公开(公告)号：US06559191B1

公开(公告)日：2003-05-06

申请号：US09653718

申请日：2000-09-01

申请人： Russell John Koveal ,  Michel A. Daage

发明人： Russell John Koveal ,  Michel A. Daage

IPC分类号： C07C2700

CPC分类号： C10G2/33 ,  B01J25/00 ,  B01J25/04 ,  B01J38/60 ,  C07C1/045 ,  C07C1/049 ,  C07C2523/75 ,  C10G2/342 ,  Y02P20/584

摘要： A method is disclosed for enhancing the activity of a particulate Dispersed Active Metal (DAM) catalyst during operation of a reactor wherein the hydrogenation of carbon monoxide to produce a mixture of hydrocarbons is being carried out comprising withdrawing a mixture of hydrocarbons and a portion of the DAM catalyst from the reactor, reducing the hydrocarbon content thereof with hydrogen at a temperature above the temperature of the reactor, oxidizing a slurry of the catalyst particles in a suitable fluid at low temperature to form an oxidized precursor, reducing the precursor at elevated temperature to reform the catalyst and returning it to the reactor. The catalyst may be passivated before returning to the reactor. The process is carried out until it is evident that the operation of the reactor will no longer be economical due to a decrease in catalyst performance or accumulation of fines at which point the catalyst is preferably renewed during operation of the reactor by a process comprising withdrawing a mixture of hydrocarbons and a portion of the DAM catalyst, reducing the hydrocarbon content thereof, heating the mixture above the melting temperature of at least one of the metals to form a melt, removing any slag that forms on the melt, cooling the melt to form a solid, reducing the particle size thereof to form a renewed particulate DAM catalyst, which is then returned to the reactor.

摘要翻译： 公开了一种用于在反应器操作期间增强颗粒分散活性金属（DAM）催化剂的活性的方法，其中一氧化碳的氢化以产生烃的混合物，其包括将烃的混合物和一部分 DAM催化剂，在高于反应器温度的温度下用氢还原其烃含量，在低温下将合适的流体中的催化剂颗粒的浆料氧化以形成氧化的前体，将前体在升高的温度下还原成 改造催化剂并将其返回反应堆。 催化剂可以在返回反应器之前被钝化。 该过程进行到直到显而易见的是，由于催化剂性能的降低或细粒积聚，反应器的操作将不再经济，此时催化剂优选在反应器操作期间被更新，包括： 碳氢化合物和DAM催化剂的一部分的混合物，降低其烃含量，将混合物加热到至少一种金属的熔融温度以形成熔体，除去在熔体上形成的任何炉渣，冷却熔体形成 固体，减小其粒度以形成更新的颗粒状DAM催化剂，然后将其返回反应器。

公开(公告)号：US06624204B1

公开(公告)日：2003-09-23

申请号：US09653914

申请日：2000-09-01

申请人： Michel A. Daage ,  Russell John Koveal ,  David Chester Long ,  Leroy Russell Clavenna ,  Trikur Anantharaman Ramanarayaman ,  James Dirickson Mumford ,  Claude Clarence Culross

发明人： Michel A. Daage ,  Russell John Koveal ,  David Chester Long ,  Leroy Russell Clavenna ,  Trikur Anantharaman Ramanarayaman ,  James Dirickson Mumford ,  Claude Clarence Culross

IPC分类号： C07C2700

CPC分类号： C10G2/33 ,  B01J25/04 ,  C07C1/045 ,  C07C1/049 ,  C07C2525/00 ,  C10G2/342 ,  Y02P20/584

摘要： A method is disclosed for renewing the activity of a Dispersed Active Metal (DAM) catalyst during operation of a reactor wherein the hydrogenation of carbon monoxide to produce a mixture of hydrocarbons is being carried out comprising withdrawing a mixture of hydrocarbons and a portion of the DAM catalyst, reducing the hydrocarbon content thereof, heating the mixture above the melting temperature of at least one of the metals of the DAM to form a melt, removing any slag that forms on the melt, cooling the melt to form a solid, reducing the particle size thereof to form a renewed particulate DAM catalyst, which is then returned to the reactor. Wherein the DAM catalyst is a Raney catalyst, a leachable metal is added to the reduced hydrocarbon mixture or the melt under non-oxidizing conditions and, after the solid is reduced to a fine particle size, extracting the leachable metal with caustic. The activity of the DAM may be modified or enhanced during the process by the addition of promoter metals, or prior to being returned to the reactor, by slurry low temperature oxidation followed by reduction at elevated temperature, and may further be enhanced by being passivated prior to being returned to the reactor. The catalyst may be withdrawn and replaced periodically or continuously during the operation of the reactor.

摘要翻译： 公开了一种用于在反应器操作期间更新分散活性金属（DAM）催化剂的活性的方法，其中一氧化碳的氢化以产生烃的混合物，其中包括抽出烃和一部分DAM的混合物 催化剂，降低其烃含量，将混合物加热至DAM金属中的至少一种的熔融温度以形成熔体，除去在熔体上形成的任何熔渣，冷却熔体以形成固体，还原颗粒 以形成更新的颗粒状DAM催化剂，然后将其返回反应器。 其中DAM催化剂是阮内催化剂，在非氧化条件下将还原的烃混合物或熔体中可浸出的金属加入，在将固体还原成细粒度后，用苛性碱萃取可浸出的金属。 在该过程中，DAM的活性可以通过加入助催化剂金属或在通过浆料低温氧化然后在升高的温度下还原而返回到反应器之前被修饰或增强，并且可以通过先前被钝化而进一步增强 返回反应堆。 催化剂可以在反应器的操作期间被定期或连续地取出和更换。

公开(公告)号：US06465529B1

公开(公告)日：2002-10-15

申请号：US09628407

申请日：2000-08-01

申请人： Michel Andre Daage ,  Russell John Koveal ,  Leroy Russell Clavenna

发明人： Michel Andre Daage ,  Russell John Koveal ,  Leroy Russell Clavenna

IPC分类号： C07C2700

CPC分类号： C10G2/332 ,  B01J21/063 ,  B01J23/75 ,  B01J23/8896 ,  B01J37/12

摘要： An aqueous low temperature oxidation (ALTO) process wherein a catalyst or catalyst precursor constituted of a solids support, or powder component, and a metal, or metals component, inclusive of cobalt, is oxidized, reduced and rendered catalytically active for conducting carbon monoxide hydrogenation reactions. The cobalt catalyst or cobalt catalyst precursor is thus contacted at low temperature with an oxidant in the presence of water (e.g., water to which an oxidant is added), sufficient to oxidize the cobalt metal, or metals component of the catalyst or catalyst precursor. On reduction, the hydrogenation activity of the cobalt catalyst is increased. All or a portion of the cobalt metal of the catalyst precursor is oxidized to form a Co2+ cationic or oxo-anionic species at least during the initial phase of the reaction. On reduction, as may be produced by contact and treatment of the oxidized catalyst or catalyst precursor with hydrogen, or a hydrogen-containing gas, the catalytic metal, or metals component of the catalyst, is reduced to metallic metal, e.g., Co, and the catalyst thereby activated, and/or the catalytic activity increased.

摘要翻译： 一种低温低温氧化（ALTO）方法，其中由固体载体或粉末组分以及包含钴的金属或金属组分构成的催化剂或催化剂前体被氧化，还原并具有催化活性以进行一氧化碳氢化 反应。 因此，钴催化剂或钴催化剂前体在水（例如添加有氧化剂的水）存在下在低温下与氧化剂接触，足以氧化钴金属或催化剂或催化剂前体的金属组分。 还原时，钴催化剂的氢化活性提高。 至少在反应的初始阶段，全部或一部分催化剂前体的钴金属被氧化形成Co 2+阳离子或氧代阴离子物质。 在还原时，如可以通过用氢气或含氢气体接触和处理氧化的催化剂或催化剂前体而产生的，催化剂的催化金属或金属组分被还原成金属金属，例如Co，和 催化剂因此被活化，和/或催化活性增加。

公开(公告)号：US06066701A

公开(公告)日：2000-05-23

申请号：US959759

申请日：1997-10-29

申请人： Russell John Koveal ,  James John McAlpin ,  Jeffrey Lawrence Brinen

发明人： Russell John Koveal ,  James John McAlpin ,  Jeffrey Lawrence Brinen

IPC分类号： B01J19/24 ,  C08F2/00 ,  C08F2/01 ,  C08F2/06 ,  C08F10/00 ,  C08G85/00

CPC分类号： B01J19/245 ,  C08F10/00 ,  B01J2219/00114 ,  B01J2219/0013 ,  B01J2219/00162 ,  B01J2219/00182

摘要： The present invention provides a method for substantially continuously polymerizing olefins comprising: introducing into a first reaction zone a fresh olefin polymerization catalyst; contacting said fresh olefin polymerization catalyst in said first reaction zone with a first vent mixture at a first feed rate and under conditions sufficient to form and avoid melting a polyolefin, wherein first vent mixture comprises unreacted olefins and a diluent vented from a second reaction zone; withdrawing a vent product of unreacted olefins and diluent from said first reaction zone; withdrawing from said first reaction zone a first product mixture comprising said catalyst and said polyolefin; passing said first product mixture to said second reaction zone; contacting said first product mixture in said second reaction zone with a second vent mixture at a second feed rate and under conditions sufficient to form and avoid melting said polyolefin, wherein said second vent mixture comprises a material selected from the group consisting of a fresh feed and a mixture comprising unreacted olefins and diluent from a third reaction zone; and, withdrawing from said second reaction zone a second product mixture comprising said catalyst and said polyolefin.

摘要翻译： 本发明提供了一种基本上连续聚合烯烃的方法，包括：将新鲜的烯烃聚合催化剂引入第一反应区; 在第一进料速率和足以形成和避免熔化聚烯烃的条件下使所述第一反应区中的所述新鲜烯烃聚合催化剂与第一排气混合物接触，其中第一排气混合物包含未反应的烯烃和从第二反应区排出的稀释剂; 从所述第一反应区抽出未反应的烯烃和稀释剂的排放产物; 从所述第一反应区抽出含有所述催化剂和所述聚烯烃的第一产物混合物; 将所述第一产物混合物通入所述第二反应区; 使所述第二反应区中的所述第一产物混合物与第二排气混合物以第二进料速率和足以形成和避免熔化所述聚烯烃的条件接触，其中所述第二排气混合物包含选自新鲜进料和 包含来自第三反应区的未反应烯烃和稀释剂的混合物; 并且从所述第二反应区抽出包含所述催化剂和所述聚烯烃的第二产物混合物。

公开(公告)号：US06753286B2

公开(公告)日：2004-06-22

申请号：US10059917

申请日：2002-01-29

申请人： Janet Renee Clark ,  Russell John Koveal ,  Michel Daage

发明人： Janet Renee Clark ,  Russell John Koveal ,  Michel Daage

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。

公开(公告)号：US06716886B2

公开(公告)日：2004-04-06

申请号：US10285985

申请日：2002-11-01

申请人： Alla Jurievna Krylova ,  Albert L'Vovich Lapidus ,  Lilia Vadimovna Sineva ,  Michel A. Daage ,  Russell John Koveal

发明人： Alla Jurievna Krylova ,  Albert L'Vovich Lapidus ,  Lilia Vadimovna Sineva ,  Michel A. Daage ,  Russell John Koveal

IPC分类号： C07C2700

CPC分类号： C10G2/332 ,  B01J25/00 ,  C10G2/333

摘要： A process of enhancing both the activity and the methane selectivity of a Dispersed Active Metal (“DAM”) hydrogenation catalyst is disclosed wherein the DAM undergoes low temperature oxidation in a slurry phase to form a stable, unique oxidized catalyst precursor that is subsequently reduced to form an enhanced catalyst by treatment with hydrogen-containing gas at elevated temperature, wherein reducible promoter metals comprising one or more of rhenium, ruthenium, palladium, iron and cobalt are added to the DAM. The promoter metals are mixed with the oxidized catalyst precursor as a solution of their reducible salts. The oxidized catalyst precursors are again recovered from the mixture and treated with hydrogen-containing gas to simultaneously form the metals and reactivate the DAM catalyst.

摘要翻译： 公开了一种提高分散活性金属（“DAM”）氢化催化剂的活性和甲烷选择性的方法，其中DAM在浆料相中经历低温氧化以形成稳定的独特的氧化催化剂前体，随后将其还原为 通过在升高的温度下用含氢气体处理形成增强的催化剂，其中将包含铼，钌，钯，铁和钴中的一种或多种的可还原助催化剂金属加入到DAM中。 助催化剂金属与其可还原盐的溶液与氧化的催化剂前体混合。 氧化的催化剂前体再次从混合物中回收并用含氢气体处理以同时形成金属并重新活化DAM催化剂。

公开(公告)号：US06706661B1

公开(公告)日：2004-03-16

申请号：US09653719

申请日：2000-09-01

申请人： Alla Jurievna Krylova ,  Albert L'Vovich Lapidus ,  Lilia Vadimovna Sineva ,  Michel A. Daage ,  Russell John Koveal

发明人： Alla Jurievna Krylova ,  Albert L'Vovich Lapidus ,  Lilia Vadimovna Sineva ,  Michel A. Daage ,  Russell John Koveal

IPC分类号： B01J2340

CPC分类号： C10G2/332 ,  B01J25/00 ,  C10G2/333

摘要： A process of enhancing both the activity and the methane selectivity of a Dispersed Active Metal (“DAM”) hydrogenation catalyst is disclosed wherein the DAM undergoes low temperature oxidation in a slurry phase to form a stable, unique oxidized catalyst precursor that is subsequently reduced to form an enhanced catalyst by treatment with hydrogen-containing gas at elevated temperature, wherein reducible promoter metals comprising one or more of rhenium, ruthenium, palladium, iron and cobalt are added to the DAM. The promoter metals are mixed with the oxidized catalyst precursor as a solution of their reducible salts. The oxidized catalyst precursors are again recovered from the mixture and treated with hydrogen-containing gas to simultaneously form the metals and reactivate the DAM catalyst.

摘要翻译： 公开了一种提高分散活性金属（“DAM”）氢化催化剂的活性和甲烷选择性的方法，其中DAM在浆料相中经历低温氧化以形成稳定的独特的氧化催化剂前体，随后将其还原为 通过在升高的温度下用含氢气体处理形成增强的催化剂，其中将包含铼，钌，钯，铁和钴中的一种或多种的可还原助催化剂金属加入到DAM中。 助催化剂金属与其可还原盐的溶液与氧化的催化剂前体混合。 氧化的催化剂前体再次从混合物中回收并用含氢气体处理以同时形成金属并重新活化DAM催化剂。

公开(公告)号：US06531518B1

公开(公告)日：2003-03-11

申请号：US09653915

申请日：2000-09-01

申请人： Albert L'Vovich Lapidus ,  Alla Jurievna Krylova ,  Lilia Vadimovna Sineva ,  Russell John Koveal ,  Michel A. Daage

发明人： Albert L'Vovich Lapidus ,  Alla Jurievna Krylova ,  Lilia Vadimovna Sineva ,  Russell John Koveal ,  Michel A. Daage

IPC分类号： C07C2700

CPC分类号： C10G2/331 ,  B01J25/00 ,  B01J37/12

摘要： A process of enhancing both the activity and the methane selectivity of a particulate Dispersed Active Metal (“DAM”) hydrogenation catalyst is disclosed wherein the DAM undergoes low temperature oxidation in a slurry phase to form a stable, unique oxidized catalyst precursor that is subsequently reduced to form an enhanced catalyst by treatment with hydrogen-containing gas at elevated temperature, wherein one or more promoter metal oxides of chromium, lanthanum and manganese are added to the DAM. Precursors of the promoter metal oxides may be combined with the DAMs prior to or during formation of the initial slurry, during the oxidation step or between recovery of the oxidized catalyst precursor and treatment of it with hydrogen-containing gas to reactivate the catalyst. Conversion of the precursors to the promoter metal oxides is carried out prior to the treatment with hydrogen-containing gas unless said treatment itself produces the conversion.

摘要翻译： 公开了一种提高颗粒分散活性金属（“DAM”）氢化催化剂的活性和甲烷选择性的方法，其中DAM在浆料相中经历低温氧化以形成稳定的独特的氧化催化剂前体，随后还原 通过在高温下用含氢气体处理形成增强的催化剂，其中将一种或多种铬，镧和锰的助催化剂金属氧化物加入到DAM中。 助催化剂金属氧化物的前体可以在氧化步骤期间或在氧化的催化剂前体的回收之前或期间在初始浆料形成之前或期间与含氢气体进行处理以重新催化催化剂，与DAM组合。 在用含氢气体处理之前，将前体转化为助催化剂金属氧化物，除非所述处理本身产生转化。

公开(公告)号：US06800579B2

公开(公告)日：2004-10-05

申请号：US10059926

申请日：2002-01-29

申请人： Michel Daage ,  Russell John Koveal ,  Min Chang

发明人： Michel Daage ,  Russell John Koveal ,  Min Chang

IPC分类号： B01J3812

CPC分类号： B01J23/96 ,  B01J23/75 ,  B01J23/94 ,  B01J38/10 ,  B01J38/12 ,  B01J38/56 ,  B01J38/68 ,  B01J2038/005 ,  C07C1/045 ,  C07C2523/75 ,  C10G2/331 ,  C10G2/332 ,  C10G2/333 ,  Y02P20/584 ,  C07C9/04

摘要： There is provided a process for regenerating the activity of used metal catalysts for the hydrogenation of carbon monoxide comprising decreasing the hydrocarbon content thereof, calcining under an oxidant-containing atmosphere, impregnating with a solution of at least one of a metal compound, calcining under an oxidant-containing atmosphere and activating by contacting with a hydrogen-contacting gas at elevated temperatures to form an active catalyst. The process regenerates and enhances both supported and dispersed active metal (DAM) catalysts. 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 operation thereof. Up to all steps may be effected in a subsequent reactor, or in specialized apparatus.

摘要翻译： 提供了一种用于再生用于一氧化碳氢化的所用金属催化剂的活性的方法，包括降低其含烃量，在含氧化剂的气氛下煅烧，用至少一种金属化合物的溶液浸渍，在 氧化剂的气氛，并通过在高温下与接触氢的气体接触而形成活性催化剂。 该方法再生并增强了负载和分散的活性金属（DAM）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，或者在催化剂可以从反应器中取出并返回到至少一个反应器之后，最好在其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。

公开(公告)号：US06777451B2

公开(公告)日：2004-08-17

申请号：US10059927

申请日：2002-01-29

申请人： Russell John Koveal ,  Michel Daage ,  Charles Harrison Mauldin ,  Janet Renee Clark

发明人： Russell John Koveal ,  Michel Daage ,  Charles Harrison Mauldin ,  Janet Renee Clark

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。