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公开(公告)号：US06787496B2
公开(公告)日：2004-09-07
申请号：US10059928
申请日：2002-01-29
IPC分类号： B01J3808
CPC分类号： C10G2/331 , B01J21/063 , B01J23/75 , B01J23/94 , B01J23/96 , B01J38/10 , B01J38/12 , B01J38/66 , B01J38/70 , C10G2/332 , C10G2/333
摘要： There is provided a process for renewing the activity of supported metal catalysts for the hydrogenation of carbon monoxide to form a mixture of hydrocarbons comprising decreasing the hydrocarbon content of the catalyst, preferably by contact with hydrogen-containing gas at elevated temperatures, impregnating under a non-oxidizing atmosphere with a solution of at least one of an ammonium salt and an alkyl ammonium salt, optionally in combination with up to five moles of ammonia per liter of solution to the point where it has absorbed a volume of solution equal to at least about 10% of its calculated pore volume; oxidizing the catalyst with a gaseous oxidant in the presence of the impregnating solution and activating the catalyst by reduction with hydrogen at elevated temperatures. Optionally, the catalyst is calcined after the oxidation step, and passivated after the activation step.
摘要翻译： 提供了一种用于更新用于氢化一氧化碳的负载型金属催化剂的活性以形成烃的混合物的方法，包括降低催化剂的烃含量，优选通过在高温下与含氢气体接触，在非水溶液下浸渍 使用至少一种铵盐和烷基铵盐的溶液的氧化气氛，任选地与每升溶液中最多5摩尔氨的组合至其吸收一定体积的溶液至少约为 其计算孔体积的10％ 在浸渍溶液存在下用气态氧化剂氧化催化剂，并通过在高温下用氢还原来活化催化剂。 任选地，在氧化步骤之后煅烧催化剂，并在活化步骤后钝化。
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公开(公告)号：US06753286B2
公开(公告)日：2004-06-22
申请号：US10059917
申请日：2002-01-29
IPC分类号： B01J3862
CPC分类号： C10G2/33 , B01J23/94 , B01J23/96 , B01J38/10 , B01J38/58 , B01J38/62 , B01J38/70 , B01J2038/005 , C10G2/332 , C10G2/333
摘要： There is provided a process for renewing the activity of used, supported metal catalysts for the hydrogenation of carbon monoxide to form a mixture of hydrocarbons comprising decreasing the hydrocarbon content of the catalyst, impregnating said catalyst under an non-oxidative atmosphere with a solution at least one weak organic acid, preferably a mono- or di-carboxylic acid, to the point where it has absorbed a volume of said solution equal to at least about 10% of its calculated pore volume, oxidizing the catalyst with a gaseous oxidant in the presence of the impregnating solution and activating the catalyst by reduction with hydrogen at elevated temperatures. Optionally, the catalyst is calcined after the oxidation step, and passivated after the activation step. A preferred means of decreasing the hydrocarbon content of the catalyst is contacting it with a hydrogen-containing gas at elevated temperatures.
摘要翻译： 提供了一种用于更新用于一氧化碳氢化的用过的负载金属催化剂以形成烃的混合物的活性的方法，包括降低催化剂的烃含量，在非氧化性气氛下用至少一种溶液浸渍所述催化剂 一种弱有机酸，优选单羧酸或二羧酸，其吸收一定体积的所述溶液等于其计算的孔体积的至少约10％，在存在下用气态氧化剂氧化催化剂 的浸渍溶液，并通过在升高的温度下用氢还原来活化催化剂。 任选地，在氧化步骤之后煅烧催化剂，并在活化步骤后钝化。 降低催化剂的烃含量的优选方法是在升高的温度下将其与含氢气体接触。
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公开(公告)号：US06777451B2
公开(公告)日：2004-08-17
申请号：US10059927
申请日：2002-01-29
IPC分类号： C07C2700
CPC分类号： B01J21/063 , B01J23/40 , B01J23/6567 , B01J23/70 , B01J23/75 , B01J23/8896 , B01J23/89 , B01J23/94 , B01J23/96 , B01J38/10 , B01J38/12 , B01J38/56 , B01J38/58 , B01J38/66 , C10G2/332 , C10G2/333
摘要： A process for enhancing metal catalysts for carbon monoxide hydrogenation comprising reducing the catalyst so that at least a portion is in the metallic state, impregnating under a non-oxidative atmosphere with a solution of a salt of at least one metal, optionally in combination with at least one of an ammonium salt, an alkyl ammonium salt, a weak organic acid and ammonia, oxidizing with a gaseous oxidant in the presence of the impregnating solution, and reducing to form an active catalyst. Used catalysts enhanced by the process are initially treated to decrease their hydrocarbon content. The treatment may be carried out in a single reactor, or by carrying out up to all steps after catalyst may be withdrawn from a reactor and returned to at least one reactor, both preferably during operations. Up to all steps may be effected in a subsequent reactor, or in specialized apparatus.
摘要翻译： 一种用于增强用于一氧化碳氢化的金属催化剂的方法，包括将催化剂还原为至少一部分处于金属状态，在非氧化性气氛下用至少一种金属的盐溶液浸渍，任选地与 至少一种铵盐，烷基铵盐，弱有机酸和氨，在浸渍溶液存在下用气态氧化剂氧化，还原形成活性催化剂。 首先处理通过该方法增强的使用的催化剂以降低它们的烃含量。 处理可以在单个反应器中进行，或者通过在催化剂可以从反应器中取出并返回到至少一个反应器中，两者优选在操作期间进行到所有步骤。 直到所有步骤都可以在随后的反应器中或在专门的装置中进行。
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公开(公告)号：US06753351B2
公开(公告)日：2004-06-22
申请号：US10059918
申请日：2002-01-29
IPC分类号： C07C2700
摘要： A process for activating a supported metal catalyst or catalyst precursor useful for the hydrogenation of carbon monoxide to form a mixture of hydrocarbons, comprising reducing with a hydrogen-containing gas at elevated temperature so that at least a portion is in the metallic state, impregnating under a non-oxidizing atmosphere with a solution of at least one member selected from the group consisting of ammonium salts, alkyl ammonium salts and weak organic acids, optionally further including ammonia, to the point where it has absorbed a volume of solution equal to at least about 10% of its calculated pore volume, oxidizing with a gaseous oxidant in the presence of the impregnating solution and reducing with hydrogen-containing gas at elevated temperatures to form an active catalyst. The steps beginning with the impregnation may be repeated. Optionally, the catalyst may be calcined after the oxidation step and/or passivated after activation.
摘要翻译： 用于活化用于氢化一氧化碳以形成烃混合物的负载型金属催化剂或催化剂前体的方法，包括在高温下用含氢气体还原，使得至少一部分处于金属状态，浸渍在 非氧化性气氛，其中选自铵盐，烷基铵盐和弱有机酸中的至少一种的溶液，任选地还包括氨，其吸收一定体积的溶液至少等于至少 其计算的孔体积的约10％，在浸渍溶液存在下用气态氧化剂氧化，并在高温下用含氢气体还原形成活性催化剂。 可以重复从浸渍开始的步骤。 任选地，催化剂可以在氧化步骤之后煅烧和/或在活化后被钝化。
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5.发明授权Slurry hydrocarbon synthesis with liquid hydroisomerization in the synthesis reactor 失效在合成反应器中进行液体加氢异构化的淤浆烃合成公开(公告)号：US06717024B2
公开(公告)日：2004-04-06
申请号：US09992141
申请日：2001-11-06
IPC分类号： C07C522
CPC分类号： C10G2/32 , B01J8/006 , B01J8/226 , B01J19/2485 , B01J2208/0084 , B01J2208/025 , C10G2/342 , C10G45/58 , Y10S208/95
摘要： A slurry Fischer-Tropsch hydrocarbon synthesis process for synthesizing liquid hydrocarbons from synthesis gas in a synthesis reactor also hydroisomerizes the synthesized hydrocarbon liquid, which comprises the slurry liquid, in one or more lift reactors immersed in the slurry body in the synthesis reactor. A monolithic catalyst is preferably used for the hydroisomerization, and slurry circulation up through the lift reactors from the surrounding slurry body, is achieved at least in part by the lift action of the hydroisomerization treat gas. Preferably, catalyst particles are also removed before the slurry contacts the catalyst. Hydroisomerization occurs while the synthesis reactor is producing hydrocarbons, without interfering with the synthesis reaction. A gas bubble reducing downcomer may be used to produce and feed the gas bubble reduced slurry into the lift reactor, thereby providing a hydraulic head assist in the slurry circulation up through and out of the lift reactor.
摘要翻译： 用于在合成反应器中从合成气中合成液态烃的浆料费 - 托烃合成方法还将合成的包含浆料液体的烃液体在浸入合成反应器中的浆料体的一个或多个提升反应器中进行加氢异构化。 优选使用整体式催化剂用于加氢异构化，并且至少部分地通过加氢异构化处理气体的提升作用实现通过来自周围淤浆体的提升反应器的浆料循环。 优选地，催化剂颗粒在浆料接触催化剂之前也被除去。 在合成反应器生产碳氢化合物的同时发生加氢异构化，而不会干扰合成反应。 气泡减少降液管可以用于产生并将气泡减少的浆料进料到提升反应器中，从而在通过和离开提升反应器的浆料循环中提供液压头辅助。
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6.发明授权In-situ hydroisomerization of synthesized hydrocarbon liquid in a slurry fischer-tropsch reactor 失效合成烃液体在浆料费 - 托反应器中的原位加氢异构化公开(公告)号：US06555725B1
公开(公告)日：2003-04-29
申请号：US09992372
申请日：2001-11-06
IPC分类号： C07C513
CPC分类号： C10G2/342 , B01J8/006 , B01J8/065 , B01J8/226 , B01J19/2485 , B01J2208/0084 , B01J2208/00849 , B01J2208/00884 , C10G45/58
摘要： A slurry Fischer-Tropsch hydrocarbon synthesis process for synthesizing liquid hydrocarbons from synthesis gas in a hydrocarbon synthesis reactor also hydroisomerizes the synthesized hydrocarbon liquid, which comprises the slurry liquid, in one or more downcomer reactors immersed in the slurry body in the synthesis reactor. A monolithic catalyst is preferably used for the hydroisomerization, and slurry circulation down through the downcomer reactors from the surrounding slurry body, is achieved at least in part by density-difference driven hydraulics created by removing gas bubbles from the slurry passed into the downcomers. Preferably, catalyst particles are also removed before the slurry contacts the catalyst. Hydroisomerization occurs while the synthesis reactor is producing hydrocarbons, without interfering with the hydrocarbon synthesis reaction.
摘要翻译： 在烃合成反应器中从合成气中合成液态烃的浆料费 - 托烃合成方法还将合成的含有浆料液体的烃液体在浸入合成反应器中的淤浆体中的一个或多个降液管反应器中加氢异构化。 优选使用整体式催化剂用于加氢异构化，并且至少部分地通过从通过下降管的浆料中除去气泡产生的密度差驱动液压来实现从周围淤浆体向下通过降液管反应器的淤浆。 优选地，催化剂颗粒在浆料接触催化剂之前也被除去。 在合成反应器生产碳氢化合物的同时发生加氢异构化，而不干扰烃的合成反应。
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公开(公告)号：US06649803B2
公开(公告)日：2003-11-18
申请号：US09992390
申请日：2001-11-06
IPC分类号： C07C522
CPC分类号： C10G2/342 , B01J8/006 , B01J8/226 , B01J8/228 , B01J19/2485 , B01J2208/0084 , B01J2208/025 , C10G45/60 , Y10S208/95
摘要： A slurry Fischer-Tropsch hydrocarbon synthesis process for synthesizing liquid hydrocarbons from synthesis gas in a synthesis reactor also hydroisomerizes the synthesized hydrocarbons in one or more external lift reactor hydroisomerizing loops outside of the reactor, but which are a part of the reactor. A monolithic catalyst is used for the hydroisomerization and slurry circulation between the synthesis reactor and one or more loops is achieved, at least in part, by the lift action of a hydrogen treat gas injected into each loop.
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8.发明授权Slurry hydrocarbon synthesis with external hydroisomerization in downcomer reactor loop 失效在降液管反应器回路中进行外部加氢异构化的淤浆烃合成公开(公告)号：US06570047B1
公开(公告)日：2003-05-27
申请号：US09992371
申请日：2001-11-06
IPC分类号： C07C522
摘要： A slurry Fischer-Tropsch hydrocarbon synthesis process for synthesizing liquid hydrocarbons from synthesis gas, in a hydrocarbon synthesis reactor, also hydroisomerizes the synthesized hydrocarbons in one or more external downcomer reactor hydroisomerizing loops outside of the reactor, but which are a part of the synthesis reactor. A monolithic catalyst is used for the hydroisomerization, and slurry circulation between the synthesis reactor and the one or more hydroisomerization loops is achieved, at least in part, by density-difference driven hydraulics created by removing gas bubbles from the slurry passed into the loop. Preferably, catalyst particles are also removed before the slurry contacts the monolithic hydroisomerization catalyst.
摘要翻译： 在烃合成反应器中从合成气中合成液态烃的浆料费 - 托烃合成方法还将合成的烃在反应器外部的一个或多个外部降液管反应器加氢异构化环中进行加氢异构化，但它们是合成反应器的一部分 。 整体式催化剂用于加氢异构化，合成反应器和一个或多个加氢异构化回路之间的淤浆循环至少部分地通过从通过循环的浆料中除去气泡而产生的密度差驱动液压来实现。 优选地，在浆料接触整体式加氢异构化催化剂之前，还除去催化剂颗粒。
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