CN1103634C - 氧化催化剂及用氧化催化剂由烯烃、氢和氧制备环氧化物的方法 - Google Patents
氧化催化剂及用氧化催化剂由烯烃、氢和氧制备环氧化物的方法 Download PDFInfo
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- CN1103634C CN1103634C CN97195498A CN97195498A CN1103634C CN 1103634 C CN1103634 C CN 1103634C CN 97195498 A CN97195498 A CN 97195498A CN 97195498 A CN97195498 A CN 97195498A CN 1103634 C CN1103634 C CN 1103634C
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- Prior art keywords
- catalyzer
- oxide catalyst
- titanium
- zeolite
- vanadium
- Prior art date
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- Expired - Lifetime
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 239000001301 oxygen Substances 0.000 title claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims description 36
- 230000008569 process Effects 0.000 title claims description 10
- 230000003647 oxidation Effects 0.000 title abstract description 8
- 238000007254 oxidation reaction Methods 0.000 title abstract description 8
- 150000002118 epoxides Chemical class 0.000 title 1
- 239000010936 titanium Substances 0.000 claims abstract description 38
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 37
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 36
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 150000001336 alkenes Chemical class 0.000 claims abstract description 20
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 18
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 11
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 6
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- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 4
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- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 3
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- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims abstract description 3
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- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 3
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- 229910017052 cobalt Inorganic materials 0.000 claims description 2
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- B01J29/00—Catalysts comprising molecular sieves
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- 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
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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
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
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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
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
- C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
Abstract
一种基于钛硅质石或钒硅质石的氧化催化剂，所述硅质石具有沸石结构，且含有0.01-30%(重量)的一种或多种选自钌、铑、钯、锇、铱、铂、铼、金和银的贵金属，该氧化催化剂已采用压缩成型法进行模制。这种氧化催化剂用于由烯烃、氢和氧制备环氧化物，特别是氧化丙烯。
Description
本发明涉及基于具有沸石结构，及含有贵金属的钛硅质石或钒硅质石的新氧化催化剂，和用这种氧化催化剂由烯烃、氢和氧制备环氧化物的方法。
含有贵金属和基于具有沸石结构的钛硅质石或钒硅质石及的氧化催化剂，和用这种氧化催化剂由烯烃、氢和氧制备环氧化物披露于WO-A96/02323。这里所用的催化剂是结晶粉末的形式。
但是，这种现有技术的氧化催化剂有一些缺点。当使用未模制的氧化催化剂时，由于它们的颗粒太细，所以例如当要进行分离时，会产生机械上的问题。
本发明的一个目的是提供不再具有现有技术缺点的环氧化催化剂。
我们已经发现，达到这个目的可以使用基于钛硅质石或钒硅质石的氧化催化剂，所述硅质石具有沸石结构，且含有0.01-30％(重量)的一种或多种选自钌、铑、钯、锇、铱、铂、铼、金和银的贵金属，其中氧化催化剂是通过压缩成型工艺模制的。
可用的压缩成型工艺，原则上是所有适合于成型的方法，如通常用于催化剂的那些方法。优选的工艺是采用常规的挤出机进行挤出成型，例如得到直径通常为1-10mm，特别是2-5mm的挤出物。如果需要加入粘合剂和/或其他助剂，则挤出最好通过混合或捏合的方法进行。如果必要，挤出后再有一个煅烧步骤。如果需要，将得到的挤出物进行粉碎，优选形成粒径为0.5-5mm特别是0.5-2mm的颗粒或小片。这些颗粒或这些小片以及通过其他方法生产的催化剂模制物实际上不含比最小颗粒直径0.5mm的颗粒更细的颗粒。
在优选的实施方案中，新模制的氧化催化剂含有最高10％(重量)，基于催化剂的总质量，的粘合剂。特别优选的粘合剂的含量是0.1-7％，特别是1-5％(重量)。适合的粘合剂原则上可以是作此用途的所有化合物，优选的是硅、铝、硼、磷、锆和/或钛的化合物，特别是氧化物。特别感兴趣的粘合剂是氧化硅，SiO2可以氧化硅溶胶的形式或四烷氧基硅烷的形式导入模制步骤。镁和铍的氧化物和粘土如蒙脱土、高岭土、膨润土、多水高岭土、地开石、珍珠陶土和ananxites也可被用作粘合剂。
压缩成型法用的助剂的例子是挤出助剂，一种常规的挤出助剂是甲基纤维素。这种助剂通常在下游的煅烧步骤被完全烧掉。
按这种方法制备的模制氧化催化剂具有高的质量-比活性及和满足所有的反应程序和反应器类型的耐磨性和硬度。
模制的氧化催化剂是基于具有沸石结构的钛硅质石或钒硅质石。已经知道，沸石是具有有序的孔道和笼形结构的结晶硅铝酸盐，其孔径在微孔的范围，也即小于0.9nm。这种沸石的网络由SiO4和AlO4四面体组成，它们经由普通的氧桥连接。这种已知结构的综述可参见例如W.M.Meier和D.H.Olson的“沸石结构类型图集”，Butterworth，2ndEd.，London1987。
不含铝的沸石，和其中硅酸盐晶格中的一些Si(IV)被钛(Ti(IV))所取代的沸石也是已知的。这些钛沸石，特别是那些具有MFI结晶结构的沸石，和它们制备的可能性见述于例如欧洲专利申请311 983或405978。除了硅和钛以外，这种物质也可含有其他的元素，如铝、锆、锡、铁、钴、镍、镓、硼或少量氟。
在新的氧化催化剂中，沸石的部分或全部的钛可被钒所取代。钛和/或钒与硅和钛和/或钒总量的摩尔比通常为0.01∶1-0.1∶1。
已经知道，具有MFI结构的钛沸石可以通过其X射线衍射图的某种图形以及在约960cm-1的红外区(IR)的骨架振动带进行确定，这些特征和碱金属的钛酸盐或结晶的和非晶的TiO2相是不同的。
典型地，制备所述的钛沸石以及钒沸石是通过含有SiO2源、钛或钒源，如二氧化钛或相应的氧化钒和含氮的有机碱(模板化合物)，例如氢氧化四丙基铵的水性混合物，在加入或不加入碱金属化合物的情况下，于高温下在耐压容器中反应几小时或几天，形成结晶的产物。将产物过滤、洗涤、干燥和在高温下煅烧除去含氮的有机碱。在这样得到的粉末中，钛或钒至少部分地存在于沸石骨架中，配位比例可以为4、5、或6倍。为了改进催化剂的特性，随后要用含硫酸的过氧化氢的溶液重复洗涤处理，此后，必须将钛沸石或钒沸石粉末再进行干燥和煅烧；继之是用碱金属化合物处理，将H型沸石转变为阳离子型沸石。用这种方法制备的钛沸石或钒沸石粉末然后按上述本发明的方法进行模制。
优选的钛沸石或钒沸石是那些具有pentasil沸石结构，特别是X射线衍射确定为BEA、MOR、TON、MTW、FER、MFI、MEL或MFI/MEL混合结构的沸石。这类沸石见述于例如W.M.Meier和D.H.Olson的“沸石结构类型图集”，Butterworth，2ndEd.，London1987。具有ZSM-48、ZSM-12、镁碱沸石、β-沸石或丝光沸石结构的含钛沸石也可用于本发明。
新氧化催化剂含有0.01-30，特别是0.05-15，尤其是0.1-8％(重量)，在各种情况下基于钛沸石或钒沸石的量，的所述贵金属。钯是特别优选的。贵金属可以在压缩成型步骤之前、之间或之后，以适合的贵金属组分的形式，例如水溶性盐的形式施加到催化剂中。
但是，在很多情况下，最好不要将贵金属组分施加到模制步骤之后的催化剂模制物中，特别是当含贵金属的催化剂不需要进行高温处理的情况。贵金属组分可以特别通过离子交换、浸渍或喷洒的方法施加到模制催化剂中。这种施加可以通过有机溶剂、氨水溶液或超临界相，如二氧化碳来实施。
通过应用上述的方法，完全可以生产很宽范围的含贵金属催化剂。因而，通过将贵金属溶液喷洒到催化剂模制物上，可以制备一类涂敷的催化剂。这个含贵金属的壳层的厚度通过浸渍的方法可以大大增加，而用离子交换法可以得到贵金属在模制物截面上基本均匀分布的催化剂颗粒。
新的模制氧化催化剂非常适合于烯烃采用氢和氧的环氧化。所以本发明也涉及由烯烃、氢和氧制备环氧化物的方法，其中烯烃通过新的氧化催化剂的非均相催化而转化。
制备环氧化物的新方法原则上可以通过所有常规的反应程序和所有常规类型的反应器进行，例如通过悬浮法或在固定床装置上进行。连续法或间歇法都可采用。但是，环氧化优选在固定床设备上进行。
根据要转化的烯烃的不同，新的环氧化反应可以在液相、气相或超临界相中进行。烯烃与氢/氧的气体混合物在液相或气相中进行反应是优选的。
如果新的环氧化反应在液相中进行，最好在1-10巴的压力下和在溶剂的存在下操作。适合的溶剂是醇类，例如甲醇、乙醇、异丙醇或叔丁醇或其混合物，和特别是水。也可以用所述的醇与水的混合物。在某些情况下，应用水或含水的溶剂体系与用纯的醇作溶剂相比，可以大大增加所需环氧化物的选择性。
通常，新环氧化反应在-20至70℃，特别是-5至50℃下进行。氢与氧的摩尔比H2∶O2通常可在1∶10-1∶1的范围内变化，特别优选的比例是1∶5-1∶1。氧与烯烃的摩尔比通常为1∶4-1∶10，优选为1∶5-1∶7。任何需要的惰性气体可以加入作为载气，特别适合的是氮。
所用的烯烃可以是任何需要的含至少一个烯类不饱和双键的有机化合物。它们可以是脂族的、芳族的或环脂族的以及具有线性或支化的结构。优选地，烯烃含有2-30个碳原子。烯烃也可含有一个以上的烯类不饱和双键，例如二烯烃或三烯烃。烯烃还可含有官能基团，如卤原子、羧基、羧酸酯官能基、羟基、醚桥、硫桥、羰基、氰基、硝基或氨基。
这种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、十一碳烯、十二碳烯、环戊烯、环己烯、双环戊二烯、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、乙烯基乙酸、烯丙醇、丙烯酸烷基酯、甲基丙烯酸烷基酯、油酸、亚油酸、亚麻酸、这种不饱和羧酸的酯和甘油酯、苯乙烯、α-甲基苯乙烯、二乙烯基苯、茚和茋。所述烯烃的混合物也可用新方法环氧化。
新方法特别适合于丙烯的环氧化，得到氧化丙烯。
新的模制氧化催化剂有许多优点。如上所述，该氧化催化剂具有高的质量-比活性，而且还不会随时间而明显降低，和足够高的硬度和耐磨性，这使得它们特别适合用于固定床装置。由于催化剂模制物没有小的和非常小的颗粒级分，这种小级分会因滞留效应而产生负影响，所以环氧化时各种各样的副产物和第二产物就少，而且相关的活性随时间的降低的情况实际上也未发现。
另一个优点是在模制的氧化催化剂中只需要少量的粘合剂，也即是不大于10％(重量)，通常，这种催化剂含有最高20％(重量)的粘合剂。如此高的粘合剂含量当然会对催化剂的活性产生不良的影响。
下面的实施例是阐述新氧化催化剂的制备和新的环氧化反应，并不意味着有任何的限制。
实施例1
将455g原硅酸四乙酯一开始就放入21的四颈烧瓶中，在30分钟内通过滴液漏斗加入15g原钛酸四异丙酯，同时进行搅拌(250rpm，浆式搅拌器)。形成一个无色透明的混合物。最后，加入800g浓度为20％(重量)的四丙基氢氧化铵溶液(碱含量＜10ppm)，并且再连续搅拌1小时。在90-100℃蒸出由于水解而形成的醇混合物(约450g)。往混合物中补加1.5l去离子水，然后将该略不透明的溶胶引入到一个2.5l的不锈钢搅拌高压釜中。
以3℃/分钟的加热速度将密闭的高压釜(锚式搅拌器，200rpm)加热到反应温度175℃。92小时后，反应完成。冷却的反应混合物(白色的悬浮液)进行离心分离，固体产物用水洗至中性。得到的固体在110℃下干燥24小时(重量为149g)。
最后，仍然残留在沸石中的样板(template)，通过在550℃的空气中煅烧5小时后除去(煅烧损失：14％(重量))。
湿化学分析表明，纯的白色产物的钛含量为1.5％(重量)，且残留的碱含量小于100ppm。以所用的SiO2计的产率为97％。晶粒大小为0.05-0.25μm，产物在约950cm-1有一典型的红外带。
实施例2
将1000g实施例1的钛硅质灰石悬浮在6l浓度为5％(重量)的硫酸和600g浓度为30％(重量)的过氧化氢溶液的混合物中，并且在80℃下搅拌2小时。此后，将按这种方式处理过的硅酸钛抽滤出来，再如此处理三次。该钛硅质灰石然后悬浮在6l水中，在80℃下搅拌2小时，再抽滤出来。这个过程再重复一次。此后，按这种方式处理的固体在150℃下干燥，然后在500℃的空气中煅烧5小时。
实施例3
将950g实施例12的钛硅质石悬浮在6l浓度为1％(重量)的乙酸钠水溶液中，并回流20分钟，此后，将钛硅质灰石抽滤出来。这个过程重复两次以上。按这种方式处理的钛硅质石然后悬浮在6l水中，回流30分钟，并抽滤出来。此过程也重复进行。然后将钛硅质石在150℃下干燥和在500℃下煅烧。
实施例4
将100g实施例3的钛硅质石与5g甲基纤维素干混。这个混合物在外加95ml水的捏合机中压缩，并且在30巴的模压下加工成直径2mm的挤出物。将这些挤出物在110℃下干燥过夜，并在500℃下煅烧5小时。未加粘合剂的挤出物的侧压强度为9.5N。
实施例5
将100g实施例3的钛硅质石与5g甲基纤维素干混。这个混合物在外加70ml水和12.5g铵-稳定的硅溶胶(LudoxAS-40，DuPont，40％(重量)的SiO2)的捏合机中压缩，并且在30巴的模压下加工成直径2mm的挤出物。将这些挤出物在110℃下干燥过夜，并在500℃下煅烧5小时。含4.8％(重量)粘合剂的挤出物的侧压强度为22.5N。
实施例6
将113g实施例5的模制钛硅质石引入带有一体化的多孔玻璃和覆盖有玻璃棉的玻璃管中。使3.8g PdCl2和25％浓度的氨水溶液慢慢地通过这个带填料的玻璃管循环。24小时以后，实际上所有的钯已被从循环液中除去。然后，催化剂挤出物在玻璃管中用水洗至无氯存在。按这种方法处理的催化剂挤出物，然后在减压下于60℃干燥16小时。
将50g Pd改性的产物在50℃的试验室烘箱(石英玻璃，直径5cm，加热区长度20cm)中，用含有20l/h的氮和1l/h的氢的气体混合物处理90分钟，烘箱的速度为50rpm。
比较例A
为了浸渍实施例3的钛硅质石粉末，首先用0.515g氯化钯(II)和120g氨溶液(25％(重量)浓度的水溶液)在室温下搅拌制备新鲜的着色溶液。在一圆底烧瓶中，将60g新制备的实施例3的钛硅质石悬浮在130g软水中。将制备的四胺-氯-钯络合物溶液全部加入，并且在旋转蒸发器中，于室温和大气压下搅拌1小时。最后，悬浮液在减压(5-19毫巴)和90-100℃下蒸发。白色的产物直接用于还原反应。
将20g Pd改性的产物在50℃的试验室烘箱(石英玻璃，直径5cm，加热区长度20cm)中，用含有20l/h的氮和1l/h的氢的气体混合物还原90分钟，烘箱的速度为50rpm。
比较例B
在一耐压的玻璃反应器中，将2g比较例A的催化剂悬浮(同时进行搅拌)在1650ml甲醇溶剂中。然后，在60℃和5巴的压力下，使含有5l/h丙烯、0.25l/h氢、1l/h氧和0.5l/h氮的气体混合物通过。用6.81出口气流进行气相色谱分析，分析结果表明，44小时后氧化丙烯为0.30％(体积)，139小时后氧化丙烯为0.68％(体积)，270小时后氧化丙烯为0.50％(体积)和360小时后氧化丙烯为0.32％(体积)。这个结果证实了在最后的220小时期间活性大大下降。
实施例7
将9.8g实施例6的催化剂安装在玻璃反应器中，用4.5kg/h甲醇水溶液的溶剂流通过上行法溢流，并使混合物循环。将6.2l/h丙烯、1.2l/h氧和0.3l/h氢计量加入210ml溶剂中，反应器入口压力调节在5巴。在约120小时期间，出口气中氧化丙烯的浓度发现为0.11％(体积)。
Claims (11)
1.一种基于钛硅质石或钒硅质石的氧化催化剂，所述硅质石具有经X-射线衍射确定为MFI、MEL、或MFI/MEL混合结构的沸石结构，且含有0.01-30重量％的一种或多种选自钌、铑、钯、锇、铱、铂、铼、金和银的贵金属，并且，基于模制催化剂总质量计的最多10重量％的粘合剂，其中该氧化催化剂已采用压缩成型工艺进行模制并且具有0.5mm的最小直径。
2.权利要求1所要求的氧化催化剂，该催化剂含有作为粘合剂的硅、铝、硼、磷、锆或钛的化合物。
3.权利要求1所要求的氧化催化剂，该催化剂在沸石的骨架上还含有一种或多种选自铝、硼、氟、锆、镓、锡、铁、钴和镍的元素。
4.权利要求1所要求的氧化催化剂，该催化剂具有钛与硅和钛之和的摩尔比为0.01∶1至0.1∶1。
5.权利要求1所要求的氧化催化剂，该催化剂具有钒与硅和钒之和的摩尔比为0.01∶1至0.1∶1。
6.权利要求1所要求的氧化催化剂，该催化剂通过在压缩成型工艺之前将以合适的贵金属组分形式的贵金属施加到催化剂上得到。
7.权利要求1所要求的氧化催化剂，该催化剂通过在压缩成型工艺期间将以合适的贵金属组分形式的贵金属施加到催化剂上得到。
8.权利要求1所要求的氧化催化剂，该催化剂通过在压缩成型工艺之后将以合适的贵金属组分形式的贵金属施加到催化剂上得到。
9.一种由烯烃、氢和氧制备环氧化物的方法，其中烯烃是用权利要求1中所要求的氧化催化剂，在非均相催化的条件下转化的。
10.权利要求9中所要求的制备环氧化物的方法，其中反应是在固定床装置上进行的。
11.权利要求9中所要求的由丙烯制备环氧丙烷的方法。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19623609A DE19623609A1 (de) | 1996-06-13 | 1996-06-13 | Oxidationskatalysator und Verfahren zur Herstellung von Epoxiden aus Olefinen, Wasserstoff und Sauerstoff unter Verwendung des Oxidationskatalysators |
| DE19623609.6 | 1996-06-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1222096A CN1222096A (zh) | 1999-07-07 |
| CN1103634C true CN1103634C (zh) | 2003-03-26 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN97195498A Expired - Lifetime CN1103634C (zh) | 1996-06-13 | 1997-05-30 | 氧化催化剂及用氧化催化剂由烯烃、氢和氧制备环氧化物的方法 |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US6008389A (zh) |
| EP (1) | EP0904151B1 (zh) |
| JP (1) | JP2000511818A (zh) |
| KR (1) | KR20000016574A (zh) |
| CN (1) | CN1103634C (zh) |
| AU (1) | AU3030997A (zh) |
| BR (1) | BR9709702A (zh) |
| CA (1) | CA2256383A1 (zh) |
| DE (2) | DE19623609A1 (zh) |
| ES (1) | ES2162300T3 (zh) |
| MX (1) | MX202663B (zh) |
| WO (1) | WO1997047386A1 (zh) |
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- 1997-05-30 CN CN97195498A patent/CN1103634C/zh not_active Expired - Lifetime
- 1997-05-30 JP JP10501133A patent/JP2000511818A/ja active Pending
- 1997-05-30 ES ES97925025T patent/ES2162300T3/es not_active Expired - Lifetime
- 1997-05-30 AU AU30309/97A patent/AU3030997A/en not_active Abandoned
- 1997-05-30 EP EP97925025A patent/EP0904151B1/de not_active Revoked
- 1997-05-30 BR BR9709702A patent/BR9709702A/pt not_active Application Discontinuation
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Also Published As
| Publication number | Publication date |
|---|---|
| CN1222096A (zh) | 1999-07-07 |
| CA2256383A1 (en) | 1997-12-18 |
| MX9810300A (en) | 1999-04-30 |
| ES2162300T3 (es) | 2001-12-16 |
| WO1997047386A1 (de) | 1997-12-18 |
| BR9709702A (pt) | 1999-08-10 |
| KR20000016574A (ko) | 2000-03-25 |
| DE59704251D1 (de) | 2001-09-13 |
| JP2000511818A (ja) | 2000-09-12 |
| MX202663B (en) | 2001-06-26 |
| US6008389A (en) | 1999-12-28 |
| AU3030997A (en) | 1998-01-07 |
| DE19623609A1 (de) | 1997-12-18 |
| EP0904151B1 (de) | 2001-08-08 |
| EP0904151A1 (de) | 1999-03-31 |
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