyst |
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| JP4183924B2 (en) | 2001-03-30 | 2008-11-19 | 日揮触媒化成株式会社 | METAL PARTICLE, PROCESS FOR PRODUCING THE PARTICLE, COATING LIQUID FOR TRANSPARENT CONDUCTIVE FILM CONTAINING THE PARTICLE, SUBSTRATE WITH TRANSPARENT CONDUCTIVE COATING, DISPLAY DEVICE |
| US6399794B1 (en) * | 2001-11-15 | 2002-06-04 | Arco Chemical Technology, L.P. | Direct epoxidation process using carbonate modifiers |
| JP4241068B2 (en) | 2002-03-07 | 2009-03-18 | 昭和電工株式会社 | Method for producing MWW type zeolite material |
| US20050277542A1 (en) * | 2004-06-14 | 2005-12-15 | Kaminsky Mark P | Catalyst regeneration process |
| ATE528298T1 (en) * | 2007-06-21 | 2011-10-15 | Sumitomo Chemical Co | METHOD FOR PRODUCING PROPYLENE OXIDE |
| JP2009233656A (en) * | 2008-03-05 | 2009-10-15 | Sumitomo Chemical Co Ltd | Method for regenerating titanosilicate catalyst |
| JP2009274062A (en) | 2008-04-17 | 2009-11-26 | Sumitomo Chemical Co Ltd | Titanosilicate |
| CN101619048B (en) * | 2008-06-30 | 2011-12-21 | 中国石油化工股份有限公司 | Method for synthesizing propylene oxide |
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