CN1416426A - 含镧系金属的环氧化催化剂 - Google Patents
含镧系金属的环氧化催化剂 Download PDFInfo
- Publication number
- CN1416426A CN1416426A CN01804579A CN01804579A CN1416426A CN 1416426 A CN1416426 A CN 1416426A CN 01804579 A CN01804579 A CN 01804579A CN 01804579 A CN01804579 A CN 01804579A CN 1416426 A CN1416426 A CN 1416426A
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- Prior art keywords
- support material
- solid support
- gold
- compound
- catalyzer
- Prior art date
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 15
- 239000002184 metal Substances 0.000 title claims abstract description 14
- 239000003054 catalyst Substances 0.000 title abstract description 20
- 238000006735 epoxidation reaction Methods 0.000 title abstract description 10
- 150000002739 metals Chemical class 0.000 title abstract description 3
- 239000010931 gold Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 28
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052737 gold Inorganic materials 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
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- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
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- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 6
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims abstract description 6
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 5
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- 229910000667 (NH4)2Ce(NO3)6 Inorganic materials 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
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- 108010021809 Alcohol dehydrogenase Proteins 0.000 description 1
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- IKULJBSBBUMZDZ-UHFFFAOYSA-N silicic acid terbium Chemical compound [Tb].[Si](O)(O)(O)O IKULJBSBBUMZDZ-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明涉及一种用分子氧和氢对烯烃进行环氧化的方法,该方法将负载在载体材料上优选为纳米粒度的含金化合物用作催化剂,所述的载体材料含有一种或多种的镧系元素。本发明也涉及负载在载体材料上优选为纳米粒度的含金化合物,所述的载体材料含有选自原子序数为58-71的金属的一种或多种元素,其中铈和钕除外。本发明还涉及上述化合物的制备方法和在这种化合物存在的条件下催化化学反应的方法。
Description
发明背景
在气相条件下用分子氧将烯烃直接部分氧化成环氧化物,长期被认为是工业催化中最重要的反应之一。由于环氧化物在聚氨酯工业中具有重要的作用,因此人们付出了诸多努力,用各种方法制备环氧化物,其中一部分已经工业化。为了由含两个以上碳原子的烯烃制备环氧化物,大多数生产技术采用过氧化氢或氯乙醇作氧化剂。例如,欧洲专利(EP-A1-0 930 308)介绍了以过氧化氢或氯乙醇为氧化剂,使用离子交换的硅酸钛用来制备环氧化物。最近,US-A-5,623,090介绍了一类新材料,用它可在氢气同时存在的条件下以分子氧为氧化剂直接制备环氧化物,例如由丙烯直接制备氧化丙烯。在该专利中要求保护,当把金沉积在二氧化钛,尤其是锐钛矿型二氧化钛上时,就可发生丙烯直接气相部分地氧化成为氧化丙烯的反应。
虽然金/二氧化钛体系尚远未工业化,且反应产率低,但它与从前已有发明的不同之处,在于它在含3个或更多碳原子的烯烃的环氧化反应中表现出的较高选择性,丙烯是一个实例。例如,含银催化剂体系虽然在制备环氧乙烷时表现出较好的产率和选择性,但在丙烯转化中却显示不出较高或有望较高的活性。因此,自Hayashi和Haruta(见Hayashi等人,烃的多相氧化反应论文集,发表于美国化学会第211次全国大会石油化学分组会,新奥尔良,LA,1996年3月24-29日)的工作之后,以后的专利主要集中在金与钛的结合使用上,它们是WO 97/34692-A1,WO 98/00413-A1,WO 98/00414-A1。专利EP-A1-0 940393是一个例外,它在元素Zr的共存下使用金。因此,本领域中目前的共识是,有助于烯烃物质部分氧化的活性物质数量是有限的。另外,Mohr、Hofmeister、Lucas和Claus在化学工程技术71期第869-873页(1999)揭示了Au/CeO2、Au/Y2O3、Au/Nd2O3可用作水合催化剂,而且Rodemerck、Ignaszewski、Lucas和Claus在化学工程技术71期第873-877页(1999)揭示Au/CeO2、Au/Y2O3、Au/Nd2O3可用于氧化CO。然而,这两个文献都没有叙述含有镧系金属和金的催化剂可用作环氧化催化剂。
发明概述
本文介绍的发明涉及用分子氧和氢对烯烃环氧化的方法。该方法的特点是将负载在载体材料上优选有纳米粒度的含金化合物用作催化剂,上述的载体材料含有一种或多种镧系元素。所有这些催化剂都不含钛元素。这些发现是令人吃惊的,因为在过去三年的深入研究中,只发现极少数含金催化剂体系可用于烯烃的环氧化反应。本发明表明在几种情况下,上述催化剂较长时间具有良好的稳定性。
本发明的另一项内容是一种负载在载体材料上优选有纳米粒度的含金化合物,所述载体材料含有选自原子序数为58-71的金属的一种或多种元素,铈和钕除外。
本发明的第三项内容是一种在负载于载体材料上优选有纳米粒度的含金化合物存在的条件下进行化学反应来催化所述化学反应的方法,所述的载体材料含有选自原子序数为58-71的金属的一种或多种元素,铈和钕除外。
本发明的第四项内容是本发明化合物的制备方法。该方法的特点是将纳米金微粒淀积在载体材料上,该载体材料含有一种或多种镧系元素。
本发明的最后一项内容是本发明化合物的制备方法。该方法的特点是用溶胶-凝胶法制备在载体材料上包含纳米金微粒的化合物。该载体材料含有一种或多种镧系元素。
发明详述
与时下用于部分氧化反应的许多催化剂一样,本发明所述的催化剂虽然对任何烯烃都可以使用,但明显最能够促进C3-C6的轻烯烃尤其是丙烯和丁烯的环氧化反应。烯烃上包含的碳-碳双键的数目通常为1,但本发明对包含一个以上碳-碳双键的烯烃也可以使用。适用于本发明的例子包括乙烯、丙烯、1-丁烯、2-丁烯、异丁烯、1-戊烯、2-戊烯、丁二烯、烯丙醇、烯丙基氯、苯乙烯、环己烯和其他类似的物质。上述催化剂还能用于气体原料中含有一种以上烯烃的环氧化反应。
使用本发明时,对反应气体中所含烯烃的浓度一般认为并没有特别苛刻的要求,可以在较宽范围内变化。在大多数情况下,气体的组成取决于所用反应器的类型、氧气和氢气的相对用量,以及稀释剂的加入量(如果需要加稀释剂的话)。对于工业化,可以预计,进入反应器的气流中烯烃的总浓度可以但不限于在5-80%(摩尔)之间变化,而该气流的其余部分则通常包含氧气、氢气和一种任选的稀释气体。
本发明方法中所用的氧可取自任一合适的来源,例如空气。不过也可以利用别的氧源,例如氮氧化物或臭氧。本发明在过氧化氢存在条件下也有效。所需氧的量取决于若干个参数,且可以在较宽范围内变化。但要得到最佳结果,烯烃和氧的摩尔比大于1被认为是重要的。如果反应器中存在大量氧气,反应的选择性常常急剧下降,因为烯烃既可发生部分氧化也可发生完全氧化。氧的存在量通常在1-20%(摩尔)之间,尽管其他比例可以采用,也能够采用。
一般认为氢源也不是重要的,可以用任何合适的氢源供氢。按照定义,任何合适的氢源可包括诸如由烷烃或醇脱氢得到的分子氢。分子氢的制备既可事先进行,也可原位进行,即可包括在反应器中进行。氢的用量取决于把烯烃转化为相应环氧化物所需的量,因而不是固定的。不过,正常操作的范围表明,反应器中所含的氢浓度通常应低于30%(摩尔),余下的是氧、烯烃和稀释剂(如果需要的话)。
加入稀释剂是可取的,但对于烯烃反应的发生并不是必需的。稀释剂的选取取决于若干因素,包括但不限于安全、成本因素和惰性程度。可用作稀释剂的备选气体是氮气、氦气、氩气或任何其他惰性气体。由于将反应物传递到催化剂表面的过程是最至关重要的因素,所以催化剂也可在液相中使用。在此情况下,浸渍催化剂的液体也应当是惰性的,并且是有助于反应气体转移到催化剂表面的良好介质。
镧系金属的原子序数范围为58-71,包括铈、镨、钕、钷、钐、铕、钆、铽、铒、镝、钬、铥、镱、镥。
在本发明中,镧系元素可以任何合适形式引入催化剂。使用例如(NH4)2Ce(NO3)6、叔丁醇铈(IV)、Nd(NO3)3Ho(CN3)3·5H2O、六水合氯化铕、五水合硝酸铕、Er(NO3)3·5H2O、六水合硝酸铥等可以制得活性催化剂。
因此,对于本发明的目的而言,催化剂原料的实际来源可以是多种多样的,且所用原料的选择最终取决于所用的制备方法。所以进一步列出许多并不会进一步加深本领域中普通技术人员对本发明的理解。
将Au负载在稀释于硅酸盐中的镧系金属体系上,同样有可能产生活性。此类非限制性例子有ZSM-5、ZSM-11、ZSM-48和MCM-41或者任何具有类似化学或物理结构的材料。通过气相法,或者更好地通过常规的溶胶-凝胶制备法,也可以制备活性催化剂。常规溶胶-凝胶制备法的例子见L.C.Klein,Ann.Rev.Mar.Sci.,15,p227及其后续著作(1985)或者是DE-A-199 20 753所披露的方法。
如本领域所熟知的,上面提到的催化剂都可以加入所有常规助催化剂,例如碱金属和碱土金属。虽然元素镧在正常情况下被认为是助催化剂,但用于本发明的目的,对于烯烃的环氧化反应被认为就是催化剂。因此要特别声明,在金存在的条件下,镧系中的每一种元素都会产生独特而不同的催化反应剂。然而应当注意到,如果1)所用镧系元素的浓度低于可选催化剂中活性组分的1%,并且2)镧系元素用作添加剂,用交岔频率测得的活性不强于添加这些元素的催化剂的活性组分,则可以将这些镧系元素作为助催化剂合理地用于不含本发明具体提到那些元素的催化剂中。
从逻辑上讲,如果需要,上述镧系金属金属元素可以按任何组合方式与金一起制备所谓的共催化剂体系。这些催化剂也可以包含在或结合于用于改善上述体系的物理性质的其它载体材料或催化剂上。非限制性例子是使用第二载体,从而把催化剂浸渍在能够增加总暴露表面积的载体上。第二载体也可以用来改善物理性质,例如控制凝结。这类载体的非限制性例子包括二氧化硅、氧化铝、硅铝酸盐、粘土、碳酸盐、沸石或它们的任意组合或混合物。
尽管对于本发明来说并不特别,但本领域所共知的是,上述催化剂可用于任何反应器,只要它能控制和混合所需氧气、氢气和烯烃。反应器可以采用间歇式操作、固定床操作、转移床操作或流化床操作,催化剂可以制成粉末或压丸。
在本发明中,金和镧系金属的负载量不是固定的。据观察,本发明中金粒的尺寸一般在2-400纳米之间变化。然而值得建议的是,为了得到尽可能高的转化率,应采用大的表面积。因此,金粒的尺寸在1-10纳米范围内通常较好。结果,金的负载量一般应足够低,即一般低于0.1原子%,以利于形成较小的纳米(nm)级原子簇。然而,可以制备含金量高于5原子%的催化剂,但这并不被看作最佳的。沉积纳米金粒的技术可见于WO 98/00413-Al、WO 98/00414-Al、WO 98/00415-Al、WO 97/34692-Al;、Haruta等人,J.Catal.,115,第301-309页(1989);Tsubota等.,“制备催化剂V”,Stud.Surf.Sci.Catal.,63,eds.,G.Poncelet et al.,Elsevier,第695-704页(1991);Kobayashi等人,Sensors and Actuators,B1第222-225(1990);Sakurai和Haruta,Catal.Today,29第361页(1996);D.Cunningham等人,Res.Chem.Intermediates,19,第1-13页(1993);Okumura等人,Solid State Ionics,95 143(1997);D.Cunningham等人,Catal.Lett.,63(1-2),第43-47页(1999)。据此,可以采用任何能将金属沉积到固体载体上的方法,例如浸渍法、共沉淀法、化学气相沉积法、离子交换技术和沉积-沉淀法。制备催化剂时,通常要求限制或避免氯带来的污染。焙烧步骤通常是需要的,但并不总是需要,可以通过快速加热/急冷过程进行,也可以通过长时间暴露在热源中进行。所需焙烧温度取决于制备方法,但一般不高于700℃。
获得活性催化剂的一种合适方法是溶胶-凝胶合成法。在此方法中,将所需镧系金属的醇盐加入到一种合适的硅烷醇化合物,例如原硅酸四乙酯、六甲基二硅氮烷、四癸氧硅烷、四丁氧硅烷、甲基-三乙氧硅烷、四乙氧硅烷、四甲氧硅烷,或基本上任何其他合适的硅烷醇,包括那些包含苯或更复杂的有机基团的硅烷醇中。通常把硅烷醇稀释于醇如乙醇、丙醇、丁醇,或任何在制备温度下呈液态的合适的醇中。向此溶液中加入含金酸性溶液,用酸调节pH。所得溶液一般是均匀的,且形成金粒均匀分散其中的凝胶。为了除去氯,我们发现仅需加热凝胶到高温例如350℃就足够了。然而,为了得到最佳结果,最好的做法一般是用不含氯或氟的水反复清洗所得的催化剂。金属金粒子可在任何温度下形成,包括室温。可以向此催化剂中加入助催化剂,以提高选择性或产率,或者增加催化剂的使用寿命。已知的例子包括碱金属锂、钠、钾和铷。
在操作中,可以预料,本发明可在20℃到250℃范围内进行操作。实际使用的温度取决于如下因素:反应气组成,或者流体的凝固点(如果是液体反应器的话),所要求的产率和选择性的高低,反应器中的压力,所用的反应器类型,所用烯烃的类型和其他会影响或要求改变操作温度的因素。一般认为压力在常压到200巴之间是比较合适的。在气相混合物反应中,气体流量(按空速测量)可以改变,并且最终取决于所用反应参数。
催化剂的再生可以通过许多常规方法中的任何一种完成,例如高温处理,或在中性或酸性试剂溶液中清洗(DE-Al-198 04 712)。
实施例
实施例1含铥的催化剂(催化剂Al)
用于制备催化剂的一种方法是溶胶-凝胶/沉积-沉淀法。这项技术一般适用于所有镧系元素。为了制备负载在铥/原硅酸四乙酯上的含金催化剂,首先将2.92毫升醇(如乙醇)与3298毫克原硅酸四乙酯混合。然后将0.345克铥化合物[本实施例中是六水合硝酸铥(III)]加入上面的混合物中。然后在此混合物中加入溶解在600微升H2O的1.67克的HNO3。再搅拌样品直到发生胶凝现象。胶凝以后,干燥样品,碾成粉末,然后在350℃加热24小时。
为了在载体上负载金,将1.0克按上述方法制得的硅酸铥化合物加入20毫升水中。将溶于10毫升水的0.02克氯金酸加入得到的悬浮液中,将此悬浮液搅拌1小时。然后向此体系中加入10毫升0.015M的柠檬酸钠,再搅拌该体系1小时。分离湿的粉末,用蒸馏水反复清洗除去氯,在100℃、200毫巴压力下干燥过夜,最后在350℃焙烧。
将焙烧所得的500毫克催化剂Al装入一气体反应池中,在100℃温度下进行试验。在此试验中,将含5.78%丙烯、75.65%氢、4.81%氧和13.76%氮稀释剂的气体以3500毫升小时-1/克催化剂的空速通入反应床。用气相色谱分析气相中的反应产物。
表1
含1原子%金和5.0原子%铥的催化剂Al | 乙醛 | 氧化丙烯 | 丙醛 | 丙酮 |
转化率 | 0.000 | 0.009 | 0.000 | 0.003 |
选择性 | 0.000 | 74.92 | 0.000 | 25.08 |
表1表明让丙烯通过用溶胶-凝胶/沉积-沉淀法制得的含金、铥和原硅酸四乙酯(TEOS)的催化剂得到的部分氧化产物的分布。
实施例2-11
用与实施例1相同的方法制备催化剂,不同之处是使用各自量的表2所示的化合物代替上述铥化合物。
表2
实施例 | 用下列化合物代替硝酸铥(III) | 用下列化合物代替硅酸铥 |
2 | 氯化镨(III) | 硅酸镨 |
3 | 硝酸钐(III) | 硅酸钐 |
4 | 六水合氯化铕 | 硅酸铕 |
5 | 2,2,6,6-四甲基庚二酸钆 | 硅酸钆 |
6 | 硝酸铽(III) | 硅酸铽 |
7 | 硝酸镝(III) | 硅酸镝 |
8 | 硬脂酸钬(III) | 硅酸钬 |
9 | 甲氧基乙醇铒 | 硅酸铒 |
10 | 五水合硝酸镱 | 硅酸镱 |
11 | 硝酸镥(III) | 硅酸镥 |
所列的所有原料都是市售的。
表3
催化剂 | 乙醛 | 氧化丙烯 | 丙醛 | 丙酮 | |
25原子%Pr | %转化率 | 0.000 | 0.014 | 0.000 | 0.023 |
%选择性 | 0.000 | 37.67 | 0.000 | 62.33 | |
35原子%Sm | %转化率 | 0.000 | 0.014 | 0.000 | 0.025 |
%选择性 | 0.000 | 35.44 | 0.000 | 64.56 | |
45原子%Eu | %转化率 | 0.007 | 0.012 | 0.023 | 0.028 |
%选择性 | 10.45 | 16.51 | 33.36 | 39.68 | |
55原子%Gd | %转化率 | 0.000 | 0.009 | 0.003 | 0.001 |
%选择性 | 0.000 | 39.9 | 23.43 | 6.67 | |
65原子%Tb | %转化率 | 0.000 | 0.007 | 0.002 | 0.004 |
%选择性 | 0.000 | 51.63 | 18.75 | 29.62 | |
75原子%Dy | %转化率 | 0.007 | 0.014 | 0.026 | 0.021 |
%选择性 | 10.19 | 21.08 | 38.21 | 30.52 | |
85原子%Ho | %转化率 | 0.000 | 0.011 | 0.005 | 0.012 |
%选择性 | 0.000 | 39.68 | 16.69 | 43.63 | |
95原子%Er | %转化率 | 0.003 | 0.028 | 0.004 | 0.006 |
%选择性 | 8.12 | 64.89 | 11.06 | 15.93 | |
105原子%Yb | %转化率 | 0.008 | 0.068 | 0.008 | 0.001 |
%选择性 | 9.15 | 80.36 | 9.11 | 1.38 | |
115原子%Lu | %转化率 | 0.013 | 0.073 | 0.046 | 0.043 |
%选择性 | 7.64 | 41.59 | 26.29 | 24.48 |
表3是将丙烯通过由溶胶-凝胶/沉积-沉淀技术制备、含1.0原子%金、原硅酸四乙酯(TEOS)和5原子%镧系金属的催化剂得到的部分氧化产物的分布。
Claims (11)
1.一种用分子氧和氢对烯烃进行环氧化的通用方法,其特征在于,是将负载在载体材料上优选为纳米粒度的含金化合物用作催化剂,所述的载体材料含有一种或多种原子序数为58-71的镧系元素。
2.如权利要求1所述的方法,其特征在于,所述的载体材料不含钛。
3.如权利要求1或2所述的方法,其特征在于,所述的烯烃为丙烯。
4.一种负载在载体材料上优选为纳米粒度的含金化合物,其特征在于,所述的载体材料含有选自原子序数为58-71的金属的一种或多种元素,其中铈和钕除外。
5.如权利要求4所述的含金化合物,其特征在于,所述的化合物不含钛。
6.按权利要求4或5所述化合物的制备方法,其特征在于,将纳米金微粒淀积在载体材料上,该载体材料含有一种或多种镧系元素。
7.如权利要求6所述的方法,其特征在于,所述的化合物不含钛。
8.按权利要求4或5所述化合物的制备方法,其特征在于,所述的化合物通过溶胶-凝胶法制备。
9.如权利要求8所述的方法,其特征在于,所述的溶胶-凝胶法中使用金属硝酸盐。
10.一种催化化学反应的方法,其特征在于,该方法是在负载于载体材料上优选为纳米粒度的含金化合物的存在条件下,进行所述的化学反应,所述的载体材料含有选自原子序数为58-71的金属的一种或多种元素,其中铈和钕除外。
11.如权利要求10所述的方法,其特征在于,所述的化合物不含钛。
Applications Claiming Priority (2)
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EP00102560.0 | 2000-02-07 | ||
EP00102560A EP1125933A1 (en) | 2000-02-07 | 2000-02-07 | Epoxidation catalyst containing metals of the lanthanoide series |
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CN1416426A true CN1416426A (zh) | 2003-05-07 |
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CN01804579A Pending CN1416426A (zh) | 2000-02-07 | 2001-01-25 | 含镧系金属的环氧化催化剂 |
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US (1) | US20030100778A1 (zh) |
EP (2) | EP1125933A1 (zh) |
JP (1) | JP2003522765A (zh) |
KR (1) | KR20020082222A (zh) |
CN (1) | CN1416426A (zh) |
AU (1) | AU2001240544A1 (zh) |
BR (1) | BR0108091A (zh) |
CA (1) | CA2399128A1 (zh) |
CZ (1) | CZ20022565A3 (zh) |
HK (1) | HK1053112A1 (zh) |
HU (1) | HUP0300004A3 (zh) |
MX (1) | MXPA02007583A (zh) |
PL (1) | PL357196A1 (zh) |
RU (1) | RU2002124126A (zh) |
WO (1) | WO2001058887A1 (zh) |
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PL2316567T3 (pl) | 2003-09-26 | 2018-07-31 | 3M Innovative Properties Co. | Katalizatory, środki aktywujące, nośniki i metodologie użyteczne do wytwarzania układów katalizatora, w szczególności gdy katalizator jest osadzany na nośnikach z wykorzystaniem fizycznego osadzania z fazy gazowej |
JP4426379B2 (ja) * | 2004-05-24 | 2010-03-03 | Tanakaホールディングス株式会社 | 触媒前駆体及び触媒、並びに、触媒前駆体及び触媒の製造方法 |
US7592001B2 (en) * | 2004-08-02 | 2009-09-22 | University Of Florida Research Foundation, Inc. | High aspect ratio metal particles and methods for forming same |
ES2261080B1 (es) * | 2005-04-19 | 2007-12-16 | Universidad Politecnica De Valencia | Procedimiento y catalizadores para la expoxidacion de compuestos olefinicos en presencia de oxigeno. |
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RU2189378C2 (ru) * | 1996-07-01 | 2002-09-20 | Дзе Дау Кемикал Компани | Способ получения олефиноксидов прямым окислением олефинов, каталитический состав для этого процесса и способ его регенерации |
EP0850936B1 (en) * | 1996-12-25 | 2004-10-27 | Agency Of Industrial Science And Technology | Method of manufacturing epoxide and catalyst for use therein |
DE19804709A1 (de) * | 1998-02-06 | 1999-08-12 | Bayer Ag | Verfahren zur katalytischen Direktoxidation ungesättigter Kohlenwasserstoffe in der Gasphase |
US5939569A (en) * | 1998-03-10 | 1999-08-17 | Jones; C. Andrew | Epoxidation process |
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2000
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2001
- 2001-01-25 CZ CZ20022565A patent/CZ20022565A3/cs unknown
- 2001-01-25 CN CN01804579A patent/CN1416426A/zh active Pending
- 2001-01-25 RU RU2002124126/04A patent/RU2002124126A/ru not_active Application Discontinuation
- 2001-01-25 EP EP01911531A patent/EP1263748A1/en not_active Withdrawn
- 2001-01-25 US US10/181,989 patent/US20030100778A1/en not_active Abandoned
- 2001-01-25 PL PL01357196A patent/PL357196A1/xx not_active Application Discontinuation
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EP1263748A1 (en) | 2002-12-11 |
HK1053112A1 (zh) | 2003-10-10 |
AU2001240544A1 (en) | 2001-08-20 |
EP1125933A1 (en) | 2001-08-22 |
CZ20022565A3 (cs) | 2002-10-16 |
JP2003522765A (ja) | 2003-07-29 |
WO2001058887A1 (en) | 2001-08-16 |
KR20020082222A (ko) | 2002-10-30 |
CA2399128A1 (en) | 2001-08-16 |
HUP0300004A3 (en) | 2005-04-28 |
US20030100778A1 (en) | 2003-05-29 |
HUP0300004A2 (hu) | 2003-04-28 |
MXPA02007583A (es) | 2003-01-28 |
PL357196A1 (en) | 2004-07-26 |
RU2002124126A (ru) | 2004-01-20 |
BR0108091A (pt) | 2002-10-29 |
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