CN1090533C - 制备流化床乙烯基乙酸酯催化剂的方法 - Google Patents
制备流化床乙烯基乙酸酯催化剂的方法 Download PDFInfo
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- CN1090533C CN1090533C CN95102729A CN95102729A CN1090533C CN 1090533 C CN1090533 C CN 1090533C CN 95102729 A CN95102729 A CN 95102729A CN 95102729 A CN95102729 A CN 95102729A CN 1090533 C CN1090533 C CN 1090533C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 161
- 238000000034 method Methods 0.000 title claims abstract description 44
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- 239000012530 fluid Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 32
- 239000002245 particle Substances 0.000 claims abstract description 44
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 15
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- 229910052791 calcium Inorganic materials 0.000 claims abstract description 7
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 6
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- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 54
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 49
- 229910052763 palladium Inorganic materials 0.000 claims description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 29
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- 239000007787 solid Substances 0.000 claims description 17
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 16
- 239000010931 gold Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 229910052737 gold Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
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- 150000001340 alkali metals Chemical class 0.000 claims description 12
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- 229910052788 barium Inorganic materials 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 6
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- 239000007789 gas Substances 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 6
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
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- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
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- -1 alkali metal salt Chemical class 0.000 abstract description 2
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- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 18
- 229910052700 potassium Inorganic materials 0.000 description 13
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- 239000002904 solvent Substances 0.000 description 10
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 9
- 235000011056 potassium acetate Nutrition 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
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- 239000012153 distilled water Substances 0.000 description 4
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- 239000000126 substance Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910004373 HOAc Inorganic materials 0.000 description 2
- 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 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- OTCKNHQTLOBDDD-UHFFFAOYSA-K gold(3+);triacetate Chemical compound [Au+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OTCKNHQTLOBDDD-UHFFFAOYSA-K 0.000 description 2
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
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- 238000001291 vacuum drying Methods 0.000 description 2
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- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- XXZCIYUJYUESMD-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-(morpholin-4-ylmethyl)pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)CN1CCOCC1 XXZCIYUJYUESMD-UHFFFAOYSA-N 0.000 description 1
- FYELSNVLZVIGTI-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-5-ethylpyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1CC)CC(=O)N1CC2=C(CC1)NN=N2 FYELSNVLZVIGTI-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 0.000 description 1
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- UCTLHLZWKJIXJI-LXIBVNSESA-N [(3s,8r,9s,10r,13s,14s)-17-chloro-16-formyl-10,13-dimethyl-2,3,4,7,8,9,11,12,14,15-decahydro-1h-cyclopenta[a]phenanthren-3-yl] acetate Chemical compound C([C@@H]12)C[C@]3(C)C(Cl)=C(C=O)C[C@H]3[C@@H]1CC=C1[C@]2(C)CC[C@H](OC(=O)C)C1 UCTLHLZWKJIXJI-LXIBVNSESA-N 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- 238000011021 bench scale process Methods 0.000 description 1
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 1
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Classifications
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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Abstract
一种制备流化床乙烯基乙酸酯(VAM)催化剂的方法,包括用含Pd和M的无卤化物金属盐的溶液浸渍一种载体,上述M包括Ba,Au,La,Nb,Ce,Zn,Pb,Ca,Sr,Sb或它们的混合物,所述载体包括基本上惰性的微球颗粒的混合物,还原所述金属盐,使在载体表面沉积Pd和M,并用至少一种无卤化物的碱金属盐浸渍该载体。用作微球载体的至少50%的颗粒粒径小于100微米,优选小于60微米。
Description
本申请是1994年2月22日申请的、序号为200130的美国专利申请的部分继续申请。
本发明涉及流化床钯—促进的催化剂的制备方法,该催化剂用于从乙烯、乙酸和含氧气体生产乙烯基乙酸酯。此外,本发明涉及一种新的流化床载体以及用该载体制备用于生产乙烯基乙酸酯的钯—促进的流化床催化剂的方法。
在催化剂存在下,乙烯、乙酸和氧一起进行气相反应制备乙烯基乙酸酯的方法是公知的。典型地,所用催化剂是固定床形式的,且负载在多孔载体材料如氧化硅或氧化铝上。
这些催化剂中早期的一些实例表明,钯和金或多或少均匀分布于整个载体上(参见,如US 3275680,3743607,和3950400以及GB1333449和南非专利687990)。人们后来意识到这是一种缺点,因为已发现,由于反应物并不大量扩散进入载体内,所以载体内部的催化物质对反应并无帮助。为了克服这个缺点,曾设计了一些新的制备催化剂的方法,以制造出活性成份集中分布在载体最外层的催化剂。例如,GB1500167中要求保护的催化剂,至少90%的钯和金分布在载体颗粒中颗粒半径距表面不超过30%的那部分中。此外,GB 1283737说明,用如碳酸钠或氢氧化钠的碱溶液预处理多孔载体,可以控制穿入多孔载体的程度。US4048096描述了已发现可制备出特别活泼的催化剂的另一种方法,而US4087622和5185308公开了制备表层浸渍的催化剂的其它方法。所有这些专利主要都是关于制备用于制造乙烯基乙酸酯的固定床催化剂的。不过,US3950400同时公开了其中的催化剂可能用于流化床反应器的信息。此外,GB1266623据说公开了一种生产乙烯基乙酸酯的流化床催化剂,该催化剂包括由各种碱、碱土或其它金属促进的钯。
如果制造乙烯基乙酸酯能够按流化床工艺方法和固定床工艺方法操作,将在经济上十分有利。来自流化床工艺的一些典型益处是:流化床反应器设计较多管式固定床反应器容易,催化剂寿命可望延长,因为不会发生由于热点而出现的失活,存在热点是固定床反应器的典型现象,连续补充催化剂可以保持最佳操作性能并实际上排除了催化剂的更换,由于可向反应器安全输入浓度相当高的氧,而不会形成可燃混合物,所以可期望生产率较高。
在发现本发明方法之前,用于流化床的钯一促进催化剂的制备方法一直没有制备出具有一些必要特性的催化剂,这些特性使产生出一种生产乙烯基乙酸酯的经济上可行的流化床工艺。本发明方法克服了现有技术中存在的问题,制备出的催化剂具有较好的操作性能和适宜的耐磨损性,可用于生产乙烯基乙酸酯。
本发明的主要目的是提供一种制备可用于生产乙烯基乙酸酯的钯—金属—碱金属促进的流化床催化剂的方法。
本发明的另一个目的是提供一种新的载体,该载体用于制备可用于流化床生产乙烯基乙酸酯的钯—金属—碱金属促进的催化剂。
本发明的另一个目的是提供一种制备可用作生产乙烯基乙酸酯的催化剂的载体的新方法。
本发明的其它目的和优点其一部分见于下面的文字说明,另一部分由说明书中可明显看出,或者通过实践本发明而加以了解。本发明的目的和优点,可利用权利要求书中特别指明的手段和组合形式予以实现和达到。
为了实现本发明的上述目的,制备流化床乙烯基乙酸酯催化剂的方法包括用含有无卤化物的钯金属盐,M和至少一种碱金属的溶液浸渍一种预制的微球载体,然后干燥该浸渍的催化剂,所述预制的微球载体中至少50%的颗粒的粒径小于100微米,所述流化床乙烯基乙酸酯催化剂其特征是具有下列通式:Pd-M-A,式中M相当于钡、金、镧、铌、铈、锌、铅、钙、锶、锑、或它们的混合物,A相当于至少一种碱金属或它们的混合物。基本上惰性的粒状载体典型地包括选自氧化铝、氧化硅、氧化锆或它们的混合物的微球颗粒。
在本发明的另一实施方案中,采用没有或基本上没有任何有机溶剂的水溶液实施该方法。
在本发明一优选实施方案中,将碱金属的金属盐分别浸到载体上,最好在浸渍了包括钯和M元素的盐溶液之后。
在本发明的另一实施方案中,将浸好的载体置于还原条件下加热,使钯和M沉积在载体表面。该还原处理可在沉积碱金属溶液之前或之后进行。
在本发明另一进一步优选的实施方案中,催化剂在低于80℃,最好在约60°-70℃之间干燥。
在本发明另一优选实施方案中,选择的基本上惰性的载体材料的粒径(颗粒直径)使得至少50%的颗粒小于60微米。优选地,至少75%的颗粒小于100微米。特别优选地,至少85%小于100微米。最后优选载体基本上没有钠。
在本发明另一实施方案中,制备乙烯基乙酸酯催化剂的载体包括孔体积为0.2-0.7cc/g,表面积100-200m2/g,至少50%的颗粒小于100微米的基本上惰性的微球颗粒的混合物。
在本发明该实施方案的优选方面中,至少75%的颗粒小于100微米,特别优选至少85%小于100微米。
在本发明的另一实施方案中,制备乙烯基乙酸酯催化剂的载体包括惰性的微球颗粒,优选氧化硅、氧化锆,氧化铝或它们的混合物,其中所述颗粒的孔体积为0.2-0.7cc/g,表面积100-200m2/g,且由80-20%的惰性载体溶胶和20-80%干燥的惰性颗粒混合物制成。
在本发明这方面的优选实施方案中,惰性颗粒的孔体积为0.3-0.65cc/g,特别优选0.4cc-0.55cc/g。
在本发明这方面的一个进一步优选的实施方案中,表面积为110-195m2/g,特别优选120-195m2/g。
本发明该实施方案的另一方面,氧化硅微球载体如下制备:将20%-80%的硅溶胶与80%-20%的高分散的硅胶(Silica aerosil)混合,在125°-280℃,优选130°-240℃的升高的温度下喷雾干燥该混合物,优选在550°-700℃,最好630°-660°之间焙烧该喷雾干燥的颗粒,以形成载体物质。
流化床乙烯基乙酸酯催化剂用的基本上惰性的载体可用下述方法制备,该法包括将80-20%(重)的含基本上惰性的微球颗粒的含水溶胶与20-80%(重)的固体的基本上惰性的颗粒材料混合制成含水混合物,喷雾干燥该含水混合物,焙烧所述颗粒使形成基本上惰性的载体。
典型地,本发明催化剂中钯、M和碱金属的重量百分数是:0.1-5.0wt%钯,优选0.2-4.0wt%,最优选0.3-约1.0wt%;大于零至10wt%碱金属,优选0.1-8.0wt%,最优选0.1-5.0wt%;大于零至约5.0wt%的M,优选0.1-约4.0wt%,最优选0.1-3.0wt%。
下面详细介绍本发明优选实施方案,这些实例只用于举例目的。
反应器测试
在工作台规模的流化床反应器内测试催化剂,催化剂最大容量为40cc。反应器内装填的典型的固体容积为30cc催化剂或催化剂加稀释剂。通常,使用足够的催化剂,使每次催化剂评价中反应器含0.093g钯金属。进行反应器测试前,将足量的惰性微球氧化硅与活性催化剂混合,达到30cc总体积。反应器装有两个进料口。在一部分实验中,使乙烯、乙酸和氧全部通过靠下的进料口进入反应器,只有氮从中心入口进入反应器。在其它实验中,通过中心入口通入额外量的氧。该中心入口位于靠下入口上方2.5"处。
反应器压力控制在115Psig,进入和离开反应器的所有管线都作了热记录,并保持在大约150-155℃,以便防止液体原料或产物冷凝。流化床反应器的典型温度可在100°-250℃,优选135°-190℃之间变化。
用配备TCD和FID两种检测器的Hewlett Packard Model 5890气相色谱联机分析反应器的气态排出物。用与含10%聚乙二醇(carbowax)20M的80/100 Chromosorb WAW和含23%SP2700的80/100Chromosorb PAW并列的13×摩尔筛柱分离氧、氮、乙烯和二氧化碳,并用TCD定量。用含4%聚乙二醇20M的80/100(carbopack)柱分离乙烯基乙酸酯和乙酸并用FID定量。
载体的制备
制备两种预制的微球氧化硅并用作实施本发明的载体。使用前,将全部载体进行筛分,在制备所用催化剂时,采用具有特定粒径分布的载体:
5%的颗粒小于105微米但大于88微米
70%的颗粒小于88微米但大于44微米
25%的颗粒小于44微米。
应当理解,上述粒径分布不意于进行限制,根据反应器尺寸和操作条件所作的粒径分布的改变都是可以采用的。
载体1
通过喷雾干燥Nalco(Nalco化学公司)氧化硅溶胶1060和DeGussa Aerosil(DeGussa化学公司)氧化硅的混合物制备载体1。干燥的载体中,80%的氧化硅来自溶胶,20%的氧化硅来自Aerosil。空气中640℃下焙烧该喷雾干燥的的微球4hr.。
Aerosil氧化硅是Degussa的发烟氧化硅的商标名称。该材料表面积高(~200m2/g),基本上没有微孔,在nm(1×10-9m)范围内粒径分布均匀,而且不含钠。其它公司也可以制备性能可与Aerosil相比的发烟氧化硅,且可用来代替Aerosil制备载体1。
Nalco氧化硅溶胶1060用在本申请中特别有利,因为在溶胶中的氧化硅颗粒有较大的平均粒径,60毫微米。这些较大的氧化硅颗粒堆积密度比较小的溶胶粒子(如在Nalco2327中为~30毫微米)小,且使制成的载体在中孔范围内的孔体积较大,而微孔体积较小。可用具有类似大的(~40-80毫微米)平均粒径氧化硅的其它氧化硅溶胶代替1060氧化硅溶胶制备载体1。
载体2
一系列含KA-160(Sud Chemie)的微球载体(载体2A-2D)制备如下:
载体2A:75%来自KA-160的SiO2与25%来自溶胶的SiO2
将750g的KA-160研磨使通过35目筛,并洗除任何水溶性杂质如氯化物离子。然后使该固体氧化硅与694.4g的Snotex-N-30(Nissan Chemical)(36wt%固体)氧化硅溶胶和556g蒸馏水混合。在瓷制球磨罐内研磨该混合物过夜。再喷雾干燥该调匀的浆液使形成适用于流化床反应目的微球颗粒。然后在空气中640℃下焙烧该微球载体4hr.。
KA-160载体的作用是在微球颗粒内提供多的孔结构。由SudChemie制备固定床载体,KA-160,该载体的性能对用于乙烯基乙酸酯催化剂的制备十分有利。适中的表面积(160m2/g),几乎没有或没有微孔,在中孔范围内的大的孔隙率(~0.57cc/g)都是KA-160的有利特性。此外,也可采用表面积和孔体积性能类似于KA-160(没有或几乎没有微孔,中孔容积~1.5-0.25cc/g,表面积80-200m2/g)的固定床催化剂载体。这些载体可代替KA-160用于制备载体2。
载体2B:65%来自KA-160的SiO2和35%来自溶胶的SiO2
该载体的制备方式类似于载体2A,只是用227.5g的kA-160,408.3g的Snotex-N-30(30wt%固体)和64g蒸馏水。
载体2C:50%来自KA-160的SiO2和50%来自溶胶的SiO2
该载体的制备方式类似于载体2A,只是用175g的KA-160和583.3g的Snotex-N-30(30wt%固体)。
载体2D:75%来自KA-160的SiO2和25%来自溶胶的SiO2
该载体的制备方式类似于载体2A,只是用262g的KA-160,219g的Nalco 2327(40wt%固体)(Nalco化学制品公司)和219g蒸馏水。
上面制备的每一种微球氧化硅可有利地用于根据本发明方法制备流化床乙烯基乙酸酯单体催化剂。对通过用活性金属浸渍制备流化床催化剂,与任何可商购到的载体相比,这些载体为本发明的乙烯基乙酸酯催化剂提供了意外的优越物理性能。下面表1包括了对全部载体所作的选择的分析数据。
表1
定型的微球氧化硅载体的物理性能
载体 | 浆液中的固体重量百分数 | 孔体积r≤4,500A(cc/g) | TotPoreVol(cc/g) | Ap堆积密度(g/cc) | SAm2/g | 焙烧时间/温度 | 磨耗损失0-20hrs |
载体1载体2A载体2B载体2C载体2D | 6250504650 | 0.390.600.390.270.62 | 0.460.600.390.330.63 | 0.780.650.720.770.60 | 124.4175.5184.4191.9156.0 | 4hr/640℃4hr/640℃4hr/640℃4hr/640℃4hr/640℃ | <5%0.33%0.35%1.65% |
催化剂制备
制备催化剂的一般方法概括如下。
典型地,利用初始润湿技术,用活性金属的一种(或几种)溶液浸渍微球载体。可将不含卤化物的活性金属、钯、M元素(如金)的化合物及乙酸钾按适宜比例溶于适宜溶剂中,再浸在微球载体上。通常希望将催化剂制备中使用的全部活性金属都溶于一份溶剂中,该溶剂的体积恰适于填满载体的孔体积。某些情况下,需用的一种促进剂可能不溶于与其它金属化合物所用的相同的溶剂。此时可用含一些金属成分的溶液浸渍载体,再用含其余成分的第二种溶液浸渍。可用的溶剂包括水和易挥发有机溶剂如4个或4个以下碳的羧酸,醇,醚,酯,和芳香族。湿催化剂干燥后,可用于生产乙烯基乙酸酯,或者,可采用所属领域技术人员公知的手段先进行还原。
一般有乙酸存在时且在升高的温度(~100℃)加热催化剂时,催化剂变成黑色并失活。或者,如果将乙酸钯溶液(有或没有其它金属乙酸盐)加热到太高的温度,或加热太长时间,溶液颜色从开始的橙红色变成浅绿色,并有黑色沉淀生成。通常,60℃是使用的安全温度,但在较短时间内可使用直到~80℃温度以溶解乙酸钯。
实例1
制备组成为0.75wt%Pd,0.32wt%Au和2.88wt%K的催化剂如下:将乙酸钯溶于乙酸金试剂的乙酸溶液内,如US4933204所述,用该混合溶液浸渍上述预制的微球载体2A。60℃下用旋转蒸发器干燥固体,再用肼(不用碱性氢氧化物)的水溶液还原Pd和Au。洗涤固体以除掉肼,干燥并用乙酸钾浸渍固体。将12.67g(16.7cc)的催化剂装入反应器进行测试。下面的表2列出各种条件下该催化剂的反应器测试结果。这些结果表明,用10.55%的O2,14.31%的HOAc,在164.9℃转化率18.2%,选择性83%。
实例2
该例催化剂组成为1.07wt%Pd,0.40wt%Au和2.89wt%K,且按GB1266623所述方法制备,只是载体与例1中所用的相同。将8.68g(11.3cc)催化剂装入反应器测试。下面的表2列出各种条件下该催化剂的反应器测试结果。用7%O2,10%HOAc,在159℃乙烯转化率8.1%,乙烯基乙酸酯选择性84.4%。
实例3
重复例2的方法,制备组成如下的催化剂:1.01wt%Pd,0.38wt%Au和2.60wt%K。但用上述的载体1。将9.2g(10.6cc)催化剂装入反应器测试。表2列出各种条件下的反应器测试结果。用与例2相同条件,该催化剂使C2H4转化率8.6,VA选择性85.3。
例2和3的催化剂的操作性能非常相似,但用载体1制备的催化剂看上去稍更活泼。由于这两种催化剂的组成几乎相同,活性上的差别可能是由于不同载体造成的。
实例4
据US3950400制备该催化剂,只是使用了上述的微球(流化床)载体1。组成为0.82wt%Pd,0.40wt%Au,0.13wt%Ba,2.69wt%K。60℃,减压下小心脱除乙酸(使用旋转蒸发器)。固体保持棕黄色。将11.57g(13.4cc)催化剂装入反应器测试。列于表2的该催化剂的反应器测试结果显示它具有较高的活性和选择性。164℃用7%氧和14%乙酸,得到的乙烯转化率12.5%,选择性87.2%。
实例5
如下制备组成为0.81wt%Pd,0.34wt%Au和2.71wt%K的催化剂:将乙酸钯(PdAc)和乙酸钾(KAc)溶于乙酸,再加乙酸金,将其浸在载体1上。60℃减压脱除乙酸,此时固体为棕黄色。该催化剂的制备类似于例1的催化剂制备,只是测试前无催化剂还原过程。将11.75g(13.2cc)催化剂装入反应器测试。表2列出各种条件下该催化剂的测试结果。用该催化剂转化率9.2%,VA选择性87.8%。
实例6
按例5制备组成为0.77wt%Pd,0.40wt%Au和2.2wt%K的催化剂。再用肼还原该固体,水洗除肼,再加额外的乙酸钾。将14.25g(17.6cc)催化剂装入反应器测试。表2示出优良的反应器测试结果。与例5相比,用该催化剂得到类似结果,转化率10.17%,选择性85.7%。
制备各种载于氧化硅型Pd/M/K催化剂,其中M不是金。评价的金属包括M=Ba,La,Sb,Pb,Ce,Nb,Ca,Zn和Sr。下面实例具体说明这些不同的金属。
实例7
制备的催化剂钯含量较低,0.88wt%Pd,该钯含量典型地用在Bayer型催化剂中,但与0.88wt%Ba同用在Hoechst型催化剂中,一般太不活泼。用乙酸作溶剂。催化剂含2.9wt%K。将15.52g(21.0cc)催化剂放入反应器中测试。在各种条件下得到的测试结果中,乙烯转化率接近10%,对VA选择性81%,如表2所列。因暴露于升高的温度(100℃)下,同时仍有乙酸存在,催化剂出现一定的失活。
实例8
用水作唯一的溶剂,制备组成为0.41wt%Pd,0.49wt%Ba和2.2wt%K的催化剂。使乙酸钯、乙酸钾和乙酸钡的混合物充分溶于可用作唯一溶剂的蒸馏水中。将24.77g(30.0cc)催化剂放入反应器中测试。表2列出各种条件下该催化剂的反应器测试结果,乙烯转化率10%,对VAM选择性85%。
用水代替乙酸作浸渍溶剂有几个重要优点。水比乙酸肯定便宜,毒性较小,腐蚀较轻。所有这些优点使用水成为一种较便宜的方法。此外,水不是钯的还原剂。如果在炉内100℃下加热,用乙酸制备的催化剂变暗至近乎黑色,而用水制备的相似催化剂仍保持其棕黄色,且仍保持优良的反应器操作性能。最后,就对载体产生的有害作用而言,水应当是较良性的溶剂。
实例9
用乙酸钯,乙酸钾和乙酸锑在乙酸中的溶液浸渍预制的微球载体。该湿固体在60℃,减压干燥。未进行催化剂的预还原处理。制成的催化剂含有0.81wt%Pd,0.70wt%Sb和2.9wt%K。将10.95g(12.8cc)催化剂放入反应器中测试。表2列出的反应器测试结果表明,乙烯转化率接近17%,选择性89%,而原料混合物中只有9mol%氧。
实例10
向含锑催化剂加钡大大削弱催化剂活性。所测试的催化剂组成为(wt%)0.71Pd,0.71Ba,0.71Sb和2.6K。将10.95g(13.5cc)催化剂放入反应器中测试。在所评价的条件下锑和钡之间无协同作用,如下面表2中的结果所示。
实例11和12
乙酸钯,乙酸镧和乙酸钾的混合物在乙酸中溶解得相当好。例11中用载体1,例12中用载体2A。将该溶液浸渍在预制载体上,并真空干燥制成表2所示的优良催化剂。催化剂11和12的组成分别是(wt%):0.77Pd,0.70La,2.7K;0.80Pd,0.57La,3.1K。例11中,反应器中放入10.95g(13.0cc)催化剂测试。例12中,反应器中放入10.95g(15.0cc)催化剂测试。转化率和选择性稍低于用含锑的催化剂,但仍相当高。
实例13
将乙酸钯,乙酸镧和乙酸钾混合物溶于水而不是乙酸,制成的催化剂组成为:0.15wt%Pd,0.34wt%La,1.4wt%K。将25.2g(30.0cc)催化剂放入反应器中测试。考虑到Pd含量相当低,乙烯转化率8%(如表2所示)是相当好的。
实例14
作为铌源的草酸铌不溶于乙酸。为此,用水溶液将草酸铌先浸渍到载体1上。载体干燥后,在其上浸渍乙酸钯和乙酸钾的乙酸溶液。将11.04g(14.0cc)催化剂放入反应器中测试。制成的催化剂组成为0.81wt%Pd,0.64wt%Nb,3.1wt%K。反应器操作性能为转化率~9%,选择性84%,满足要求,但该催化剂似乎比预期的失活得快。
实例15和16
按两种不同含量加钙作为促进剂:(1)与例7中钡的mol%相同,(2)接近例7中钡的wt%。两种情况中都用载体2A。例15中,将10.95(15.8cc)催化剂放入反应器中测试。例16中,将10.95g(15.4cc)催化剂放入反应器中测试。两种催化剂操作性能都不好,如表2所示。但钙含量越低,转化率和选择性越高。进一步调节钙含量有可能改进催化剂操作性能。
实例17和18
按上述一般步骤,将金属溶于乙酸并在60℃真空干燥,制备铈促进的催化剂(例17)和锌促进的催化剂(例18)。两例中都用载体2A。催化剂的最后组成是,例17:0.80wt%Pd,0.69wt%Ce,2.8wt%K;例18:0.81wt%Pd,0.33wt%Zn和2.9wt%K。例17中,将10.96g(15.6cc)催化剂放入反应器中测试。例18中,用10.96g(15.6cc)催化剂。这些催化剂的测试实验显示出其具有的潜力,如表2所示。将促进剂含量和还原处理最佳化可能十分有利。尤其是,铈显示出非常好的初始活性。
实例19和20
例19和20催化剂的制备,用与例17和18相同的载体和基本上相同的工艺方法,只是用Pb和Sr代替Ce和Zn。例19催化剂的最后组成是(wt%):0.81Pd,0.70Pb,2.9K。例20催化剂的最后组成是(wt%):0.80Pd,0.68sr,2.7K。例19中,将11.71g(13.2cc)催化剂放入反应器中测试。例20中用10.95g(15.4cc)催化剂。如表2所示,铅促进的催化剂较预期的失活得快,而锶促进的催化剂活性低,选择性较差。
表2
表2 | ||||||||||
实验数据汇编 浸渍型流化床VAM催化剂 | ||||||||||
RUN # | % C2H4 | % VA | BED T | TOTAL | FEED COMPOSITON | Psig | HRS | |||
CONV | SEL | (C) | FLOW | O2 | N2 | C2H4 | HOAC | |||
实例1 | ||||||||||
1 | 14.42 | 85.38 | 163.0 | 396.41 | 7.040 | 30.65 | 47.930 | 14.380 | 115 | 0.8 |
2 | 14.87 | 87.16 | 161.5 | 396.41 | 7.040 | 30.65 | 47.930 | 14.380 | 115 | 2.4 |
3 | 14.46 | 86.00 | 161.9 | 396.41 | 7.040 | 30.65 | 47.930 | 14.380 | 115 | 2.9 |
4 | 18.20 | 83.06 | 164.9 | 396.41 | 10.550 | 27.17 | 47.970 | 14.310 | 115 | 3.9 |
5 | 17.95 | 86.86 | 161.7 | 418.63 | 10.010 | 31.17 | 45.390 | 13.430 | 115 | 6.0 |
6 | 17.38 | 88.86 | 155.5 | 418.63 | 10.010 | 31.17 | 45.390 | 13.430 | 115 | 6.3 |
7 | 17.57 | 87.80 | 158.2 | 418.63 | 10.010 | 31.17 | 45.390 | 13.430 | 115 | 6.9 |
8 | 17.01 | 88.05 | 157.2 | 418.63 | 10.010 | 31.17 | 45.390 | 13.430 | 115 | 7.2 |
9 | 19.03 | 85.21 | 165.2 | 426.13 | 11.590 | 30.62 | 44.590 | 13.200 | 115 | 7.6 |
实例2 | ||||||||||
1 | 7.54 | 82.59 | 159.4 | 361.70 | 7.460 | 29.31 | 52.810 | 10.420 | 115 | 1.5 |
2 | 7.67 | 82.99 | 160.4 | 361.70 | 7.460 | 29.31 | 52.810 | 10.420 | 115 | 1.8 |
3 | 7.79 | 83.77 | 159.8 | 361.70 | 7.460 | 29.31 | 52.810 | 10.420 | 115 | 2.0 |
4 | 7.96 | 84.20 | 160.0 | 361.70 | 7.460 | 29.31 | 52.810 | 10.420 | 115 | 2.3 |
5 | 7.97 | 84.28 | 159.6 | 361.70 | 7.460 | 29.31 | 52.810 | 10.420 | 115 | 2.6 |
6 | 8.05 | 84.43 | 159.6 | 361.70 | 7.460 | 29.31 | 52.810 | 10.420 | 115 | 3.0 |
7 | 4.32 | 88.03 | 154.4 | 365.00 | 7.370 | 29.97 | 52.330 | 10.330 | 115 | 4.4 |
8 | 4.82 | 85.51 | 160.4 | 365.00 | 7.370 | 29.97 | 52.330 | 10.330 | 115 | 5.4 |
9 | 4.88 | 85.55 | 160.9 | 365.00 | 7.370 | 29.97 | 52.330 | 10.330 | 115 | 5.8 |
10 | 4.93 | 85.61 | 160.9 | 365.00 | 7.370 | 29.97 | 52.330 | 10.330 | 115 | 6.1 |
11 | 6.19 | 86.15 | 159.1 | 365.00 | 7.370 | 29.97 | 52.330 | 10.330 | 115 | 8.3 |
12 | 6.17 | 86.03 | 159.1 | 365.00 | 7.370 | 29.97 | 52.330 | 10.330 | 115 | 8.7 |
RUN # | % C2H4 | % VA | BED T | TOTAL | FEED COMPOSITON | Psig | HRS | |||
CONV | SEL | (C) | FLOW | O2 | N2 | C2H4 | HOAC | |||
13 | 6.18 | 85.97 | 159.1 | 365.00 | 7.370 | 29.97 | 52.330 | 10.330 | 115 | 9.1 |
14 | 6.39 | 84.54 | 161.0 | 365.00 | 7.370 | 29.97 | 52.330 | 10.330 | 115 | 9.5 |
15 | 6.54 | 85.10 | 161.0 | 365.00 | 7.370 | 29.97 | 52.330 | 10.330 | 115 | 9.8 |
16 | 6.66 | 85.40 | 161.0 | 365.00 | 7.370 | 29.97 | 52.330 | 10.330 | 115 | 10.2 |
实例3 | ||||||||||
1 | 8.83 | 84.17 | 160.0 | 362.80 | 7.610 | 29.36 | 52.650 | 10.390 | 115 | 1.7 |
2 | 8.81 | 84.65 | 159.0 | 362.80 | 7.610 | 29.36 | 52.650 | 10.390 | 115 | 2.5 |
3 | 8.68 | 85.17 | 159.0 | 362.80 | 7.610 | 29.36 | 52.650 | 10.390 | 115 | 3.6 |
4 | 8.64 | 85.30 | 159.0 | 362.80 | 7.610 | 29.36 | 52.650 | 10.390 | 115 | 4.1 |
实例4 | ||||||||||
1 | 11.48 | 88.68 | 162.0 | 396.41 | 7.040 | 30.65 | 47.930 | 14.380 | 115 | 3.7 |
2 | 11.49 | 87.63 | 162.0 | 396.41 | 7.040 | 30.65 | 47.930 | 14.380 | 115 | 4.1 |
3 | 12.46 | 87.24 | 164.0 | 396.41 | 7.040 | 30.65 | 47.930 | 14.380 | 115 | 4.5 |
4 | 12.76 | 86.06 | 165.0 | 396.41 | 7.040 | 30.65 | 47.930 | 14.380 | 115 | 4.9 |
实例5 | ||||||||||
1 | 7.64 | 87.33 | 158.7 | 396.41 | 7.040 | 30.65 | 47.930 | 14.380 | 115 | 0.5 |
2 | 9.17 | 87.84 | 161.0 | 396.41 | 7.040 | 30.65 | 47.930 | 14.380 | 115 | 0.9 |
3 | 8.64 | 89.49 | 157.0 | 396.41 | 7.040 | 30.65 | 47.930 | 14.380 | 115 | 1.3 |
实例6 | ||||||||||
1 | 9.89 | 84.22 | 161.3 | 363.60 | 7.450 | 29.65 | 52.530 | 10.369 | 115 | 5.1 |
2 | 10.45 | 83.70 | 163.1 | 363.60 | 7.450 | 29.65 | 52.530 | 10.369 | 115 | 5.6 |
3 | 10.14 | 85.54 | 160.0 | 363.60 | 7.450 | 29.65 | 52.530 | 10.369 | 115 | 6.1 |
4 | 10.17 | 85.65 | 159.2 | 363.60 | 7.450 | 29.65 | 52.530 | 10.369 | 115 | 6.6 |
5 | 14.53 | 85.18 | 161.0 | 382.60 | 10.795 | 24.49 | 49.922 | 14.794 | 115 | 10.3 |
RUN # | % C2H4 | % VA | BED T | TOTAL | FEED COMPOSITON | Psig | HRS | |||
CONV | SEL | (C) | FLOW | O2 | N2 | C2H4 | HOAC | |||
6 | 14.84 | 85.46 | 160.0 | 382.60 | 10.795 | 24.49 | 49.922 | 14.794 | 115 | 10.8 |
7 | 15.30 | 85.84 | 159.6 | 382.60 | 10.795 | 24.49 | 49.922 | 14.794 | 115 | 11.2 |
8 | 17.23 | 87.88 | 159.6 | 382.60 | 10.795 | 24.49 | 49.922 | 14.794 | 115 | 11.7 |
9 | 15.52 | 85.98 | 159.6 | 382.60 | 10.795 | 24.49 | 49.922 | 14.794 | 115 | 12.2 |
实例7 | ||||||||||
1 | 9.38 | 78.05 | 162.7 | 363.90 | 7.610 | 29.60 | 51.940 | 10.850 | 115 | 0.8 |
2 | 9.74 | 80.27 | 160.8 | 363.90 | 7.610 | 29.60 | 51.940 | 10.850 | 115 | 1.6 |
3 | 9.77 | 80.97 | 160.6 | 363.90 | 7.610 | 29.60 | 51.940 | 10.850 | 115 | 2.6 |
4 | 9.62 | 81.73 | 160.6 | 363.90 | 7.610 | 29.60 | 51.940 | 10.850 | 115 | 3.6 |
5 | 9.67 | 82.93 | 159.8 | 363.90 | 7.610 | 29.60 | 51.940 | 10.850 | 115 | 4.5 |
实例8 | ||||||||||
1 | 10.61 | 85.55 | 161.0 | 362.30 | 7.730 | 29.70 | 52.170 | 10.410 | 115 | 2.0 |
2 | 9.83 | 85.42 | 161.0 | 362.30 | 7.730 | 29.70 | 52.170 | 10.410 | 115 | 4.0 |
实例9 | ||||||||||
1 | 14.75 | 88.30 | 158.0 | 408.20 | 7.450 | 31.97 | 46.790 | 13.790 | 115 | 2.2 |
2 | 14.70 | 88.90 | 157.0 | 408.20 | 7.450 | 31.97 | 46.790 | 13.790 | 115 | 2.6 |
3 | 14.69 | 89.60 | 157.0 | 408.20 | 7.450 | 31.97 | 46.790 | 13.790 | 115 | 2.9 |
4 | 14.44 | 89.90 | 157.0 | 408.20 | 7.450 | 31.97 | 46.790 | 13.790 | 115 | 3.3 |
5 | 16.63 | 88.30 | 158.0 | 414.90 | 8.940 | 31.45 | 46.040 | 13.570 | 115 | 3.8 |
6 | 17.15 | 88.50 | 158.0 | 414.90 | 8.940 | 31.45 | 46.040 | 13.570 | 115 | 4.1 |
7 | 16.93 | 89.20 | 158.0 | 414.90 | 8.940 | 31.45 | 46.040 | 13.570 | 115 | 4.5 |
8 | 16.09 | 89.30 | 157.0 | 414.90 | 8.940 | 31.45 | 46.040 | 13.570 | 115 | 4.8 |
9 | 16.94 | 88.20 | 160.0 | 414.90 | 8.940 | 31.45 | 46.040 | 13.570 | 115 | 5.2 |
10 | 17.14 | 88.40 | 160.0 | 414.90 | 8.940 | 31.45 | 46.040 | 13.570 | 115 | 5.6 |
11 | 16.87 | 89.10 | 160.0 | 414.90 | 8.940 | 31.45 | 46.040 | 13.570 | 115 | 5.9 |
RUN # | % C2H4 | % VA | BED T | TOTAL | FEED COMPOSITON | Psig | HRS | |||
CONV | SEL | (C) | FLOW | O2 | N2 | C2H4 | HOAC | |||
12 | 16.54 | 89.20 | 160.0 | 414.90 | 8.940 | 31.45 | 46.040 | 13.570 | 115 | 6.3 |
13 | 14.54 | 88.70 | 163.0 | 418.60 | 9.680 | 31.18 | 45.630 | 13.520 | 115 | 9.8 |
14 | 14.39 | 88.80 | 162.0 | 418.60 | 9.680 | 31.18 | 45.630 | 13.520 | 115 | 10.1 |
15 | 14.10 | 89.10 | 161.0 | 418.60 | 9.680 | 31.18 | 45.630 | 13.520 | 115 | 10.5 |
16 | 15.10 | 88.10 | 165.0 | 418.60 | 9.680 | 31.18 | 45.630 | 13.520 | 115 | 10.8 |
17 | 15.13 | 87.60 | 165.0 | 418.60 | 9.680 | 31.18 | 45.630 | 13.520 | 115 | 11.2 |
18 | 15.71 | 87.60 | 168.0 | 418.60 | 9.680 | 31.18 | 45.630 | 13.520 | 115 | 11.5 |
19 | 15.19 | 87.60 | 166.0 | 418.60 | 9.680 | 31.18 | 45.630 | 13.520 | 115 | 11.9 |
实例10 | ||||||||||
1 | 1.90 | 91.40 | 154.0 | 418.30 | 9.980 | 31.20 | 45.660 | 13.460 | 115 | 3.0 |
2 | 1.99 | 90.90 | 154.0 | 418.30 | 9.980 | 31.20 | 45.660 | 13.460 | 115 | 3.3 |
3 | 2.73 | 88.50 | 162.0 | 418.30 | 9.980 | 31.20 | 45.660 | 13.460 | 115 | 3.6 |
4 | 3.52 | 87.30 | 163.0 | 418.30 | 9.980 | 31.20 | 45.660 | 13.460 | 115 | 4.0 |
5 | 4.61 | 86.80 | 163.0 | 418.30 | 9.980 | 31.20 | 45.660 | 13.460 | 115 | 4.3 |
6 | 6.53 | 82.00 | 169.0 | 418.30 | 9.980 | 31.20 | 45.660 | 13.460 | 115 | 4.7 |
7 | 7.75 | 80.70 | 173.0 | 418.30 | 9.980 | 31.20 | 45.660 | 13.460 | 115 | 5.0 |
8 | 8.73 | 80.60 | 176.0 | 418.30 | 9.980 | 31.20 | 45.660 | 13.460 | 115 | 5.4 |
9 | 8.93 | 82.10 | 175.0 | 418.30 | 9.980 | 31.20 | 45.660 | 13.460 | 115 | 5.7 |
实例11 | ||||||||||
1 | 13.27 | 86.90 | 159.0 | 408.20 | 7.450 | 31.97 | 46.790 | 13.790 | 115 | 1.3 |
2 | 13.89 | 87.00 | 159.0 | 408.20 | 7.450 | 31.97 | 46.790 | 13.790 | 115 | 1.6 |
3 | 13.88 | 87.20 | 159.0 | 408.20 | 7.450 | 31.97 | 46.790 | 13.790 | 115 | 2.0 |
4 | 13.88 | 87.30 | 159.0 | 408.20 | 7.450 | 31.97 | 46.790 | 13.790 | 115 | 2.3 |
5 | 13.74 | 87.40 | 159.0 | 408.20 | 7.450 | 31.97 | 46.790 | 13.790 | 115 | 2.6 |
6 | 15.82 | 85.30 | 162.0 | 418.30 | 9.980 | 31.20 | 45.660 | 13.460 | 115 | 3.5 |
7 | 15.96 | 84.80 | 162.0 | 418.30 | 9.980 | 31.20 | 45.660 | 13.460 | 115 | 3.9 |
RUN # | % C2H4 | % VA | BED T | TOTAL | FEED COMPOSITON | Psig | HRS | |||
CONV | SEL | (C) | FLOW | O2 | N2 | C2H4 | HOAC | |||
8 | 15.64 | 85.30 | 161.0 | 418.30 | 9.980 | 31.20 | 45.660 | 13.460 | 115 | 4.2 |
9 | 15.65 | 85.70 | 160.0 | 418.30 | 9.980 | 31.20 | 45.660 | 13.460 | 115 | 4.5 |
10 | 16.28 | 84.50 | 164.0 | 418.30 | 9.980 | 31.20 | 45.660 | 13.460 | 115 | 4.9 |
11 | 16.28 | 84.60 | 165.0 | 418.30 | 9.980 | 31.20 | 45.660 | 13.460 | 115 | 5.2 |
12 | 16.51 | 84.70 | 165.0 | 418.30 | 9.980 | 31.20 | 45.660 | 13.460 | 115 | 5.6 |
13 | 16.51 | 84.70 | 165.0 | 418.30 | 9.980 | 31.20 | 45.660 | 13.460 | 115 | 5.8 |
实例12 | ||||||||||
1 | 13.46 | 83.11 | 159.6 | 407.63 | 6.750 | 32.50 | 46.980 | 13.770 | 115 | 1.4 |
2 | 13.88 | 84.15 | 159.6 | 407.63 | 6.750 | 32.50 | 46.980 | 13.770 | 115 | 1.8 |
3 | 13.85 | 84.39 | 159.0 | 407.63 | 6.750 | 32.50 | 46.980 | 13.770 | 115 | 2.2 |
4 | 14.01 | 84.91 | 159.0 | 407.63 | 6.750 | 32.50 | 46.980 | 13.770 | 115 | 2.7 |
5 | 13.67 | 85.31 | 158.0 | 407.63 | 6.750 | 32.50 | 46.980 | 13.770 | 115 | 3.1 |
6 | 13.96 | 84.51 | 163.5 | 421.03 | 9.710 | 31.47 | 45.480 | 13.330 | 115 | 4.8 |
7 | 13.03 | 85.43 | 160.0 | 421.03 | 9.710 | 31.47 | 45.480 | 13.330 | 115 | 5.6 |
8 | 12.35 | 85.95 | 159.0 | 421.03 | 9.710 | 31.47 | 45.480 | 13.330 | 115 | 6.5 |
9 | 11.90 | 86.00 | 157.0 | 421.03 | 9.710 | 31.47 | 45.480 | 13.330 | 115 | 6.9 |
10 | 11.54 | 86.24 | 156.0 | 421.03 | 9.710 | 31.47 | 45.480 | 13.330 | 115 | 7.3 |
11 | 11.41 | 86.62 | 156.0 | 421.03 | 9.710 | 31.47 | 45.480 | 13.330 | 115 | 7.8 |
实例13 | ||||||||||
1 | 8.90 | 84.34 | 157.2 | 421.91 | 9.690 | 31.40 | 45.390 | 13.510 | 115 | 0.8 |
2 | 8.54 | 83.98 | 156.0 | 421.91 | 9.690 | 31.40 | 45.390 | 13.510 | 115 | 1.5 |
3 | 8.22 | 84.26 | 163.2 | 421.91 | 9.690 | 31.40 | 45.390 | 13.510 | 115 | 2.5 |
4 | 7.42 | 84.87 | 157.4 | 421.91 | 9.690 | 31.40 | 45.390 | 13.510 | 115 | 3.4 |
5 | 6.97 | 85.27 | 156.5 | 421.91 | 9.690 | 31.40 | 45.390 | 13.510 | 115 | 4.2 |
RUN # | % C2H4 | % VA | BED T | TOTAL | FEED COMPOSITON | Psig | HRS | |||
CONV | SEL | (C) | FLOW | O2 | N2 | C2H4 | HOAC | |||
实例14 | ||||||||||
1 | 10.74 | 81.77 | 164.4 | 408.07 | 6.739 | 32.47 | 46.928 | 13.863 | 115 | 0.5 |
2 | 9.98 | 84.55 | 161.1 | 408.07 | 6.739 | 32.47 | 46.928 | 13.863 | 115 | 0.9 |
3 | 9.24 | 86.01 | 159.0 | 408.07 | 6.739 | 32.47 | 46.928 | 13.863 | 115 | 1.4 |
4 | 10.61 | 83.39 | 165.0 | 421.47 | 9.704 | 31.44 | 45.436 | 13.422 | 115 | 4.0 |
5 | 10.13 | 83.92 | 165.8 | 421.47 | 9.704 | 31.44 | 45.436 | 13.422 | 115 | 4.4 |
6 | 8.69 | 86.00 | 162.0 | 421.47 | 9.704 | 31.44 | 45.436 | 13.422 | 115 | 5.3 |
实例15 | ||||||||||
1 | 7.45 | 83.44 | 159.0 | 408.07 | 6.739 | 32.47 | 46.928 | 13.863 | 115 | 0.9 |
2 | 7.47 | 84.09 | 158.0 | 408.07 | 6.739 | 32.47 | 46.928 | 13.863 | 115 | 1.3 |
3 | 7.15 | 84.60 | 158.0 | 408.07 | 6.739 | 32.47 | 46.928 | 13.863 | 115 | 1.8 |
4 | 6.63 | 85.15 | 157.0 | 408.07 | 6.739 | 32.47 | 46.928 | 13.863 | 115 | 2.6 |
5 | 7.60 | 82.18 | 159.0 | 421.47 | 9.704 | 31.44 | 45.436 | 13.422 | 115 | 3.9 |
6 | 6.99 | 82.28 | 159.0 | 421.47 | 9.704 | 31.44 | 45.436 | 13.422 | 115 | 4.8 |
7 | 6.14 | 83.52 | 158.0 | 421.47 | 9.704 | 31.44 | 45.436 | 13.422 | 115 | 6.0 |
实例16 | ||||||||||
1 | 4.78 | 80.03 | 155.6 | 408.51 | 6.730 | 32.43 | 46.880 | 13.960 | 115 | 2.5 |
实例17 | ||||||||||
1 | 11.99 | 85.37 | 159.5 | 408.51 | 6.730 | 32.43 | 46.880 | 13.960 | 115 | 1.5 |
2 | 11.68 | 85.86 | 159.5 | 408.51 | 6.730 | 32.43 | 46.880 | 13.960 | 115 | 1.9 |
3 | 11.41 | 86.28 | 158.0 | 408.51 | 6.730 | 32.43 | 46.880 | 13.960 | 115 | 2.3 |
4 | 10.95 | 87.07 | 156.3 | 408.51 | 6.730 | 32.43 | 46.880 | 13.960 | 115 | 2.7 |
5 | 10.29 | 87.36 | 156.6 | 408.51 | 6.730 | 32.43 | 46.880 | 13.960 | 115 | 3.2 |
6 | 11.38 | 86.38 | 157.3 | 421.91 | 9.694 | 31.41 | 45.389 | 13.512 | 115 | 3.6 |
7 | 11.60 | 85.38 | 159.0 | 421.91 | 9.694 | 31.41 | 45.389 | 13.512 | 115 | 4.5 |
RUN # | % C2H4 | % VA | BED T | TOTAL | FEED COMPOSITON | Psig | HRS | |||
CONV | SEL | (C) | FLOW | O2 | N2 | C2H4 | HOAC | |||
8 | 11.11 | 85.98 | 158.9 | 421.91 | 9.694 | 31.41 | 45.389 | 13.512 | 115 | 5.3 |
9 | 10.52 | 86.48 | 159.9 | 421.91 | 9.694 | 31.41 | 45.389 | 13.512 | 115 | 6.2 |
实例18 | ||||||||||
1 | 12.01 | 80.41 | 170.0 | 408.51 | 6.730 | 32.43 | 46.880 | 13.960 | 115 | 1.1 |
2 | 10.91 | 85.10 | 156.7 | 408.51 | 6.730 | 32.43 | 46.880 | 13.960 | 115 | 1.6 |
3 | 12.39 | 84.94 | 159.0 | 421.91 | 9.694 | 31.41 | 45.389 | 13.512 | 115 | 2.4 |
4 | 10.89 | 84.98 | 161.0 | 421.91 | 9.694 | 31.41 | 45.389 | 13.512 | 115 | 3.3 |
5 | 11.13 | 85.42 | 161.0 | 421.91 | 9.694 | 31.41 | 45.389 | 13.512 | 115 | 3.7 |
6 | 10.12 | 86.21 | 159.0 | 421.91 | 9.694 | 31.41 | 45.389 | 13.512 | 115 | 5.0 |
7 | 8.68 | 88.28 | 156.0 | 421.91 | 9.694 | 31.41 | 45.389 | 13.512 | 115 | 6.7 |
8 | 7.41 | 89.84 | 154.7 | 421.91 | 9.694 | 31.41 | 45.389 | 13.512 | 115 | 9.3 |
实例19 | ||||||||||
1 | 10.66 | 84.76 | 162.9 | 408.51 | 6.730 | 32.43 | 46.880 | 13.960 | 115 | 1.4 |
2 | 9.34 | 85.79 | 158.5 | 408.51 | 6.730 | 32.43 | 46.880 | 13.960 | 115 | 2.3 |
3 | 8.82 | 86.11 | 158.5 | 421.91 | 9.694 | 31.41 | 45.389 | 13.512 | 115 | 3.1 |
4 | 7.34 | 87.94 | 158.5 | 421.91 | 9.694 | 31.41 | 45.389 | 13.512 | 115 | 4.4 |
实例20 | ||||||||||
1 | 6.06 | 82.27 | 156.8 | 408.51 | 6.730 | 32.43 | 46.880 | 13.960 | 115 | 1.4 |
2 | 5.66 | 83.00 | 156.8 | 408.51 | 6.730 | 32.43 | 46.880 | 13.960 | 115 | 3.1 |
3 | 5.11 | 83.60 | 156.8 | 408.51 | 6.730 | 32.43 | 46.880 | 13.960 | 115 | 6.1 |
Claims (26)
1.一种流化床乙烯基乙酸酯催化剂,其特征在于浸渍在基本上惰性的预制微球颗粒载体上的包括Pd-M-A的通式,式中M相当于钡、金、镧、铌、铈、锌、铅、钙、锶、锑或它们的混合物;A相当于至少一种碱金属,其中基本上惰性的微球颗粒载体选自氧化硅,氧化锆,氧化铝及它们的混合物,所述载体的孔体积为0.2-0.7cc/g,表面积可达200m2/g,且至少50%的载体颗粒尺寸小于100微米。
2.如权利要求1所述的催化剂,其中载体包括基本上惰性的微球颗粒混合物,所述微球颗粒的孔体积为0.2-0.7cc/g,表面积为100-200m2/g,且至少50%的所述颗粒小于100微米。
3.如权利要求1所述的催化剂,其中至少75%的微球载体颗粒小于100微米。
4.如权利要求1所述的催化剂,其中基本上惰性的微球颗粒选自氧化硅。
5.如权利要求1所述的催化剂,其中M选自锑。
6.如权利要求1所述的催化剂,其中在无钡存在时,M选为金。
7.如权利要求1所述的催化剂,其中孔体积为0.3-0.65cc/g,表面积为100-195m2/g,且至少75%的颗粒小于100微米。
8.如权利要求1所述的催化剂,其中基本惰性的载体是通过如下方法制备的:将80-20重量%含基本上惰性的微球颗粒的水溶胶与20-80重量%基本上惰性的固体颗粒材料混合形成含水混合物,喷雾干燥所述含水混合物,焙烧所述颗粒使成为基本上惰性的载体。
9.如权利要求8所述的催化剂,其中所述的水溶胶包括平均粒径为约40-80毫微米的二氧化硅。
10.如权利要求8所述的催化剂,其中基本上惰性的固体颗粒材料包括很小或没有微孔、中孔体积约为1.5-0.25cc/g且表面积为80-200m2/g的二氧化硅。
11.如权利要求8所述的催化剂,其中所述的含水混合物在125-280℃的温度下进行喷雾干燥。
12.如权利要求11所述的催化剂,其中所述的喷雾干燥颗粒在550-700℃的温度下进行焙烧。
13.如权利要求1所述的催化剂,其中钯的重量百分含量为0.1-5.0重量%。
14.如权利要求1所述的催化剂,该催化剂包括大于0-10重量%的碱金属。
15.如权利要求14所述的催化剂,该催化剂包括0.1-8.0重量%的碱金属。
16.如权利要求1所述的催化剂,该催化剂包括大于0-5.0重量%的M。
17.如权利要求16所述的催化剂,该催化剂包括0.1-4.0重量%的M。
18.一种制备如权利要求1-17中任一项所述的流化床乙烯基乙酸酯催化剂的方法,包括用含钯、M和至少一种碱金属的无卤化物金属盐溶液浸渍预制的基本上惰性的微球颗粒载体,所述载体中至少50%的颗粒尺寸小于100微米,然后在低于80℃的温度下干燥所述浸渍过的预制载体。
19.如权利要求18所述的方法,其中预制的基本上惰性的微球载体用基本上不含有机溶剂的含水溶液浸渍。
20.如权利要求18所述的方法,其中先将碱金属单独浸渍到微球载体材料上,再干燥该载体。
21.如权利要求20所述的方法,其中先用含钯和M的无卤化物盐的溶液浸渍微球载体,再将碱金属浸到载体上。
22.一种制备乙烯基乙酸酯的方法,包括使乙烯、乙酸和氧一起在气相中、在流化床催化剂存在下反应,其中所述催化剂是权利要求1-17中任一项所述的催化剂。
23.一种制备乙烯基乙酸酯的方法,包括使乙烯、乙酸和氧一起在气相中、在流化床催化剂存在下反应,其中所述催化剂是权利要求18所述的方法制得的催化剂。
24.一种制备乙烯基乙酸酯的方法,包括使乙烯、乙酸和氧一起在气相中、在流化床催化剂存在下反应,其中所述催化剂是权利要求19所述的方法制得的催化剂。
25.一种制备乙烯基乙酸酯的方法,包括使乙烯、乙酸和氧一起在气相中、在流化床催化剂存在下反应,其中所述催化剂是权利要求20所述的方法制得的催化剂。
26.一种制备乙烯基乙酸酯的方法,包括使乙烯、乙酸和氧一起在气相中、在流化床催化剂存在下反应,其中所述催化剂是权利要求21所述的方法制得的催化剂。
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US200130 | 1994-02-22 | ||
US200,130 | 1994-02-22 | ||
US08/200,130 US5466652A (en) | 1994-02-22 | 1994-02-22 | Process for the preparation of vinyl acetate catalyst |
US376180 | 1995-01-20 | ||
US08/376,180 US5591688A (en) | 1994-02-22 | 1995-01-20 | Process for the preparation of fluid bed vinyl acetate catalyst |
US376,180 | 1995-01-20 |
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CN1112460A CN1112460A (zh) | 1995-11-29 |
CN1090533C true CN1090533C (zh) | 2002-09-11 |
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EP (1) | EP0672453B1 (zh) |
JP (1) | JPH0838900A (zh) |
CN (1) | CN1090533C (zh) |
BR (1) | BR9500736A (zh) |
CA (1) | CA2143042A1 (zh) |
DE (2) | DE69535514T2 (zh) |
ES (2) | ES2287994T3 (zh) |
FI (1) | FI950819A (zh) |
NO (1) | NO313743B1 (zh) |
NZ (1) | NZ270546A (zh) |
RU (1) | RU2149055C1 (zh) |
SG (1) | SG47363A1 (zh) |
TW (2) | TW533092B (zh) |
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US6395676B2 (en) | 1994-02-22 | 2002-05-28 | The Standard Oil Company | Process for the preparation of fluid bed vinyl acetate catalyst |
IN188013B (zh) * | 1995-05-23 | 2002-08-10 | Hoechst Celanese Corp | |
DE19613791C2 (de) * | 1996-04-04 | 2002-01-31 | Celanese Chem Europe Gmbh | Katalysator, Verfahren zu seiner Herstellung und Verfahren zur Herstellung von Vinylacetat |
TW377306B (en) * | 1996-12-16 | 1999-12-21 | Asahi Chemical Ind | Noble metal support |
DE19755023C2 (de) * | 1997-12-11 | 2000-03-09 | Celanese Chem Europe Gmbh | Katalysator und Verfahren zur Herstellung von Vinylacetat |
GB9817363D0 (en) | 1998-08-11 | 1998-10-07 | Bp Chem Int Ltd | Process for the production of vinyl acetate |
GB9817365D0 (en) | 1998-08-11 | 1998-10-07 | Bp Chem Int Ltd | Process for the production of vinyl acetate |
GB9819221D0 (en) | 1998-09-04 | 1998-10-28 | Bp Chem Int Ltd | Process for the production of acetic acid |
US6358882B1 (en) * | 1998-12-08 | 2002-03-19 | The Standard Oil Company | Fluid bed vinyl acetate catalyst |
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 |
CN1090996C (zh) * | 1999-03-30 | 2002-09-18 | 中国石油化工集团公司 | 生产醋酸乙烯催化剂的制备方法 |
GB0014583D0 (en) * | 2000-06-14 | 2000-08-09 | Bp Chem Int Ltd | Process |
GB0014584D0 (en) * | 2000-06-14 | 2000-08-09 | Bp Chem Int Ltd | Apparatus and process |
US6534438B1 (en) * | 2000-07-26 | 2003-03-18 | Bp Chemicals Limited | Catalyst composition |
GB0026242D0 (en) | 2000-10-26 | 2000-12-13 | Bp Chem Int Ltd | Apparatus and process |
US6916891B2 (en) * | 2001-02-28 | 2005-07-12 | The Standard Oil Company | Attrition resistant inorganic microspheroidal particles |
TWI304359B (en) * | 2001-12-04 | 2008-12-21 | Bp Chem Int Ltd | Oxidation process in fluidised bed reactor |
GB0201378D0 (en) * | 2002-01-22 | 2002-03-13 | Bp Chem Int Ltd | Process |
US7718811B2 (en) | 2002-11-26 | 2010-05-18 | Ineos Europe Limited | Oxidation process in fluidised bed reactor |
CA2547313C (en) * | 2003-12-19 | 2010-11-02 | Celanese International Corporation | Halide free precursors for catalysts |
TW201236755A (en) | 2003-12-19 | 2012-09-16 | Celanese Int Corp | Halide free precursors for catalysts |
ZA200704864B (en) * | 2004-12-20 | 2008-08-27 | Celanese Int Corp | Modified support materials for catalysts |
US8227369B2 (en) | 2005-05-25 | 2012-07-24 | Celanese International Corp. | Layered composition and processes for preparing and using the composition |
DE102007025223A1 (de) * | 2007-05-31 | 2008-12-04 | Süd-Chemie AG | Zirkoniumoxid-dotierter VAM-Schalenkatalysator, Verfahren zu dessen Herstellung sowie dessen Verwendung |
CN101884916B (zh) * | 2009-05-13 | 2012-05-30 | 中国石油化工股份有限公司 | 用于流化床工艺制醋酸乙烯的催化剂载体的制备方法 |
CN101942229B (zh) * | 2009-07-06 | 2013-03-06 | 中国石油化工股份有限公司 | 含有孔道保护剂的多孔二氧化硅的制备方法 |
JP5961166B2 (ja) * | 2010-08-26 | 2016-08-02 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | 高活性水性ガスシフト触媒、その製造方法と利用 |
CN103237784B (zh) | 2010-10-28 | 2015-11-25 | 国际人造丝公司 | 用于生产具有低杂质含量的乙酸乙烯酯组合物的方法 |
US8884052B2 (en) | 2011-12-15 | 2014-11-11 | Celanese International Corporation | Production of diacetoxyethylene by direct acetoxylation |
WO2014039304A1 (en) | 2012-09-06 | 2014-03-13 | Celanese International Corporation | Processes for producing vinyl acetate |
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DE3709401A1 (de) * | 1987-03-21 | 1988-09-29 | Huels Chemische Werke Ag | Verfahren zur herstellung eines katalysators fuer die hydratation von olefinen zu alkoholen |
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-
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- 1995-02-17 ES ES99112752T patent/ES2287994T3/es not_active Expired - Lifetime
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- 1995-02-22 JP JP7034161A patent/JPH0838900A/ja active Pending
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- 1995-02-22 FI FI950819A patent/FI950819A/fi not_active Application Discontinuation
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JPH0838900A (ja) | 1996-02-13 |
FI950819A (fi) | 1995-08-23 |
ES2249764T3 (es) | 2006-04-01 |
DE69534557T2 (de) | 2006-06-01 |
EP0672453B1 (en) | 2005-11-02 |
EP0672453A2 (en) | 1995-09-20 |
NO950645D0 (no) | 1995-02-21 |
BR9500736A (pt) | 1995-10-31 |
NO313743B1 (no) | 2002-11-25 |
DE69535514T2 (de) | 2008-02-14 |
NZ270546A (en) | 1996-12-20 |
CA2143042A1 (en) | 1995-08-23 |
CN1112460A (zh) | 1995-11-29 |
NO950645L (no) | 1995-08-23 |
FI950819A0 (fi) | 1995-02-22 |
EP0672453A3 (en) | 1996-01-17 |
RU2149055C1 (ru) | 2000-05-20 |
DE69534557D1 (de) | 2005-12-08 |
TW496773B (en) | 2002-08-01 |
SG47363A1 (en) | 1998-04-17 |
DE69535514D1 (de) | 2007-07-26 |
RU95102482A (ru) | 1996-11-20 |
ES2287994T3 (es) | 2007-12-16 |
TW533092B (en) | 2003-05-21 |
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