CN1212637A - 用于加速氧化反应的基于钛-或钒沸石和惰性网状织物的网状催化剂 - Google Patents
用于加速氧化反应的基于钛-或钒沸石和惰性网状织物的网状催化剂 Download PDFInfo
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- CN1212637A CN1212637A CN97192687A CN97192687A CN1212637A CN 1212637 A CN1212637 A CN 1212637A CN 97192687 A CN97192687 A CN 97192687A CN 97192687 A CN97192687 A CN 97192687A CN 1212637 A CN1212637 A CN 1212637A
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- Prior art keywords
- titanium
- zeolite
- vanadium
- catalyst
- reticulated
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Abstract
本文涉及一种基于钛-或钒沸石和惰性网状织物的网状催化剂,它适用于加速氧化反应如烯烃的环氧化、过氧化氢的制备或羟胺的合成。
Description
本发明涉及基于钛-或钒沸石和惰性网状物的网状催化剂以及它在加速氧化反应中的应用。本发明还涉及制备环氧化物、过氧化氢和羟胺的有关方法。
钛沸石是已知适宜于作为氧化反应的催化剂。例如在EP-A 100119(1)中描述了在溶剂存在下丙烯与过氧化氢水溶液在钛沸石上能进行环氧化以形成环氧丙烷的方法。用氨和过氧化氢在钛硅质岩石上反应从环已酮制备环己酮肟可参见EP-A 208 311(2)以及用过氧化氢在合成沸石上进行芳族化合物羟基化可由GB-A 2 116 974(3)中得知。用过氧化氢在钛硅质岩石上氧化饱和的脂肪族碳氢化合物在EP-A 376 453(4)中已有描述。
以丙烯,氢和氧作原料制备环氧丙烷的合成方法在DE-A 44 25672(5)中已作叙述并在(5)中引证发表。以官能化沸石作为催化剂。
在所述的文献(1)至(5)中未提及网状编织物作为载体。但没有沸石的网状催化剂在上述其它应用方面也是已知的。再者由EP-A511 739(6)已知膜片在分离方法中的应用,该膜片包含氧化铝载体,该载体上由沸石晶体涂敷有一层薄膜。Yamazaki和Tsutsumi在“Microp.Mater.5(1995),245-253(7)上叙述了将Mordenit(一种沸石-结构体)载在不锈钢或聚四氟乙烯上制成膜片的制备和性能。由Calis等在化学工程技术(Chem.-Ing.-Tech.)67(1995),777-780(8)发表了在铜丝网上载以沸石作为废气净化的还原性催化剂(DeNox)。但(6)至(8)中所述的沸石并不含钛或钒。
如(6)至(8)所述的这些类型载体仅仅是专门作为环氧化方法的问题提出的,因此是不能应用的,因为甚至痕量的碱金属都可能导致钛-和钒沸石在氧化反应上失去催化活性。例如(7)和(8)是以含有碱金属的沸石-合成凝胶作为起始材料。
本发明的目的是,制备改进的催化剂,特别是用于从烯烃制备环氧化物的催化剂,使其不再具有现有技术的缺点。尤其是催化剂能最经济地制备并有很高的效率。
为此找到了一种基于钛-或钒沸石和惰性网状物的网状催化剂。
惰性网状物,即网状载体,特别是金属丝网,优选的是由金属,如不锈钢、铜、银、铝或镍或合金如黄铜或堪塔尔铬铝钴耐热钢(铁/铬/铝/钴)、塑料如聚四氟乙烯、氧化铝如α-氧化铝、玻璃纤维、碳纤维或石墨。也可采用上述多种网状织物材料的组合物。
由于痕量碱金属就可使钛-和钒沸石在氧化反应中失去催化活性,所以本发明的网状催化剂中碱金属的含量(特别是钠和钾)优选小于500ppm,特别优选小于100ppm,尤其是小于40ppm,其含量是基于钛-或钒沸石的重量计算。利用适宜的制备方法能达到如此低的碱金属含量。
沸石已知是一种具有有序沟道和骨架结构的结晶的硅酸铝,它的孔径处于微孔范围,即小于0.9nm。此种沸石的网状是由SiO4-和AlO4-四面体组成,它以共用氧桥键相联结。其已知的结构概况可参见W.M.Meier和D.H.Olson的“沸石结构类型图谱集”(Atlas of Zeolite Structure Type),Butterworth,2nd Ed.,London 1987。
已知一种沸石不含铝,同时其硅晶格中硅(Ⅳ)的位置部分被钛(Ⅳ)所取代。此种钛沸石,特别是这种MFI型的晶体结构,以及其制备的可能性,已在EP-A 311 983或EP-A 405 978上已有叙述。除含硅和钛外,此种材料也可含有另外的元素如铝,镓,硼或少量的氟。
本发明的网状催化剂中,沸石中的钛能部分的或全部由钒取代。钛和/或钒对硅加钛和/或钒总和的克分子比一般处于0.01∶1至0.1∶1范围内。
已知具有MFI-结构的钛沸石能以伦琴射线衍射图以及附加的在约960cm-1处的红外区的晶格振动谱带来鉴证,同时区分碱金属钛酸盐或晶体和非晶型TiO2相。
上述钛-或钒沸石通常用下列方法制备:由SiO2-原料、钛或钒原料如二氧化钛或相应的氧化钒与含氮的有机碱(“模键化合物”)如氢氧化四丙基铵的水溶液混合物,在压力罐中于高温下反应几小时或几天,形成晶体产物。将其过滤、洗涤、干燥,然后在高温下焙烧,以去除有机氮基。所得粉末中钛或钒至少部分的以4、5或6倍配位键交替的处于沸石晶格中。为了改善催化剂性能可用硫酸酸化的过氧化氢溶液多次洗涤处理,然后粉末状钛-或钒沸石必须重新干燥和焙烧。粉末状钛-或钒沸石必须按目前技术作最后处理,附加适宜的惰性粘合剂以成型,从而提供一种可操作的催化剂。
希望使用构型MFI,BEA,MTW,TON或MOR的钛沸石作为催化剂时,也出现一些严重的缺点。
将制得的钛沸石粉成形加工成可操作的催化剂是很费事的,在用或不用惰性粘合剂进行挤压成形后,还费耗费大量能量和时间进行干燥和焙烧。用熔融或烧结方法形成较大的沸石晶体也是有缺点的。此外以固定床排列传统成形的钛沸石,难以达到高的催化剂利用率,另一方面难以减少沿反应器纵向的压力降。在气相中氧化时,又希望有高的气体速度,以便通过短的停留时间来防止连续反应。这些问题通过本发明已得到解决。
在文献(5)中已叙述了具有沸石结构的钛-或钒硅质岩是优选的钛-或钒沸石,最好具有戊硅沸石结构,特别是用伦琴射线证实的MFI,MEL或MFI/MEL混合结构型。这种类型的沸石在W.M.Meier和D.H.Olson的“沸石结构类型图谱集”(Atlas of ZeoliteStructure Types)Butterworths,2nd Ed.,London 1987中已叙述。对本发明还可有具有ZSM-48、ZSM-12、镁碱沸石或β-沸石和丝光沸石结构的含钛沸石。
在另一优选实施方案中,本发明的网状催化剂还含有选自金、银、铼、钌、铑、钯、锇、铱和铂的一种和多种贵金属,其含量为钛沸石或钒沸石量的0.01-30%(重量),特别是0.05-15%(重量),尤其是0.1-8%(重量)。当使用具有沸石结构的钛-或钒硅质岩时,特别优选的是同时应用上述量的上述的贵金属。
在本发明中,钛-或钒沸石,有时组合以贵金属或含贵金属的化合物,在一惰性网状织物上结晶,最好是在卤化四烷基铵稀水溶液并附加有氨或四烷基氢氧化铵的存在下用SiO2-原料与钛-或钒组分进行水热反应。按本发明方法有可能得到产率高的钛-或钒沸石晶体,并且是直接呈片状的,无碱金属的初晶体。按本发明方法可优选获得MFI,MEL,MTW,BEA,TON或MOR结构型的可用以催化的钛硅酸盐沸石,优选的方法是,按已叙述的方法以可溶性的、水或水-醇溶液的钛化合物形式将钛组分在反应混合物的水热反应时加入。
按本发明的对网状催化剂的无碱金属的制备方法使其有可能使此材料在350-600℃,优选为400-550℃和特别是在450-550℃下热处理后,直接的和没有离子交换的以一种催化活性的形式存在于网状织物上,并能作为催化剂应用。
本发明网状催化剂的催化活性物的含量,即含有或不含有贵金属的钛-或钒沸石一般为1-30%(重量),特别是5-20%(重量)。
涂敷有钛-或钒沸石的网状织物可按已知方法成形为单块,它可与反应器的几何形状直接最佳的相适应。
按本发明的网状催化剂也可有利的用于当反应热要经良好的导体如网状催化剂金属体快速的输入或排出的情况或者用于在气流式反应器中单块状的网状填料要起到附加的静态混合器功能或者在气相中于高速气体流速下要保证沿反应器纵向的压力降非常小的情况。
本发明的网状催化剂的制备是特别的简单,因为惰性载体在钛-或钒沸石的结晶工艺步骤中通常已转变成为本发明的网状催化剂。
本发明的基于钛-或钒沸石和惰性网状织物的网状催化剂非常适用于加速氧化反应。氧化反应在这里应理解为尤其是烯烃双键化合物的环氧化作用、氢氧化成过氧化氢、氨氧化反应和羟基化如从芳烃制备酚类。
因此本发明也提供一种用氧或供氧的化合物从烯烃制备环氧化合物的方法,它的特征是,在有本发明的基于钛-或钒沸石和惰性网状织物的网状催化剂存在下,使烯烃起反应。
根据欲反应的烯烃与氧源,本发明的环氧化作用可在液相中、气相中或超临界相中进行。假如用过氧化氢水溶液进行的环氧化适宜在液相中进行,而用氢/氧气体混合物的烯烃反应可在液相中或在气相中进行。
假如环氧化作用是用过氧化氢水溶液,例如用10至15%(重量)的过氧化氢水溶液作为供氧化合物进行时,单使用本发明的基于钛-或钒沸石的网状催化剂而不含贵金属即可得到显著的结果。与此相反,例如用氢气/氧气气体混合物作为氧源,在许多情况下建议在本发明的网状催化剂中引入所述的贵金属,特别优选的是含贵金属的网状催化剂,该催化剂含有具有沸石结构的钛-或钒硅质岩。
本发明的在液相中的环氧化作用最好在压力为1-10巴,并有溶剂存在下进行。合适的溶剂包括醇类如甲醇,乙醇,异丙醇或叔丁醇或其混合物和特别是水。也可使用上述的醇类与水的混合物。在某些情况下,应用水或含水溶剂系统与应用纯醇类作溶剂相比较,可明显提高所需环氧化物的选择性。
本发明的环氧化作用一般是在-20-70℃下,特别是-5-50℃下进行。应用氢/氧气体混合物时,氢与氧的克分子比通常在H2∶O2=1∶10-1∶1范围内变动,特别有利的是在1∶5-1∶1。氧与烯烃的克分子比一般为1∶4至1∶10,优选为1∶5-1∶7。可加入任意一种惰性气体作为载气,氮气特别适宜。
所使用的烯烃可以是任何一种至少含有一个乙烯基不饱和双键的有机化合物。该化合物可以是脂族,芳香族的或环脂族的化合物,它可以是直链的或支链的。烯烃最好含2至30个碳原子。也可以含有一个以上的乙烯基不饱和双键,如二烯或三烯烃。烯烃还可含有附加的官能团如卤素原子,羧基,羧酸脂官能团,羟基,醚桥键,硫桥键,羰基官能团,氰基,硝基或胺基。
此类烯烃的典型例子是乙烯,丙烯,1-丁烯,顺-和反-2-丁烯,1,3-丁二烯,戊烯,异戊二烯,己烯,辛烯,壬烯,癸烯,十一烯,十二烯,环戊烯,环己烯、二环戊二烯,亚甲基环丙烷,乙烯基环己烷,乙烯基环己烯,烯丙基氯,丙烯酸,甲基丙烯酸,巴豆酸,醋酸乙烯,烯丙醇,烷基丙烯酯、烷基甲基丙烯酸酯,油酸,亚油酸,亚麻酸,酯类和此类不饱和脂肪酸的甘油酯类,苯乙烯,α-甲基苯乙烯,二乙烯基苯,茚和芪,按本发明方法也可环化上述的烯烃混合物。
本发明方法特别适宜于丙烯环氧化以生成环氧丙烷。
本发明也提供由氢气和氧气生产过氧化氢的方法,其特征是,采用本发明的基于钛-或钒沸石和惰性网状织物的网状催化剂,反应通常以非均相催化进行。采用网状催化剂获得特好的结果,该催化剂含有具有沸石结构的钛-或钒硅质岩,并最好含有基于钛-或钒硅质岩总量的0.01-30%(重量)的一种或多种上述贵金属。
本发明还提供一种由氨或相应的胺类、氢和氧制备羟胺的方法,其特征是,反应在基于钛-或钒沸石和惰性网状织物的网状催化剂存在下进行。采用网状催化剂获得特好的结果,该催化剂含有具有沸石结构的钛-或钒硅质岩,并最好含有基于钛-或钒硅质岩总量的0.01-30%(重量)的一种或多种上述贵金属。
本发明的网状催化剂特别适于制备未取代的羟胺,但也适于制备取代的羟胺,它们是由相应的胺、氢和氧制备的,例如环状胺或脂族胺如环己胺,在反应条件下其一部分进一步反应以形成相应的内酰胺。
在液相中制备羟胺,最好在压力为1-100巴和有溶剂存在下进行。合适的溶剂为醇类如甲醇,乙醇,异丙醇或叔-丁醇或其混合物以及特别是水。也可以采用这些醇类和水的混合物。在某些情况下,应用水和含水溶剂系统与应用纯醇类作溶剂相比较,可明显提高所需产品的选择性。
按本发明制备所需羟胺的反应一般在-5°-70℃,特别是20°-50℃下进行。氢与氧的克分子比通常能在H2∶O2=1∶10-1∶1范围内变化,在1∶2.5-1∶1是特别有利的。氧与氨的克分子比一般在1∶1-1∶3,优选为1∶1.5-1∶1.7。可加入任意一种惰性气体作为载气,氮气特别适宜。
下面实例将详细的阐述本发明的网状催化剂的制备方法,以及本发明的网状催化剂的催化性能,但不应将此理解为是一种限制。
实例1
本实例描述用不锈钢网作为载体材料的本发明的网状催化剂的制备。
在一带搅拌器的烧瓶中放置329克去离子水,并在搅拌下于一个半小时内滴加22.7克四异丙基原钛酸盐。将白色的悬浮液冷却到5℃。然后加入272克过氧化氢水溶液(30%(重量),在水中),并将所形成的橙红色溶液再搅拌39分钟。再加入704克氨溶液(25%(重量),在水中)同时在室温下保持所形成的黄色悬浮液15小时,最后在80℃下加热3小时,以便分解掉过量的过氧化氢。
将58.8克四丙基溴化铵、88.7克二氧化硅(Degussa公司的硅胶200)、122.4克去离子水和626克上述的钛酸盐-水解悬浮液在聚丙烯塑料杯中均匀化。
在衬有聚四氟乙烯的高压釜中加入二块10.8克和11.9克的不锈钢丝网(钢1.4401),并加入150克上述合成的钛沸石。此混合物在175℃下结晶168小时。
结晶结束后移出此网,用水洗涤成中性,在120℃下干燥和在500℃下于合成空气(3%(体积)的氧,97%(体积)的氮)中焙烧。用压缩空气流吹除掉松散的附着的剩余凝胶。由于钛沸石在网上结晶使二块网增加的重量各为8.7或8.0%(重量)。此网不再经预处理用于实例3中制备环氧丙烷。
对比实例A
此对比实例描述具有MFI-结构的钛硅质岩石的制备,按EP 376453(4)中的现有技术进行。
将30毫升四乙基原钛酸盐在搅拌下(300转/分)在15分钟内滴到375毫升的预先冷却至2℃的去离子水中,然后加入360毫升冷的过氧化氢溶液(30%(重量),在水中),以形成橙红色溶液,将其连续搅拌2小时。然后加入625毫升四丙基氢氧化铵水溶液(20%(重量),在水中)和一小时后再加入100克胶态的硅溶胶(40)%(重量)SiO2,Du Pont公司的Ludox AS-40)。将此混合物在室温下保持过夜,第二天在80℃下加热,并同时搅拌(300转/分)7小时,将其转到2升带搅拌的压力容器中,并在175℃下持续反应240小时。
过滤出冷却后的反应混合物,用去离子水多次洗涤滤饼至中性,在120℃下干燥过夜,然后在550℃的空气中焙烧。以所加的SiO2计算,钛硅质岩的收率为93%。经伦琴衍射图证实为MFI-结构的纯钛硅质岩。
实例2
本实例描述以石墨网作为载体材料来制备本发明的网状催化剂。
在一带搅拌器的烧瓶中放置329克去离子水,并在搅拌下于一个半小时内滴加22.7克四异丙基原钛酸盐。将白色悬浮液冷却至5℃。再加入272克过氧化氢溶液(30%(重量),在水中),并将所形成的橙红色溶液再搅拌30分钟。然后加入704克氨溶液(25%(重量),在水中),同时在室温下保持所形成的黄色悬浮液15小时,最后在80℃下加热3小时,以便分解掉过量的过氧化氢。
将58.8克四丙基溴化铵、88.7克二氧化硅(Degussa公司的硅胶200)、122.4克去离子水和626克上述的钛酸盐-水解悬浮液在聚丙烯塑料杯中均匀化。
在衬有聚四氟乙烯的高压釜中加入2块5.2克和5.3克的石墨织网(KDL公司8042,200克/米2),并加入150克上述合成的钛沸石。此混合物在175℃下结晶168小时。
结晶结束后移出此网,用水洗涤成中性,在120℃下干燥和在500℃的氮气氛中焙烧。用压缩空气吹除掉松散的附着的剩余凝胶。由于钛沸石在网上结晶使二块材料增加的重量各为10.4或8.7%(重量)。此网块不再经预处理用于实例4中制备环氧丙烷。
对比实例B和C
本合成实例描述了在同时使用氨溶液时由四丙基氢氧化铵替换四丙基溴化铵时的影响。
在带搅拌器和回流冷凝器的玻璃烧瓶中,45.1克去离子水冷至5℃。于15分钟内滴加入6.9克四异丙基原钛酸盐和81.4克过氧化氢水溶液(30%(重量),在水中)。将211.0克氨溶液(25%(重量),在水中)加到所形成的橙红色溶液中,并让所形成的物料过夜受热至室温。最后在搅拌下加热3小时至80℃。可能出现的重量损失通过加入适量氨溶液补偿。
取156.8克上述制备好的溶液与56.0克四丙基氢氧化铵溶液(20%(重量),在水中)和52.8克LudoxAS-40硅溶胶(Du Pont公司产品)在三分钟内相混合,并将混合物转入聚四氟乙烯衬里的高压釜中,同时密闭(下面称为B组分)。
再取156.5克最初制备的溶液与在44.8克水中的14.7克四丙基溴化铵和53.1克LudoxAS-40硅溶胶(Du Pont公司产品)于三分钟内相混合,并将混合物转入聚四氟乙烯衬里的高压釜中,同时密闭(下面称为C组分)。
组分B和C各在183-185℃下反应192小时。过滤出结晶的反应产物,洗涤成中性,干燥和在500℃空气中经5小时焙烧。此两对比实例的产品性能见下表:
组分 | 收率 | Si/Ti[克分子] | 钾[%(重量)] | 大小[1μm] | 形状 |
B | 96% | 36 | 0.001 | 0.1 | 球形 |
C | 95% | 36 | 0.001 | 26 | 小片形 |
实例3
本实例描述用实例1的催化剂制备本发明的环氧丙烷。
在玻璃高压釜中用实例1提供的9克催化剂网在45毫升甲醇中配成悬浮液。将高压釜冷却至-30℃,压入20.5克丙烯,然后将高压釜升温到0℃。在20分钟内加入30克的30%(重量)H2O2的水溶液,并在0℃下搅拌反应混合物5小时。反应结束后用气相色谱测定溶解的环氧丙烷的量。测得环氧丙烷的量为1.65%(重量)。
实例4
本实例描述用实例2的催化剂制备本发明的环氧丙烷。
在玻璃高压釜中用实例2提供的15克催化剂网在45毫升的甲醇中配成悬浮液。将高压釜冷却至-30℃,压入19.7克丙烯,然后将高压釜升温至0℃。在25分钟内加入40.6克的30%(重量)H2O2的水溶液,并在0℃下搅拌反应混合物5小时。反应结束后用气相色谱测定的已溶解的环氧丙烷的量为4.9%(重量)。
实例1至4表明,本发明的网状催化剂易于制备,并且在环氧化作用上比用对比实例B-E中所述的惯用的多步法所载上的钛沸石有更好的结果。
对比实例D
此实例描述用对比实例B提供的未成形的催化剂制备环氧丙烷。
在玻璃高压釜中将由对比实例B提供的1.5克催化剂在45毫升的甲醇中配成悬浮液,将高压釜冷至-30℃,压入23.5克丙烯,并将高压釜加热到0℃。再在20分钟内加进28.9克30%(重量)H2O2水溶液,并在0℃下继续搅拌该混合物5小时。反应结束后用气相色谱测定的已溶解的环氧丙烷的量为3.7%(重量)。
对比实例E
此实例描述用对比实例B提供的已成形的催化剂制备环氧丙烷。
将对比实例B的100克催化剂与12.5克LudoxAS-40、5克甲基纤维素和70毫升水组合,并在捏和机中辗实120分钟,并加工成直径为2毫米的挤出物。该挤出物在110℃下干燥过夜,并在500℃下焙烧5小时。将此所得的挤出物加工成碎粒(粒度约为1毫米)。
在玻璃高压釜中将1.5克此种催化剂碎粒在45毫升甲醇中配成悬浮液。将高压釜冷至-30℃,压入29.7克丙烯,并将高压釜加热到0℃。在20分钟内加入31克的30%(重量)H2O2水溶液,并继续搅拌该混合物5小时。反应结束后用气相色谱测定的已溶解的环氧丙烷的量为2.6%(重量)。
这表明,成形明显地减少原始材料的催化活性。(参见对比实例D,它含3.7%(重量)的环氧丙烷)。
Claims (10)
1.一种基于钛-或钒沸石和惰性网状织物的网状催化剂。
2.按权利要求1的网状催化剂,其惰性网状织物是由金属、塑料、氧化铝、玻璃纤维、碳纤维和/或石墨组成。
3.按权利要求1或2的网状催化剂,其碱金属含量小于钛-或钒沸石重量的500ppm。
4.按权利要求1-3任一的网状催化剂,该催化剂含具有沸石结构的钛-或钒硅质岩并含一种或多种选自金,银,铼,钌,铑,钯,锇,铱和铂的贵金属,其含量为钛-或钒硅质岩量的0.01-30%(重量)。
5.按权利要求1-4任一的制备网状催化剂的方法,其特征在于,钛-或钒沸石和需要时还有贵金属或含贵金属的化合物在惰性的网状织物上的晶化。
6.基于钛-或钒沸石和惰性网状织物的网状催化剂在加速氧化反应中的应用。
7.一种利用氧或供氧化合物从烯烃制备环氧化物的方法,其特征在于,烯烃在有基于钛-或钒沸石和惰性网状织物的网状催化剂存在下进行反应。
8.一种按权利要求7制备环氧丙烷的方法。
9.一种由氢和氧制备过氧化氢的方法,其特征在于,在有基于钛-或钒沸石和惰性网状织物的网状催化剂存在下进行反应。
10.一种由氨或相应的胺、氢和氧制备羟胺的方法,其特征在于,在有基于钛-或钒沸石和惰性网状织物的网状催化剂存在下进行反应。
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DE271101C (zh) * | ||||
IT1150699B (it) * | 1982-03-19 | 1986-12-17 | Anic Spa | Procedimento per la ossidrilazione di idrocarburi aromatici |
IT1152299B (it) * | 1982-07-28 | 1986-12-31 | Anic Spa | Procedimento per l'espossidazione di composti olefinici |
IT1214622B (it) * | 1985-07-10 | 1990-01-18 | Montedipe Spa | Processo catalitico per laproduzione di cicloesanonossima. |
DD271101A1 (de) * | 1988-03-28 | 1989-08-23 | Univ Dresden Tech | Herstellung von hochsilicatischen fe- und fe-al-zeolithen |
KR0151712B1 (ko) * | 1988-11-08 | 1998-10-15 | 피터 챨스 보우덴 | 포화탄화수소 사슬의 산화 |
EP0388094A1 (en) * | 1989-03-10 | 1990-09-19 | Sakai Chemical Industry Co., Ltd., | Methods of ozone decomposition and catalyst structures used therein |
JPH05105420A (ja) * | 1991-03-29 | 1993-04-27 | Ngk Insulators Ltd | ゼオライト結晶体の合成膜およびその製造方法 |
US5262550A (en) * | 1992-04-30 | 1993-11-16 | Arco Chemical Technology, L.P. | Epoxidation process using titanium-rich silicalite catalysts |
NL9201940A (nl) * | 1992-11-05 | 1994-06-01 | Univ Delft Tech | Katalysatorsysteem van het gestructureerde type. |
RU2140819C1 (ru) * | 1993-12-23 | 1999-11-10 | Арко Кемикал Текнолоджи, Л.П. | Титансодержащий цеолит, способ его получения (варианты), способ эпоксидирования олефинов и дичетвертичное аммониевое соединение для получения титансодержащего цеолита |
DE4425672A1 (de) * | 1994-07-20 | 1996-01-25 | Basf Ag | Oxidationskatalysator, Verfahren zu seiner Herstellung und Oxidationsverfahren unter Verwendung des Oxidationskatalysators |
US5912367A (en) * | 1997-07-01 | 1999-06-15 | Arco Chemical Technology, L.P. | High efficiency epoxidation process |
US6008388A (en) * | 1998-04-16 | 1999-12-28 | Arco Chemical Technology, L.P. | Epoxidation process |
-
1996
- 1996-02-29 DE DE19607577A patent/DE19607577A1/de not_active Withdrawn
-
1997
- 1997-02-20 CN CN97192687A patent/CN1091656C/zh not_active Expired - Fee Related
- 1997-02-20 EP EP97903335A patent/EP0883439B1/de not_active Expired - Lifetime
- 1997-02-20 ES ES97903335T patent/ES2160323T3/es not_active Expired - Lifetime
- 1997-02-20 AU AU17932/97A patent/AU1793297A/en not_active Abandoned
- 1997-02-20 KR KR1019980706229A patent/KR19990082496A/ko not_active Application Discontinuation
- 1997-02-20 CA CA002243463A patent/CA2243463A1/en not_active Abandoned
- 1997-02-20 JP JP9530560A patent/JP2000506060A/ja active Pending
- 1997-02-20 DE DE59703861T patent/DE59703861D1/de not_active Expired - Fee Related
- 1997-02-20 US US09/117,293 patent/US6106797A/en not_active Expired - Fee Related
- 1997-02-20 WO PCT/EP1997/000804 patent/WO1997031711A1/de not_active Application Discontinuation
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114426551A (zh) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | 一种制备二氧化双环戊二烯dcpddo的方法 |
CN114426551B (zh) * | 2020-10-15 | 2024-02-02 | 中国石油化工股份有限公司 | 一种制备二氧化双环戊二烯dcpddo的方法 |
Also Published As
Publication number | Publication date |
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US6106797A (en) | 2000-08-22 |
CA2243463A1 (en) | 1997-09-04 |
CN1091656C (zh) | 2002-10-02 |
JP2000506060A (ja) | 2000-05-23 |
ES2160323T3 (es) | 2001-11-01 |
KR19990082496A (ko) | 1999-11-25 |
AU1793297A (en) | 1997-09-16 |
EP0883439A1 (de) | 1998-12-16 |
DE59703861D1 (de) | 2001-07-26 |
EP0883439B1 (de) | 2001-06-20 |
WO1997031711A1 (de) | 1997-09-04 |
DE19607577A1 (de) | 1997-09-04 |
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