WO2013002355A1 - Procédé de production d'un oxyde d'alkylène et catalyseur contenant du palladium utilisé pour ce faire - Google Patents
Procédé de production d'un oxyde d'alkylène et catalyseur contenant du palladium utilisé pour ce faire Download PDFInfo
- Publication number
- WO2013002355A1 WO2013002355A1 PCT/JP2012/066634 JP2012066634W WO2013002355A1 WO 2013002355 A1 WO2013002355 A1 WO 2013002355A1 JP 2012066634 W JP2012066634 W JP 2012066634W WO 2013002355 A1 WO2013002355 A1 WO 2013002355A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- palladium
- alkylene oxide
- containing catalyst
- producing
- carbon
- Prior art date
Links
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 239
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 118
- 239000003054 catalyst Substances 0.000 title claims abstract description 109
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 82
- 125000002947 alkylene group Chemical group 0.000 title claims abstract description 57
- 150000001875 compounds Chemical class 0.000 claims abstract description 88
- 239000000203 mixture Substances 0.000 claims abstract description 68
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 59
- 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 47
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 47
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000007789 gas Substances 0.000 claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 150000001336 alkenes Chemical class 0.000 claims abstract description 23
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000005977 Ethylene Substances 0.000 claims abstract description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 10
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 claims abstract description 9
- 229940117927 ethylene oxide Drugs 0.000 claims abstract description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 63
- 239000002904 solvent Substances 0.000 claims description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 33
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 33
- 125000004432 carbon atom Chemical group C* 0.000 claims description 28
- 238000002441 X-ray diffraction Methods 0.000 claims description 27
- 239000002245 particle Substances 0.000 claims description 17
- 239000003960 organic solvent Substances 0.000 claims description 15
- 230000003197 catalytic effect Effects 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 230000001747 exhibiting effect Effects 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 50
- 238000000034 method Methods 0.000 description 58
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 53
- -1 l-anthanum Chemical compound 0.000 description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 29
- 239000010936 titanium Substances 0.000 description 26
- 239000002243 precursor Substances 0.000 description 25
- 239000000243 solution Substances 0.000 description 25
- 229910052719 titanium Inorganic materials 0.000 description 24
- 238000011282 treatment Methods 0.000 description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 20
- 239000011148 porous material Substances 0.000 description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 17
- 239000002253 acid Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 13
- 239000002994 raw material Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 239000000872 buffer Substances 0.000 description 12
- 238000005259 measurement Methods 0.000 description 12
- 239000013643 reference control Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 238000002156 mixing Methods 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 229910017604 nitric acid Inorganic materials 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 229910001873 dinitrogen Inorganic materials 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 239000002210 silicon-based material Substances 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 7
- 229910021485 fumed silica Inorganic materials 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- 150000007522 mineralic acids Chemical class 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 125000004430 oxygen atom Chemical group O* 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229910052795 boron group element Inorganic materials 0.000 description 6
- 229910001882 dioxygen Inorganic materials 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 150000002825 nitriles Chemical class 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 150000003863 ammonium salts Chemical class 0.000 description 5
- 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 5
- 229910052796 boron Inorganic materials 0.000 description 5
- 238000004891 communication Methods 0.000 description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 230000001172 regenerating effect Effects 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000004056 anthraquinones Chemical class 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 4
- 235000019838 diammonium phosphate Nutrition 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000000977 initiatory effect Effects 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
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 125000005210 alkyl ammonium group Chemical group 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 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
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
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- KWIPUXXIFQQMKN-UHFFFAOYSA-N 2-azaniumyl-3-(4-cyanophenyl)propanoate Chemical compound OC(=O)C(N)CC1=CC=C(C#N)C=C1 KWIPUXXIFQQMKN-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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
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- 239000005695 Ammonium acetate Substances 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910002483 Cu Ka Inorganic materials 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
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- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 2
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- 229910052779 Neodymium Inorganic materials 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 229940090948 ammonium benzoate Drugs 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 229940085991 phosphate ion Drugs 0.000 description 1
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- 229910052913 potassium silicate Inorganic materials 0.000 description 1
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 229940006465 strontium cation Drugs 0.000 description 1
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 description 1
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- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- VKFFEYLSKIYTSJ-UHFFFAOYSA-N tetraazanium;phosphonato phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])(=O)OP([O-])([O-])=O VKFFEYLSKIYTSJ-UHFFFAOYSA-N 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 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
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 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
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
- 229940070710 valerate Drugs 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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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
-
- 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
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- 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
-
- 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
- B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
-
- 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
- B01J37/16—Reducing
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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
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
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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
- 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
- B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
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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
- B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
- B01J2235/15—X-ray diffraction
Definitions
- the ⁇ present . invention relates to a method for producing an alkylene oxide and a palladium-containing catalyst and the like used for the same.
- Patent Document 1 discloses, as a- noble metal support that is a first catalyst, for example, one in which palladium tetraammine chloride is supported on activated carbon.
- a method for producing propylene oxide from oxygen, hydrogen and propylene using a titanosilicate that is a second catalyst, is also described.
- An object to be achieved by the ' present invention is to provide a production method and a novel catalyst and the like used for the same that result in providing a high production amount of an alkylene oxide in a reaction for producing an alkylene oxide from oxygen, hydrogen and an olefin by using together with a titanosilicate-containing catalyst.
- the present invention provides: 1. a method for producing an alkylene oxide, comprising the step of reacting oxygen, hydrogen and an olefin, in the presence of a carbon-containing gas-treated palladium-containing catalyst which is ⁇ obtained by contacting a palladium-containing composition comprising palladium and a carrier with a compound selected from the group consisting of acetylene, ethylene and carbon monoxide and a titanosilicate-containing catalyst (hereinafter, may be referred to as the alkylene oxide production method of the present invention) ;
- the palladium-containing catalyst is a palladium-containing catalyst whose catalytic activity has been recovered or regenerated by previously contacting with a carbon- supplying compound having 4 or less carbon atoms that is gaseous under conditions of ordinary temperature and pressure;
- a carbon-containing gas-treated palladium- containing catalyst which is obtained by contacting a palladium-containing composition comprising palladium and a carrier with a compound selected from the group consisting of acetylene, ethylene and carbon monoxide (hereinafter, may , be ' referred to as the palladium-containing catalyst of the present invention) ; 1
- the carrier is a carrier selected from the group consisting of activated carbon, AI2O3, and Zr0 2 ;
- Fig. 1 is a graph showing x-ray diffraction spectra of "palladium-containing catalyst B" that is the palladium-containing catalyst of the present invention and "palladium-containing composition B".
- the alkylene oxide production method of the present invention includes the step of reacting oxygen, hydrogen and an olefin, in the presence of a carbon-containing gas- treated palladium-containing catalyst which- is obtained by contacting a palladium-containing composition comprising palladium and a carrier with a compound selected from the group consisting of acetylene, ethylene and carbon monoxide and a titanosilicate-containing catalyst.
- the carbon-containing gas-treated palladium-containing catalyst (i.e., the palladium-containing catalyst of the present invention) used for the alkylene oxide production method of the present invention is obtained by contacting a palladium-containing composition comprising palladium and a carrier with a compound selected from the group consisting of acetylene, ethylene and carbon monoxide (hereinafter, a carbon-containing gas) as described above.
- examples of the "carrier” include oxides such as silica, alumina, titania, zirconia, niobia and the like, hydroxides such as ' niobic acid, zirconic acid, tungstic acid, titanic acid and the like, carbon materials such as activated carbon, carbon black, graphite, carbon nanotubes and the like, and mixtures thereof.
- Preferred examples thereof include zirconia, alumina, titania, and activated carbon. More preferred examples thereof include zirconia.
- the titanosilicate-containing catalyst of the present invention may be used as a carrier.
- the "palladium-containing composition comprising palladium and a carrier” can be obtained by, for example, using a method of supporting a palladium colloid or a palladium compound by a known method or the like and then heat-treating the resultant.
- the preferred palladium-containing composition include a palladium-containing composition substantially comprising palladium and a carrier.
- examples ' of impurities are also possible.
- the palladium-containing composition in minute amounts include noble metals such- as gold, platinum, osmium, iridium, silver, rhenium and the like, alkali metals such as lithium, sodium, potassium, rubidium, cesium and the like, alkaline-earth metals such as magnesium, calcium, strontium, barium and the like, rare-earth metals such as scandium, yttrium, l-anthanum, cerium, praseodymium, neodymium and the like, iron, titanium, manganese, molybdenum and tin.
- noble metals such- as gold, platinum, osmium, iridium, silver, rhenium and the like
- alkali metals such as lithium, sodium, potassium, rubidium, cesium and the like
- alkaline-earth metals such as magnesium, calcium, strontium, barium and the like
- rare-earth metals such as scandium, yttrium, l-
- Examples of the "palladium colloid” include the Pd colloid and the like described in, for example, JP-A 2002-
- examples of the "palladium compound” include tetravalent palladium compounds such as sodium hexachloropalladate ( IV) tetrahydrate , potassium hexachloropalladate ( IV) and ,the like; and divalent palladium compounds such as palladium ( II ) chloride, palladium ( II ) bromide, palladium ( II ) acetate, palladium ( II ) acetylacetonate, dichlorobis (benzonitrile) palladium ( II.) , dichlorobis (acetonitrile) palladium (II) ,
- tetravalent palladium compounds such as sodium hexachloropalladate ( IV) tetrahydrate , potassium hexachloropalladate ( IV) and ,the like
- divalent palladium compounds such as palladium ( II ) chloride, palladium ( II ) bromide, palladium ( II ) acetate, palladium ( II
- dichlorotetraammine palladium ( I I ) dibromotetraammine palladium (II ) , dichloro ( cycloocta-1 , 5-diene ) palladium ( II ) , palladium ( II ) tri luoroacetate and the like.
- support method examples include ordinary wet support methods such as impregnation method, dipping method, wet adsorption method, ion-exchange method and solvent evaporation method, and methods combining these methods.
- Examples of the solvent used in the above wet support methods include aqueous solvents,- nonaqueous solvents, ⁇ and mixed solvents of these.
- the solvent include water such as pure water, ion-exchanged water, tap water, industrial water and the like; alcohols such as methanol, ethanol, isopropanol, hexanol, octanol and the like; hydrocarbon solvents such as pentane, petroleum ether, hexane, cyclohexane, benzene, toluene, xylene and the like; ketones such as acetone, ethyl methyl ketone, cyclohexanone , acetophenone and the like; halogenated hydrocarbon solvents such as methyl chloride, methylene chloride, chloroform, carbon tetrachloride, dichloroethane , tetrachloroethane, propyl chloride, chlorobenzene, dichlorobenzene, methyl fluoride and the like; esters such as methyl acetate, ethyl acetate, propyl
- the used amount of the solvent is not particularly limited, but is preferably an amount sufficient to contact the whole of the used carrier.
- the used " amount of the solvent is large excess for the above appropriate amount, a drying treatment will take a long time.
- the used amount of the solvent is too small for the above appropriate amount, homogenous dispersion on the carrier will not be easy.
- Examples of the operation system in supporting by the above wet support method include standing .method, stirring method, solution flow method, solvent refluxing method, and a method combining these methods.
- a palladium-containing composition may be obtained by using the above support method.
- the palladium-containing composition may be usually recovered by separating and removing an excess content of the solvent or the noble metal-containing solution or by evaporating an excess content of the solvent or the palladium-containing solution.
- Examples of the method for separating and removing an excess content of the solvent or the palladium-containing solution ' include ordinary solid-liquid separation methods such . as filtration, centrifugation, decantation and the like.
- examples of the method of evaporating an excess content of the solvent or the palladium- containing solution include natural evaporation method, reduced-pressure evaporation method, blast evaporation method, and gas distribution bubbling evaporation method.
- the palladium-containing composition obtained ⁇ as described above can be further subjected to usual drying by heating treatment with an oven or the like, or subjected to a known appropriate pretreatment or activation treatment such as a heat treatment by an inert gas, a reduction treatment by a reducing gas such as hydrogen, an oxidation treatment by air or the like, or a treatment combining these treatments, directly and as necessary.
- a known appropriate pretreatment or activation treatment such as a heat treatment by an inert gas, a reduction treatment by a reducing gas such as hydrogen, an oxidation treatment by air or the like, or a treatment combining these treatments, directly and as necessary.
- the content of palladium contained in the palladium- containing composition is, for example, 0.00001 parts by weight or more, preferably, for example, 0.01 parts by weight or more, more preferably, for example, 0.1 parts by weight or more, further preferably, for example, in the range of 0.01 to 20 parts by weight, and particularly preferably, for example, in the range of 0.1 to 5 parts by weight, based on 100 parts by weight of the palladium- containing composition.
- the palladium-containing catalyst of the present invention can contain impurities contained in minute amounts in the "palladium-containing composition comprising palladium and a caxrier" that is a raw material.
- impurities include, as described above, noble metals such as gold, platinum, osmium, iridium, silver, rhenium and the like, alkali metals such as lithium, sodium, potassium, rubidium, cesium and the like, alkaline- earth metals , such as magnesium, calcium, strontium, ⁇ barium and the like, rare-earth metals- such as scandium, yttrium, lanthanum, cerium, praseodymium, neodymium ' and the like, iron, titanium, manganese, molybdenum, and tin.
- noble metals such as gold, platinum, osmium, iridium, silver, rhenium and the like
- alkali metals such as lithium, sodium, potassium, rubidium, ces
- any method may be used for contacting the palladium- containing composition comprising palladium and a carrier with the compound selected from the group consisting of acetylene, ethylene and carbon monoxide, and examples thereof include (1) a dry method in which the palladium- containing composition comprising palladium and a carrier is filled in a reactor, then the compound is circulated while retaining heat, ' and (2) a wet method in ⁇ which the palladium-containing composition comprising palladium and a carrier suspended in a solvent or the like in a sealed container such as an autoclave is mixed together with the compound and retained at the ' same . temperature, or the compound is circulated by bubbling or the like.
- the temperature of the contact step is, for example, in the range of 25°C to 500°C, preferably, for example, in the range of 50°C to 300°C, and more preferably, for example, in the range of 100°C to 200°C.
- the pressure of the contact step is, for example, in the range of 0 to 10 MPa by a gauge pressure.
- the lower limit of the contact time of the contact step is, for example, 10 minutes, preferably, for example, 2 hours, more preferably, for example, 10 hours, and further preferably, for example, 12 hours.
- the upper limit of the contact time of the contact step is, for example, 120 hours, preferably, for example, 72 hours, more preferably, for example, 30 hours, and further preferably, for example, 24 hours.
- the palladium-containing composition comprising palladium and a carrier may be in the state of being mixed together with the titanosilicate- containing catalyst set forth below.
- the palladium catalyst of the present invention may be further subjected to usual drying by heating treatment with an oven or the like, or subjected to a known appropriate pretreatment or activation treatment such as a heat treatment by an inert gas, a reduction treatment by a reducing gas such as hydrogen, an oxidation treatment by air or the like, or a treatment combining these treatments, directly and as necessary, and may be used in the reaction as a catalyst.
- a known appropriate pretreatment or activation treatment such as a heat treatment by an inert gas, a reduction treatment by a reducing gas such as hydrogen, an oxidation treatment by air or the like, or a treatment combining these treatments, directly and as necessary, and may be used in the reaction as a catalyst.
- Examples of the palladium catalyst of the present invention include those having the value of crystal face spacing of a (111) face of a palladium metal calculated from a diffraction angle measured by an x-ray diffraction analysis of 2.270 A or more. This is one physical property value for confirming that, by subjecting the palladium- containing composition comprising palladium and a carrier to the step of contacting with the compound selected from the group consisting of acetylene, ethylene and carbon monoxide, the carbon derived from the above is introduced into the palladium-containing composition.
- the above physical property value is not enough for the confirmation by the effect of the background value or the like in the measurement, depending on the type of the carrier contained in the palladium-containing composition, but the above physical property value is particularly useful, for example, when the carrier is carbon such as activated carbon, carbon black, graphite, carbon nanotubes or the like, or a mixture thereof;
- An x-ray diffraction pattern may be measured by using a commercially available general x-ray diffraction device using copper K-alpha radiation as a radiation source.
- a commercially available general x-ray diffraction device using copper K-alpha radiation as a radiation source Specifically, for example, using the palladium catalyst of the present invention or the palladium-containing composition as a sample, the measurement may be carried out by using an x-ray diffraction device such as RINT 2500 V manufactured by Rigaku Corporation under the following conditions.
- the palladium-containing catalyst of- the present invention can be used as a catalyst for producing an alkylene oxide from hydrogen, oxygen and an olefin.
- the palladium-containing catalyst of , the present invention is used together with a titanosilicate-containing catalyst (more specifically, used together in ' the form- where both the titanosilicate-containing catalyst and the palladium-containing catalyst of the present invention are integrated or in the form where both are individually independent) and results in providing a high production amount of an olefin oxide in a reaction for producing propylene oxide from oxygen, hydrogen and propylene.
- titanosilicate particles examples include a catalyst called titanosilicate particles.
- the titanosilicate particles substantially having tetracoordinated Ti, in which the maximum absorption peak within a wavelength range of 210 to 230 nm appears for an ultraviolet visible absorption spectrum within a wavelength range of 200 to 400 nm,- are preferable (e.g., see Chemical Communications 1026-1027 (2002) Figs. 2 (d) and (e) ) .
- the ultraviolet visible absorption spectrum may be measured based on a diffuse reflectance method using an ultraviolet visible spectrophotometer equipped, with a diffuse reflecting device.
- titanosilicate particles When the titanosilicate particles are used as a catalyst in, for example, a method for producing hydrogen peroxide such that oxygen and hydrogen are reacted in the presence of the palladium-containing catalyst of the present invention, titanosilicate particles previously contacted with hydrogen peroxide are preferably used.
- the concentration of hydrogen peroxide subjected to the contact is, for example, in the range of 0.0001% to 50% by weight.
- titanosilicate particles include those described in the following 1 to 7.
- Crystalline titanosilicates having fine pores of 10-membered oxygen ring having fine pores of 10-membered oxygen ring:
- TS-1 having a MFI structure (e.g., U.S. Patent No. 4,410,501), TS-2 having a MEL structure (e.g., Journal of Catalysis 130, 440-446, (1991)), Ti-ZSM-48 having a MRE structure ,(e.g., Zeolites 15, 164-170, (1995)), Ti-FER having a . FER structure (e.g., Journal of Materials Chemistry 8, 1685-1686 (1998)), and the like.
- Crystalline titanosilicates having fine pores of 12-membered oxygen ring having fine pores of 12-membered oxygen ring:
- Ti-Beta having a BEA structure e.g., Journal of
- Ti-ZSM-12 having an MTW structure e.g., Zeolites 15, 236-242, (1995)
- Ti-MOR having an MOR structure
- Ti-ITQ-7 having an ISV structure
- Ti-MCM-68 having an MSE structure
- Ti-MWW having an MWW structure
- Ti-UTD-1 having a DON structure e.g., Studies in Surface Science and Catalysis 15, 519-525, (1995)), and the like.
- Ti-ITQ-6 e.g., Angewandte Chemie International Edition 39, 1499-1501, (2000), and the like.
- a Ti-MWW precursor e.g., EP-1731515-A1
- Ti-YNU-1 e.g., Angewandte Chemie International Edition 43, 236-240, (2004)
- Ti-MCM-36 e.g., Catalysis Letters 113, 160-164, (2007)
- Ti-MCM-56 e.g., Microporous and Mesoporous Materials 113, 435-444, (2008)
- Ti-MCM-41 e.g., Microporous Materials 10, 259-271,
- Ti-MCM-48 e.g., Chemical Communications 145-146, (1996)
- Ti-SBA-15 e.g., Chemistry of Materials 14,. 1657- 1664, (2002)
- fine pore means a fine pore constituted from an Si-0 bond or a Ti-0 bond.
- examples of the fine pore include a fine pore in the form of a half cup called a side pocket .(namely, it is not necessary to penetrate primary particles of the titanosilicate) .
- not less than X-membered oxygen ring means that the number of the oxygen atoms is not less than X in (a) a ⁇ cross-section of the narrowest part of a fine pore, or (b) a ring structure at the fine pore entrance.
- X-membered oxygen ring is confirmed by, for example, an analysis of an x-ray diffraction pattern, and when the titanosilicate particles have a- known structure, it can be easily confirmed by comparison with an x-ray diffraction pattern of the known one.
- the "layered titanosilicate” is a generic name of . titanosilicates having a layered structure, such as layered precursors of a crystalline titanosilicate, and a titanosilicate in which spaces between ⁇ layers in a crystalline titanosilicate are expanded. Whether or not a titanosilicate has a layered structure can be confirmed by an electron microscope or measurement of an x-ray diffraction pattern.
- the "layered precursor” refers to a titanosilicate which forms a crystalline titanosilicate by carrying out a treatment such as dehydration condensation and the like. It can be easily determined that a layered titanosilicate has fine pores of not less than 12-membered oxygen ring from the structure of a corresponding crystalline titanosilicate.
- the "mesoporous titanosilicate” is a generic name of titanosilicates having regular mesofine pores.
- the regular mesopore refers to a. structure in which mesopores are regularly and repeatedly arranged.
- the "mesofine pore” refers to a fine pore having a fine pore diameter of 2 to 10 nm.
- the "silylated titanosilicate” refers to a compound obtainable by treating the titanosilicates 1 to 4 as described above with a silylating agent.
- the silylating agent include 1 , 1 , 1 , 3 , 3 , 3-hexamethyl disilazane and trimethylchlorosilane (e.g., EP. 1,488,853 Al) .
- a hydrogen peroxide treatment may be used.
- concentration of the hydrogen peroxide solution in the hydrogen peroxide treatment is, for example, in the range of 0.0001% to 50% by weight.
- Examples of the solvent of the hydrogen peroxide ' solution include water, and the solvents used in the alkylene oxide production method of the . present invention.
- the temperature of the hydrogen peroxide treatment is, for example, in the range of 0°C to 100°C and preferably in the range of 0°C to 60°C.
- the treatment (mixing) time of the hydrogen peroxide treatment depends on the concentration of hydrogen peroxide, and is, for example, in the range of 10 minutes to 10 hours and preferably, for example, in the range of 1 hour to 3 hours.
- titanosilicate particles preferred examples thereof include the titanosilicate having fine pores of not less than 12-membered oxygen ring.
- a titanosilicate may be a crystalline titanosilicate or -a layered titanosilicate.
- Specific examples of the titanosilicate having fine pores of not less than 12- membered oxygen ring include Ti-MWW and a Ti-MWW precursor.
- titanosilicate particles having fine pores of not less than 12-membered oxygen ring the titanosilicate particles exhibiting an x-ray diffraction pattern having peaks at the following '' positions shown as lattice plane spacings are preferable.
- An x-ray diffraction pattern may be measured by using a commercially available general x-ray diffraction device using copper K-alpha radiation as a radiation source. Specifically, for example, using ' the titanosilicate particles as a sample, the measurement may be carried out by using an x-ray diffraction device such as RINT 2500 V manufactured by Rigaku Corporation under the following conditions.
- titanosilicate particles having the x-ray diffraction pattern as described above include a Ti-MWW precursor (e.g., titanosilicate particles described in JP-A 2005-262164), Ti-YNU-1 (e.g., titanosilicate particles described in Angewandte Chemie International Edition, 43, 236-240, (2004)), crystalline titanosilicates , Ti-MWW which is a crystalline titanosilicate having an MWW structure in the IZA (International Zeolite Association) structure code (e.g., titanosilicate particles described in JP-A 2003-327425), and Ti-MCM-68 which is a crystalline titanosilicate having an MSE structure in the IZA structure code .-(e.g., titanosilicate particles described in JP-A 2008-50186) .
- a Ti-MWW precursor e.g., titanosilicate particles described in JP-A 2005-262164
- Ti-YNU-1 e.
- the Ti-MWW precursor is a titanosilicate having a layered structure and refers to a substance which forms- Ti- MWW by dehydration condensation of the Ti-MWW precursor.
- the dehydration condensation is usually conducted by heating the Ti-MWW precursor at a temperature of over 200°C and not more than 1000°C, and preferably in the range of 300°C to 650°C.
- the Ti-MWW precursor may be treated with a structure-directing agent as set forth below in the production process.
- the Ti-MWW precursor obtained as described above may be again treated with a structure-directing agent as set forth below. These are also called as the "Ti-MWW precursor" in the present invention.
- the . Ti-MWW precursor can be used as a catalyst in various oxidation reactions and the like.
- the molar ratio of silicon to nitrogen (Si/N ratio) of the Ti-MWW precursor is, for example, in the range of 5 to 100 and preferably, for example,- in the range of 10 to 20.
- Examples of the method for producing a Ti-MWW precursor include the following various methods .
- Step (1-1) a method comprising the step of heating a mixture comprising a structure-directing agent, a compound containing a group 13 element of the periodic table of the elements (hereinafter, may be referred to as a "group 13 element-containing compound”), a silicon- containing compound, a titanium-containing compound and water (hereinafter, may be referred to as "Step (1-1)") and the step of mixing a layered compound, obtained in Step (1- 1) and an acid.
- Step (2-1) a method comprising the step of heating a mixture comprising a structure-directing agent, a group 13 element-containing compound, a silicon-containing compound and water (hereinafter, may be referred “ to as “Step (2-1)") and the step of mixing a layered compound obtained in Step (2-1), a titanium-containing compound and an acid.
- Step (2-1) a method comprising the step of heating a mixture comprising a structure-directing agent, a group 13 element-containing compound, a silicon-containing compound and water
- Step (3-1) a method comprising the step of heating a mixture comprising a structure-directing agent, a group 13 element-containing compound, a silicon-containing compound, a titanium-containing compound and water (hereinafter, may be referred to as "Step (3-1)") and the step of mixing a layered compound obtained in Step (3-1), a titanium-containing compound and an acid.
- Fourth method a method comprising the steps of firing layered borosilicate obtainable by heating a mixture comprising a structure-directing agent, a group 13 element- containing compound, a silicon-containing compound and water (preferably after contacting with an acid to remove the structure-directing agent) to obtain B-MWW, removing boron by an acid or the like from the resulting B-MWW, then adding a structure-directing agent,- a titanium-containing compound and water thereto, heating the resulting mixture to obtain a layered compound, and contacting the resulting compound with about 6 M nitric acid (see, for example, Chemical Communication, 1026-1027, (2002)).
- the Ti-MWW precursor obtained by the first to fourth methods is preferably further additionally treated with a structure-directing agent for adjusting the molar ratio of silicon to nitrogen (Si/N ratio) to a predetermined value (e.g., a range of from 10 to 20).
- a structure-directing agent for adjusting the molar ratio of silicon to nitrogen (Si/N ratio) to a predetermined value (e.g., a range of from 10 to 20).
- a titanosilicate-containing catalyst is mixed with a structure-directing agent and water in a sealed pressure resistant container such as an autoclave, and the sealed pressure resistant container is sealed, then allowed to stand still or stirred and mixed under heating and pressure, to obtain a mixed liquid, and a solid product may be obtained by separation from the obtained mixed liquid using a method such as filtration or centrifugation .
- these are mixed ⁇ in a glass flask in the atmosphere by stirring, or without stirring, to obtain a mixed liquid, and a solid product may be obtained by separation from the obtained mixed liquid using a method such as filtration or . centrifugation .
- the obtained titanosilicate-containing catalyst may be washed using water or the like.
- the washing may be properly performed while observing the amount of a washing liquid or the pH of a wash filtrate, as occasion demands.
- the obtained washed product may be dried, for example, in the range of 0°C to 200°C by, for example, draught drying, drying under reduced pressure, or vacuum freeze drying, to an extent that weight ' reduction is not observed.
- the temperature used in the above mixing operation is, for example, from 0°C to 250°C, preferably from 20°C to 200°C, and more preferably from 50°C to 180°C.
- the mixing time used in the above mixing operation is, for example, in the range of 1 hour to 720 hours, preferably in the range of 2 hours to 720 hours, more preferably in the range of 4 hours to 720 hours, and particularly preferably in the range of 8 hours to 720 " hours.
- the pressure used in the above mixing operation is not particularly limited, and is, for example, in the range of 0 to 10 MPa by a gauge pressure.
- the amount of a titanium-containing compound used in the above various methods is, for example, in the range of 0.001 to 1 part by ' weight and preferably, for example, in the range of 0.01 to 0.5 parts by weight, as the weight of titanium atoms in the titanium-containing compound, based on 1 part by weight of the obtained layered compound.
- Examples of the acid used in the above various methods include inorganic acids such as nitric acid, hydrochloric acid, sulfuric acid, perchloric acid, boric acid, fluorosulfonic acid and the like, organic acids such as formic acid, acetic acid, propionic acid, tartaric acid and the like, and combinations of two or more thereof.
- Preferred examples thereof include acids containing at least one inorganic acid having a redox potential higher than that of tetravalent titanium.
- examples of the "inorganic acid having a redox potential higher than that of tetravalent titanium” include nitric acid, perchloric acid, fluorosulfonic acid, a combination of nitric acid and sulfuric acid, and a combination of nitric acid and boric acid.
- the acid used in the above various methods is usually used in the state of a solution prepared by being dissolved in a solvent.
- a solvent examples include water, alcohol solvents, ether solvents, ester solvents, ketone solvents, and mixtures thereof. Preferred examples thereof include water.
- the concentration of the acid contained in the solution is, for example, in the range of 0.01 to 20 mol/1.
- the concentration of the inorganic acid is preferably, for example, in the range of 1 to 5 mol/1.
- Examples of the "group 13 element of the periodic table of the elements" used in the method for producing a Ti-MWW precursor include a boron-containing compound, an aluminum-containing compound, and a gallium-containing compound. Preferred examples thereof include a boron- containing compound.
- boron-containing compound examples include boric acid, borates, boron oxide, boron halide, and a trialkyl boron compound having an alkyl group having 1 to 4 'carbon atoms. Preferred examples thereof include boron.
- Examples of the aluminum-containing compound include sodium aluminate.
- gallium-containing compound examples include gallium oxide.
- the amount of the group 13 element-containing compound used in the method for producing a Ti-MWW precursor is, for example, in the range of 0.01 to 10 mol and' preferably in the range of 0.1 to 5 mol, based on 1 mol of silicon contained in the silicon-containing compound.
- Examples of the "silicon-containing compound" used in the method for producing a Ti-MWW precursor include silicic acid, silicates, silicon oxide, silicon halide, tetraalkyl orthosilicate, and colloidal silica. Preferred examples thereof include orthosilicic acid, metasilicic acid, and metadisilicic acid.
- silicates examples include alkali metal silicates such as sodium silicate, potassium silicate and the like, and alkaline-earth metal silicates such as calcium silicate, magnesium silicate and the like-.
- Examples of the silicon oxide include crystalline silica such as quartz, and amorphous silica such as fumed silica. Preferred examples thereof include fumed silica.
- fumed silica generally commercially available fumed silica having a BET specific surface area of 50 to 380 m 2 /g may be used. Among them, fumed silica having a BET specific surface area of 50 to 200 mm 2 /g is preferable for easy handling.
- fumed silica having a BET specific surface area of 100 to 380 mm 2 /g is preferable since it easily dissolves in an aqueous solution
- Examples of the silicon halide include silicon tetrachloride and silicon tetrafluoride .
- Examples of the tetraalkyl orthosilicate include tetramethyl orthosilicate and tetraethyl orthosilicate.
- titanium alkoxide examples include titanium alkoxides which have an alkoxy group having 1 to 4 carbon atoms, for example, tetramethyl orthotitanate, tetraethyl orthotitanate, tetraisopropyl orthotitanate, . and tetra-n- butyl orthotitanate.
- Preferred examples thereof include titanium alkoxides. More preferred examples thereof include tetra-n-butyl ' orthotitanate .
- Examples of the organic acid salts of titanium include titanium acetate.
- titanium nitrate examples include titanium nitrate, titanium sulfate, titanium phosphate, and titanium perchlorate.
- titanium halide examples include titanium tetrachloride.
- titanium oxide examples include, titanium dioxide.
- Examples of the "water” used in the method for producing a Ti-MWW precursor include purified water such as distilled water, ion-exchanged water and the like.
- the amount of the water used in the method ' for producing a Ti-MWW precursor is, for example, in the range of 5 to 20 mol and preferably in the range of 10 to 50 mol, based on 1 mol of silicon contained in the silicon- containing compound.
- Examples of the "structure-directing agent" used in the method for producing a Ti-MWW precursor include piperidine, hexamethyleneimine, N, N, N-trimethyl-l-adamantanammonium salts (e.g., ⁇ , ⁇ , ⁇ - trimethyl-l-adamantanammonium hydroxide, N, N, N-trimethyl-1- adamantanammonium iodide, etc.), and octyltrimethylammonium salts (e.g., octyltrimethylammonium hydroxide, octyltrimethylammoriium bromide, etc.) (see, for example, Chemistry Letters 916-917 (2007)).
- Preferred examples thereof include piperidine and hexamethyleneimine. These compounds may be used alone or may be used as a mixture of two or more thereof at an arbitrary ratio.
- the amount of the structure-directing agent used in the method for producing a Ti-MWW precursor is, for example, in the range of 0.1 to 5 mol and preferably, for example, in the range of 0.5 to 3 mol, based on 1 mol of silicon contained in the silicon-containing compound.
- the amount of' the structure-directing agent used in the treatment of a Ti-MWW precursor with a structure- directing agent is, for example, in the range of 0.001 to 100 parts by weight and preferably, for example, in the range of 0.1 to 10 parts by weight, based on 1 part by weight of- the titanosilicate .
- the used amount of the titanosilicate-containing catalyst used for the reaction in the alkylene oxide production method of the present invention varies depending on the type, reaction conditions and the like, and is, for example, in the range of 0.01 to 20 parts by weight, preferably in the range of 0.1 to 10 parts by weight, and more preferably in the range of 0.5 to 8 parts by weight, based on 100 parts by weight of the mixture of an acetonitrile-containing solvent, the palladium-containing catalyst of the present invention, the titanosilicate- containing catalyst, and the raw materials present in the reaction system.
- the used amount of the palladium-containing catalyst of the present invention used for the reaction in the alkylene oxide production method of the present invention varies depending on the type, reaction conditions and the like, and is, for example, in the range of 0.01 to 20 parts by weight, preferably in the range of 0.1 to 10 parts by weight, and more preferably in the range of 0.5 to 8 parts by weight, based on 100 parts by weight of the mixture of an . acetonitrile-containin . g solvent, the palladium- containing catalyst of the present invention, the titanosilicate-containing catalyst, and the raw materials present in the reaction system.
- acetonitrile-containing solvent refers to a solvent containing acetonitrile
- the acetonitrile-containing solvent may contain a solvent other than acetonitrile.
- the solvent other than acetonitrile include organic solvents other ⁇ than acetonitrile and water.
- the weight ratio of the .acetonitrile contained in the acetonitrile-containing solvent is, for example, 50% or more and preferably in the range of 60% to 100%.
- Examples of the "olefin” that is one of the raw materials used for the reaction in the alkylene oxide production method of the present invention include a hydrocarbyl group optionally having a substituent, and compounds in which hydrogen is bound to a carbon atom constituting an olefin double bond.
- hydrocarbyl group include a hydroxyl group, a halogen atom, a carbonyl group, an alkoxycarbonyl group, a cyano group, and a nitro group. Also, examples of the
- hydrocarbyl group include saturated hydrocarbyl groups such as an alkyl group and the like.
- alkenes having 2 to 10 carbon atoms include ethylene, propylene, . butene, pentene, hexene, heptene, octene, nonene, decene, 2-butene, isobutene, 2- pentene, 3-pentene, 2-hexene, 3-hexene, 4-methyl-l-pentene., 2-heptene, 3-heptene, ' 2-octene, 3-octene, 2-nonene, 3- nonene, 2-decene, and 3-decene.
- examples of the "cycloalkenes having 4 to 10 carbon atoms" include cyclobutene, cyclopentene , cyclohexene, cycloheptene , cyclooctene, cyclononene, and cyclodecene.
- ⁇ include alkenes having 2 to 10 carbon atoms. More preferred examples thereof include alkenes -having 2 to 5 ' carbon atoms. Particularly preferred examples thereof include propylene.
- the "olefin” that is one of the raw materials used for the reaction in the alkylene oxide production method of the present invention is "propylene”
- examples of the propylene include those produced by pyrolysis, heavy oil catalytic cracking, or methanol catalytic reforming.
- the propylene may be refined propylene or may be crude propylene obtained without undergoing a refining process or the like.
- Examples of preferred propylene include propylene having a purity of 90% by volume or more and preferably a purity of 95% by volume or more.
- examples of impurities contained in propylene include propane, cyclopropane, methylacetylene, propadiene, butadiene, butanes, butenes, ethylene, ethane, methane, and hydrogen.
- the form of the propylene is, for example, a gaseous form or a liquid form.
- examples of the "liquid form” ' include (i) propylene in liquid form by itself and (ii) a mixed ' liquid obtained by dissolving propylene in an organic solvent or a mixed solvent of an organic solvent and water.
- examples of the "gaseous form” include (i) propylene in gaseous form by itself and (ii) a mixed gas of gaseous propylene and other gas components such as a nitrogen gas and a hydrogen gas.
- the amount of the olefin such as the propylene varies depending on the type, reaction conditions and the like, and is, for example, 0.01 parts by weight or more and preferably 0.1 parts by weight or more, based on 100 parts by weight of the mixture of the acetonitrile-containing solvent, the titanosilicate-containing catalyst, and the raw materials present in the reaction system.
- the content of titanium atoms in the titanosilicate contained in ' the titanosilicate-containing catalyst used in the alkylene oxide production method of the- present invention is, for example, in the range of 0.001 to 0.1 mol and preferably in the range. of 0.005 to 0.05 mol, based on 1 mol of the content of silicon atoms.
- the weight ratio of a noble metal to a titanosilicate is, for example, in the range of 0.01% to 100% by weight- and preferably, for example, in the range of 0.1% to 20% by weight .
- Examples of the solvent used in the alkylene oxide production method of the present invention include the same solvents as those used in the hydrogen peroxide production method of the present invention.
- Preferred examples thereof include a nitrile solvent by itself, and a mixed solvent- .of a nitrile solvent and water. More preferred examples thereof- include a mixed solvent of acetonitrile and water.
- the ratio (weight ratio) of water to an organic solvent when a mixture of water and an organic solvent is used is, -for example, in the range of 90 : 10 to 0.01 : 99.99 and preferably in the range of 50 : 50 to 0.1 : 99.9.
- the "buffer” refers to a compound including an anion and a cation that provide a- pH buffering action.
- the buffer is preferably dissolved in a reaction solution, but the buffer may be previously, contained in the palladium- containing catalyst of the present invention.
- the amount of the buffer used is, for example, in the range of 0.001 to 100 mmol/kg, based on 1 kg of the solvent.
- the reaction temperature in the alkylene oxide production method of the present invention is, for example, in the range of 0°C to 200°C and preferably, for example, in the range of 40°C to 150°C.
- the reaction pressure gauge pressure
- the reaction pressure is, for example, a pressure of 0.1 MPa or more, preferably, for example, a pressure of 1 MPa or more, more preferably, for example, a pressure of 10 MPa or more, and further more preferably, for example, a pressure of 20 MPa or more.
- an ammonium salt, an alkylammonium salt, an- alkyl aryl ammonium salt and the like may be present in the reaction system.
- a buffer is prone to prevent reduction of catalytic activity, further , increase catalytic activity, improve the efficiency in utilizing oxygen and hydrogen, and the like, and thus can be present in the reaction system.
- the "buffer” refers to a compound such as a salt that provides a buffering action to the hydrogen ion concentration of a solution.
- the amount of the buffer is, for example, an amount not less than the solubility of the buffer in the mixture of an acetonitrile-containing solvent, the palladium- containing catalyst of the present invention, and the raw materials present in the reaction system, and preferably, for example, in the range of 0.001 to 100 mmol based on 1 kg of the mixture.
- buffers comprising (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 ion, a nitrate ion, a hydroxide ion, and a carboxylate ion having 1 to 10 carbon atoms; and (2) a cation selected from the group consisting of ammonium, alkylammonium having 1 to 20 carbon atoms, alkyl aryl ammonium having 7 to 20 carbon atoms, alkali metal cations and alkaline-earth metal cations.
- an anion selected from the group consisting of a sulfate ion, a hydrogen sul
- Examples of the "carboxylate ion having 1 to 10 carbon atoms" include an acetate ion, a formate ion, an acetate ion, a propionate ion, a butyrate ion, a valerate ion, a caproate ion, a caprylate ion, a caprate ion, and a benzoate ion.
- alkylammonium having ' 1 to 20 carbon atoms examples include tetramethylammonium, tetraethylammonium, tetra-n-propylammonium, tetra-n—butylammonium, and cetyltrimethylammonium.
- Examples of the "cation selected from the group consisting of alkali metal cations and alkaline-earth metal cations" include a lithium cation, a sodium cation, a potassium cation, a rubidium cation, a cesium cation, a magnesium cation, a calcium cation, a strontium cation, and a barium cation.
- Examples of the preferred buffer include ammonium salts of carboxylic acids having 1 to 10 carbon atoms such as ammonium sulfate, ammonium hydrogen sulfate, ammonium carbonate, ammonium hydrogen carbonate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate, ammonium hydrogen pyrophosphate, ammonium pyrophosphate, ammonium benzoate, ammonium acetate and the like, ammonium salts of inorganic acids such as ammonium chloride, ammonium nitrate and the like, and ammonium salts of carboxylic acids such as ammonium acetate and the like, and preferred examples of ammonium salts include ammonium benzoate, ammonium dihydrogen phosphate, and ' diammonium hydrogen phosphate.
- the reaction in the alkylene oxide production method of the present invention is preferably continuously carried out.
- the raw materials are continuously fed to an epoxidation reaction tank in which the acetonitrile- containing solvent and a catalyst are accommodated, to make the reaction in the alkylene oxide production method of the present invention proceed in the epoxidation reaction tank.
- the mixed gas of oxygen and hydrogen is preferably handled in the coexistence of a dilution gas.
- a dilution gas examples include nitrogen, argon, carbon dioxide, methane, ethane, and propane, preferably nitrogen and propane, and more preferably nitrogen .
- the mixing ratio when ' oxygen, hydrogen, propylene and a dilution gas are handled in the form of a mixture with a case where the dilution gas is a nitrogen gas as an example, the mixing ratio with a - total concentration of hydrogen and propylene of 4.9% by volume or less, an oxygen concentration of 9% by volume or less, and the rest of the nitrogen gas, or with a total concentration of hydrogen and propylene of 50% by volume or more, an oxygen concentration of 50% by volume or less, and the rest of the nitrogen gas is preferable.
- oxygen other than an oxygen gas, air containing oxygen may be usecL
- oxygen gas there can be used a cheap oxygen gas produced by a pressure swing method and a high-purity oxygen gas produced by cryogenic separation or the like.
- the feed amount of oxygen is, for example, in the range of 0.005 to 10 mol and preferably in the range of 0.05 to 5 mol based on 1 mol of the fed propylene.
- Examples of the hydrogen include those obtained by steam-reforming hydrocarbons.
- the purity of hydrogen is, for example, 80% by volume or more and preferably 90% by volume or more.
- the feed amount of hydrogen is, for example, in the range of 0.05 to 10 mol and preferably in the range of 0.05 to 5 mol based on 1 mol of the fed propylene.
- Examples of ' the quinoid compound include compounds represented by the formula (1) :
- R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or, R 1 and R 2 , or R 3 and R 4 are bonded to each other, and form 1 a benzene ring optionally having a substituent or a naphthalene ring optionally having a substituent together with the carbon atoms to which R 1 , R 2 , R 3 and R 4 are each bonded, and X and Y each independently represent an oxygen atom or a NH group.
- ( 1 ) include : ⁇
- R 5 , R 6 , R 7 and R 8 each independently represent a hydrogen atom, a hydroxyl group, or an alkyl group (e.g., an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or the like) .
- Preferred examples of X and Y in the compound represented by the formula (1) include an oxygen atom.
- Examples of the compound represented by the formula (1) include quinone compounds such as benzoquinone, naphthoquinone and the like; anthraquinone ; .
- 2- alkylanthraquinone compounds such as 2-ethylanthraquinone , 2-t-butylanthraquinone, 2-amylanthraquinone , 2- methylanthraquinone, 2-butylanthraquinone, 2-t- amylanthraquinone, 2-isopropylanthraquinone , 2-s- butylanthraquinone, 2-s-amylanthraquinone and the like; polyalkylanthraquinone compounds such as 1 / 3- diethylanthraquinone, 2 , 3-dimethylanthraquinone , 1 / 4- dimethylanthraquinone, 2 , 7-dimethylanthraquinone and the like; .
- polyhydroxyanthraquinone compounds such as 2,6- dihydroxyanthraquinone and the like; p-quinoid compounds such as naphthoquinone, 1 , 4 -phenanthraquinone and the like; and o-quinoid compounds such as 1 , 2-phenanthraquinone, 3,4- phenanthraquinone, 9, 10-phenanthraquinone and the like.
- Preferred examples thereof include anthraquinone, and 2- alkylanthraquinone compounds (in the formula (2), X and Y represent an oxygen atom, R 5 represents an alkyl group, R 6 represents hydrogen, and R 7 and R 8 represent a hydrogen atom) .
- the amount of the quinoid compound used in the reaction in the alkylene oxide production method of the present invention is, for example, in the range of 0.001 to 500 mmol and preferably in the range of 0.01 to 50 mmol, per 1 kg of the solvent.
- the quinoid compound may be prepared by oxidizing a dihydro-form of the quinoid compound in the reaction system using oxygen or the like.
- a compound obtained by hydrogenating a quinoid compound such as 9,10- anthracenediol or hydroquinone may be added to a liquid phase, thereby being oxidized by oxygen in the reaction system to generate and use a quinoid compound.
- dihydro-form of the quinoid compound examples include a compound represented by the formula (3) that is a dihydro-form of the compound represented by the formula (1) :
- R 1 , R 2 , R 3 , R 4 , X and Y represent the same as defined above, and
- preferred ' compounds include dihydro-forms corresponding to the preferred quinoid compounds.
- preferred examples of X and Y in the compounds represented by the formula (3) and the compounds represented by the formula (4) include dihydro-forms corresponding to the preferred quinoid compounds.
- the palladium-containing catalyst of the present invention may be previously contacted with a carbon-supplying compound having 4 or less carbon atoms that is gaseous ⁇ under conditions of ordinary temperature and pressure.
- Any method may be used for contacting the %; palladium- containing catalyst of the present invention with a carbon- supplying compound having 4 or less carbon atoms that is gaseous under conditions of ordinary temperature and pressure, and examples thereof include (1) a dry method in which the palladium-containing catalyst of the present invention is filled in a reactor, then the compound is circulated while retaining heat, and (2) a wet method in which the palladium-containing catalyst of the present invention suspended in a solvent or the like in a sealed container such as an autoclave is mixed together with the compound and retained at the same temperature, or the compound is circulated by bubbling or the like.
- Examples of the "carbon-supplying compound having 4 or less carbon atoms that is gaseous under conditions of ordinary temperature and pressure" used in the step of recovering and regenerating catalytic activity include carbon monoxide, methane, ethane, propane, butane, ethylene, propylene, butene, and butadiene. Preferred examples thereof include propylene and the like.
- the temperature of the step of recovering and regenerating catalytic activity is, for example, in the range of 25°C to 500°C, preferably, for example, in the range of 50°C to 300°C, and more preferably, for example, in the range of 100°C to 200°C.
- the pressure of the step of recovering and regenerating catalytic activity is, for example, in the range of 0 to 10 MPa by a gauge pressure.
- the lower limit of the contact time of the step of recovering and regenerating catalytic activity is, for example, 10 minutes, preferably, for example, 2 hours, more preferably, for example,- 10 hours, and further preferably, for example, 12 hours.
- the upper limit of the contact time of the step- of recovering and regenerating catalytic activity is, for example, 120 hours, preferably, for example, 72 hours, more preferably, for example, 30 hours, and further preferably, for example, 24 hours.
- the palladium-containing composition comprising palladium and a carrier may be in the state of being mixed together with the' titanosilicate- containing catalyst set forth below.
- the palladium-containing catalyst of the present invention can be used as a catalyst for producing hydrogen peroxide from oxygen and hydrogen.
- the method for producing hydrogen peroxide will be described.
- the method for producing hydrogen peroxide utilizing the palladium-containing catalyst of the present invention includes the step of reacting oxygen and hydrogen in the presence of the palladium-containing catalyst of the present invention.
- Oxygen and hydrogen are necessary in the above step. Any source of supply of oxygen and hydrogen can be used, and examples of the source of supply of oxygen include a high-purity oxygen gas produced by cryogenic separation or the like, a cheap oxygen gas produced by a pressure swing method, and air.
- the molar ratio of hydrogen to oxygen (H 2 : 0 2 ) used in the above step is, for example, in the range of 1 : 50 to 50 : 1, preferably, in the range of.1 : 10 to 10 : 1, and more preferably, for example, in the range of 1 : 5 to 5 : 1.
- an inert gas can be used for dilution in the above step.
- an appropriate inert gas include helium, argon, nitrogen, and carbon dioxide. Preferable examples thereof include nitrogen.
- the inert gas is made .present in the reaction system, whereby the levels of oxygen and hydrogen in the reaction mixture . can be advantageously kept out of explosion limit.
- the above step may be carried out in the presence of a solvent.
- Examples of the solvent used in the above step include water, organic solvents, and mixtures thereof.
- Examples of the organic solvent include alcohol solvents having 1 to 12 carbon atoms such as methanol, ethanol, isopropyl alcohol, t-butyl alcohol, glycerin and the like, ketone solvents having 3 to 12 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone , cyclohexanone and the like, nitrile solvents having 2 to 12 carbon atoms such .
- ether solvents such as diethyl ether, tetrahydrofuran, propylene glycol dimethyl ether and the like, aliphatic hydrocarbon solvents having 5 to 12 carbon atoms such as pentane, cyclopentane, hexane, cyclohexane, ethylene dichloride, chloroform and the like, aromatic hydrocarbon solvents having 6 to 12 carbon atoms such as benzene, toluene, xylene, chlorobenzene and the like, ester solvents such as ethyl acetate, butyl acetate, propylene glycol diacetate and the like, and mixtures thereof.
- a nitrile solvent alone or an alcohol solvent alone and mixed solvents of a nitrile solvent or an alcohol solvent and water. More preferable examples thereof include mixed
- the ratio (weight ratio) of water to an organic solvent when a mixture of water and an organic solvent is used is, for example, in the range of 90 : 10 to 0.01 : 99.99 and preferably in the range of 50 : 50 to 0.1 : 99.9.
- the method for producing hydrogen peroxide can be carried out in various modes such as continuous flow, semi- batch and batch, and is preferably carried out in a continuous flow mode.
- the palladium-containing catalyst of the present invention can be used in a slurry or a fixed bed.
- the reaction temperature in the method for producing hydrogen peroxide is, for example, in the range of 0°C to 100°C and preferably,, for example, in the range of 20°C to 60°C.
- the lower limit of the reaction pressure in the method for producing hydrogen peroxide is, for example, 0.1 MPa and preferably, for example, 1 MPa.
- the upper limit is, for example, 20 MPa and preferably, for example, 10 MPa.
- Examples of the acid used in the method for producing hydrogen peroxide include inorganic acids such as nitric acid, sulfuric acid, phosphoric acid, hydrochloric acid, hydrobromic acid and the like, and organic acids such as pyrophosphoric acid, acetic acid and the like.
- the amount of the acid used in the method for producing hydrogen peroxide is, for example, in the range of 0.1 to 1000 parts per million by weight, preferably in the range of 0.1 to 100 parts per million by weight, and more preferably in the range of 1 to 10 parts per million by weight, based on 1 part by weight of the reaction mixture .
- the titanosilicate-containing catalyst was determined by a sample weighted to 10 to 20 mg based on oxygen circulating combustion and TCD detection systems using SUMIGRAPH (manufactured by " Sumika Chemical Analysis Service, Ltd.) ' (reaction temperature of 850°C, reduction temperature of 600°C) .
- SUMIGRAPH manufactured by " Sumika Chemical Analysis Service, Ltd.
- a column packed with porous polymer beads was used as a separation column, and acetanilide was used as a standard sample.
- x-Ray diffraction patterns of the palladium-containing catalyst of the present invention and the palladium- containing composition were measured by using the following device under the following measurement conditions.
- UV-Vis Ultraviolet Visible Absorption Spectrum
- the titanosilicate-containing catalyst of the present invention was thoroughly pulverized in an agate mortar and further formed into pellets (7 mm ⁇ ) ) to prepare a sample for measurement.
- An ultraviolet visible absorption spectrum of the resulting sample for measurement was measured by using the following device under the following measurement conditions.
- Diffusion reflector Pulraying Mantis manufactured by HARRICK
- a I L recovery flask was charged with 20 g of zirconium oxide (DAIICHI KIGENSO KAGAKU KOGYO CO., LTD., trade name: RSC-100) and 300 mL of water, and the substances were stirred at 20°C under air.
- To this suspension was slowly added dropwise 100 mL of an aqueous solution containing 1.90 mmol of Pd colloid (manufactured by JGC Catalysts and Chemicals Ltd., see JP-A 2002-294301, Example 1 and the like) at room temperature under air. After dropwise addition, the suspension was further stirred at room temperature under air for 8 hours.
- the concentration of palladium contained in the palladiumcontaining composition A was 1.14% by weight in terms of a palladium metal (an analysis value based on an ICP emission analysis) .
- a glass firing tube was filled, with 10 g of the palladium-containing composition A obtained in Reference Control Example 1, and a 100% ethylene gas was passed on the solid at 25°C at a flow rate of 10 mL/minute. Further, the temperature of the content was increased to 200°C over 2 hours under a flow of ethylene gas, and the content was further kept at the same temperature for 6 hours. After completion, the gas was immediately replaced with a nitrogen gas at 100 mL/minute, and the content was allowed to cool at room temperature to obtain the palladium- containing catalyst A of the present invention.
- the concentration of palladium contained in the palladium- containing catalyst A was 1.14% by weight in terms of a palladium metal (an analysis value based on an ICP emission analysis) .
- a I L recovery flask was charged with 3 g of activated carbon (manufactured by Wako Pure Chemical Industries, Ltd., trade name: activated carbon, powder) and 225 mL of acetonitrile (manufactured by NACALAI TESQUE, INC.), and the substances were stirred at 20°C under air. ' To the resulting suspension was slowly added dropwise 35 mL of acetonitrile containing 0.0647 g of palladium acetate (manufactured by Aldrich) at room temperature under air.
- the concentration of palladium contained in the palladium- containing composition B was 1.01% by weight in terms of a palladium metal (an analysis value based on an ICP emission analysis) .
- a glass firing tube was filled with 1.43 g of the palladium-containing composition B obtained in Reference Control Example 2, and a 100% ethylene gas was passed on the solid at 25°C at a flow rate of 10 mL/minute. Further, the temperature of .the content was increased to 200°C over 2 hours under a flow of ethylene gas, and the content was further kept at the same temperature for 6 hours. After completion, the gas was immediately replaced with a nitrogen gas at 100 mL/minute, and the content was allowed to cool at room temperature to obtain the palladium- containing catalyst B of the present invention.
- the concentration of palladium contained in the palladium- containing catalyst B was 1.01% by weight in terms of a palladium metal (an analysis value based on an ICP emission analysis ) .
- x-ray diffraction patterns of the palladium- containing catalyst B of the present invention obtained above and the palladium-containing composition B obtained in Reference Control Example 2 are shown in Fig. 1. It is obvious that the palladium-containing catalyst B of the present invention has a value of crystal face spacing of a (111) face of a palladium metal of 2.270 A or more.
- the temperature of the content in the autoclave was increased to 150°C over 8 hours while- ' rotating the anchor type stirring ⁇ blades .
- the temperature was kept at the same temperature for 120 hours, and the content in the autoclave, was cooled to obtain a suspended solution as a- reactant.
- the resulting suspended solution was filtrated, then the product on the filter was washed with ion-exchanged water until the washed filtrate had a pH around 10.
- a metal container with glass lining 200 L, equipped with a jacket and a reflux tube
- 3 kg of the resulting layered compound 158. kg of a 2 M aqueous nitric acid solution and 0.38 kg of TBOT.
- the jacket temperature of the container was increased to 115°C, kept at the same temperature for 9 hours, and further increased to a jacket temperature of 124°C, and the content was refluxed at the same temperature for 7 hours. After reflux, heating of the jacket was stopped to cool the content to room temperature.
- the resulting content was filtrated, then the product on the filter was washed with ion-exchanged water until the washed filtrate had a pH around 5.
- the product on the filter after washing was dried (drying temperature: 80°C) until mass decrease was not observed to obtain a white solid, and furthermore, the white solid, was pulverized to obtain a white powder.
- a part of the resulting white powder was filled in a glass tube, and the temperature was increased from room temperature to 530°C over 2 hours under a 6 L (0°C, in terms of 1 atm) /hour of nitrogen gas stream and kept at the same temperature for 2 hours. Thereafter , . the nitrogen gas stream was replaced with a 6 L (0°C, in terms of 1 atm) /hour of air stream, and the temperature was kept at 530°C for.4 hours .
- a 1.5 L autoclave was charged with 150 g of the white powder fired as described above, 300 g of pyperidine, and 600 g of ion-exchanged water in an air atmosphere at room temperature. The charged content was dissolved under the same atmosphere at the same temperature while stirring and then the mixture was further aged for 1.5 hours. The aged solution was transferred to a 1.5 L autoclave equipped with one anchor type stirring blade, and then the autoclave was sealed. An air-tight test was carried out at 1.0 MPa (gauge pressure) using an argon gas, then the autoclave was depressurized and again sealed.
- the temperature of ⁇ the content in the autoclave was increased to 150°C over 4 hours while rotating the anchor type stirring blade. Thereafter, the content was heated for 1 day so as to keep a temperature in the range of from 150 to 170°C with 160°C as a guide.
- the resulting suspended solution was filtrated, then the product on the filter was washed with ion-exchanged water heated to about 100°C until the washed filtrate had a pH around 9 to obtain a white solid.
- the resulting white solid was sufficiently dried at 150°C using a vacuum drier and then pulverized to obtain a white powder.
- the white powder had a Ti content of 2.06% by mass, a Si content of 36.3% by mass, and a N content of 0.91% by weight.
- an x-ray diffraction pattern of the white powder was confirmed to have peaks of 12.4 d/A, 11.2 d/A, 9.0 d/A, 6.2 d/A, 3.9 d/A, and 3.4 d/A.
- the white powder was proved to show the maximum absorption peak at 213 nm for an ultraviolet visible absorption spectrum in a wavelength range of 200 to 400 nm, and was confirmed to be a Ti- WW precursor.
- a 0.5 L-volume autoclave was charged with 1.14 g of the titanosilicate-containing catalyst obtained in Example 3, 0.53 g of the palladium-containing catalyst A of the present invention obtained in Example 1 and 117 g of a solution of water/acetonitrile at a ratio of 30/70 (weight ratio) , and then the autoclave was sealed.
- 3.8/3.1/93.0/86.9/6.3 was fed to the autoclave at a rate of 107 NL/h, - and 0.7 mmol/kg of anthraquinone and a solution of water containing 3.0 mmol/kg of diammonium hydrogen phosphate/acetonitrile at a ratio of 30/70 (weight ratio) were fed to the autoclave at a rate of 117 g/h, and then the reaction mixture was taken out through a filter from the autoclave, to carry out a continuous reaction.
- the conditions of the continuous reaction were a temperature of 50°C, a pressure of 0.8 MPa (gauge pressure) and a residence time of 60 minutes.
- Example 4 The same procedures as in Example 4 were carried out except for using the palladium-containing composition obtained in Reference Control Example 1 in place of the palladium-containing catalyst A of the present invention, to produce propylene oxide. Sampling was performed at 2 hours and 5 hours after the initiation of the reaction, and the sampled liquid and gas phases were analyzed by using gas chromatography. The results showed that the production amount of propylene oxide was 77.5 mmol/g (palladium supporter) /h (average of the results after 3 and 5 hours).
- Example 4 The same procedures as in Example 4 were carried out except for using the palladium-containing catalyst B obtained in Example 2 in place of the palladium-containing catalyst A of the present invention, to produce propylene oxide. Sampling was performed at 2 hours and 5 hours after the initiation of the reaction, and the sampled liquid and gas phases were analyzed by using gas chromatography. The results showed that the production amount of propylene oxide was 60.4 mmol/g (palladium supporter) /h (average of the results after 3 and 5 hours) .
- Example 4 The same procedures as in Example 4 were carried out except for using the palladium-containing composition B obtained in Reference Control Example 2 in place of the palladium-containing catalyst A of the present invention, to produce propylene oxide.
- Sampling was performed at 2 hours and 5. hours after the initiation of the reaction, and the sampled liquid and gas phases were analyzed by using gas chromatography. The results showed that the production amount of propylene oxide was 56.8 mmol/g (palladium supporter) /h (average of the results after 3 and 5 hours) .
- a 0.5 L-volume autoclave is charged with 1.14 g of the titanosilicate-containing catalyst obtained in Example 3, 0.53 g of the palladium-containing catalyst A of the present invention obtained in Example 1 or the palladium- containing composition A obtained in Reference Control Example and 117 g of a solution of water/acetonitrile at a ratio of 30/70 (weight ratio) , and then the autoclave is sealed.
- 3.8/3.1/93.0/86.9/6.3 is fed to the autoclave at a rate of 107 NL/h, and 0.7 mmol/kg of anthraquinone and a solution of water containing 3.0 mmol/kg of diammonium hydrogen phosphate/acet ' bnitrile at a ratio of 30/70 (weight ratio) are fed to the autoclave at a rate of 117 g/h, then the reaction mixture is taken out through a filter from the autoclave, to carry out a continuous reaction.
- the conditions of the continuous reaction are a temperature of
- the conditions of the continuous reaction are a temperature of 40°C, a pressure of 0.8 MPa (gauge pressure.) and a residence time of 45 minutes, to produce hydrogen peroxide.
- the present invention by using together with a titanosilicate-containing catalyst, it is possible to provide a catalyst that results in providing a high production amount of an alkylene oxide in a reaction for producing an alkylene oxide from oxygen, hydrogen and an olefin .
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Epoxy Compounds (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
Un objet de la présente invention est de pourvoir à un procédé de production et à un nouveau catalyseur et autre utilisé pour ce faire qui permettent d'obtenir un rendement élevé d'oxyde d'alkylène dans une réaction de production d'oxyde d'alkylène à partir d'oxygène, d'hydrogène et d'une oléfine faisant également appel à un catalyseur contenant un silicate de titane. Cet objet peut être atteint par un procédé de production d'oxyde d'alkylène selon l'invention, comprenant l'étape de mise en réaction de l'oxygène, de l'hydrogène et d'une oléfine, en présence d'un catalyseur contenant du palladium traité par un gaz carboné qui est obtenu par mise en contact d'une composition contenant du palladium comprenant du palladium et un véhicule avec un composé choisi dans le groupe constitué par l'acétylène, l'éthylène et le monoxyde de carbone. Un catalyseur contenant un silicate de titane, et un catalyseur contenant du palladium traité par un gaz carboné et autre utilisés pour ce faire sont également décrits.
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JP2011-141538 | 2011-06-27 | ||
JP2011141538A JP2013006806A (ja) | 2011-06-27 | 2011-06-27 | アルキレンオキサイドの製造方法及びそれに用いられるパラジウム含有触媒 |
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PCT/JP2012/066634 WO2013002355A1 (fr) | 2011-06-27 | 2012-06-22 | Procédé de production d'un oxyde d'alkylène et catalyseur contenant du palladium utilisé pour ce faire |
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JP (1) | JP2013006806A (fr) |
BE (1) | BE1020163A3 (fr) |
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WO2006049698A1 (fr) * | 2004-10-29 | 2006-05-11 | Lyondell Chemical Technology, L.P. | Époxydation catalytique modulée par le monoxyde de carbone, le méthylacétylène ou le propadiène |
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- 2011-06-27 JP JP2011141538A patent/JP2013006806A/ja not_active Withdrawn
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- 2012-06-26 BE BE2012/0431A patent/BE1020163A3/nl active
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NL1039702A (nl) | 2013-01-02 |
JP2013006806A (ja) | 2013-01-10 |
BE1020163A3 (nl) | 2013-05-07 |
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