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1.发明授权
公开(公告)号：US6143844A
公开(公告)日：2000-11-07
申请号：US58806
申请日：1998-04-13
IPC分类号： C08F4/02 , B01J31/22 , B01J37/02 , C08F4/619 , C08F4/6192 , C08F4/639 , C08F4/6392 , C08F4/64 , C08F4/642 , C08F4/659 , C08F4/6592 , C08F4/76 , C08F10/00 , C08F10/02 , C08F110/02 , C08F4/44
CPC分类号： B01J31/143 , B01J31/1616 , B01J31/2295 , B01J31/38 , B01J37/0238 , C08F10/00 , C08F10/02 , C08F4/65912 , B01J21/08 , B01J2531/40 , B01J2531/46 , B01J2531/48 , B01J2531/49 , B01J2531/50 , B01J2531/60 , C08F110/02 , C08F2410/03 , C08F4/6192 , C08F4/65908 , C08F4/6592 , C08F4/65925 , Y10S526/901 , Y10S526/907 , Y10S526/943
摘要： Provided are heterogeneous catalysts for homo- and copolymerization of olefins as well as a method for preparing these catalysts, which comprise at least one metallocene compound of a Group 4A, 5A or 6A (Hubbard) transition metal on a solid inorganic support. The method comprises the steps of vaporizing the metallocene compound, treating the support material with the vaporized metallocene compound at a temperature which is sufficiently high to keep the metallocene compound in the vaporous state, contacting the support material with an amount of the vaporized metallocene compound which is sufficient to allow for a reaction between the metallocene compound and at least a substantial part of the available surface sites capable of reacting therewith, removing the rest of the metallocene compound not bound to the support, and optionally treating the product thus obtained with an activating agent. The catalysts are active even if very low amounts of activator agents, such as alumoxane, are used. Furthermore, the polymerization performance of the catalysts can be regulated during the preparation of the catalysts. Thus, by using different support pretreatment temperatures, or by using two or more different metallocenes, and by altering the order in which they are added on the support, it is possible to control and regulate the activity of the catalysts and the polymer properties, such as molecular weight and molecular weight distribution.
摘要翻译： 提供了用于烯烃均聚和共聚的非均相催化剂以及制备这些催化剂的方法，其包含至少一种在固体无机载体上的4A，5A或6A族（Hubbard）过渡金属茂金属化合物。 该方法包括以下步骤：气化金属茂化合物，在足够高的温度下用汽化金属茂化合物处理载体材料以保持茂金属化合物处于气态，使载体材料与一定量的气化茂金属化合物接触， 足以允许茂金属化合物与能够反应的至少大部分可用表面位点之间的反应，除去未结合到载体上的其余的金属茂化合物，以及任选地用活化的方法处理由此获得的产物 代理商 即使使用非常少量的活化剂如铝氧烷，催化剂也是有活性的。 此外，可以在制备催化剂期间调节催化剂的聚合性能。 因此，通过使用不同的载体预处理温度，或通过使用两种或更多种不同的金属茂，并通过改变它们在载体上的添加顺序，可以控制和调节催化剂的活性和聚合物性质，例如 作为分子量和分子量分布。
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公开(公告)号：US5880055A
公开(公告)日：1999-03-09
申请号：US843610
申请日：1997-04-10
CPC分类号： C08F10/00 , B01J37/0238
摘要： The present invention concerns heterogeneous catalysts for polymerization of olefins. The catalysts include at least one Group IVa metal compound on a solid inorganic oxidic support. According to the invention the catalysts are prepared by vapourizing at least one solid Group IVa metal halide compound and routing the vapour of the metal halide compound into a reaction chamber, wherein the vapour is reacted with the support at a temperature of about 250.degree. to about 450.degree. C. in order to bind said metal halide compound to said support. Any metal compound not bound to said support as well as any volatile reaction products emanating from the reaction between said metal halide compound and said support are then removed from the reaction chamber in the vapour phase. Optionally, the product obtained is treated with an organic aluminum compound to increase the catalytic activity of said catalyst. The catalysts thus prepared are very well suited for polymerization of ethylene or copolymerization of ethylene with other alpha-olefins, such as propylene, butylene, 4-methyl-1-pentene and hexene. A polymerization process employing the novel catalyst will provide products of the Ultra High Molecular Weight-type (UHMWPE) having very broad MWD.
摘要翻译： 本发明涉及用于烯烃聚合的多相催化剂。 催化剂包括在固体无机氧化物载体上的至少一种IVa族金属化合物。 根据本发明，催化剂是通过将至少一种固体IVa族金属卤化物化合物挥发并将金属卤化物化合物的蒸气引导到反应室中制备的，其中蒸气在约250°至约 450℃，以便将所述金属卤化物化合物结合到所述载体上。 然后在气相中从反应室中除去未结合到所述载体上的任何金属化合物以及从所述金属卤化物和所述载体之间的反应产生的任何挥发性反应产物。 任选地，将获得的产物用有机铝化合物处理以增加所述催化剂的催化活性。 如此制备的催化剂非常适合于乙烯的聚合或乙烯与其它α-烯烃如丙烯，丁烯，4-甲基-1-戊烯和己烯的共聚合。 采用新型催化剂的聚合方法将提供具有非常宽MWD的超高分子量型（UHMWPE）产品。
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公开(公告)号：US06534431B1
公开(公告)日：2003-03-18
申请号：US08881254
申请日：1997-06-24
申请人： Tuomo Suntola , Eeva-Liisa Lakomaa , Hilkka Knuuttila , Pekka Knuuttila , Outi Krause , Sven Lindfors
发明人： Tuomo Suntola , Eeva-Liisa Lakomaa , Hilkka Knuuttila , Pekka Knuuttila , Outi Krause , Sven Lindfors
IPC分类号： C23L1608
CPC分类号： B01J37/0238 , B01J23/26 , B01J23/36 , B01J29/061
摘要： The invention relates to a process and to an apparatus for preparing a heterogeneous catalyst having at least one catalytically active species bound to the surface of a support material. According to the process, the surface of the support is first pretreated. A catalyst reagent containing the catalytically active species or its precursor is vaporized and the vapor is routed into a reaction chamber where it is brought to interact with the support material. The catalyst reagent not bound to the support is withdrawn from the reaction chamber in gaseous form. If necessary, the species bound to the support is posttreated in order to convert it into a catalytically active form. According to the invention, the amount of catalyst reagent brought into the reaction chamber is at least equal to, preferably in excess of the number of available binding sites on the surface. The temperature of the support of kept higher than the condensation temperature of the vapor and at the same time at a sufficiently high level to attain the thermal activation energy needed for forming bonds between the active species and the support. By binding the catalytically active species in this way to the support it is possible to provide a heterogeneous catalyst having a high activity even at small amounts of the active species.
摘要翻译： 本发明涉及一种制备具有结合到载体材料表面的至少一种催化活性物质的多相催化剂的方法和装置。 根据该方法，首先预处理载体的表面。 含有催化活性物质或其前体的催化剂试剂被蒸发，并且蒸气被引导到反应室中，在该反应室中使其与载体材料相互作用。 未与载体结合的催化剂试剂以气态形式从反应室中排出。 如果需要，结合到载体上的物质进行后处理，以将其转化为催化活性形式。 根据本发明，进入反应室的催化剂试剂的量至少等于，优选地超过表面上可用结合位点的数量。 载体的温度保持高于蒸气的冷凝温度，并且同时具有足够高的水平以获得在活性物质和载体之间形成键所需的热活化能。 通过将催化活性物质以这种方式结合到载体上，即使在少量的活性物质中也可以提供具有高活性的多相催化剂。
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4.发明授权Catalyst for metathetic reactions of hydrocarbons and method for forming the catalyst 失效碳氢化合物反应催化剂及催化剂形成方法
公开(公告)号：US5183796A
公开(公告)日：1993-02-02
申请号：US641904
申请日：1991-01-16
CPC分类号： B01J23/36 , B01J37/0238 , C07C6/04 , C07C2521/04 , C07C2523/36
摘要： The present invention concerns a heterogenic catalyst suited to the metathesis reactions of hydrocarbons in particular. Such a catalyst includes an inorganic oxide support, typically consisting of .gamma.-alumina, having rhenium oxide absorbed onto its surface. The catalyst in accordance with the invention is prepared by vapourizing a precursor of rhenium, preferably rhenium heptoxide, preferably at a temperature of at least 160.degree. C., and routing the vapour into a reaction chamber where they are brought to interaction with the support material. The temperature of the support material is kept above the condensation temperature of the vapour and simultaneously sufficiently high so as to attain the thermal activation energy level necessary for the generation of bonds between the rhenium oxide and the support material. According to the invention, the process is carried out preferredly within a temperature range of approx. 160.degree. . . . 500.degree. C. The rhenium oxide precursor is introduced in vapour phase in an amount, which is at least equal to or, preferably, in excess of the number of available binding sites on the support material surface. The activity of a catalyst even with a very low content of catalytic metal species is as high as the activity of a catalyst of appreciably higher content of rhenium that has been prepared by the methods of conventional technology.
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公开(公告)号：US06500780B1
公开(公告)日：2002-12-31
申请号：US08840274
申请日：1997-04-14
申请人： Tuomo Suntola , Suvi Haukka , Arla Kytökivi , Eeva-Liisa Lakomaa , Marina Lindblad , Jukka Hietala , Harri Hokkanen , Hilkka Knuuttila , Pekka Knuuttila , Outi Krause , Lars Peter Lindfors
发明人： Tuomo Suntola , Suvi Haukka , Arla Kytökivi , Eeva-Liisa Lakomaa , Marina Lindblad , Jukka Hietala , Harri Hokkanen , Hilkka Knuuttila , Pekka Knuuttila , Outi Krause , Lars Peter Lindfors
IPC分类号： B01J3702
CPC分类号： B01J37/0238 , B01J21/063 , B01J23/26 , B01J23/30
摘要： The present invention concerns a method for preparing heterogeneous catalysts. According to the method, preparation is carried out under such process conditions in which the bonding of compounds from the gas phase onto the surface of a support material is primarily determined by the properties of the support surface. The constituents contained in the reagent are then selectively bonded to the bonding sites of the support material surface, thus forming stable surface bonds. According to the invention, the number of surface-bond sites available for preparing a stable product with surface bonds is controlled by varying the reaction temperature and/or selecting a suitable reagent. The invention makes it possible to control the metal content of the end product at a predetermined level.
摘要翻译： 本发明涉及一种制备非均相催化剂的方法。 根据该方法，在这样的工艺条件下进行制备，其中化合物从气相到载体材料的表面上的键合主要由支撑体表面的性质决定。 然后将包含在试剂中的组分选择性地结合到载体材料表面的结合位点，从而形成稳定的表面键。 根据本发明，通过改变反应温度和/或选择合适的试剂来控制可用于制备具有表面键的稳定产物的表面键合位点的数目。 本发明使得能够将最终产品的金属含量控制在预定水平。
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6.发明授权
公开(公告)号：US5767032A
公开(公告)日：1998-06-16
申请号：US905799
申请日：1997-08-12
IPC分类号： C08F4/02 , B01J31/22 , B01J37/02 , C08F4/619 , C08F4/6192 , C08F4/639 , C08F4/6392 , C08F4/64 , C08F4/642 , C08F4/659 , C08F4/6592 , C08F4/76 , C08F10/00 , C08F10/02 , C08F110/02
CPC分类号： B01J31/143 , B01J31/1616 , B01J31/2295 , B01J31/38 , B01J37/0238 , C08F10/00 , C08F10/02 , C08F4/65912 , B01J21/08 , B01J2531/40 , B01J2531/46 , B01J2531/48 , B01J2531/49 , B01J2531/50 , B01J2531/60 , C08F110/02 , C08F2410/03 , C08F4/6192 , C08F4/65908 , C08F4/6592 , C08F4/65925 , Y10S526/901 , Y10S526/907 , Y10S526/943
摘要： Provided are heterogeneous catalysts for homo- and copolymerization of olefins as well as a method for preparing these catalysts, which comprise at least one metallocene compound of a Group 4A, 5A or 6A (Hubbard) transition metal on a solid inorganic support. The mtehod comprises the steps of vaporizing the metallocene compound, treating the support material with the vaporized metallocene compound at a temperature which is sufficiently high to keep the metallocene compound in the vaporous state, contacting the support material with an amount of the vaporized metallocene compound which is sufficient to allow for a reaction between the metallocene compound and at least a substantial part of the available surface sites capable of reacting therewith, removing the rest of the metallocene compound not bound to the support, and optionally treating the product thus obtained with an activating agent. The catalysts are active even if very low amounts of activator agents, such as alumoxane, are used. Furthermore, the polymerization performance of the catalysts can be regulated during the preparation of the catalysts. Thus, by using different support pretreatment temperatures, or by using two or more different metallocenes, and by altering the order in which they are added on the support, it is possible to control and regulate the activity of the catalysts and the polymer properties, such as molecular weight and molecular weight distribution.
摘要翻译： 提供了用于烯烃均聚和共聚的非均相催化剂以及制备这些催化剂的方法，其包含至少一种在固体无机载体上的4A，5A或6A族（Hubbard）过渡金属茂金属化合物。 该方法包括蒸发茂金属化合物的步骤，在足够高的温度下用蒸发的金属茂化合物处理载体材料以保持茂金属化合物处于气态，使载体材料与一定量的汽化金属茂化合物接触， 足以允许茂金属化合物与能够反应的至少大部分可用表面位点之间的反应，除去未结合到载体上的其余的金属茂化合物，以及任选地用活化的方法处理由此获得的产物 代理商 即使使用非常少量的活化剂如铝氧烷，催化剂也是有活性的。 此外，可以在制备催化剂期间调节催化剂的聚合性能。 因此，通过使用不同的载体预处理温度，或通过使用两种或更多种不同的金属茂，并通过改变它们在载体上的添加顺序，可以控制和调节催化剂的活性和聚合物性质，例如 作为分子量和分子量分布。
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公开(公告)号：US5290748A
公开(公告)日：1994-03-01
申请号：US912211
申请日：1992-07-16
CPC分类号： C08F10/00 , B01J37/0238 , B01J21/06 , B01J23/26 , B01J23/30
摘要： The present invention concerns a polymerization catalyst of olefins, said catalyst containing an active chromium compound on an inorganic support. The catalyst in accordance with the invention is prepared by vaporizing a precursor of chromium oxide such as chromyl chloride and allowing the chromium oxide vapor to react with the surface of, e.g., silica gel support material at 160.degree. . . . 500.degree. C. A selective binding of the chromium oxide to the support material is achieved by keeping the vapor pressure sufficiently high and the duration of interaction with the support sufficiently long so as to maintain an excess of the chromium compound in relation to the number of available binding sites on the support material. The activity of a catalyst in accordance with the invention even with a very low content of catalytic metal is as high as the activity of a catalyst of an appreciably higher metal content that has been prepared by the methods of the conventional technology.
摘要翻译： 本发明涉及烯烃的聚合催化剂，所述催化剂在无机载体上含有活性铬化合物。 根据本发明的催化剂是通过使铬氧化物的前体如氯化氯蒸发并使铬氧化物蒸气与例如硅胶支撑材料的表面在160度反应来制备的。 。 。 通过保持蒸汽压力足够高并且与载体的相互作用的持续时间足够长以便使铬化合物的过量相对于载体材料的数量保持不变，实现铬氧化物与载体材料的选择性结合 支撑材料上的可用结合位点。 即使使用非常低含量的催化金属，根据本发明的催化剂的活性与通过常规技术方法制备的显着更高的金属含量的催化剂的活性一样高。
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公开(公告)号：US5183794A
公开(公告)日：1993-02-02
申请号：US641907
申请日：1991-01-16
CPC分类号： C08F10/00
摘要： The present invention concerns a catalyst for the polymerization of olefins, and a method for preparing the same said catalyst constituting an inorganic support material with catalytically active chromium and titanium compounds bound on its surface. The catalyst is prepared according to the invention by bringing the catalytically active metal compounds sequentially in vapor phase onto the support material surface in excess amounts in relation to the binding sites available on the support material surface. The support material temperature is maintained above the condensation temperature of the vapor, preferably above 160.degree. C., and simultaneously sufficiently high so as to achieve the thermal activation energy necessary for the generation of bonds between the support material and the catalytically active material or its compound. To avoid desorption of the chemisorbed compounds, the temperature is kept below approx. 500.degree. C. The activity of a catalyst in accordance with the invention even with very low contents of the catalytic metals is as high as the activity of a catalyst of multiply higher metal contents that has been prepared by the methods of the conventional technoloyg.
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公开(公告)号：US5124293A
公开(公告)日：1992-06-23
申请号：US641908
申请日：1991-01-16
IPC分类号： B01J29/06 , B01J37/02 , C07B61/00 , C07C2/76 , C07C15/02 , C10G35/095 , C10G45/64 , C10G45/68
CPC分类号： C10G45/68 , B01J29/061 , B01J37/0238 , C07C2/76 , C10G35/095 , C10G2400/02
摘要： The present invention concerns a catalyst suited to the aromatization reaction of light hydrocarbons. Such a heterogeneous catalyst contains zinc bound to a zeolite support material. The catalyst in accordance with the invention is prepared by adsorbing the zinc onto the surface of the zeolite support material directly from the vapor phase by way of chemisorption. The zeolite compound acting thus as the support material is here heated to a temperature which is above the condensation temperature of the zinc vapor. Advantageously, the preparation has been carried out at temperatures above 390.degree. C. The zinc vapor has been brought to contact the zeolite support material, whereby the vapor pressure of zinc is maintained sufficiently high and the duration of its interaction with the support material sufficiently long so as to provide at least one equal amount of or, preferably, an excess of zinc in relation to the available binding sites of the support material. In order to avoid the desorption of absorbed zinc, temperature in the preparation reaction of the catalyst in accordance with the invention has been maintained below 550.degree. C.
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