CN102753265B - Titania-alumina loaded palladium catalyst - Google Patents
Titania-alumina loaded palladium catalyst Download PDFInfo
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- CN102753265B CN102753265B CN201080064074.1A CN201080064074A CN102753265B CN 102753265 B CN102753265 B CN 102753265B CN 201080064074 A CN201080064074 A CN 201080064074A CN 102753265 B CN102753265 B CN 102753265B
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- Prior art keywords
- catalyst
- alkene
- acetoxylation
- extrudate
- weight
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 51
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- XTXRWKRVRITETP-UHFFFAOYSA-N vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001884 aluminium oxide Inorganic materials 0.000 claims abstract description 13
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 12
- 239000001913 cellulose Substances 0.000 claims description 18
- 229920002678 cellulose Polymers 0.000 claims description 18
- 150000001336 alkenes Chemical class 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 17
- 238000006137 acetoxylation reaction Methods 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 238000001125 extrusion Methods 0.000 claims description 10
- 239000005977 Ethylene Substances 0.000 claims description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- 239000010931 gold Substances 0.000 claims description 8
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 125000004181 carboxyalkyl group Chemical group 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 2
- 230000003647 oxidation Effects 0.000 claims 2
- 238000007254 oxidation reaction Methods 0.000 claims 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- 150000002118 epoxides Chemical class 0.000 claims 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims 1
- 230000003197 catalytic Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- -1 alkoxyl Titanium Chemical compound 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000001307 helium Substances 0.000 description 5
- 229910052734 helium Inorganic materials 0.000 description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium(0) Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000012190 activator Substances 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N precursor Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000002940 palladium Chemical class 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M Aluminium hydroxide oxide Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitrogen oxide Substances O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N Palladium(II) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052756 noble gas Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 150000003608 titanium Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2R,3R,4S,5R,6S)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2S,3R,4S,5R,6R)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2R,3R,4S,5R,6R)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- NBBCSVFUAZCEJU-UHFFFAOYSA-N Auric chloride Chemical compound [Cl-][Cl-][Au+3][Cl-] NBBCSVFUAZCEJU-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate dianion Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N Cesium Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910003244 Na2PdCl4 Inorganic materials 0.000 description 1
- 229940038031 Nitrogen 10 % Drugs 0.000 description 1
- 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 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 241000048284 Potato virus P Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910000831 Steel 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 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 1
- NDQKGYXNMLOECO-UHFFFAOYSA-N acetic acid;potassium Chemical compound [K].CC(O)=O NDQKGYXNMLOECO-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001339 alkali metal compounds Chemical group 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium(0) Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001186 cumulative Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000000816 ethylene group Chemical class [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxyl anion Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon(0) Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910052813 nitrogen oxide Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative Effects 0.000 description 1
- RFLFDJSIZCCYIP-UHFFFAOYSA-L palladium(2+);sulfate Chemical compound [Pd+2].[O-]S([O-])(=O)=O RFLFDJSIZCCYIP-UHFFFAOYSA-L 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001308 poly(aminoacid) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000630 rising Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
Abstract
The present invention discloses the catalyst of a kind of palladium comprising and being carried on titania alumina extrudate.Extrudate comprises at least 80% weight titanium dioxide and 0.1 to 15% weight aluminium oxide.The palladium catalyst prepared from titania alumina extrudate has significantly higher crushing strength.The present invention also improves its catalytic performance in vinyl acetate manufactures.
Description
Invention field
The present invention relates to comprise the catalyst of the palladium being carried on titania-alumina carrier.
Background of invention
The catalyst comprising the palladium and the 11st race's metal that are carried on titanium dioxide can be used for the acetoxylation of catalyzed alkene,
See for example United States Patent (USP) 6,022,823, U.S. Patent Application Publication 2008/0146721 and 2008/0281122.But, from
Catalyst prepared by titania extrudate typically has low crushing strength.The catalyst with low crushing strength tends to instead
Answer in device and grind, cause pressure in the reactor to decline, and block process pipe.Accordingly, it would be desirable to research and development have high crush-strength
Catalyst.
Summary of the invention
The present invention is the catalyst of a kind of palladium comprising and being carried on extrudate.Extrudate comprises at least 80% weight dioxy
Change titanium and 0.1 to 15% weight aluminium oxide.The palladium catalyst prepared from titania-alumina extrudate has significantly higher
Crushing strength and good activity.
Accompanying drawing is sketched
Fig. 1 shows crushing strength and its alumina content of the catalyst being carried on titania-alumina extrudate
Dependency.
Detailed Description Of The Invention
The present invention is the catalyst of a kind of palladium comprising and being carried on titania-alumina extrudate, described extrudate
Comprise at least 80% weight titanium dioxide and 0.1 to 15% weight aluminium oxide.Its preferably containing at least 85% weight is (more preferably at least
90% weight) titanium dioxide and 0.2 to 10% weight (more preferably 0.5 to 5% weight) aluminium oxide.
In order to prepare extrudate, titanium dioxide or titanium dioxide precursor and aluminium oxide or alumina precursor are suitable for any
Method (such as, grind or knead) is mixed into paste.Industrial, chloride process, sulfate process, hydro-thermal method or titanium tetrachloride can be passed through
Pyrohydrolysis prepare titanium dioxide.The example being suitable for titanium dioxide includes Millennium Inorganic Chemicals's
TiONA®DT-51, DT-52, DT-51D, DT-40 and DT-20.Applicable titanium dioxide precursor includes titanium salt, halogenated titanium, alkoxyl
Titanium, titanium oxyhalide etc..The example being suitable for aluminium oxide includes the DISPERAL of Sasol®、PURAL®、PURALOX®.It is suitable for aluminium oxide
Precursor includes aluminum alkoxide and aluminium salt.
Formed with solvent and stick with paste.The example being suitable for solvent includes water, alcohol, ester, amide etc. and mixture thereof.Preferably solvent is
Water and alcohol.Water is most preferred.
Available extrusion aid is formed to be stuck with paste.Be suitable for extrusion aid include carboxylic acid, alkyl ammonium compound, amino alcohol, cellulose,
Cellulose derivative, starch, polyacrylate, polymethacrylates, poly-(vinyl alcohol), PVP, poly-
(aminoacid), polyethers, poly-(oxolane), metal carboxylate etc. and mixture thereof.The example of cellulose derivative includes carboxylic alkane
Base sodium cellulosate, hydroxy alkyl cellulose and methylcellulose.Preferably extrusion aid includes that carboxyl alkyl cellulose sodium and hydroxyalkyl are fine
The combination of dimension element.The carboxyl alkyl cellulose of 3:1 to 1:1 is with hydroxy alkyl cellulose weight ratio more preferably.
Carboxyl alkyl cellulose is to have the carboxylic being attached to form some hydroxyls of the glucopyra sugar monomer of cellulosic backbone
The cellulose derivative of alkyl.It uses usually used as its sodium salt-carboxyl alkyl cellulose sodium.Carboxymethyl cellulose is preferably used
Sodium salt.
Hydroxy alkyl cellulose is cellulose derivative wherein repeating some hydroxyls hydroxyalkylation in glucose unit
Thing.Preferably hydroxyalkyl is 2-hydroxyethyl or 2-hydroxypropyl.
The extrusion stuck with paste produces and comprises solvent and the extrudate of possible extrusion aid.Extrusion be wherein stick with paste squeeze through mould or hole with
Produce the manufacture process of the long materials of constant cross-section.General extrusion process plastics or the food used, and form adsorbent or catalysis
Agent.Any conventional extruders can be used.Extrudate is generally of the diameter of 0.5 to 10mm, concrete 1 to 5mm.The screw type being suitable for
Extruder is described in " Particle Size Enlargement " (particle diameter increase), Handbook of Powder
Technology, vol. 1 (1980) pp.112-22.
Calcining extrudate.Preferably calcine and carry out in oxygen-containing atmosphere, with the organic substance (example comprised in the extrudate that burnouts
As, residual solvent, extrusion aid etc.).Calcining can be carried out at 400 to 1000 DEG C, more preferably 450 to 700 DEG C.Sometimes, at the beginning of useful
Begin calcining extrudate in inert atmosphere (such as, nitrogen, helium), to thermally decompose the organic compound comprised in extrudate, then burns
Organic substance in oxygen-containing atmosphere to the greatest extent.
Catalyst generally comprises 0.05 to 3% weight palladium and the 11st race's metal of optional 0.05 to 1.5% weight.More preferably urge
Agent comprises 0.5 to 1.5% weight palladium and 0.25 to 0.75% weight gold.
In order to prepare catalyst, the extrudate of calcining typically processes with the aqueous solution of palladium salt.The concentration of solution used and amount
Depend on the desired concn of palladium in final catalyst.Then remove water, leave the palladium salt of deposition on extrudate.The palladium salt being suitable for
Including Palladous chloride., sodium chloropalladite, Palladous nitrate. and palladium sulfate.11st race's slaine in company with adding palladium or can add in single step
To extrudate.Such as, the aqueous solution of auric chloride, tetra chlorauric acid, sodium terachloraurate etc. can be used.
The extrudate of dipping is calcined in inertia or oxidizing gas the temperature of 100 DEG C to 600 DEG C, such as helium, nitrogen, argon,
Neon, nitrogen oxides, oxygen, air, carbon dioxide etc..It is used as the mixture of above-mentioned gas.Preferably calcine at nitrogen, oxygen or air
Or its mixture carries out general 0.1 and 5 hour.
After firing, products therefrom is made to reduce, to convert at least part of palladium and the 11st race's metal (if use), with preparation
The catalyst of reduction.Generally available any known method uses conventional reduction agent, such as ammonia, carbon monoxide, hydrogen, hydrocarbon, alkene,
Aldehyde, alcohol, hydrazine, primary amine, carboxylic acid, carboxylate and carboxylate.Hydrogen, ethylene, propylene, alkaline hydrazine and alkaline formaldehyde are highly useful going back
Former dose, ethylene and hydrogen are particularly preferred.Although pure hydrogen can be used, but more typically use hydrogen and noble gas (such as nitrogen, helium,
Argon etc.) mixture.These mixture generally comprise a maximum of about of 50% volume (vol.%) hydrogen, more typically comprise about 5 to 25% volumes
Hydrogen and 75 to 95% volume noble gases.Recovery time is generally 0.1 to 5 hour.Reduction temperature used can be 20 to 600 DEG C.
Catalyst can be used for the acetoxylation of alkene (such as ethylene or propylene), to produce acetoxylation alkene, example
Such as vinyl acetate or allyl acetate.In acetoxylation is reacted, preferably use the catalyst of strengthening, the catalyst of strengthening
The catalyst of reduction can be joined by activator to prepare.Activator is alkali or alkaline earth metal compound, the example be potassium, sodium,
Hydroxide, acetate, nitrate, carbonate and the bicarbonate of caesium, magnesium, barium etc..Potassium salt is preferred activator.Activator
Content can be 0.1 to 15% weight of catalyst, preferably 0.5 to 10% weight.
Present invention additionally comprises the method preparing vinyl acetate, described method includes making to comprise entering of ethylene, oxygen and acetic acid
Material reacts in the presence of a catalyst.
Charging generally comprises 20 to 70% molar ethylenes, 2 to 8% mole oxygen and 2 to 20% mole of acetic acid.Charging can comprise dilute
Release agent.The example being suitable for diluent includes propane, nitrogen, helium, argon, carbon dioxide etc. and mixture thereof.
Reaction general in fixed bed reactors 100 to 250 DEG C (preferably 125 to 200 DEG C) temperature and 15 to
Carry out under the pressure of 500psig.
Embodiment 1
Extrudate preparation and sign:
By D-T51 titanium dioxide (178.2g), aluminium oxide (DISPERAL®P2, purchased from Sasol, 1.8g), high-purity
WALOCELTMC sodium carboxymethyl cellulose (The Dow Chemical Company, 3.8g), poly-(ethylene oxide) (MW=100,
000,3.4g) and cellulose derivative (METHOCELTMK4M, purchased from The Dow Chemical Company, 1.8g) mix 5
Minute.Water (100g), ammonium hydroxide aqueous solution (14.8M, 10.5g) and benzylalcohol (1.3g) are joined mixture, and further
Mixing produces sticks with paste.Paste is put into the Bonnot 1-inch extruder (The of the die face in 2 holes being equipped with diameter 1/8 inch
Bonnot Company) hopper in.
Collect extrudate, and be dried 12 hours at 80 DEG C in atmosphere, calcine the most in atmosphere.Make calcining heat with 2
DEG C/min speed be increased to 500 DEG C from room temperature, 500 DEG C keep 2 hours, with the speed of 10 DEG C/min from 500 DEG C of risings
To 700 DEG C, keep 3 hours at 700 DEG C, be then reduced to room temperature.
Pd-Au catalyst
By NaHCO3Powder (2.7g) is slowly added into and comprises Na2PdCl4·3H2O(3.1g)、NaAuCl4·2H2O
(1.1g) and the aqueous solution of water (23.5g).Mixture is stirred at room temperature 10 minutes.Solution pipette is sprayed onto the extrusion through calcining
On thing (100g), make them roll in rotary flask simultaneously.Once complete dipping, with heating gun, the flask of rotation is heated to
About 100 DEG C.Make the extrudate being through impregnation with roll other 30 minutes at 100 DEG C, be then placed in baking oven experiencing 2 hours at 80 DEG C,
It is subsequently cooled to room temperature.
The extrudate of drying is washed with warm water (50 to 80 DEG C), until can be by making washing filter liquor and 1% weight nitric acid
Precipitation is observed in silver solution mixing, and detection does not has chloride.After having washed, at 80 to 100 DEG C of dry catalysts, to remove water.
Then they are heated 3 hours in atmosphere at 230 DEG C, flow down at nitrogen and heat 30 minutes at 230 DEG C.In nitrogen 10% mole
Flowing down of hydrogen raises the temperature to 500 DEG C, keeps 3 hours, is subsequently cooled to room temperature.
Extrudate aqueous solution (1L) washing comprising 10% w acetic acid potassium and 1% weight percent potassium hydroxide.Scrubbed squeezes
Go out thing to be dried 2 hours at 125 DEG C under nitrogen.Obtain palladium-gold catalyst.Catalyst comprises 0.93% weight Pd, 0.54% weight Au
With 1.5% weight K.
Some physical propertys of catalyst are shown in Table 1.The crushing strength of catalyst Chatillon crushing strength is analyzed
Instrument (Model DPP 50) is measured.Power measure 1/8 inch of long extrudate fracture by 25 times needed for is averaged, and obtains report value.
Bulk density is measured by 40g catalyst being put into 100mL graduated cylinder (1 " nominal outside diameter).Rap graduated cylinder, until apparent volume is not
Change again, then by quality divided by this value, bulk density calculated.By adding pellet to 50mL water in the second graduated cylinder, then
Rap all spaces of filling, measure voidage.The cumulative volume individually shared from water and pellet deducts the gained water yield, to measure water
The voidage occupied.Being poured through basket by mixture, shake is removed excessive water, is then weighed by wet extrudate, measures total
Pore volume.The quality exceeding initial 40g catalyst is increased density the measuring as pore volume divided by water.
Prepared by vinyl acetate:
In fixed bed reactors (rustless steel, 1 inch of O.D.), test palladium-gold catalyst is prepared for vinyl acetate.
By reactor catalyst (10g) and inertia Alpha-alumina cylindrical pellets (1/8 " diameter, surface area 4m2/ g, pore volume
0.25mL/g, 25g) mixture fill.Charging comprise 46.1% mole of helium, 33.9% molar ethylene, 11.48% mole of acetic acid,
4.2% mole oxygen and 4.2% mole of nitrogen.Reactor pressure is 80psig, in standard temperature and pressure (STP) relative to catalyst volume
Space velocity is 3050h-1.Reactor fluidisation sand bath cooling, temperature is set in 130 DEG C.Product stream passes through gas chromatogram (GC)
Analyze.OTR, oxygen selective, the oxygen productivity (yield) of generation vinyl acetate between 40 to 50h and generate on stream
The ethylene selectivity of vinyl acetate calculates from GC result, is listed in table 1.By the oxygen amount of consumption divided by delivering to reactor
Total oxygen demand, calculates OTR.The oxygen selective generating vinyl acetate is that the oxygen amount consumed in preparing vinyl acetate is removed
With the total oxygen demand consumed.The oxygen productivity generating vinyl acetate is the product that OTR is multiplied by oxygen selective.Generate acetic acid second
The ethylene selectivity of alkene ester is that the ethylene volume consumed in preparing vinyl acetate is divided by the total ethylene volume consumed.Catalyst Production
Ability is the vinyl acetate grams/liter catalyst hour of preparation.
Embodiment 2 and Comparative Example 3,4
The method repeating embodiment 1 with the formula shown in table 1.
Table 1 and Fig. 1 shows, is carried on and has 1 and 10% palladium-gold of titania-alumina extrudate of weight aluminium oxide
Catalyst has the porosity similar to the catalyst being carried on titania extrudate, but has surface area and the improvement of increase
Activity, and have more significantly higher than the catalyst (Comparative Example 4) prepared from titania extrudate anti-crushing by force
Degree.But, the catalyst prepared from the extrudate comprising 20% weight aluminium oxide and 80% weight titanium dioxide obtains ratio from dioxy
Change the vinyl acetate production ability that the catalyst prepared of titanium extrudate is lower, even if it has large surface area.Comparative
The low activity that embodiment 3 obtains is likely due to the formation of smaller hole, as shown in its large surface area
Table 1
。
Claims (14)
1. comprising a catalyst for the acetoxylation for alkene of the palladium being carried on extrudate, described extrudate comprises
At least 80% weight titanium dioxide and 0.1 to 15% weight aluminium oxide, wherein extrudate by use comprise carboxyl alkyl cellulose and
Prepared by the extrusion aid of hydroxy alkyl cellulose.
2. the catalyst of the acetoxylation for alkene of claim 1, wherein extrudate comprises 0.2 to 10% weight oxidation
Aluminum.
3. the catalyst of the acetoxylation for alkene of claim 1, wherein extrudate comprises 0.5 to 5% weight oxidation
Aluminum.
4. the catalyst of the acetoxylation for alkene of claim 1, the catalysis of the described acetoxylation for alkene
Agent comprises the 11st race's metal further.
5. the catalyst of the acetoxylation for alkene of claim 4, wherein the 11st race's metal is gold.
6. the catalyst of the acetoxylation for alkene of claim 1, wherein the amount of palladium is the described acetyl for alkene
0.05 to 3% weight of the catalyst of epoxide.
7. the catalyst of the acetoxylation for alkene of claim 1, wherein carboxyl alkyl cellulose and hydroxy alkyl cellulose
Weight ratio be 3:1 to 1:1.
8. the catalyst of the acetoxylation for alkene of claim 1, wherein hydroxy alkyl cellulose is selected from methyl 2-hydroxyl
Propyl cellulose, methyl 2-hydroxy ethyl cellulose and mixture thereof.
9. the catalyst of the acetoxylation for alkene of claim 1, wherein extrudate is forged the temperature of 650 to 750 DEG C
Burn.
10. the method preparing vinyl acetate, described method include making ethylene, oxygen and acetic acid claim 1 for
React in the presence of the catalyst of the acetoxylation of alkene.
The method of 11. claim 10, wherein extrudate comprises 0.2 to 10% weight aluminium oxide.
The method of 12. claim 10, wherein extrudate comprises 0.5 to 5% weight aluminium oxide.
The method of 13. claim 10, wherein the catalyst for the acetoxylation of alkene of claim 1 comprises further
11st race's metal.
The method of 14. claim 13, wherein the 11st race's metal is gold.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12/653563 | 2009-12-16 | ||
| US12/653,592 US8273682B2 (en) | 2009-12-16 | 2009-12-16 | Preparation of palladium-gold catalyst |
| US12/653,563 US8329611B2 (en) | 2009-12-16 | 2009-12-16 | Titania-containing extrudate |
| US12/653592 | 2009-12-16 | ||
| US12/657,893 US8507720B2 (en) | 2010-01-29 | 2010-01-29 | Titania-alumina supported palladium catalyst |
| US12/657893 | 2010-01-29 | ||
| PCT/US2010/057387 WO2011075279A1 (en) | 2009-12-16 | 2010-11-19 | Titania-alumina supported palladium catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102753265A CN102753265A (en) | 2012-10-24 |
| CN102753265B true CN102753265B (en) | 2016-11-30 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1235561A (en) * | 1996-10-31 | 1999-11-17 | 米兰纽姆石化公司 | Improved process for production of supported palladium-gold catalysts |
| CN1364855A (en) * | 2000-12-29 | 2002-08-21 | 中国石油化工股份有限公司 | Selective hydrogenization catalyst and its preparing method and use |
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1235561A (en) * | 1996-10-31 | 1999-11-17 | 米兰纽姆石化公司 | Improved process for production of supported palladium-gold catalysts |
| CN1364855A (en) * | 2000-12-29 | 2002-08-21 | 中国石油化工股份有限公司 | Selective hydrogenization catalyst and its preparing method and use |
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