CN101583418A - 无机氧化物挤出物 - Google Patents
无机氧化物挤出物 Download PDFInfo
- Publication number
- CN101583418A CN101583418A CNA2007800472829A CN200780047282A CN101583418A CN 101583418 A CN101583418 A CN 101583418A CN A2007800472829 A CNA2007800472829 A CN A2007800472829A CN 200780047282 A CN200780047282 A CN 200780047282A CN 101583418 A CN101583418 A CN 101583418A
- Authority
- CN
- China
- Prior art keywords
- extrudate
- inorganic oxide
- catalyst
- burnt
- zeolite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052809 inorganic oxide Inorganic materials 0.000 title claims abstract description 32
- 229920000642 polymer Polymers 0.000 claims abstract description 70
- 239000003054 catalyst Substances 0.000 claims abstract description 64
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 53
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000001301 oxygen Substances 0.000 claims abstract description 36
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 36
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000010457 zeolite Substances 0.000 claims abstract description 34
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 31
- 239000010931 gold Substances 0.000 claims abstract description 22
- 229910052737 gold Inorganic materials 0.000 claims abstract description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000005977 Ethylene Substances 0.000 claims abstract description 13
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 12
- 150000003624 transition metals Chemical class 0.000 claims abstract description 12
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 9
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 32
- 229920000570 polyether Polymers 0.000 claims description 29
- 239000000178 monomer Substances 0.000 claims description 25
- 238000007254 oxidation reaction Methods 0.000 claims description 23
- 239000004408 titanium dioxide Substances 0.000 claims description 23
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 22
- 230000003647 oxidation Effects 0.000 claims description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 230000003252 repetitive effect Effects 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 16
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract 3
- 238000010348 incorporation Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 33
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 26
- -1 alkoxy silane Chemical compound 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 238000001125 extrusion Methods 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 15
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 229910052763 palladium Inorganic materials 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 239000003570 air Substances 0.000 description 10
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 10
- 150000001336 alkenes Chemical class 0.000 description 9
- 239000002808 molecular sieve Substances 0.000 description 9
- 229920001451 polypropylene glycol Polymers 0.000 description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 229920005604 random copolymer Polymers 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 7
- 239000002202 Polyethylene glycol Substances 0.000 description 7
- 239000000908 ammonium hydroxide Substances 0.000 description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- 150000007942 carboxylates Chemical class 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 229960002163 hydrogen peroxide Drugs 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000004927 clay Substances 0.000 description 5
- 229910052570 clay Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 150000002576 ketones Chemical class 0.000 description 5
- 239000011976 maleic acid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 239000002253 acid Substances 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000006053 organic reaction Methods 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 229910004339 Ti-Si Inorganic materials 0.000 description 3
- 229910010978 Ti—Si Inorganic materials 0.000 description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 125000005210 alkyl ammonium group Chemical group 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- CVEPFOUZABPRMK-UHFFFAOYSA-N 2-methylprop-2-enoic acid;styrene Chemical compound CC(=C)C(O)=O.C=CC1=CC=CC=C1 CVEPFOUZABPRMK-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 102220500397 Neutral and basic amino acid transport protein rBAT_M41T_mutation Human genes 0.000 description 2
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 229960004217 benzyl alcohol Drugs 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920003086 cellulose ether Polymers 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 2
- 229940018557 citraconic acid Drugs 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 239000012229 microporous material Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 150000002924 oxiranes Chemical group 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 150000003568 thioethers Chemical group 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 241000611009 Nematalosa come Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- QFHMNFAUXJAINK-UHFFFAOYSA-N [1-(carbamoylamino)-2-methylpropyl]urea Chemical group NC(=O)NC(C(C)C)NC(N)=O QFHMNFAUXJAINK-UHFFFAOYSA-N 0.000 description 1
- PWQLZSHJRGGLBC-UHFFFAOYSA-N acetonitrile;carbon dioxide Chemical compound CC#N.O=C=O PWQLZSHJRGGLBC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229960003753 nitric oxide Drugs 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920001308 poly(aminoacid) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- OSFBJERFMQCEQY-UHFFFAOYSA-N propylidene Chemical group [CH]CC OSFBJERFMQCEQY-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229960004029 silicic acid Drugs 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 210000000689 upper leg Anatomy 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Classifications
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62625—Wet mixtures
- C04B35/62635—Mixing details
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
- C04B35/6265—Thermal treatment of powders or mixtures thereof other than sintering involving reduction or oxidation
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
- C04B35/62655—Drying, e.g. freeze-drying, spray-drying, microwave or supercritical drying
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
- C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B35/63424—Polyacrylates; Polymethacrylates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
- C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B35/63488—Polyethers, e.g. alkylphenol polyglycolether, polyethylene glycol [PEG], polyethylene oxide [PEO]
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
- C04B38/063—Preparing or treating the raw materials individually or as batches
- C04B38/0635—Compounding ingredients
- C04B38/0645—Burnable, meltable, sublimable materials
- C04B38/067—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
- C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
- C07C67/055—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation in the presence of platinum group metals or their compounds
-
- 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
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0045—Polymers chosen for their physico-chemical characteristics
- C04B2103/0059—Graft (co-)polymers
- C04B2103/006—Comb polymers
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00034—Physico-chemical characteristics of the mixtures
- C04B2111/00129—Extrudable mixtures
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/0081—Uses not provided for elsewhere in C04B2111/00 as catalysts or catalyst carriers
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3289—Noble metal oxides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/40—Metallic constituents or additives not added as binding phase
- C04B2235/408—Noble metals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/602—Making the green bodies or pre-forms by moulding
- C04B2235/6021—Extrusion moulding
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/72—Products characterised by the absence or the low content of specific components, e.g. alkali metal free alumina ceramics
- C04B2235/721—Carbon content
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明公开了一种包含无机氧化物和梳形支化聚合物的挤出物。煅烧过的挤出物是有用的催化剂或催化剂载体。利用本发明煅烧过的二氧化钛挤出物制备的钯－金催化剂可用于从乙烯、乙酸和氧气或含氧气体制备乙酸乙烯酯。使用本发明煅烧过的过渡金属沸石挤出物作为利用过氧化氢来氧化有机化合物中的催化剂。加入梳形支化聚合物提高了无机氧化物挤出物的机械性能。
Description
发明领域
本发明涉及包含无机氧化物和梳形支化聚合物的挤出物。
发明背景
无机氧化物挤出物是有用的催化剂或催化剂载体(Stiles，A.B.，“Supports Other Than Alumina(氧化铝以外的载体)，”CatalystSupports and Supported Catalysts(催化剂载体和带载体的催化剂)(1987)Butterworths Publishers，57-85页)。通常使用挤出助剂如聚醚多元醇、聚丙烯酸、纤维素或淀粉来促进挤出并提高挤出物的物理和/或机械性能(参见例如，美国专利4,039,474、4,888,319、4,119,474和6,706,658)。尽管进行了许多尝试，但仍需要新方法来制备具有提高的物理和/或机械性能的挤出物。
发明概述
本发明为包含无机氧化物和梳形支化聚合物的挤出物。煅烧过的挤出物用作催化剂或催化剂载体。本发明还包括用于制备乙酸乙烯酯的方法，所述方法包括在用煅烧过的二氧化钛挤出物制备的钯-金催化剂存在下使得乙烯、乙酸、和氧气或含氧气的气体反应。本发明还包括氧化方法，所述氧化方法包括在煅烧过的过渡金属沸石挤出物存在下使得有机化合物与过氧化氢反应。令人惊奇地，并入梳形支化聚合物提高了无机氧化物挤出物的机械性能。
发明详述
在一个方面中，本发明为包含无机氧化物和梳形支化聚合物的挤出物。所述无机氧化物为金属氧化物、非金属氧化物、混合氧化物等、及其混合物。它们包括例如二氧化硅、氧化铝、二氧化钛、氧化锆、氧化镁、二氧化硅-氧化铝、二氧化硅-二氧化钛、二氧化硅-氧化镁、沸石、粘土等、及其混合物。适合的二氧化硅包括例如二氧化硅凝胶、沉淀二氧化硅和热解硅石(参见Walter H.Waddell，“Silica，Amorphous，”(二氧化硅，无定形)Kirk-Othmer Encyclopedia ofChemical Technology online edition(Kirk-Other化学技术百科全书在线版)，2006)。适合的二氧化钛为金红石或锐钛矿、或两种相态的混合物。可通过氯化物法、硫酸盐法、水热法或四氯化钛火焰水解法来制造二氧化钛(参见Egerton，T.A.，Kirk-Othmer Encyclopedia ofChemical Technology(Kirk-Othmer化学技术百科全书)中的“TitaniumCompounds，Inorganic”(钛化合物，无机)，在线版，2006)。
无机氧化物还包括水合无机氧化物(或氢氧化物)。例如，当由无机氧化物前体(例如四烷氧基硅烷)形成无机氧化物(例如二氧化硅)时，形成水合无机氧化物(例如，水合氧化硅或氢氧化硅)。可以使用无机氧化物前体如金属氢氧化物、烷氧基硅烷、烷氧基钛酸酯(alkoxytitanates)、烷氧基铝酸酯(alkoxyaluminates)或烷氧基锆酸酯(alkoxyzirconates)。它们包括例如四烷氧基硅烷、四烷氧基钛、四烷氧基锆、三烷氧基铝。这些前体在形成挤出物期间转变成无机氧化物或水合无机氧化物(或氢氧化物)。
适合的无机氧化物包括中孔性分子筛如MCM-41、MCM-48；参见Vartuli，J.C.等人，“Potential Applications for M41S TypeMesoporous Molecular Sieves(M41S型中孔性分子筛的潜在应用)”，Studies in Surface Science and Catalysis：Mesoporous MolecularSieves(表面科学和催化剂研究：中孔性分子筛)(1998)ElsevierScience B.V.13-22页。
能够在“Chapter 2.Clay as Potential Catalyst Material(第二章.作为潜在催化剂材料的粘土)，”Zeolite，Clay，and HeteropolyAcid in Organic Reactions(有机反应中的沸石、粘土和杂环多元酸)(1992)Kodansha Ltd.(讲谈社)，东京，49-98页中发现适合的粘土。
沸石为具有明确定义的结构的多微孔结晶固体。通常它们除了氧之外，还包含一种以上的Si、Ge、Al、B或P等。在世界的许多地方许多沸石作为矿石天然存在且被广泛开采。其他的是为了商业上的特殊用途而合成和制备的。沸石有能力充当化学反应的催化剂，所述化学反应大部分在沸石内部空腔内发生。在许多有机反应中使用酸性沸石催化剂，所述有机反应包括裂化、异构化和烷基化；参见W.O.Haag，“Catalysis by Zeolites-Science and Technology(沸石催化-科学与技术)，”Zeolites and Related Microporous Materials：State of Art1994(沸石和相关多微孔材料：技术状况1994)(1994)ElsevierScience B.V.1375-94页。
过渡金属沸石(在它们的骨架中包含过渡金属的沸石)为用于许多有机转化如氧化反应的有用催化剂(参见New Developments inSelective Oxidation(选择性氧化的新进展)，33-38页)。过渡金属为3-12族的元素。所述过渡金属的第一行为从Sc到Zn的元素。优选的过渡金属为Ti、V、Mn、Fe、Co、Cr、Zr、Nb、Mo和W。当将过渡金属沸石用于氧化反应时，尤其优选Ti、V、Mo和W。最优选Ti。优选的钛沸石为钛硅酸盐(titanosilicate)。优选地，在它们的晶格骨架中不包含除钛、硅和氧之外的元素(参见R.Szostak，“Non-aluminosilicate Molecular Sieves(非铝硅酸盐分子筛)”，Molecular Sieves：Principles of Synthesis and Identification(分子筛：合成和表征原理)(1989)Van Nostrand Reinhold，205-82页)。在晶格中可存在少量杂质如硼、铁、铝、钠、磷、铜等、及其混合物。所述杂质的量优选少于0.5wt％，更优选少于0.1wt％。优选的钛硅酸盐通常具有对应下列经验式的组成：xTiO2·(1-x)SiO2，其中x为0.0001～0.5000。更优选地，x的值为0.01～0.125。沸石的晶格骨架中Si∶Ti的摩尔比优选为9.5∶1～99∶1，最优选9.5∶1～60∶1。尤其优选的钛沸石为钛硅沸石(titanium silicalites)(参见Catal.Rev.-Sci.Eng.，39(3)(1997)209)。这些物质的实例包括TS-1(钛硅沸石-1，一种具有类似于ZSM-5铝硅酸盐的MFI拓扑的钛硅沸石)、TS-2(具有类似于ZSM-11铝硅酸盐的MEL拓扑)和TS-3(如比利时专利1,001,038中所述)。具有与沸石β、丝光沸石和ZSM-12同晶型骨架结构的钛沸石也适于使用。最优选TS-1。
通常在有机模板试剂存在下制备沸石(参见例如美国专利6,849,570)。适合的模板试剂包括烷基胺、季铵化合物等。当沸石结晶时，在其晶体结构内通常包含有机模板试剂。可以将含模板试剂的沸石用于本发明中。优选使用不含模板的沸石。
当挤出物包含两种或两种以上无机氧化物的混合物时，可以把一种或多种氧化物用作粘合剂。粘合剂为本领域内所熟知的。例如，在沸石-二氧化硅挤出物中，沸石充当催化剂的活性组分而二氧化硅粘结并增强所述挤出物。
挤出物包含梳形支化聚合物。梳形支化聚合物包括聚合物骨架、羧基侧链和聚醚侧链。所述羧基侧链包含羧酸、羧酸盐或两者的混合物。优选的羧基侧链为羧酸基(-COOH)。
所述聚醚侧链优选由下式表示：
其中，n为3～500，更优选10～250；R为含碳原子的有机部分，所述碳原子通过单共价键连接到氧原子上。所述聚醚可包括两种或多种含不同R部分的不同重复单元。R可以为芳族基或脂族基。优选饱和脂族基。特别优选的是亚烷基，例如亚乙基、亚丙基、1，4-亚丁基、亚异丙基、或亚异丁基；最优选的是亚乙基和亚丙基。优选的聚醚因此是聚氧化烯烃，例如聚氧乙烯、聚氧丙烯、和氧化丙烯/氧化乙烯共聚物。
所述聚醚侧链可以通过任意适当的化学键连接在梳形支化聚合物的骨架上。所述键可以是酯基、酰胺基、酰亚胺基、醚基、胺基或硫醚官能团，或者碳-碳键。优选地，在通过聚合丙烯酸和聚醚丙烯酸酯大分子单体(见以下，还见美国专利序号：6034208)制备梳形支化聚合物和通过将聚醚胺接枝到聚丙烯酸上制备聚合物时(见例如美国专利5393343)，所述聚醚侧链通过酯基、酰胺基、或酰亚胺官能团连接在所述聚合物骨架上，
梳形支化聚合物中的羧基侧链与聚醚侧链的摩尔比不是关键的。一般，所述摩尔比在1∶1～200∶1范围内。优选地，该比值在2∶1～50∶1范围内。
优选的梳形支化聚合物包含乙烯型羧酸单体和聚醚大分子单体的重复单元。乙烯型羧酸单体包含碳-碳双键和羧基，例如羧酸、羧酸盐、或羧酸酐。适合的乙烯型羧酸单体含有3～10个碳原子。实例包括丙烯酸、甲基丙烯酸、巴豆酸、乙烯基乙酸、4-戊酸、马来酸、马来酸酐、衣康酸、中康酸、富马酸、柠康酸、和它们的混合物。优选地，所述乙烯型羧酸单体是丙烯酸类，例如丙烯酸、甲基丙烯酸、马来酸、马来酸酐、富马酸和它们的混合物。更优选地，它是丙烯酸、甲基丙烯酸、或二者的混合物。
适合的聚醚大分子单体具有聚醚链和碳-碳双键，该双键可以在聚醚链的末端或在聚醚链内。实例包括聚醚单丙烯酸酯、聚醚单甲基丙烯酸酯、聚醚单烯丙基醚、聚醚单马来酸酯和聚醚单富马酸酯。所述大分子单体中的聚醚部分可以是具有数均分子量(Mn)在约500～约10000范围内的烯化氧聚合物。适合的烯化氧包括环氧乙烷、环氧丙烷、1，2-环氧丁烷等，和它们的混合物。所述聚醚大分子单体优选具有0～5个羟基。所述聚醚大分子单体可以是直链或支链聚合物、均聚物、或共聚物、和无规共聚物或嵌段共聚物。
聚醚大分子单体的实例是聚丙二醇丙烯酸酯或聚丙二醇甲基丙烯酸酯、聚乙二醇丙烯酸酯或聚乙二醇甲基丙烯酸酯、聚(1，4-丁二醇)丙烯酸酯或聚(1，4-丁二醇)甲基丙烯酸酯、聚乙二醇甲醚丙烯酸酯或聚乙二醇甲醚甲基丙烯酸酯、氧化乙烯和氧化丙烯嵌段或无规共聚物的丙烯酸酯或甲基丙烯酸酯、聚丙二醇烯丙基醚、聚乙二醇烯丙基醚、聚丙二醇马来酸单酯、等和它们的混合物。优选的聚醚大分子单体是聚丙二醇丙烯酸酯或聚丙二醇甲基丙烯酸酯、聚乙二醇丙烯酸酯或聚乙二醇甲基丙烯酸酯、氧化乙烯和氧化丙烯共聚物的丙烯酸酯或甲基丙烯酸酯。更优选的是氧化乙烯/氧化丙烯共聚物的丙烯酸酯或甲基丙烯酸酯。
可以通过含有羟基或羧酸基的烯属底物与一个或多个烯化氧在美国专利序号6034208中描述的催化剂存在下的烷氧基化反应制备所述聚醚大分子单体。在另一实施例中，通过四氢呋喃在烯丙醇和碱催化剂(例如氢氧化钾或氢氧化钠)存在下的聚合反应制备聚(1，4-丁二醇)烯丙基醚。还可以使用固体碱催化剂(见例如美国专利序号6680406，6455711和7074944)。
乙烯型羧酸单体与聚醚大分子单体之比通常在1∶99～99∶1(重量比)范围内。优选的范围是5∶95～75∶25。
很多方法可以用来制备梳形支化聚合物。一种方法涉及乙烯型羧酸单体与聚醚大分子单体的共聚反应(见美国专利序号6034208和6815513)。优选地，所述单体是丙烯酸类。更优选地，所述单体是丙烯酸、甲基丙烯酸或二者的混合物。
当通过乙烯型羧酸单体和聚醚大分子单体的共聚反应制备梳形支化聚合物时，其它共聚单体可以共聚。所述共聚单体包括烯烃、乙烯基芳族化合物、乙烯基卤化物、乙烯基酯、乙烯基吡咯烷酮、共轭二烯、不饱和磺酸、不饱和磷酸等和它们的混合物。使用的共聚单体的量通常＜单体总量的50wt％，优选＜单体总量的20wt％。美国专利序号6214958和6815513中描述了制备梳形支化聚合物的方法。
制备梳形支化聚合物的另一种适合的方法是使羧基聚合物与聚醚胺反应。羧基聚合物是包含羧基侧链的聚合物，包括羧酸、羧酸盐和羧酸酐。羧基聚合物的实例是乙烯型羧酸单体(例如丙烯酸、甲基丙烯酸、马来酸、富马酸、柠康酸、衣康酸或二羧酸单酯)的均聚物或共聚物。优选烯丙酸或甲基烯丙酸的均聚物或共聚物。所述羧基聚合物可以含有衍生自其它乙烯基单体，例如苯乙烯、α-甲基苯乙烯、磺化苯乙烯、马来酸、丙烯腈、丁二烯等，的单元。此类其它乙烯基单体衍生的单元，存在时，可达全部聚合物的20wt％，优选达全部聚合物的10wt％。
聚醚胺用来使羧基聚合物接枝可以形成合意的梳形支化聚合物。聚醚胺含有在聚合物骨架内或作为端基的胺基。美国专利序号5393343和6139623中公开了通过使聚醚胺接枝到羧基聚合物上制备梳形支化聚合物的方法。
为了制备挤出物，通常使用任意适合方法如研磨或捏合来混合无机氧化物和梳形支化聚合物。所述操作通常在10～150℃、优选在室温下进行。所述研磨或捏合可以在任意压力、优选在0.1～10个大气压下进行。通常，所述操作持续1分钟～10小时。
通常将所述混合物制成硬面团以用于挤出。如果需要，可以向混合物中添加溶剂。适合的溶剂包括水、醇、醚、酯、酰胺、芳香烃溶剂、卤代溶剂等、及其混合物。优选的溶剂为水和醇。最优选水。
通过挤出法来制备本发明的挤出物，挤出法是推挤物料使其穿过模具或孔口产生固定横截面的长物体的制造方法。通常使用挤出法来加工塑料或食品，并用于形成吸附剂或催化剂。可以使用任意常规挤出机。通常挤出物的直径为0.5～10mm，尤其为1～5mm。在“ParticleSize Enlargement(粒径扩大)”，Handbook of Powder Technology(粉 末技术手册)，第1卷，(1980)，112-22页中描述了一种适合的螺旋式挤出机。
梳形支化聚合物充当挤出助剂。挤出助剂有助于混合、研磨和挤出操作，并可提高挤出物的机械和/或物理性能如破碎强度、表面积、孔径或孔体积。例如，挤出助剂可提高无机粒子在捏合、成型、干燥和煅烧期间的桥接(bridging)和/或确保挤出物在挤出和煅烧期间的机械稳定性。挤出助剂还能够帮助溶剂更加均匀地分散在整个糊剂中。通常在煅烧期间除去挤出助剂。当使用金属羧酸盐作为挤出助剂时，通常将金属(例如，其氧化物)在煅烧期间并入到挤出物中。
挤出物可包括其它挤出助剂，所述挤出助剂包括例如烷基胺、羧酸、烷基铵化合物、氨基醇、纤维素、纤维素醚、淀粉、聚丙烯酸酯、聚甲基丙烯酸酯、聚(乙烯醇)、聚(乙烯基吡咯烷酮)、聚(氨基酸)、聚醚、聚(四氢呋喃)、金属羧酸盐等、及其混合物。纤维素醚的实例包括羧甲基纤维素钠、羟乙基纤维素、甲基纤维素及其衍生物。优选的聚(氧化烯)为聚(氧化乙烯)、聚(氧化丙烯)、或氧化乙烯和氧化丙烯的共聚物(参见美国专利6,706,658)。
制造的挤出物包含至少10wt％、优选至少20wt％、更优选至少30wt％的无机氧化物和至少0.1wt％的梳形支化聚合物。
可以对挤出物进行干燥。干燥操作从挤出物中除去至少一部分溶剂(例如水、乙醇)。所述干燥可以在大气压或真空下于10～200℃下进行。所述干燥可以在空气或惰性气氛中进行。
可以对挤出物进行煅烧以制备煅烧过的挤出物。优选地，在含氧气的气氛中进行煅烧以烧掉包含在挤出物中的有机物质(例如残留的溶剂、挤出助剂、模板试剂)。所述煅烧可以在400～1000℃、更优选在450～700℃下进行。有时，在惰性气氛(例如氮气、氦气)中对挤出物进行初始煅烧以将包含在挤出物中的有机化合物热分解，然后在含氧气氛中烧掉有机物质是有利的。通常，煅烧之后的煅烧过的挤出物包含0.5wt％以下的碳。优选其包含0.1wt％以下的碳。
本发明包括用于制备乙酸乙烯酯的方法。所述方法包括乙烯、乙酸和氧气或含氧气体在钯-金催化剂存在下反应，所述钯-金催化剂包含在本发明煅烧过的二氧化钛挤出物上附载的钯-金。
所述钯-金催化剂通常通过浸渍技术制备。一般地，煅烧过的二氧化钛挤出物同时、或通常情况是利用钯和金的盐的水溶液来处相继理。所使用溶液的浓度和量取决于最终催化剂中钯和金的期望浓度。然后除去水以将钯和金的盐沉积在挤出物上。代表性的钯和金的盐包括氯化钯、氯亚钯酸钠、硝酸钯、硫酸钯、氯化金、四氯金酸、四氯金酸钠等。考虑到它们的高水溶性和快速可用性，最经常使用的是四氯金酸和氯化钯或氯亚钯酸钠的溶液。
所述钯-金催化剂可包含碱金属。可以在钯和/或金的盐溶液中添加碱金属化合物。或者，在用碱金属化合物水溶液处理之前，利用钯和金的溶液对二氧化钛挤出物进行浸渍。优选的碱金属为钾。
在惰性或氧化气体如氦气、氮气、氩气、氖气、氮氧化物、氧气、空气、二氧化碳等中于100℃～600℃范围的温度下对浸渍的二氧化钛挤出物进行煅烧。还可使用前述气体的混合物。在本发明高度有用的实施方案中，在氮气、氧气或空气、或其混合物中进行煅烧。能够改变煅烧时间，但是通常为0.5～5小时。
在煅烧步骤之后，将得到的产物进行化学还原以将至少一部分钯和金的盐转变成相应金属。通常，能够使用任意熟知的使用常规还原剂的方法，所述常规还原剂诸如氨、一氧化碳、氢、烃、烯烃、醛、醇、联氨、肼、羧酸、羧酸盐和羧酸酯。氢、乙烯、丙烯、碱性肼和碱性甲醛是非常有用的还原剂，且尤其优选乙烯和氢。尽管可以使用纯氢，但是更经常的是利用氢和惰性气体如氮、氦、氩等的混合物。这些混合物通常包含高达约体积百分比(vol％)为50％的氢，更典型地，包含约5～25vol％的氢和75～95vol％的惰性气体。还原时间通常在1～5小时内变化。用于还原的温度为20～600℃。
通过本发明的方法制造的钯-金催化剂通常包含0.05～3wt％的钯和0.05～3wt％的金。更优选地，所述催化剂包含0.5～1.5wt％的钯和0.25～0.75wt％的金。
美国专利5,332,710、5,347,046、5,567,839、6,022,823、6,696,596和6,849,243中所述的负载钯-金催化剂的制备方法适用于本钯-金催化剂。
通常，将乙酸、乙烯和氧气或含氧气体在100～220℃、优选120～200℃和0.1～2.5MPa、优选0.1～2MPa下流过钯-金催化剂来制备乙酸乙烯酯。将未反应的组分循环。在某些情况下，用惰性气体如氮气或二氧化碳进行稀释也是有利地。在循环操作模式中，二氧化碳尤其适用于稀释，因为在反应期间通常会形成二氧化碳。
本发明还包括氧化方法，所述氧化方法包括将有机化合物和过氧化氢在本发明煅烧过的过渡金属沸石挤出物存在下进行反应。
本方法中将应用在前面部分中所讨论的适合的和优选的过渡金属沸石挤出物及其制备方法。
可以氧化多种有机化合物。实例包括烯烃、烷烃、芳烃、醇、醛、酮和硫醚等。
在一个优选的氧化方法中，有机化合物为烯烃，且氧化产物为环氧化物。适合的烯烃包括有至少一个碳-碳双键和碳原子数通常为2～60的任意一种烯烃。优选烯烃为含2～30个碳原子的无环烯烃。在特别优选的方法中，烯烃为丙烯且环氧化物为环氧丙烷。
本发明的另一个优选氧化方法是将烷烃氧化成醇、酮或其他氧化产物。所述方法是有价值的，因为氧化产物通常比不含官能团的烃更有价值。适合的烷烃包括含卤素、氧、芳基等、及其混合物的那些烷烃。实例包括乙烷、丙烷、正丁烷、异丁烷、甲苯、乙苯、异丙基苯。
其他氧化反应包括：例如将芳烃氧化成酚、将酚氧化成邻苯二酚、将酮氧化成酯或内酯、将硫醚氧化成亚砜和/或砜；将醛或酮在氨或胺存在下进行氨肟化(ammoximation)以制备肟(例如，将环己酮转变成环己酮肟)。
可以使用连续流、半间歇或间歇式进行所述氧化步骤。优选在连续固定床或多个分开的固定床中进行所述氧化。在1～200bar和0～250℃、更优选20～200℃范围的温度下进行工作是有利地。
所述氧化方法可以使用溶剂。适合的溶剂在反应条件下为液体。它们包括例如：含氧的烃如醇；芳族和脂族溶剂如甲苯和己烷；氯代芳烃和脂族溶剂如氯苯和二氯甲烷；腈类如乙腈；二氧化碳和水。适合的含氧溶剂包括醇、醚、酯、酮、二氧化碳、水等、及其混合物。优选的含氧溶剂包括水和低级脂族C1-C4的醇如甲醇、乙醇、异丙醇、叔丁醇及其混合物。能够使用氟代醇。
在氧化步骤中使用缓冲剂是有利的。通常将缓冲剂添加至溶剂中以形成缓冲剂溶液，或添加至过氧化氢溶液中。还可以直接把缓冲剂添加至氧化反应混合物中。在反应中使用缓冲剂以提高反应速度和/或选择性。用于本发明中的缓冲剂包括任意适合的含氧酸盐，所述含氧酸盐在混合物中的性质和比例使得含氧酸盐溶液的pH为3～10，更优选4～9，最优选5～8。适合的含氧酸盐包括阴离子和阳离子。所述阴离子可包括磷酸根、碳酸根、碳酸氢根、硫酸根、羧酸根(例如，醋酸根)、硼酸根、氢氧根、硅酸根、铝硅酸根等。所述阳离子可以选自氨基、烷基铵(例如四烷基铵、吡啶)、烷基磷鎓、碱金属和碱土金属离子等。实例包括NH4、NBu4、NMe4、Li、Na、K、Cs、Mg、和Ca阳离子。优选的缓冲剂包含选自磷酸根、碳酸根、重碳酸根、硫酸根、氢氧化物和醋酸根的阴离子；和选自氨基、烷基铵、烷基磷鎓、碱金属和碱土金属离子的阳离子。缓冲剂优选含有多于一种适合的盐的混合物。一般，溶剂中的缓冲剂的浓度为0.0001M～1M，优选为0.0005M～0.3M。所述缓冲剂可以包括氢氧化铵，该氢氧化铵可以通过向所述反应体系中加入氨气形成。例如，人们可以使用pH＝12～14的氢氧化铵溶液平衡反应体系的pH值。更优选的缓冲剂包括碱金属磷酸盐、磷酸铵和氢氧化铵。
以下实施例仅说明本发明。本领域技术人员会认出在本发明的精神和权利要求范围之内的很多变化。
实施例1：梳形支化聚合物A
在1L反应釜中进行反应，所述反应釜装配有搅拌器、温度控制器、加热装置、氮气吹扫装置和产物出口。设定出口管使得反应器容纳约320mL原料。存在三个进口加料泵，一个用于单体在水中的混合物，一个用于引发剂，一个用于链转移剂。产物出口管连接到第二个反应器，所述第二个反应器装配由搅拌器、温度控制器、加热装置和氮气吹扫装置。第二个反应器是按照反应达到稳态后收集产生的所有产物需要的尺寸设计的。向第一反应器充入50mL的水以覆盖搅拌器，然后向所述反应器吹扫氮气并持续约20分钟。将氧化乙烯/氧化丙烯无规共聚物的甲基丙烯酸酯(2070g，0.414mol)、甲基丙烯酸(99.9g，1.16mol)和水(1719g)的混合物充入单体进料罐中，所述氧化乙烯/氧化丙烯无规共聚物中氧化乙烯/氧化丙烯的重量比为70∶30且数均分子量为约5000。将过硫酸铵水溶液(1.25wt％)充入引发剂原料储罐，并将3-巯基丙酸水溶液(2.2wt％)充入链转移剂原料储罐。将反应器加热至65℃，然后启动进料泵以262g/小时的进料速度供应单体、以29mL/小时的进料速度供应引发剂、并以19mL/小时的进料速度供应链转移剂。将反应温度保持在65℃，并向反应器中连续充入氮气。将反应器流出物转向(diverted)直至反应达到稳定状态，然后在第二反应器中收集产物并持续约40分钟。其后，在65℃下对第二反应器加热3小时以完成反应。将收集的产物称为聚合物A。
实施例2：梳形支化聚合物B
按实施例1中所述进行反应。将氧化乙烯/氧化丙烯无规共聚物的甲基丙烯酸酯(900g，0.3mol)、丙烯酸(136g，1.83mol)和水(610g)的混合物充入单体进料罐中，所述氧化乙烯/氧化丙烯无规共聚物中氧化乙烯/氧化丙烯的重量比为70∶30且数均分子量为约3000。在连续充入氮气的条件下将反应器加热至65℃。启动进料泵以150g/小时的进料速度供应单体、以28.5mL/小时的速度供应引发剂、并以30.5mL/小时的进料速度供应链转移剂。将反应器流出物转向直至反应达到稳定状态，然后在第二反应器中收集产物并持续约1小时。在该段时间结束，对第二反应器加热另外3小时以完成反应。将产物称为聚合物B(MW为45000)。
用氢氧化铵水溶液对聚合物B的试样进行滴定以得到pH＝2.8的试样，将所述试样称为聚合物B-1。聚合物B-1包含43wt％的固体。
实施例3：梳形支化聚合物C
按实施例1中所述进行反应。将氧化乙烯/氧化丙烯无规共聚物的甲基丙烯酸酯(1800g，0.6mol)、甲基丙烯酸(146g，1.7mol)和水(1495g)的混合物充入单体进料罐中，所述氧化乙烯/氧化丙烯无规共聚物中氧化乙烯/氧化丙烯的重量比为70∶30且数均分子量为约3000。将水(50mL)充入反应器中。将反应器加热至65℃，然后启动进料泵以370g/小时的进料速度供应单体、以41.8mL/小时的速度供应引发剂、并以36mL/小时的进料速度供应链转移剂。将反应温度保持为65℃并向反应器连续充入氮气。将反应器流出物转向直至反应达到稳定状态，然后在第二反应器中收集产物并持续约12小时。在该段时间结束，对第二反应器另外加热3小时以完成反应。将收集的产物用稀释的苛性碱溶液处理以得到40wt％的固体且pH为4。将最终产物称为聚合物C。
实施例4：用聚合物A制备二氧化钛挤出物
将二氧化钛粉末(DT51，Millennium Chemicals，400g)、羧甲基纤维素(8.2g)、实施例1中制备的聚合物A(5.5g固体)、水(217g)和浓的氢氧化铵(14.8M，16g)合并。将该疏松混合物(loose mixture)转移至Thermo Haake Rheomix 3000混合器(625mL内体积)中，并用σ形叶片捏合30分钟。利用Thermo Haake Rheocord 300p驱动装置以50转/分钟(rpm)的反向旋转方式来旋转所述叶片。驱动装置测量了保持叶片的rpm所需要的扭矩，并将该值作为时间的函数进行积分以确定30分钟内所消耗的总能量。
将糊剂从混料罐中取出并在密封塑料袋中陈化24小时。然后使用具有Rheocord 300p驱动装置的Thermo Haake Rheomex 202p将所述糊剂挤出成1/8英寸的圆柱体。将挤出物在空气中于室温下干燥24小时，然后在105℃下干燥16小时。然后，在空气中煅烧所述挤出物。以1℃/分钟的升温速度，将煅烧炉温度从室温升至500℃，在500℃下保持1小时，然后以10℃/分钟的速度将温度从500℃升至700℃，并最终在700℃下保持6小时，然后冷却。
煅烧过的二氧化钛挤出物的某些物理性能列于表1中。用Chatillon破碎强度分析仪(型号：DPP 50)测量了煅烧过的二氧化钛挤出物的破碎强度。对25次测量中破坏所需要的力取平均值以提供报告值。通过将40g挤出物放入100mL带刻度量筒(1英寸标称外径)中来测量松密度。轻敲所述带刻度量筒直至表观体积不再变化，然后将该值除质量以计算整体体积。通过向第二个带刻度量筒的50mL水中添加颗粒并轻敲直至所有空隙都被填满，以确定空隙率。用水和单独采用的颗粒的体积之和减去得到的水平面，以确定由水占据的空隙体积。通过将混合物倾倒以使其通过筛篮、摇动以除去过剩水、然后对湿的挤出物称重，由此确定总的孔体积。将总共最初40g挤出物所增加的质量除水的密度作为孔体积的测量值。
实施例5：利用聚合物B制备二氧化钛挤出物
除了使用实施例2中制备的聚合物B(5.5g固体)代替聚合物A之外，重复实施例4的程序。
实施例6：利用聚合物C制备二氧化钛挤出物
除了使用实施例3中制备的聚合物C(5.5g固体)代替聚合物A之外，重复实施例4的程序。
比较例7：利用聚(氧化乙烯)制备二氧化钛挤出物
除了使用聚(氧化乙烯)(Alpha Aesar，M.W.＝100000，5.5g)代替聚合物A之外，重复实施例4的程序。
表1.二氧化钛挤出物的制备和性质
| 实施例 | 4 | 5 | 6 | 比较例7 |
| 挤出助剂 | 聚合物A | 聚合物B | 聚合物C | 聚(氧化乙烯) |
| 总混合能(KJ) | 42.6 | 42.7 | 44.3 | 48.4 |
| 破碎强度(lbs) | 31.88 | 32.98 | 36.96 | 36.88 |
| 整体密度(g/ml) | 1.03 | 0.88 | 0.96 | 1.1 |
| 空隙率(％) | 67.9 | 71.4 | 70.0 | 67.9 |
| 孔体积(mL/g) | 30.1 | 32.5 | 19.9 | 26.8 |
实施例8：在二氧化钛上负载Au/Pd(催化剂D)
将NaAuCl4(0.987g)、Na2PdCl4(2.645g)和NaHCO3(2.760g)溶于水(24mL)中。使用一次性玻璃吸管将所述溶液施加到实施例4中制备的二氧化钛挤出物(100g)上，同时使得挤出物在转盘上翻滚，直至填满所有的挤出物孔体积。将灌注过的挤出物翻滚另外30分钟，然后使用热风枪于80～85℃下干燥1小时。然后在炉子中于105℃的空气中再对所述挤出物干燥16小时，然后使用Soxhlet抽提器用热去离子水充分冲洗以除去氯化物。
将上述挤出物在1.5英寸标称外径的管式反应器中于70psig、210℃的流动空气(流速为200mL/分钟)中加热3小时。在用氮气吹扫反应器之后，在70psig下向反应器中导入(500mL/分钟)气体混合物(氮气中混入20vol％的氢气)。以10℃/分钟的速度将温度升至500℃，并在500℃下保持3小时。用氮气吹扫反应器并在氮气流下将制得的催化剂冷却至室温。
将挤出物(25g)与含5wt％醋酸钾和0.5wt％氢氧化钾的水溶液(50mL)在室温下接触10分钟。将混合物倾析，并在105℃下的炉子中在空气中对处理过的催化剂干燥4小时。制得催化剂D。
实施例9～11：在二氧化钛上负载Au/Pd(催化剂E、F、G)
除了使用实施例5、6、7中制备的挤出物之外，重复实施例8的程序。
实施例12～14：催化剂测试
在固定床反应器(不锈钢，标称1英寸外径)中将催化剂D、E和F用于乙酸乙烯酯生产中以对其进行评价。床体积为30mL，并将催化剂与惰性α氧化铝圆柱形颗粒(直径为1/8英寸、表面积为4m2/g、孔体积为0.25mL/g)混合，所述氧化铝和催化剂的重量比为2.5∶1。进料包含84.7wt％的乙烯、9.9wt％的乙酸、3.8wt％的氧气和1.6wt％的氮气。反应器压力为80psig且在标准温度和压力下，相对于催化剂床的空速为3800/小时。使用流态化砂浴来冷却反应器，并将砂浴温度设定为130℃。通过气相色谱(GC)来分析产物流股。根据GC结果来计算100小时后流股上用于乙酸乙烯酯的氧气的转化率、选择性和收率，并列于表2中。将消耗的氧气量除以进入反应器的氧气进料总量，以计算氧气转化率。氧气选择性为将用于生成乙酸乙烯酯的氧气消耗量除以总的氧气消耗量。氧气的收率为氧气转化率乘以氧气选择性而得到的结果。
表2中的结果显示了挤出助剂对催化剂性能的影响。
表2.生成乙酸乙烯酯的催化剂性能
| 实施例 | 12 | 13 | 14 |
| 催化剂 | D | E | F |
| 挤出助剂 | 聚合物A | 聚合物B | 聚合物C |
| 氧气转化率(％) | 44.5 | 33.4 | 39.5 |
| 氧气选择性(％) | 77.4 | 76.6 | 74.6 |
| 氧气收率(％) | 34.4 | 25.6 | 29.5 |
实施例15～17：二氧化钛挤出物和催化剂
除了使用羧甲基纤维素钠和苄醇来代替作为挤出助剂的羧甲基纤维素之外，按照实施例4中所述的程序，使用三种不同浓度的聚合物A(实施例1中所制备的)制备了挤出物(表3)。根据实施例8的程序，利用煅烧过的挤出物制备了催化剂G、H和I。根据实施例12～14的程序对催化剂G、H和I进行了评价。试验结果示于表3中。
表3.挤出物的制备和催化剂性能
| 实施例 | 15 | 16 | 17 |
| 挤出物的制备 | |||
| 二氧化钛(wt％) | 61.8 | 61.1 | 60.4 |
| 水(wt％) | 33.1 | 32.7 | 32.4 |
| 聚合物A(wt％) | 0.8 | 2.0 | 3.0 |
| 羧甲基纤维素，钠盐(wt％) | 1.3 | 1.3 | 1.2 |
| 苄醇(wt％) | 0.5 | 0.5 | 0.5 |
| 氢氧化铵(wt.％) | 1.9 | 1.8 | 1.8 |
| 催化剂性能 | |||
| 催化剂 | G | H | I |
| 氧气转化率(％) | 32.0 | 46.2 | 20.9 |
| 氧气选择性(％) | 80.0 | 75.4 | 73.8 |
| 氧气收率(％) | 25.7 | 34.8 | 15.4 |
实施例18：催化剂测试
除了将砂浴温度设定为135℃以代替130℃之外，通过实施例12～14中所述的程序来测试催化剂D。测试结果示于表4中。
比较例19：催化剂测试
根据实施例18中所述的程序对催化剂G进行了测试。测试结果示于表4中。
实施例18和19的对比表明，催化剂D(由利用聚合物A作为挤出助剂制造的挤出物制备的)的性能优于催化剂G(利用聚(氧化乙烯)作为挤出助剂制造的)的。
表4.生成乙酸乙烯酯中的催化剂性能
| 实施例 | 18 | 比较例19 |
| 催化剂 | D | G |
| 挤出助剂 | 聚合物A | 聚(氧化乙烯) |
| 氧气转化率(％) | 51.8 | 50.6 |
| 氧气选择性(％) | 74.2 | 70.8 |
| 氧气收率(％) | 38.4 | 35.8 |
实施例20：TS-1挤出物(催化剂J)
根据美国专利4,410,501和4,833,260中公开的程序制备了Titanium silicalite-1(TS-1)试样。将所述试样在550℃下进行煅烧。
在塑料烧杯中混合TS-1(60g)、羧甲基纤维素钠盐(Sigma-Aldrich，2.72g)和聚氧化乙烯(PEO)粉末(0.88g)。将该混合物添加至具有3∶2旋转构型的σ叶片的Brabender预混合器研磨机(Brabender Prep-Mixer muller)(450mL)。所述研磨机由C.W.Brabender Prep-Center电动机驱动装置(型号为具有5个HP电动机的DT-51)驱动。在以20～30rpm对所述混合物研磨10分钟之后，添加聚合物B-1(17.1g)并混合5分钟。在30r pm下向糊剂中添加Ludox硅溶胶(AS-40，Aldrich，40.18g)。在40rpm混合速度下，添加蒸馏过的、去离子(DIUF)水(11.1g)。对其继续研磨另外的5分钟。将糊剂转移至塑料袋中陈化过夜。
使用Brabender单螺旋、3/4英寸、10∶1的挤出机来挤出所述陈化糊剂，所述挤出机安装有1/16英寸的单模。将所述糊剂添加至进料斗并用特氟隆(Teflon)棒推入螺杆中。以10rpm在23℃下进行挤出。挤出机机头中的压力为约50～150psig。将挤出物收集在玻璃托盘中。在空气中干燥18小时后，将所述挤出物在空气中于550℃的马弗炉中煅烧8小时(升温速率：2～5℃/分钟)。挤出物催化剂(催化剂J)包含1.5wt％的Ti、0.17wt％的Na和小于100ppm的Al。氮气BET表面积为340m2/g。颗粒的破碎强度为2.36lbs。通过使用Chatillon-AntekDFS数字测力计来测量破碎强度，在MT试验台上安装有平台板并使用5～8mm长度范围的10个挤出物的平均值。在“断裂检测(BreakDetect)”模式下设置所述DFS测力计，所述测力计将挤出物断裂之前向其施加的最大力(单位：lbs)储存起来。按ASTM D 4179-01中所述来记录用于全体挤出物破碎所施加的力。
实施例21：丙烯的环氧化
通过下列程序可对实施例20中制备的TS-1挤出物(催化剂J)进行测试。将催化剂J(10g)包装在SS管式反应器(内径为1/2英寸)中。将15wt％在甲醇/水溶剂(重量比：3/1)的过氧化氢并含100ppm氢氧化铵的溶液以0.54/h(每克催化剂每小时内流过的过氧化氢的克数)的重时空速流经催化剂床。在反应器压力为约300psig下，将丙烯和过氧化氢溶液一起向反应器进料，使得液相中丙烯为约30wt％。将反应器温度保持在60～65℃。在过氧化氢转化率为95～99％时，预计氧化丙烯的选择性为85～90％。氧化丙烯的选择性为形成的氧化丙烯的摩尔数占所消耗过氧化氢的摩尔数的百分比。作为副产物，预计会形成少量的丙二醇甲基醚和丙二醇。
Claims (20)
1.包含无机氧化物和梳形支化聚合物的挤出物，其中所述无机氧化物占所述挤出物的至少10wt％，且所述梳形支化聚合物占所述挤出物的至少1wt％。
2.权利要求1的挤出物，其中所述梳形支化聚合物包含乙烯型羧酸单体和聚醚大分子单体的重复单元。
3.权利要求2的挤出物，其中所述乙烯型羧酸单体为丙烯酸类单体。
4.权利要求2的挤出物，其中所述乙烯型羧酸单体选自丙烯酸、甲基丙烯酸及其混合物。
5.权利要求1的挤出物，其中所述无机氧化物选自二氧化硅、氧化铝、二氧化钛、沸石及其混合物。
6.权利要求1的挤出物，其中所述无机氧化物为二氧化钛。
7.权利要求1的挤出物，其中所述无机氧化物为沸石。
8.权利要求1的挤出物，其中所述无机氧化物为钛沸石。
9.权利要求1的挤出物，其中所述无机氧化物为TS-1。
10.煅烧过的权利要求1的挤出物。
11.权利要求10的煅烧过的挤出物，其中所述煅烧在含氧气体存在下进行。
12.权利要求10的煅烧过的挤出物，其中所述煅烧在450～700℃的温度下进行。
13.权利要求10的煅烧过的挤出物，其中所述无机氧化物为二氧化钛。
14.权利要求10的煅烧过的挤出物，其中所述无机氧化物为过渡金属沸石。
15.权利要求10的煅烧过的挤出物，其中所述无机氧化物为TS-1。
16.乙酸乙烯酯的制备方法，包括在利用权利要求13的煅烧过的挤出物制备的钯-金催化剂存在下使乙烯、乙酸和氧气进行反应。
17.权利要求16的方法，其中所述钯-金催化剂包含碱金属。
18.氧化方法，包括在权利要求14的煅烧过的挤出物存在下使有机化合物和过氧化氢反应。
19.权利要求18的方法，其中所述有机化合物为丙烯。
20.权利要求18的方法，其中所述过渡金属沸石为TS-1。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/641,482 US7825204B2 (en) | 2006-12-19 | 2006-12-19 | Inorganic oxide extrudates |
| US11/641,482 | 2006-12-19 | ||
| PCT/US2007/024221 WO2008088452A2 (en) | 2006-12-19 | 2007-11-20 | Inorganic oxide extrudates useful as catalysts or catalyst supports |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101583418A true CN101583418A (zh) | 2009-11-18 |
| CN101583418B CN101583418B (zh) | 2013-05-08 |
Family
ID=39528237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007800472829A Active CN101583418B (zh) | 2006-12-19 | 2007-11-20 | 无机氧化物挤出物 |
Country Status (9)
| Country | Link |
|---|---|
| US (2) | US7825204B2 (zh) |
| EP (1) | EP2104561A2 (zh) |
| KR (1) | KR101431007B1 (zh) |
| CN (1) | CN101583418B (zh) |
| BR (1) | BRPI0721293A2 (zh) |
| CA (1) | CA2670941C (zh) |
| MY (2) | MY156545A (zh) |
| RU (1) | RU2451545C2 (zh) |
| WO (1) | WO2008088452A2 (zh) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102740964A (zh) * | 2009-12-16 | 2012-10-17 | 莱昂德尔化学技术公司 | 钯-金催化剂的制备 |
| CN102753265A (zh) * | 2009-12-16 | 2012-10-24 | 莱昂德尔化学技术公司 | 二氧化钛-氧化铝负载钯催化剂 |
| CN113784790A (zh) * | 2019-04-29 | 2021-12-10 | 巴斯夫欧洲公司 | 包含mfi型钛硅沸石和硅粘合剂的模制品、其制备方法及作为催化剂的用途 |
| CN116550383A (zh) * | 2023-07-12 | 2023-08-08 | 中国天辰工程有限公司 | 一种不饱和醋酸酯及其催化剂的制备方法 |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100121100A1 (en) * | 2008-11-12 | 2010-05-13 | Daniel Travis Shay | Supported palladium-gold catalysts and preparation of vinyl acetate therewith |
| WO2010150676A1 (ja) * | 2009-06-22 | 2010-12-29 | 日揮株式会社 | 低級オレフィン製造用触媒およびそれを用いた低級オレフィンの製造方法 |
| US8273682B2 (en) * | 2009-12-16 | 2012-09-25 | Lyondell Chemical Technology, L.P. | Preparation of palladium-gold catalyst |
| US8507720B2 (en) * | 2010-01-29 | 2013-08-13 | Lyondell Chemical Technology, L.P. | Titania-alumina supported palladium catalyst |
| US8329611B2 (en) * | 2009-12-16 | 2012-12-11 | Lyondell Chemical Technology, L,P. | Titania-containing extrudate |
| WO2011104170A1 (en) * | 2010-02-24 | 2011-09-01 | Evonik Degussa Gmbh | Thermally and mechanically stable precious metal-loaded catalysts |
| US20110306748A1 (en) | 2010-06-11 | 2011-12-15 | Daniel Travis Shay | Titania-alumina-tungsta extrudate and its use |
| US20120022224A1 (en) | 2010-07-22 | 2012-01-26 | Geraldine Tosin | Particles Including Zeolite Catalysts And Their Use In Oligomerization Processes |
| WO2012033562A1 (en) | 2010-09-07 | 2012-03-15 | Exxonmobil Chemical Patents Inc. | Extrudates including zeolite catalysts and their use in oligomerization processes |
| US9550705B2 (en) | 2011-07-25 | 2017-01-24 | Exxonmobill Chemical Patents Inc. | Olefin oligomerization process |
| WO2013013885A2 (en) | 2011-07-25 | 2013-01-31 | Exxonmobil Chemical Patents Inc. | Integrated nitrile poison adsorption and desorption system |
| US9505685B2 (en) | 2011-07-25 | 2016-11-29 | Exxonmobil Chemical Patents Inc. | Olefin oligomerization process |
| WO2013013884A2 (en) | 2011-07-25 | 2013-01-31 | Exxonmobil Chemical Patents Inc. | Process for nitrile removal from hydrocarbon feeds |
| US9573861B2 (en) | 2011-07-25 | 2017-02-21 | Exxonmobil Chemical Patents Inc. | Olefin oligomerization process |
| CN103553068B (zh) * | 2013-11-14 | 2016-03-16 | 黑龙江大学 | 一种制备ts-1分子筛的方法 |
| EA201791539A1 (ru) | 2015-02-10 | 2017-12-29 | Сирис Энерджи, Инк. | Способ деполимеризации |
| US10508063B2 (en) | 2015-03-20 | 2019-12-17 | Exxonmobil Chemical Patents Inc. | Olefin oligomerization in the presence of cyclopentene |
| CN109952151B (zh) * | 2016-11-17 | 2022-06-03 | 利安德巴塞尔乙酰有限责任公司 | 用于用来产生乙酸乙烯酯单体的增强的催化剂的氧化铝载体的压碎强度和孔隙率 |
| CN113751073B (zh) * | 2020-06-02 | 2024-01-30 | 中国石油化工股份有限公司 | 乙烯法醋酸乙烯催化剂 |
Family Cites Families (34)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4039474A (en) | 1975-10-20 | 1977-08-02 | Nalco Chemical Company | Silica-alumina catalysts |
| US4119474A (en) | 1977-07-13 | 1978-10-10 | American Cyanamid Company | Microcrystalline cellulose as extrusion aid/combustible filler for alumina |
| IT1127311B (it) | 1979-12-21 | 1986-05-21 | Anic Spa | Materiale sintetico,cristallino,poroso costituito da ossidi di silicio e titanio,metodo per la sua preparazione e suoi usi |
| IT1152299B (it) | 1982-07-28 | 1986-12-31 | Anic Spa | Procedimento per l'espossidazione di composti olefinici |
| JPS60122770A (ja) | 1983-12-06 | 1985-07-01 | 株式会社日本触媒 | セラミツクス成形のためのバインダ− |
| JPS60155567A (ja) | 1984-01-24 | 1985-08-15 | 日立化成工業株式会社 | セラミツク用バインダ−の製造法 |
| GB2193713B (en) | 1986-07-14 | 1990-12-05 | Cabot Corp | Method of producing perovskite-type compounds. |
| GB8724436D0 (en) | 1987-10-19 | 1987-11-25 | Shell Int Research | Silica-alumina extrudates |
| IT1216500B (it) | 1988-03-23 | 1990-03-08 | Eniricerche S P A Milano Enich | Procedimento per la preparazione di materiali sintetici cristallini porosi costituiti da ossidi di silicio e titanio. |
| GB8906726D0 (en) * | 1989-03-23 | 1989-05-10 | Shell Int Research | Titania extrudates |
| US5332710A (en) | 1992-10-14 | 1994-07-26 | Hoechst Celanese Corporation | Vinyl acetate catalyst preparation method |
| US5347046A (en) | 1993-05-25 | 1994-09-13 | Engelhard Corporation | Catalyst and process for using same for the preparation of unsaturated carboxylic acid esters |
| JP3385654B2 (ja) | 1993-07-07 | 2003-03-10 | 日本油脂株式会社 | セラミックス成形体の製造方法 |
| US5393343A (en) | 1993-09-29 | 1995-02-28 | W. R. Grace & Co.-Conn. | Cement and cement composition having improved rheological properties |
| CA2135021A1 (en) | 1993-11-19 | 1995-05-20 | David J. Gulliver | Process for the preparation of catalysts for use in the production of vinyl acetate |
| US5824622A (en) | 1994-01-12 | 1998-10-20 | E. I. Du Pont De Nemours And Company | Porous microcomposite of perfluorinated ion-exchange polymer and metal oxide, a network of silica, or a network of metal oxide and silica derived via a sol-gel process |
| AU5057096A (en) * | 1995-04-24 | 1996-11-07 | Rohm And Haas Company | Method for forming extruded parts from inorganic material |
| US6022823A (en) | 1995-11-07 | 2000-02-08 | Millennium Petrochemicals, Inc. | Process for the production of supported palladium-gold catalysts |
| GB9622911D0 (en) * | 1996-11-04 | 1997-01-08 | Bp Chem Int Ltd | Process |
| JP2001509127A (ja) | 1997-01-21 | 2001-07-10 | ダブリユ・アール・グレイス・アンド・カンパニー・コネテイカツト | 乳化された櫛形ポリマーおよび脱泡剤組成物ならびにその調製法 |
| US5854386A (en) | 1997-08-25 | 1998-12-29 | Arco Chemical Technology, L.P. | Stabilizers for polymer polyols |
| ES2158701T3 (es) | 1997-09-05 | 2001-09-01 | Basf Ag | Procedimiento mejorado para la obtencion de politetrahidrofurano. |
| GB9810928D0 (en) * | 1998-05-22 | 1998-07-22 | Bp Chem Int Ltd | Catalyst and process |
| DE19843693A1 (de) | 1998-09-24 | 2000-03-30 | Degussa | Trägerkatalysator für die Produktion von Vinylacetatmonomer |
| DE19914066A1 (de) | 1999-03-27 | 2000-10-05 | Celanese Chem Europe Gmbh | Katalysatoren für die Gasphasenoxidation von Ethylen und Essigsäure zu Vinylacetat, Verfahren zu ihrer Herstellung und ihre Verwendung |
| DE19920390C2 (de) | 1999-05-04 | 2002-08-01 | Celanese Chem Europe Gmbh | Katalysator und Verfahren zur Herstellung von Vinylacetat |
| US6214958B1 (en) * | 1999-07-21 | 2001-04-10 | Arco Chemical Technology, L.P. | Process for preparing comb-branched polymers |
| EP1138387A1 (de) | 2000-03-29 | 2001-10-04 | Degussa AG | Verfahren zur Herstellung eines Titansilicalitformkörpers |
| DE10110139A1 (de) | 2001-03-02 | 2002-09-12 | Basf Ag | Formkörper und Verfahren zu dessen Herstellung |
| DE10139293A1 (de) | 2001-08-09 | 2003-02-27 | Basf Ag | Verbessertes Verfahren zur Herstellung von Polytetrahydrofuran |
| US6706658B2 (en) | 2001-12-21 | 2004-03-16 | Engelhard Corporation | Catalyst for purification of aromatic acids |
| WO2005030680A1 (en) | 2003-09-30 | 2005-04-07 | Shell Internationale Research Maatschappij B.V. | Titania supports for fisher-tropsch catalysts |
| CA2596294A1 (en) | 2005-03-23 | 2006-09-28 | Sekisui Chemical Co., Ltd. | Thermally disappearing resin particle |
| JP2008024553A (ja) * | 2006-07-21 | 2008-02-07 | Sanyo Chem Ind Ltd | セラミック押出成形用分散剤 |
-
2006
- 2006-12-19 US US11/641,482 patent/US7825204B2/en active Active
-
2007
- 2007-11-20 CA CA2670941A patent/CA2670941C/en active Active
- 2007-11-20 KR KR1020097012838A patent/KR101431007B1/ko active IP Right Grant
- 2007-11-20 CN CN2007800472829A patent/CN101583418B/zh active Active
- 2007-11-20 MY MYPI2012003584A patent/MY156545A/en unknown
- 2007-11-20 WO PCT/US2007/024221 patent/WO2008088452A2/en active Application Filing
- 2007-11-20 BR BRPI0721293-3A patent/BRPI0721293A2/pt not_active Application Discontinuation
- 2007-11-20 MY MYPI20092482A patent/MY146027A/en unknown
- 2007-11-20 RU RU2009122939/04A patent/RU2451545C2/ru active
- 2007-11-20 EP EP07862141A patent/EP2104561A2/en not_active Ceased
-
2010
- 2010-09-16 US US12/807,884 patent/US7855304B1/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102740964A (zh) * | 2009-12-16 | 2012-10-17 | 莱昂德尔化学技术公司 | 钯-金催化剂的制备 |
| CN102753265A (zh) * | 2009-12-16 | 2012-10-24 | 莱昂德尔化学技术公司 | 二氧化钛-氧化铝负载钯催化剂 |
| CN113784790A (zh) * | 2019-04-29 | 2021-12-10 | 巴斯夫欧洲公司 | 包含mfi型钛硅沸石和硅粘合剂的模制品、其制备方法及作为催化剂的用途 |
| CN116550383A (zh) * | 2023-07-12 | 2023-08-08 | 中国天辰工程有限公司 | 一种不饱和醋酸酯及其催化剂的制备方法 |
| CN116550383B (zh) * | 2023-07-12 | 2023-10-31 | 中国天辰工程有限公司 | 一种不饱和醋酸酯及其催化剂的制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| MY156545A (en) | 2016-02-26 |
| WO2008088452A3 (en) | 2008-10-02 |
| WO2008088452A2 (en) | 2008-07-24 |
| US7855304B1 (en) | 2010-12-21 |
| RU2009122939A (ru) | 2011-01-27 |
| MY146027A (en) | 2012-06-15 |
| RU2451545C2 (ru) | 2012-05-27 |
| CA2670941C (en) | 2015-05-12 |
| CA2670941A1 (en) | 2008-07-24 |
| KR101431007B1 (ko) | 2014-08-18 |
| CN101583418B (zh) | 2013-05-08 |
| EP2104561A2 (en) | 2009-09-30 |
| US20080146721A1 (en) | 2008-06-19 |
| BRPI0721293A2 (pt) | 2014-03-25 |
| KR20090101191A (ko) | 2009-09-24 |
| US7825204B2 (en) | 2010-11-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101583418B (zh) | 无机氧化物挤出物 | |
| US7387981B1 (en) | Direct epoxidation catalyst and process | |
| US7563740B2 (en) | Direct epoxidation process | |
| CN100408168C (zh) | 负载的银催化剂和使用该催化剂的环氧化方法 | |
| CN1300125C (zh) | 使用混合催化剂体系进行直接环氧化的方法 | |
| CN1134302C (zh) | 用于芳香烃的气相催化氧化反应的涂层型催化剂的制备方法及由此方法得到的催化剂 | |
| EP1351947B2 (en) | Epoxidation catalyst and process for the production thereof | |
| CN1274680C (zh) | 使用含溴化物试剂预处理的混合催化剂体系进行直接环氧化的方法 | |
| CN1026099C (zh) | 用钼酸盐催化剂组合物氧化脂族烃的方法 | |
| ES2282265T3 (es) | Procedimiento para la preparacion de un oxido de alquileno. | |
| CN101835768A (zh) | 使用改进的催化剂组合物的直接环氧化方法 | |
| JP4384041B2 (ja) | ポリテトラヒドロフランおよびテトラヒドロフランコポリマーのモノエステルおよびジエステルの製法 | |
| CZ20022565A3 (cs) | Epoxidační katalyzátory obsahující kovy řady lanthanoidů | |
| JP6182333B2 (ja) | グリセリン類含有重合体及びその製造方法 | |
| CN101835767A (zh) | 使用混合催化剂体系的直接环氧化方法 | |
| WO2012048528A1 (zh) | 一种烯烃环氧化的方法 | |
| JP2003104978A (ja) | エポキシドの製造方法 | |
| CN102327776A (zh) | 环氧化催化剂、制备该催化剂的方法和氧化烯的生产方法 | |
| JP2005536474A (ja) | 担持酸化ニオブ触媒を使用するエポキシ化方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |