CN1330646A - 从烯烃制备环氧化物的综合方法 - Google Patents
从烯烃制备环氧化物的综合方法 Download PDFInfo
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- CN1330646A CN1330646A CN99814351A CN99814351A CN1330646A CN 1330646 A CN1330646 A CN 1330646A CN 99814351 A CN99814351 A CN 99814351A CN 99814351 A CN99814351 A CN 99814351A CN 1330646 A CN1330646 A CN 1330646A
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Epoxy Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明涉及制备环氧化烯烃的综合方法。在第一步中,由元素氢和氧产生稀过氧化氢溶液,其随后在钛硅存在下与烯烃进行液相环氧化作用,转化为环氧化烯烃。将溶剂返回H2O2过程。
Description
本发明涉及制备环氧化烯烃的综合方法。在第一步中,利用催化剂,由元素氢和氧制备稀过氧化氢溶液,其随后在钛硅(Titansilikalit)存在下在与烯烃的液相环氧化反应中反应,生成环氧化烯烃,再将溶剂返回H2O2过程。
氧化丙烯是化学工业中最重要的基本化工原料之一。其应用领域超过60%在塑料领域,特别是在用于合成聚氨酯的聚醚多醇的制备中。此外,氧化丙烯衍生物在二醇领域,特别是润滑剂和防冻剂领域,也占有相当大的市场份额。
环氧化烯烃的制备基本上是公知的。用烯烃作为起始物料,通过各种方法将其氧化。然而,基于生态学的原因,优选利用过氧化氢或空气进行氧化。
在由烷基蒽氢醌和烷基蒽醌组成的氧化还原体系存在下可以利用纯氧作为氧化剂进行钛硅催化的环氧化反应(US 5 221 795)。此反应的缺点是有机化合物的氧化分解导致持续损失少量蒽醌及有机溶剂。
用含铂金属的钛硅,使用分子氧和分子氢组成的气体混合物可以以低产率(约1至2%)和60至70%不能令人满意的氧化丙烯选择性将丙烯氧化(WO-97/47 386,WO-96/023 023)。作为副反应出现的加氢反应产生大量作为副产物的丙烷。
专利US-5 623 090和WO-98/00 413-15公开了在氢存在下利用分子氧将丙烯直接环氧化成氧化丙烯。利用市售的含细分散性金微粒的二氧化钛作为催化剂。除了产率低外,所有这些方法的缺点是由于催化剂含金,使其花费很高。因此,从经济角度考虑,仍然完全需要开发具有显著好的催化活性且催化剂使用寿命大大增加的催化剂。
US 4 833 260描述了有效允许利用氧化剂过氧化氢在液相中进行烯烃环氧化作用的钛硅催化剂。在所述硅质岩情况下,钛取代了少部分晶格硅(US 4 410 501)。然而,由于作为氧化剂的过氧化氢成本高,至今仍阻碍其大规模地应用。因为出于安全原因,必须精密地观测过氧化氢制备过程中氢和氧的浓度,所以利用过氧化氢的大部分成本是由于其本身产生的。主要获得了含低浓度过氧化氢的反应溶液,然后必须以高花费的操作将其浓缩、纯化及稳定。
过氧化氢的制备基本上是先有技术状态。
长期以来就公知,也可以利用适合的催化剂由元素氢和氧直接制备过氧化氢。
长期以来也公知,气态氧和氢的混合物产生爆炸性气体混合物。因此,所有工业H2O2过程都是利用氢和氧的间接化合进行的。
目前,世界上超过90%的过氧化氢生产是通过蒽醌法进行的,其中烷基蒽醌典型地用作化工助剂。此反应的缺点是由于有机化合物的氧化和热分解导致持续损失少量蒽醌和有机溶剂,及高花费的萃取、纯化和蒸馏步骤。
由元素氢和氧直接合成过氧化氢是广泛研究努力的目的,但是,至今仍不能产生任何工业应用。除了安全问题,最重要的问题是防止生成的过氧化氢随后分解成水和氧。通过在高速流动下操作的连续过程来克服此问题。然而,结果是,由于低反应速率,排出物中过氧化氢浓度对于工业上使用该方法来说太低。
关于利用含钯催化剂由氢和氧制备过氧化氢,US 4 009 252公开了氧气和氢气的最佳比率为1.5∶1至20∶1,即在爆炸范围内。
最常利用第8副族的过渡金属,主要是钯或铂,作为催化活性物种。可以将贵金属应用于不同的载体如TiO2、SiO2、Al2O3、Teflon、活性炭或由织物例如V4a生产的催化剂单块上,最常用活性炭。许多公司和机构对基于此催化体系的方法申请了专利,例如,诸如US 4279 883、US 4 661 337、EP-117 306和DE-196 42 770。
US 4 336 238和US 4 336 239描述了在任选也含有水的有机溶剂或溶剂混合物中利用含钯催化剂由氢和氧生成过氧化氢的反应。利用含少于5vol.%氢的气体混合物反应获得的过氧化氢浓度最高为2.4wt%,其对经济性使用来说太低。此外,在操作285小时之后,催化剂活性已经降至初始值的69%,这对工业使用来说仍太低。
US 5 352 645和WO-92/04 976描述了喷雾干燥的胶态硅胶的特殊固体载体。EP-627 381公开了以高抗酸性为特点的铌、钽、钼或钨的氧化物用作载体材料。
然而,在所提及的各说明书中,总是通过非常不适合于工业应用的批量或半连续法制备过氧化氢。此外,反应时间短,所以得不出关于催化剂使用寿命的任何结论。
DE-A-196 42 770公开了利用含钯催化剂单块如用钯浸渍的V4a网或织物制备过氧化氢。用C1-C3醇或其与水的混合物作溶剂。主要利用钯作为催化活性组分;适合的助催化剂优选为贵金属,如铂、铑、金和银。
因为低过氧化氢浓度,及在某些情况下存在溶剂,传统的过氧化氢装置不能接受所有这些方法。
至今还没有公开报道过由丙烯和过氧化氢一步法制备氧化丙烯,其中,利用没有经过浓缩并且只进行了粗的予纯化的过氧化氢溶液,在丙烯氧化之后,再将其返回过氧化氢制备过程中。
令人惊讶地,本申请人已经发现,来自于制备过程的、没有浓缩且只进行粗的予纯化的过氧化氢溶液可直接用于在其中x为0.0001至0.04范围内的通式xTiO2·(1-x)SiO2的合成的含钛原子的沸石存在下通过烯烃与过氧化氢的催化环氧化作用制备环氧化烯烃、特别是氧化丙烯的过程中。
第一步中制备的水的或水-醇的过氧化氢溶液在经过稍微纯化后在所说的合成的含钛原子的沸石存在下可以选择性地与烯烃反应生成环氧化烯烃。所述方法为溶剂的分离和返回创造了条件,因此,不需进行另外纯化,就可以再将其返回过氧化氢制备过程。
因此,本发明涉及由烯烃和醇的或水-醇的稀过氧化氢溶液制备环氧化烯烃的方法,该方法是在其中x为0.0001至0.04范围内的通式xTiO2·(1-x)SiO2的合成的含钛原子的沸石存在下进行的,其特征在于,包括以下步骤:
a)使用含作为活性组分的主要是第8副族元素的催化剂,通过氢与氧连续反应来制备醇的或水-醇的稀过氧化氢溶液,其中,这些溶液可以任选地还含有稳定剂,
b)任选地钝化稳定剂,
c)使烯烃与所述的醇的或水-醇的稀过氧化氢溶液反应,
d)将环氧化烯烃分离,
e)任选地除去所述的醇的或水-醇的稀过氧化氢溶液中的稳定剂,
f)将所述的醇的或水-醇的稀过氧化氢溶液返回到制备过程a)中,
其中,在各个辅助步骤之间,不分离出所述的醇的或水-醇的稀过氧化氢溶液。
可以将本发明所述的方法用于所有的烯烃。优选含1至12个碳原子的不饱和烃,特别是乙烯、丙烯、1-丁烯、2-丁烯、丁二烯、戊烯、己烯、异戊二烯、辛烯和环己烯。
醇的或水-醇的稀过氧化氢溶液通常含H2O2量为0.5至15wt%,特别为2至7wt%。
醇、水或其混合物是制备过氧化氢过程中适合的反应介质。
适合的醇是所有本领域技术人员公知的醇,如甲醇、乙醇、丙醇、异丙醇、丁醇、戊醇、己醇、庚醇和辛醇。当然,也可以是这些醇的支链形式,如异丁醇、仲丁醇和叔丁醇。优选使用的醇为甲醇。当然,水也可以是被去矿化(软化)或被蒸馏过的。优选利用溢流式反应器进行过氧化氢的合成。
适合的催化剂是所有本领域技术人员公知的用于氢和氧连续反应生成过氧化氢的催化剂。优选含作为活性组分的主要是第8副族元素、特别是钯的催化剂。催化剂优选以成形催化剂形式使用。成形催化剂是其中活性催化剂组分负载在载体表面上的催化剂,特别是特殊成形的载体,如拉西环、Sattei bodies、金属螺旋线或线网环。在Rmpp-Chemie-Lexikon,第9版,第1453页及其后各页中可找到更多的例子。也优选利用催化剂单块。通常由织物、针织品、薄膜、多孔金属板和/或金属片制备催化剂单块。开孔泡沫塑料如聚氨酯、陶瓷制品或三聚氰胺树脂泡沫塑料也适合。将活性催化剂组分施加到这些催化剂单块上。为了增加催化活性,催化剂任选地含有其它金属如铂、铑、铱、铜、银和/或金的添加剂。钯与添加剂的比率为100∶1至1∶10,特别为10∶1至1∶1。钯和添加剂含量通常为5·10-4至1wt%,特别为10-3至0.15wt%。更详细的叙述参见DE-196 42 770,其公开了优选的制备醇的或水-醇的稀过氧化氢溶液的方法。
然而,下述文献所述方法也适合:DE-26 15 625,DE-26 55 920;US 4 279 883,US 4 661 337,US 4 336 239,US 4 379 778,US4 389 390,EP-117 306,US 4 889 705,US 4 681 751,US 4 772 458,US4 240 933,US 4 832 938,WO-92/04 277,US 5 169 618,EP-579109,EP-623 552和WO-96/0538。
醇的或水-醇的稀过氧化氢溶液通常含有阻止生成的过氧化氢分解的稳定剂。该稳定剂通常为无机酸,如盐酸、硫酸和磷酸,优选盐酸和硫酸。其用量通常为10-4至10-1mol/L,优选5至25·10-3mol/L。
可以任选地存在其它稳定剂,如US 4 889 705和US 4 681 751中所述的那些稳定剂。特别有利的是诸如碱金属溴化物、碱金属氯化物、碱金属磷酸盐和碱金属硫酸盐之类的盐,更特别为氯化钠、溴化钠、氯化钾和溴化钾。通常它们用量为0.5至10mmol/L,优选0.5至2mmol/L。
尽管证明所加量的酸有利于稳定过氧化氢,但是它们导致在第二步进行的环氧化反应中环氧化烯烃的选择性急剧降低。在酸和水存在下,生成的环氧化物水解成相应的二醇和低聚醚。因此,必须保持非常低的酸浓度和溴离子浓度(酸含量<0.5wt%)。
因此,在本发明的综合法中,在稀过氧化氢溶液与烯烃反应之前,使其呈pH中性、弱酸性或弱碱性是有利的。优选pH值范围为4至9,特别为5至8,更特别为5.5至7.5。优选通过适合的离子交换剂来完成,但是本领域技术人员公知的其它中和稀过氧化氢溶液的方法也适合。
适合的离子交换剂由例如交联的聚合物组成。可以将这些载体材料广泛地应用于非均相催化的有机反应中。其结构和功能变化的灵活性允许固定实际上所有的催化活性组分。在催化反应中,强酸性聚合物,例如用磺酸基团官能化的那些,常常可以替代无机酸。可以用碱将这些酸性聚合物可逆地转化为中和了的碱形式。Ullmann’sEncyclopedia of Industrial Chemistry,第5版,(1989),A14,p.393-411中所述的离子交换剂也是适合的。
令人惊讶地,如果在含无机酸的稀的过氧化氢溶液与烯烃反应之前,用阳离子交换剂以所述的方法将其部分或全部中和,就可达到>85%的固定的氧化丙烯选择性。
优选以EP-A1-100 119所述的方法进行烯烃与所述的醇的或水-醇的稀过氧化氢溶液的反应。在此方法中,在其中x为0.0001至0.04范围内的通式xTiO2·(1-x)SiO2的合成的含钛原子的沸石存在下,由烯烃和醇的或水-醇的稀过氧化氢溶液制得了环氧化烯烃。通过此处特别提及的EP-A1-200 260,EP-A1-230 949,DE-A1-196 23 608和DE-A1-196 23 611的具体的实施方案改进此方法是有利的。然而,本发明的综合法中也可以使用在其中x为0.0001至0.04范围内的通式xTiO2·(1-x)SiO2的合成的含钛原予的沸石存在下由烯烃和醇的或水-醇的稀过氧化氢溶液制备环氧化烯烃的其它方法。
用钒原子部分或全部取代钛原子也是有利的。将其中x为0.0001至0.04范围内的通式xTiO2·(1-x)SiO2的合成的含钛原子的沸石的表面酸中心中和(例如用碱金属盐,如乙酸钠)也是有利的。
以常规方法如蒸馏,任选地在减压下,将生成的环氧化烯烃分离。
对于H2O2的形成,反应介质必须尽可能地富质子,而对于环氧化作用,反应介质则必须尽可能地贫质子。对于将初始使用的、现在其过氧化氢浓度已降低了的醇的或水-醇的稀过氧化氢溶液返回到醇的或水-醇的稀过氧化氢溶液的制备过程中来说,在氧化丙烯分离以后将任选地钝化或中和后的稳定剂再次除去可能是有利的。这可以通过将相应的离子交换剂加入到贫化的过氧化氢溶液中或使之通过贫化的过氧化氢溶液来完成。特别有利的是以任选地改变了反应参数的方式再次使先前使用过的阳离子交换剂再生。当然,在此阶段,也可以加入另外的稳定剂,或替代已经用尽或损失的稳定剂。
适合的离子交换剂为例如以磺酸基团官能化的有机和/或无机聚合物(如来自Bayer AG,D的离子交换剂(如Lewatit,BayerCatalystK1131或K2431)或来自Rohm和Haas,USA的离子交换剂(如Amberlist36 W,Amberlist3 WET,DuoliteARC9652))。Ullmann’s Encyclopedia of Industrial Chemistry,第5版,(1989),A 14,p.393-411所述的离子交换剂也是适合的。
最后,再将贫化的过氧化氢溶液返回到醇的或水-醇的稀过氧化氢溶液制备过程(步骤a)中。
以此方法制得的环氧化烯烃特别为氧化乙烯和氧化丙烯。
以此方法制得的环氧化烯烃以高纯度著称。整个工艺在生态和经济上非常节省和耐用。
以此方法制得的环氧化烯烃可以用于所有本领域技术人员公知的应用,如聚醚多醇、二醇(润滑剂和防冻剂)和氧化丙烯衍生物的制备及医药领域物品的杀菌。
实施例
实施例1
利用V4A织物催化剂载体的催化剂块的制备
与DE 196 42 770 A1相类似,由波曲状光滑的V4A网状物(材料:1.4571;网眼大小:200μm;线径:150μm)生产的圆柱形V4A单块。
通过常规方法利用溶剂脱去单块载体中的脂,将其置于80ml蒸馏水中;将5ml 10%[Pd(NH3)4](NO3)2溶液加入其中,在80℃下搅拌24小时。将单块从液相中分离出来,洗涤4次,每次用100ml软化水,在110℃下干燥2小时,然后在200℃和氮气氛围中将其还原2小时(通过所述胺配合物热分解发生自还原,同时生成氨)。
实施例2
a)过氧化氢制备
以搅拌器轴线为中心,将实施例1的单块Pd催化剂安装在具有气体搅拌器、导热体控温、压力保持在70bar及中央数据采集系统的400ml V4A搅拌式高压釜中。氢、氧和反应介质的给料管线位于反应器的底部。通过反应器盖上的输出管,连续地移走液相/气相混合物。
反应介质由含0.3wt%硫酸、0.03wt%磷酸和5ppm溴化物(以溴化钠形式)的甲醇组成。反应介质在20bar恒压下,与60l/h恒定的氮气流一起,以100g/h的体积流速流过反应器。在反应开始时,以同样总体积流速的、体积比为92∶8的氧和氢替代氮气流。
得到的甲醇/水溶液中过氧化氢浓度为2至6wt%过氧化氢,由2a)得到的溶液直接应用于实施例2b)。
b)实施例2a)中的H2SO4/H3PO4/H2O2甲醇溶液的中和
离子交换剂的予处理:将100g Lewatit S 100(Bayer)加入300g10%NaOH中,搅拌2小时,然后过滤,用总共1.5升水分批洗涤,直到洗液显示出pH中性。为了水-醇交换,每次将钠形式的阳离子交换剂加入100g甲醇中,搅拌3次,每次搅拌30分钟。
用100g甲醇将予处理过的离子交换剂转移到色谱柱中(直径3cm,长30cm,Lewatit填料高12cm)。
在50分钟内,将251g H2SO4/H3PO4/H2O2甲醇溶液通过预处理过的离子交换剂,然后用150ml甲醇冲洗,收集流出物,分成10份,每份约50ml。通过滴定分析法测定流出物及每份中酸含量和H2O2含量。过氧化氢完全离开色谱柱,即没有分解。一次通过色谱柱可以将其中所含的硫酸和磷酸中和约75-85%(图1)。
酸滴定:称出约10g样品,加水使混合物接近约150ml,加入5滴1%酚酞溶液之后,以0.1n NaOH(0.4g/l)滴定(空白值<1滴)。
H2O2滴定:将60ml硫酸(1mol/l)加入1g样品中;加水使混合物接近约170ml,以0.1n KMnO4(3.16g/l)滴定(空白值<1滴)。实施例2b)的溶液直接用于实施例2c)。
c)氧化丙烯的制备
1升搅拌式高压釜具有磁力搅拌器、以水控制温度、热电偶及在反应器底部有由2b)新近制得的部分中和的过氧化氢溶液(约3至5%)和气态丙烯的给料管。在一个典型的制备方法中,将500g稀过氧化氢溶液于45℃下加入以氮气冲洗过的反应器中,在剧烈搅拌下,如EP-A1-100 119所述将2g含钛量为2.8wt%的合成钛硅悬浮并将气态丙烯计量加入至压力为4bar。随着反应,计量加入更多的丙烯;因此压力保持4bar不变。在此条件下,非常快地和选择性地进行环氧化作用生成氧化丙烯。70分钟后,已经消耗了超过95%的过氧化氢,发现氧化丙烯的选择性为85至92%(图1)。
d)脱去2b)的稳定剂
通过蒸馏移去氧化丙烯以后,将来自2c)的贫化的溶液以相反的方向通过2b)中所用的色谱柱。
将中和过的酸再转化成酸形式,至含量超过70至80%。pH值<1。
Claims (8)
1.由烯烃和醇的或水-醇的稀过氧化氢溶液制备环氧化烯烃的方法,该方法是在其中x在0.0001至0.04范围内的通式xTiO2·(1-x)SiO2的合成的含钛原子的沸石存在下进行的,其特征在于,包括以下步骤:
a)利用含作为活性组分的主要是第8副族元素的催化剂,通过氢与氧连续反应制备醇的或水-醇的稀过氧化氢溶液,其中,这些溶液可以任选地还含有稳定剂,
b)任选地钝化稳定剂,
c)使烯烃与所述的醇的或水-醇的稀过氧化氢溶液反应,
d)将环氧化烯烃分离,
e)任选地除去所述的醇的或水-醇的稀过氧化氢溶液中的稳定剂,
f)将所述的醇的或水-醇的稀过氧化氢溶液返回制备过程a)中,
其中,在各个辅助步骤之间,不分离出所述的醇的或水-醇的稀过氧化氢溶液。
2.权利要求1所述的方法,其特征在于,利用钯或钯-金属混合物作为步骤a)中的催化剂。
3.权利要求1或2所述的方法,其特征在于,步骤a)中所说的溶液含无机酸作为稳定剂。
4.权利要求1至3任一项或多项所述的方法,其特征在于,通过离子交换剂进行稳定剂的钝化。
5.权利要求1至4任一项或多项所述的方法,其特征在于,通过离子交换剂进行稳定剂的除去。
6.权利要求1至5任一项或多项所述的方法,其特征在于,所用的烯烃为丙烯。
7.权利要求1至6任一项或多项所述的方法制得的环氧化烯烃。
8.权利要求7的环氧化烯烃用于聚醚多醇、润滑剂、防冻剂或二醇的制备及用于医药领域物品的杀菌的应用。
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DE19857137A DE19857137A1 (de) | 1998-12-11 | 1998-12-11 | Integriertes Verfahren zur Herstellung von Epoxiden aus Olefinen |
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EP (1) | EP1137643B1 (zh) |
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DE10153546A1 (de) | 2001-10-30 | 2003-05-22 | Degussa | Direktsynthese von Wasserstoffperoxid und deren Integration in Oxidationsprozesse |
JP2003327581A (ja) * | 2002-03-04 | 2003-11-19 | Sumitomo Chem Co Ltd | プロピレンオキサイドの製造方法 |
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PT1618111E (pt) | 2003-04-25 | 2015-02-05 | Cadila Healthcare Ltd | Sais de clopidogrel e processo de preparação |
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ITMI20032552A1 (it) * | 2003-12-22 | 2005-06-23 | Polimeri Europa Spa | Procedimento per la rimozione di acido solforico presente in soluzioni essenzialmente alcoliche di h202 proveniente da sintesi diretta |
ITMI20032553A1 (it) * | 2003-12-22 | 2005-06-23 | Polimeri Europa Spa | Procedimento per la rimozione degli acidi inorganici e delle impurezze metalliche presenti in soluzioni essenzialmente alcoliche di h202 proveniente da sintesi iretta |
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KR20010080724A (ko) | 2001-08-22 |
JP2002532483A (ja) | 2002-10-02 |
CA2353826A1 (en) | 2000-06-22 |
US6504040B1 (en) | 2003-01-07 |
DE59903881D1 (de) | 2003-01-30 |
DE19857137A1 (de) | 2000-06-15 |
CN1129589C (zh) | 2003-12-03 |
TWI232860B (en) | 2005-05-21 |
AU1778800A (en) | 2000-07-03 |
ID30069A (id) | 2001-11-01 |
WO2000035894A1 (de) | 2000-06-22 |
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