CN1248572A - 乙酸乙烯酯的制备方法 - Google Patents
乙酸乙烯酯的制备方法 Download PDFInfo
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- CN1248572A CN1248572A CN99119114A CN99119114A CN1248572A CN 1248572 A CN1248572 A CN 1248572A CN 99119114 A CN99119114 A CN 99119114A CN 99119114 A CN99119114 A CN 99119114A CN 1248572 A CN1248572 A CN 1248572A
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- 238000000034 method Methods 0.000 title claims abstract description 27
- 230000008569 process Effects 0.000 title abstract description 3
- 238000002360 preparation method Methods 0.000 title description 15
- -1 ethylene acetate ester Chemical class 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 18
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
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- 239000001301 oxygen Substances 0.000 claims abstract description 14
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- 239000000203 mixture Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 239000010931 gold Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
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- 239000000463 material Substances 0.000 claims description 5
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- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
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- 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 claims description 3
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- 229910052708 sodium Inorganic materials 0.000 claims description 3
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- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 2
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- 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 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910003803 Gold(III) chloride Inorganic materials 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
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- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- ACOGMWBDRJJKNB-UHFFFAOYSA-N acetic acid;ethene Chemical compound C=C.CC(O)=O ACOGMWBDRJJKNB-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- 230000008033 biological extinction Effects 0.000 description 1
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- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
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- LPPHVGKXKXBSRU-UHFFFAOYSA-N gold 2-methylpropanoic acid Chemical compound [Au].CC(C(=O)O)C LPPHVGKXKXBSRU-UHFFFAOYSA-N 0.000 description 1
- 150000002344 gold compounds Chemical class 0.000 description 1
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 1
- 229940076131 gold trichloride Drugs 0.000 description 1
- 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 1
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 description 1
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- 150000002816 nickel compounds Chemical class 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 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
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- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/12—Acetic acid esters
- C07C69/14—Acetic acid esters of monohydroxylic compounds
- C07C69/145—Acetic acid esters of monohydroxylic compounds of unsaturated alcohols
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Abstract
一种制备乙酸乙烯酯的方法,其中将乙烯、液态乙酸和含氧气体加入到含催化剂的流化床反应器中,其中催化剂含有Ⅷ族金属、助催化剂和共助催化剂,通过限制共助催化剂的含量最高为催化剂的6重量%而减少了催化剂的粘性。
Description
本发明涉及乙酸乙烯酯的制备方法。
乙酸乙烯酯在商业上通常是通过在制备乙酸乙烯酯的活性催化剂的存在下，将乙酸和乙烯与分子氧接触而制备的。
适用于制备乙酸乙烯酯的催化剂可以含有VIII族的金属、助催化剂和任选的共—助催化剂。例如，EP A-0672453公开了在乙酸的存在下，通过催化氧化乙烯制备乙酸乙烯酯的方法，其中催化剂是含有助催化剂和共—助催化剂的负载的钯催化剂。
已发现当催化剂用在流化床反应器中且乙酸以液态加入到反应器时，催化剂颗粒会变粘并连在一起，特别在操作的延续时期因此而结块。在极端的情况下，会失去流化态，导致反应器停车。
欧洲专利公开EP-0847982-A涉及制备乙酸乙烯酯的流化床的方法，其中将液体加入流化床反应器以为了除去热量的目的。加入流化床的液体可以是包括乙酸反应物的反应物。助催化剂，例如乙酸钾可以溶解在进入流化床的液体中。在这里描述的实施例中，催化剂具有负载有0.44Pd、0.36Au和2.5K(重量％)的金属。钾的量对应于6.3重量％的乙酸钾。尽管催化剂没有聚结并去流体，但没有证据表明实验的规模或实验进行的时间。
我们已发现可以通过限制催化剂组合物中的共—助催化剂物质的量以避免粘性的问题。
相应地，本发明提供了一种制备乙酸乙烯酯的方法，其包括将乙烯、液态乙酸和含氧气体加入到流化床反应器中，并且在流化床催化剂物质的存在下，乙烯、乙酸和氧气在流化床反应器中于升温下反应，所述催化剂物质中包括VIII族金属、助催化剂和共—助催化剂，反应器中存在的所述共—助催化剂的量最多为催化剂的6重量％。
本发明提供了制备乙酸乙烯酯的方法，其避免了催化剂变粘并最终形成结块的问题，特别是经过操作的延续时期(例如大于7天)。
本发明的催化剂是流化床催化剂物质，包括VIII族的金属、助催化剂和共—助催化剂。这些化合物适于负载在载体上。
关于VIII族的金属，优选的金属为钯。钯的合适的来源包括氯化钯(II)、四氯钯(II)钠或四氯钯(II)钾(Na2PdCl4或K2PdCl4)、乙酸钯、H2PdCl4、硝酸钯(II)或硫酸钯(II)。以催化剂的总重量计，金属的浓度可以大于0.2重量％，优选大于0.5重量％，特别是约为1重量％。金属的浓度可以高至10重量％。
除了VIII族金属之外，催化剂含有助催化剂。适合的助催化剂包括金、铜、镉和/或镍化合物。优选的助催化剂为金。金的合适的来源包括氯化金、四氯金酸(HAuCl4)、NaAuCl4、KAuCl4、二甲基乙酸金、乙酰金酸钡或乙酸金。优选的金化合物为HAuCl4。助催化剂金属在精制催化剂中的含量可以为0.1-10重量％。
催化剂组分中助催化剂物质的浓度为最高为催化剂组分的6重量％。适合的共助催化剂包括I族、II族、镧系或过渡金属，例如镉、钡、钾、钠、铁、锰、镍、锑，和/或镧，其以盐，例如乙酸盐存在于精制催化剂中。优选的盐为乙酸钾或乙酸钠。催化剂组分中共—助催化剂的浓度最高为催化剂的6重量％，优选为催化剂的3.5-5.5重量％，特别是约为5重量％。
催化剂物质是负载的催化剂。适合的催化剂的载体包括多孔硅石、氧化铝、硅石/氧化铝、二氧化钛、硅石/二氧化钛、氧化锆或碳。优选的载体为硅石。以每克载体计，适合的载体的孔体积可以为0.2-3.5mL、表面积可以为5-800m2、表观堆积密度可以为0.3-1.5g.mL。载体一般具有的粒子大小分布为至少60％的催化剂粒子的粒子直径小于2×10-4m(200微米)。优选至少50％，更优选至少80％，最优选90％的催化剂粒子具有的粒子直径小于1.05×10-4m(105微米)。优选最多40％催化剂粒子的直径小于4×10-5m(40微米)。
可以通过任何适合的方法制备催化剂，例如EP-A-0672453中描述的方法。适合的催化剂制备工艺的第一步包括用含有可溶性盐形式的所需VIII族金属和助催化剂金属的溶液浸渍载体材料。这些盐的例子是可溶性卤化物衍生物。浸渍的溶液优选为水溶液，且所用的溶液的体积对应于载体孔体积的50-100％，优选孔体积的50-99％。
浸渍过的载体在环境温度或减压下，在金属还原之前，于环境温度至150℃下干燥，优选60-130℃。为了将这些材料转化为金属态，用还原剂，例如乙烯、肼、甲醛或氢处理浸渍过的载体。如果使用氢，为了使还原进行完全，通常需要将催化剂加热至100-850℃。
在上述步骤进行之后，还原的催化剂水洗并干燥。随后用所需量的共助催化剂浸渍干燥后的载体，并随后将其干燥。或者，湿的、还原的、水洗的材料用共助催化剂浸渍并随后干燥。
可以根据乙酸乙烯酯的最大收率和选择性而改变催化剂的制备方法，以使催化剂效能最佳。
本发明的方法包括在催化剂物质的存在下，将乙烯、乙酸和含氧气体反应。乙烯可以以完全纯净的状态使用，或以与氮气、甲烷、乙烷、二氧化碳和水中的一种或多种的混合蒸汽形式，或以与氢气、C2/C4烯烃或烷烃中的一种或多种混合使用。反应器的总进料中，乙烯可以至少为60摩尔％。
适合的含氧气体可以是空气或分子氧含量比空气中的高或低的气体。适合的气体可以是被合适的稀释剂，例如氮气、氩气或二氧化碳稀释的氧气。优选气体为氧气。
乙酸以液态进入反应器。一部分酸任选可以以蒸气态加入。乙酸优选为粗乙酸。合适地，液态乙酸可以以任何适合的加入方法加入到流化床反应器中，例如可以是气体感应雾化喷嘴或液体喷淋式喷嘴。一种或多种喷嘴可用于该目的。此外，循环的乙酸也可以加入反应器。循环的乙酸可以事先与粗乙酸混合或采用分别加入的方式加入到反应器中。循环的乙酸可以合适地含有水。合适地，以加入反应器中的酸和水流的总量计，循环物流中水的浓度，即反应器进料中水的浓度少于6重量％，优选少于4重量％，更优选少于3重量％。应当进行液体加入流化床的常规预防措施，例如避免表面变冷。
已知在这样的催化剂工艺中，催化剂的活性会因为各种原因随时间下降。特别是因为共助催化剂的挥发性，使得催化剂物质中的共助催化剂的水平随时间而减少。这导致了催化剂的活性和选择性的丧失。为了保持催化剂中共助催化剂的浓度恒定，即浓度少于6重量％，新鲜共助催化剂可以在反应期间加入到催化剂中。合适地，这样的操作可以通过将共助催化剂加入到液态乙酸原料或液态循环乙酸中进行。共助催化剂也可以以溶液，例如水溶液或酸溶液直接加入，通过适合的加入方法，例如喷嘴喷入反应器中。在各种情况下，共助催化剂与催化剂物质接触。
反应在流化床反应器中进行，并且可以合适地在温度为100-400℃，优选140-210℃，以及压力为105-2×106Pa表压(1-20巴)，优选6×105-1.5×106Pa表压(6-15巴)，特别优选7×105-1.2×106Pa表压(7-12巴)下进行。
参照图1和下面的实施例阐述本发明，图1是用于本发明的反应器体系的示意图。
实施例在稳态下操作的全循环中试装置中进行。装置见图1所示，包括进料系统、反应气/液分离装置、气体循环装置、产物回收装置和液体循环装置。参照图1，来自储藏库(1)中的新鲜乙酸和循环乙酸与一些循环气体(3)一起泵送至流化床(2)中的双流体喷嘴。残余的循环气体原料(3)、新鲜乙烯(4)和氧气(5)进入风室，并通过烧结板进入反应器。新鲜氧气(6)可以直接进入流化床。超高部分(freeboard section)用于脱离催化剂(7)。气态产物通过烧结过滤部件(未表示)经出口(8)离开反应器。使用泵体系控制反应器温度，其中，热传热流体通过反应器壁上的三个夹套(未表示)。所有的装置均由316L不锈钢制造。
实施例1是本发明的实施例。对比实施例A未根据本发明，其中的工艺所用的催化剂未根据本发明，其共助催化剂的含量超过6重量％。
实施例1
(a)催化剂载体的制备
通过喷射干燥的硅溶胶1060(从Nalco chemical Company购得)和Aerosil硅石(从Degussa Chemical Company购得)的混合物制备载体。在干燥过的载体中，80％硅溶胶来自溶胶，而20％硅石来自Aerosil。在640℃将喷射干燥过的微球体煅烧4小时。用于催化剂制备的载体的粒子大小分布如下：
粒子大小(微米) ％
＞3×10-4m(＞300) 2
4.4×10-5m-3×10-4m(44-300) 68
＜4.4×10-5(＜44) 30
应该理解，粒子大小分布并不限于以上给出的，该分布根据反应器尺寸和操作条件而改变。
(b)催化剂的制备
通过初始湿度法，用Na2PdCl4.xH2O(含1000gPd)和AuCl4.xH2O(含400gAu)溶解在蒸馏水中的溶液浸渍从上述步骤(a)得到的硅石载体(54.4kg)。得到的混合物完全混合，静置1小时并干燥过夜。
然后将浸渍得到的原料缓慢加入到N2H4溶于蒸馏水的5％的溶液中，混合物间歇搅拌，静置。随后，过滤混合物并用4×400升蒸馏水洗涤。得到的固体干燥过夜。
通过初始湿度法，用乙酸钾(2.8kg)溶液浸渍原料。得到的混合物完全混合，静置1小时并干燥过夜。将催化剂过筛，以除去粒子大小大于106微米的粒子。
得到的催化剂含有1.45重量％钯、0.65重量％金和4.3重量％乙酸钾。
(c)乙酸乙烯酯的制备
将上述步骤(b)得到的催化剂4.5kg加入反应器中。反应器在8×105Pa表压(8巴)下操作，其中床温度分布：底部145℃，中间152.5℃，顶部155℃。在双流体喷嘴液/气重量比为2.05∶1的工艺条件下，在总反应器入口速率为13.2厘米/秒，进入催化剂床的的总原料组分的摩尔百分比分别为乙烯∶氧气∶乙酸∶惰性物质为58.9∶4.9∶11∶25.2。在这些条件下，反应进行超过28天，未产生不正常操作。
实施例A(对比实施例)
(a)催化剂载体的制备
如以上实施例1所述制备载体。
(b)催化剂的制备
根据初始湿度(incipient wetness)，用Na2PdCl4.xH2O(含1850gPd)和AuCl4.xH2O(含740gAu)溶解在蒸馏水中的溶液浸渍从上述步骤(a)得到的硅石载体(54.4kg)。得到的混合物完全混合，静置1小时并干燥过夜。
将一部分浸渍得到的原料(18g)缓慢加入到N2H4溶于蒸馏水的10％的溶液中，混合物间歇搅拌下静置。随后，过滤混合物并用4×200升蒸馏水洗涤。得到的固体干燥过夜。
根据初始湿度，用乙酸钾(1.4kg)水溶液浸渍原料。得到的混合物完全混合，静置1小时并干燥过夜。
得到的催化剂含有3.1重量％钯、1.26重量％金和6.3重量％乙酸钾。
(c)乙酸乙烯酯的制备
将上述步骤(b)得到的含6.3重量％乙酸钾的催化剂3.45kg加入反应器中。反应器在8×105Pa表压(8巴)下操作，床温度分布：底部150℃，中间155℃，顶部155℃。在双流体喷嘴液/气重量比为2.14∶1的工艺条件下，在总反应器入口速率为6.7厘米/秒，进入催化剂床的的总原料组分的摩尔百分比分别为乙烯∶氧气∶乙酸∶惰性物质为47∶3∶22∶28。在操作进行7天后，反应器出口的测得的氧气突然增加，产率降至接近零。这表明催化剂床不能进行适当地流动，可能变粘，这样就不能适当地混合气体原料。将操作停止并将催化剂在150℃下干燥12小时。催化剂从反应器中排出，回收自由流动的催化剂和结块。自由流动的催化剂分析含有2.1重量％钾，结块中分析含有4.8重量％钾。这些结果表明当床变粘并缺乏流动时，发生了迁移。
Claims (12)
1.一种制备乙酸乙烯酯的方法，其包括将乙烯、液态乙酸和含氧气体加入到流化床反应器中，并且在流化床催化剂物质的存在下，使乙烯、乙酸和氧气在流化床反应器中于升温下反应，所述催化剂物质包括VIII族金属、助催化剂和共助催化剂，反应器中所述共助催化剂的量最多为催化剂的6重量％。
2.如权利要求1所述的方法，其中VIII族金属为钯。
3.如权利要求1或2所述的方法，其中以催化剂的总重量计，VIII族金属的浓度大于0.2重量％，且最高为催化剂重量的10重量％。
4.如在先权利要求中任意一个所述的方法，其中助催化剂选自金、铜、镉、镍及其混合物。
5.如在先权利要求中任意一个所述的方法，其中以催化剂物质中的金属的重量计，助催化剂的含量为0.1-10重量％。
6.如在先权利要求中任意一个所述的方法，其中共助催化剂选自I族、II族、镧系和过渡金属的盐。
7.如权利要求6所述的方法，其中共助催化剂选自镉、钡、钾、钠、铁、锰、镍、锑、镧的盐及其混合物。
8.如在先权利要求中任意一个所述的方法，其中共助催化剂的浓度为催化剂的3.5-5.5重量％，优选约5重量％。
9.如在先权利要求中任意一个所述的方法，其中共助催化剂在反应期间加入到催化剂中。
10.如权利要求9所述的方法，其中所述加入的共助催化剂是加入到液态乙酸原料或液态循环乙酸中。
11.如权利要求9所述的方法，其中所述加入的共助催化剂是通过注入装置，以溶液喷射入反应器中的。
12.如权利要求11所述的方法，其中所述加入的共助催化剂是以水溶液或酸溶液形式加入的。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100519501C (zh) * | 2001-12-04 | 2009-07-29 | 英国石油化学品有限公司 | 流化床反应器中的氧化工艺 |
| CN114425454A (zh) * | 2020-10-14 | 2022-05-03 | 中国石油化工股份有限公司 | 醋酸乙烯催化剂及醋酸乙烯合成方法 |
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| 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 |
| US6794332B2 (en) * | 2000-07-07 | 2004-09-21 | Saudi Basic Industries Corporation | Highly selective shell impregnated catalyst of improved space time yield for production of vinyl acetate |
| US6420308B1 (en) * | 2000-07-07 | 2002-07-16 | Saudi Basic Industries Corp | Highly selective shell impregnated catalyst of improved space time yield for production of vinyl acetate |
| US6534438B1 (en) * | 2000-07-26 | 2003-03-18 | Bp Chemicals Limited | Catalyst composition |
| EP1288188A1 (en) * | 2001-08-28 | 2003-03-05 | Avantium International B.V. | Supported catalyst composition, processes for the preparation thereof and use of the supported catalyst composition |
| US7718811B2 (en) | 2002-11-26 | 2010-05-18 | Ineos Europe Limited | Oxidation process in fluidised bed reactor |
| TW200539941A (en) * | 2003-12-19 | 2005-12-16 | Celanese Int Corp | Methods of making alkenyl alkanoates |
| CA2586584C (en) * | 2004-12-20 | 2011-01-18 | Celanese International Corporation | 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 |
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| GB979552A (en) * | 1961-05-12 | 1965-01-06 | Printing Packaging & Allied Tr | Improvements in or relating to photosensitive printing plates |
| DE1793474C3 (de) | 1968-09-24 | 1974-05-22 | Knapsack Ag, 5033 Huerth-Knapsack | Verfahren zur Herstellung von Vinylacetat |
| SU383274A3 (zh) | 1968-09-24 | 1973-05-25 | ||
| DE69534557T2 (de) | 1994-02-22 | 2006-06-01 | The Standard Oil Co., Cleveland | Verfahren zur Herstellung eines Katalysators für die Herstellung von Vinylacetat in einem Wirbelbett |
| US5665667A (en) * | 1994-06-02 | 1997-09-09 | The Standard Oil Company | Process for the preparation of vinyl acetate catalyst |
| DE69511464T2 (de) | 1994-06-02 | 1999-12-16 | The Standard Oil Co., Cleveland | Fliessbett-Verfahren zur Acetoxylierung von Äthylen zur Herstellung von Vinylacetat |
| GB9622911D0 (en) | 1996-11-04 | 1997-01-08 | Bp Chem Int Ltd | Process |
| GB9625599D0 (en) * | 1996-12-10 | 1997-01-29 | Bp Chem Int Ltd | Process |
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1999
- 1999-07-23 ES ES99305874T patent/ES2226292T3/es not_active Expired - Lifetime
- 1999-07-23 DE DE69919285T patent/DE69919285T2/de not_active Expired - Fee Related
- 1999-07-23 EP EP99305874A patent/EP0985655B1/en not_active Expired - Lifetime
- 1999-07-29 US US09/363,011 patent/US6350901B1/en not_active Expired - Fee Related
- 1999-07-30 TW TW088113041A patent/TW552253B/zh not_active IP Right Cessation
- 1999-08-05 SG SG9903773A patent/SG85663A1/en unknown
- 1999-08-09 KR KR1019990032619A patent/KR100620298B1/ko not_active Expired - Fee Related
- 1999-08-10 CA CA002280221A patent/CA2280221A1/en not_active Abandoned
- 1999-08-10 JP JP11226994A patent/JP2000063324A/ja not_active Withdrawn
- 1999-08-11 MX MXPA99007415A patent/MXPA99007415A/es not_active Application Discontinuation
- 1999-08-11 CN CN991191145A patent/CN1216849C/zh not_active Expired - Fee Related
- 1999-08-11 BR BR9916139-7A patent/BR9916139A/pt not_active Application Discontinuation
- 1999-09-28 SA SA99200625A patent/SA99200625B1/ar unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100519501C (zh) * | 2001-12-04 | 2009-07-29 | 英国石油化学品有限公司 | 流化床反应器中的氧化工艺 |
| CN114425454A (zh) * | 2020-10-14 | 2022-05-03 | 中国石油化工股份有限公司 | 醋酸乙烯催化剂及醋酸乙烯合成方法 |
| CN114425454B (zh) * | 2020-10-14 | 2024-02-02 | 中国石油化工股份有限公司 | 醋酸乙烯催化剂及醋酸乙烯合成方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20000017199A (ko) | 2000-03-25 |
| CN1216849C (zh) | 2005-08-31 |
| SA99200625B1 (ar) | 2006-09-25 |
| EP0985655A1 (en) | 2000-03-15 |
| BR9916139A (pt) | 2001-07-24 |
| KR100620298B1 (ko) | 2006-09-06 |
| TW552253B (en) | 2003-09-11 |
| DE69919285D1 (de) | 2004-09-16 |
| DE69919285T2 (de) | 2005-09-08 |
| MXPA99007415A (es) | 2004-12-03 |
| EP0985655B1 (en) | 2004-08-11 |
| CA2280221A1 (en) | 2000-02-11 |
| JP2000063324A (ja) | 2000-02-29 |
| SG85663A1 (en) | 2002-01-15 |
| ES2226292T3 (es) | 2005-03-16 |
| US6350901B1 (en) | 2002-02-26 |
| GB9817365D0 (en) | 1998-10-07 |
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