公开(公告)号：US06232495B1

公开(公告)日：2001-05-15

申请号：US09245157

申请日：1999-02-04

申请人： Eustathios Vassiliou ,  Mark W. Dassel ,  Ader M. Rostami ,  Douglas J. Dudgeon ,  David C. DeCoster

发明人： Eustathios Vassiliou ,  Mark W. Dassel ,  Ader M. Rostami ,  Douglas J. Dudgeon ,  David C. DeCoster

IPC分类号： C07C5131

CPC分类号： C07C51/313 ,  Y02P20/584 ,  C07C55/14

摘要： This invention relates to methods and reactor devices for controlling the oxidation of hydrocarbons to dibasic acids, in the presence of a cobalt catalyst and a monobasic acid, such as acetic acid, by treating the catalyst from the reaction mixture, outside the oxidation zone, after the oxidation has taken place at least partially. In one preferred embodiment, the catalyst is reduced to contain, preferably predominantly and more preferably substantially, cobalt ions in valence II, and at least partially precipitated by de-watering and/or thermal treatment. In a different preferred embodiment, the catalyst in the reaction mixture is first oxidized or maintained, preferably predominantly and more preferably substantially, at valence III, the reaction mixture is de-watered, the catalyst is reduced, preferably predominantly and more preferably substantially, to valence II, causing precipitation either spontaneously at a predetermined temperature or after further thermal treatment. The precipitated catalyst is preferably recycled directly or indirectly.

摘要翻译： 本发明涉及在钴催化剂和一元酸如乙酸的存在下，通过在氧化区之外处理来自反应混合物的催化剂，在氧化区外处理催化剂，在氧化区外处理碳酸氢盐氧化成二元酸的方法和反应器装置 氧化至少部分发生。 在一个优选的实施方案中，将催化剂还原为含有，优选主要且更优选基本上为II价的钴离子，并且至少部分地通过脱水和/或热处理沉淀。 在不同的优选实施方案中，反应混合物中的催化剂首先被氧化或维持，优选主要且更优选基本上为III价，反应混合物脱水，催化剂被还原，优选主要且更优选基本上为 化合价II，在预定温度或进一步热处理后自发沉淀。 沉淀的催化剂优选直接或间接回收。

公开(公告)号：US06433221B1

公开(公告)日：2002-08-13

申请号：US09345693

申请日：1999-06-30

申请人： Ader M. Rostami ,  Douglas J. Dudgeon ,  David C. DeCoster ,  Mark W. Dassel ,  Eustathios Vassiliou

发明人： Ader M. Rostami ,  Douglas J. Dudgeon ,  David C. DeCoster ,  Mark W. Dassel ,  Eustathios Vassiliou

IPC分类号： C07C5131

CPC分类号： C07C51/313 ,  C07C51/42 ,  Y02P20/584 ,  C07C55/14

摘要： This invention relates to methods of controlling the oxidation of cyclohexane to adipic acid in the presence of a monobasic acid solvent, by separating the catalyst from the reaction mixture, outside the reaction zone. Substantially all the unreacted cyclohexane, the majority of adipic acid, and substantially all the monobasic acid solvent are preferably removed. A protic solvent, may be added intermittently or continuously in the reaction mixture during the removal of the monobasic acid solvent, preferably by distillation, for preventing solids precipitation. A dipolar aprotic solvent is then added in the presence of an adequate amount of the protic solvent to maintain a single liquid phase, followed by a step of formation of two liquid phases, a solids-free protic liquid phase containing substantially all the catalyst, and a solids-free aprotic liquid phase containing at least the majority of ingredients of the reaction mixture. The formation of the two phases is performed by a process selected from a group consisting of lowering the first temperature to a second temperature, adding additional protic solvent, adding an apolar aprotic solvent, and a combination thereof.

摘要翻译： 本发明涉及在一元酸溶剂存在下，通过将反应混合物中的催化剂从反应区域外分离来控制环己烷氧化成己二酸的方法。 基本上所有未反应的环己烷，大多数己二酸和基本上所有的一元酸溶剂都是优选的。 在去除一元酸溶剂期间，优选通过蒸馏，可以在反应混合物中间歇地或连续地添加质子溶剂，以防止固体沉淀。 然后在足够量的质子溶剂的存在下加入偶极非质子溶剂以维持单一液相，随后形成两个液相，含有基本上所有催化剂的无固体质子液相的步骤，以及 含有至少大部分反应混合物成分的无固体的非质子液相。 两相的形成通过选自降低第一温度至第二温度，加入另外的质子溶剂，加入非极性非质子溶剂及其组合的组中的方法进行。

公开(公告)号：US06258981B1

公开(公告)日：2001-07-10

申请号：US09506053

申请日：2000-02-17

申请人： David Richardson ,  Cheng Xu ,  Khalil Abboud

发明人： David Richardson ,  Cheng Xu ,  Khalil Abboud

IPC分类号： C07C5131

CPC分类号： C07C51/31 ,  B01J31/182 ,  B01J31/183 ,  B01J2531/821 ,  B01J2531/842 ,  C07C51/313 ,  C07C55/14

摘要： Disclosed are catalysts useful for catalyzing the synthesis of adipic acid from cyclohexane and oxygen. Also disclosed are methods of making the catalysts, methods of using the catalysts to catalyze the production of adipic acid from cyclohexane and oxygen, and kits containing the catalysts.

摘要翻译： 公开了可用于催化由环己烷和氧合成己二酸的催化剂。 还公开了制备催化剂的方法，使用催化剂催化由环己烷和氧气生产己二酸的方法，以及含有催化剂的试剂盒。

公开(公告)号：US06392093B1

公开(公告)日：2002-05-21

申请号：US09715928

申请日：2000-11-17

申请人： Puthusseril Varkey Saji ,  Chandra Ratnasamy ,  Sarada Gopinathan

发明人： Puthusseril Varkey Saji ,  Chandra Ratnasamy ,  Sarada Gopinathan

IPC分类号： C07C5131

CPC分类号： C07C51/313 ,  C07C55/14

摘要： The present invention relates to an improved process for the oxidation of cyclohexane to adipic acid using air as an oxidant and a solid organotransition metal complex as a catalyst. The process comprises comprises reacting cyclohexane with air in the presence of a solid catalyst containing an encapsulated salen or substituted salen metal complex wherein some of the hydrogen atoms of the said organomanganese complex have been substituted by one or more electron withdrawing groups, at a temperature in the range of 20 to 120° C., at a pressure in the range of 50 to 1000 psi, in the presence or absence of solvents, with or without a promoter and isolating the adipic acid formed by conventional methods, such as filtration and centrifugation.

摘要翻译： 本发明涉及使用空气作为氧化剂和作为催化剂的固体有机过渡金属络合物将环己烷氧化成己二酸的改进方法。 该方法包括在含有包封的salen或取代的salen金属络合物的固体催化剂存在下使环己烷与空气反应，其中所述有机锰络合物的一些氢原子已被一个或多个吸电子基团取代， 在存在或不存在溶剂的条件下，在20至120℃的范围内，在50至1000psi的压力范围内，具有或不具有助催化剂并分离通过常规方法如过滤和离心形成的己二酸 。

公开(公告)号：US06359173B1

公开(公告)日：2002-03-19

申请号：US08989910

申请日：1997-12-12

申请人： Sharon M. Aldrich ,  David C. DeCoster ,  Eustathios Vassiliou ,  Mark W. Dassel ,  Ader M. Rostami

发明人： Sharon M. Aldrich ,  David C. DeCoster ,  Eustathios Vassiliou ,  Mark W. Dassel ,  Ader M. Rostami

IPC分类号： C07C5131

CPC分类号： C07C51/42 ,  B01D3/346 ,  B01J10/002 ,  B01J19/0006 ,  B01J19/006 ,  B01J19/18 ,  B01J19/26 ,  B01J2219/00058 ,  B01J2219/00065 ,  B01J2219/00067 ,  B01J2219/00083 ,  B01J2219/00101 ,  B01J2219/00128 ,  B01J2219/00162 ,  B01J2219/00164 ,  B01J2219/00186 ,  B01J2219/00777 ,  C07C51/265 ,  C07C51/313 ,  C07C63/16 ,  C07C63/24 ,  C07C63/26 ,  C07C55/14

摘要： Methods and devices for controlling the reaction of a hydrocarbon to an acid by making phase-related adjustments are disclosed. In order to improve reaction rate and reactivity of the oxidation, a single phase at the operating temperature is attained and maintained by adjusting one or more of gaseous oxidant flow rate, pressure in the reaction zone, temperature in the reaction zone, feed rate of hydrocarbon, feed rate of solvent, feed rate of water if water is being fed, feed rate of the catalyst and other parameters. Methods and devices are also disclosed, wherein a hydrocarbon is reacted at a steady state with a gaseous oxidant to form an acid in a liquid mixture. The amount of water is maintained between a maximum level of water, over which maximum level the substantially single liquid phase is transformed to two liquid phases, and a minimum level under which catalyst precipitates. Further, methods are disclosed, wherein the temperature of the mixture is lowered to a point at which solid dibasic acid is precipitated, while maintaining a single liquid phase, and optionally all the catalyst in solution. At least part of the formed acid is then removed. The preferred hydrocarbon is cyclohexane, the preferred acid is adipic acid, the preferred solvent is acetic acid, and the preferred catalyst is cobalt(II) acetate tetrahydrate.

摘要翻译： 公开了通过进行相位调节来控制烃与酸的反应的方法和装置。 为了提高反应速率和氧化反应性，通过调节一种或多种气态氧化剂流量，反应区中的压力，反应区中的温度，烃的进料速率来获得并保持在操作温度下的单相 ，溶剂的进料速率，加水的进料速率，催化剂的进料速率等参数。 还公开了方法和装置，其中烃在稳定状态下与气态氧化剂反应以在液体混合物中形成酸。 水的量保持在最大水位之间，其中基本上单个液相的最大水平转变为两个液相，以及催化剂沉淀的最低水平。 此外，公开了一种方法，其中混合物的温度降低到固体二元酸沉淀的点，同时保持单一液相，以及任选地所有催化剂在溶液中。 然后除去形成的酸的至少一部分。 优选的烃是环己烷，优选的酸是己二酸，优选的溶剂是乙酸，优选的催化剂是乙酸钴（II）四水合物。

公开(公告)号：US06307100B1

公开(公告)日：2001-10-23

申请号：US09642496

申请日：2000-08-18

申请人： David Richardson ,  Cheng Xu ,  Khalil Abboud ,  Garry K. Weakley

发明人： David Richardson ,  Cheng Xu ,  Khalil Abboud ,  Garry K. Weakley

IPC分类号： C07C5131

CPC分类号： C07C51/31 ,  B01J31/182 ,  B01J2531/821 ,  B01J2531/842 ,  C07C51/313 ,  C07C55/14

摘要： Disclosed are catalysts useful for catalyzing the synthesis of adipic acid from cyclohexane and oxygen. Also disclosed are methods of making the catalysts, methods of using the catalysts to catalyze the production of adipic acid from cyclohexane and oxygen, and kits containing the catalysts.

公开(公告)号：US06833473B1

公开(公告)日：2004-12-21

申请号：US09270480

申请日：1999-03-15

申请人： Markku Ahotupa

发明人： Markku Ahotupa

IPC分类号： C07C5131

CPC分类号： G01N33/491 ,  G01N33/92 ,  G01N2800/044

摘要： Kits are provided for use in the screening of the risk for, the diagnosis, management and research of atherosclerosis and coronary heart disease comprising means for isolating LDL from a serum or plasma sample for the preparation of a LDL fraction, and means for separating the lipids from the LDL fraction to obtain a lipid fraction. The kit can further include a means for use in the determination of the level of conjugated dienes (LDL-BDC) in the lipid fraction. The invention also relates to a kit for in the above mentioned purpose including means for isolating LDL from a serum or plasma sample for the preparation of a LDL fraction, and means for use in the determination of the antioxidant potential of LDL in the sample. The invention further provides a kit for use in the above mentioned purpose including means for isolating LDL from a serum or plasma sample for the preparation of a LDL fraction, means for separating the lipids from the LDL fraction to obtain a lipid fraction, means for use determination of LDL-BDC in the lipid fraction, and means for use in the determination of the antioxidant potential of LDL in the sample. Additional kits and improved methods for analysis of LDL-BDC and/or LDL-TRAP are provided.

摘要翻译： 用于筛选动脉粥样硬化和冠心病的风险，诊断，管理和研究的试剂盒包括用于从用于制备LDL级分的血清或血浆样品中分离LDL的方法，以及用于分离脂质的方法 从LDL级分获得脂质级分。 试剂盒可以进一步包括用于测定脂质级分中的共轭二烯（LDL-BDC）水平的方法。 本发明还涉及用于上述目的的试剂盒，包括用于从用于制备LDL级分的血清或血浆样品中分离LDL的方法，以及用于测定样品中LDL抗氧化作用的方法。 本发明还提供了用于上述目的的试剂盒，包括用于从用于制备LDL级分的血清或血浆样品中分离LDL的方法，用于从LDL级分分离脂质以获得脂质部分，使用手段 在脂质部分中测定LDL-BDC，以及用于测定样品中LDL抗氧化能力的方法。 提供了额外的试剂盒和改进的LDL-BDC和/或LDL-TRAP分析方法。

公开(公告)号：US06563001B1

公开(公告)日：2003-05-13

申请号：US09787116

申请日：2001-06-12

申请人： Michel Costantini ,  Eric Fache ,  Gilbert Marin

发明人： Michel Costantini ,  Eric Fache ,  Gilbert Marin

IPC分类号： C07C5131

CPC分类号： C07C51/44 ,  C07C51/43 ,  C07C51/487 ,  C07C55/14

摘要： The present invention relates to an improved process for processing the reaction mixture from the direct oxidation of hydrocarbon into carboxylic acid, using molecular oxygen or a gas containing it, in the liquid phase, in a solvent and in the presence of a catalyst dissolved in the reaction medium, characterized in that the said process comprises: when the composition of the reaction mixture allows it, a decantation into two liquid phases: a nonpolar upper phase and a polar lower phase; a distillation of the said lower phase or, where appropriate, of all of the reaction mixture, thus separating, on the one hand, a distillate and, on the other hand, the distillation residue comprising the acids formed, the catalyst, the heavy compounds, at least some of the solvent and, if any, the reaction intermediates and side products; a purification treatment by oxidation, using molecular oxygen or a gas containing it or using oxygen donors, of the distillation residue obtained above, a distillation of the reaction solvent and the reaction intermediates and side products which may still remain in the mixture, a crystallization of the carboxylic acid produced in the reaction; a recrystallization from water of the carboxylic acid produced in the reaction.

摘要翻译： 本发明涉及一种改进的方法，用于在液相中，在溶剂中和在溶解在该溶剂中的催化剂存在下，使用分子氧或含有它的气体将烃直接氧化成羧酸， 反应介质，其特征在于所述方法包括：当反应混合物的组成允许时，倾析成两个液相：非极性上相和极性下相;所述下相的蒸馏，或在适当的情况下， 一方面分离出馏出物，另一方面，分离形成的酸的蒸馏残渣，催化剂，重质化合物，至少一些溶剂，如果有的话， 反应中间体和副产物;通过氧化，使用分子氧或含有它或使用氧供体的气体，上述获得的蒸馏残渣进行纯化处理，蒸馏o 反应溶剂和反应中间体和副产物，它们仍然残留在混合物中，结晶反应中产生的羧酸;从反应中产生的羧酸的水中重结晶。

公开(公告)号：US06235932B1

公开(公告)日：2001-05-22

申请号：US09392460

申请日：1999-09-09

申请人： Sanjib Mall ,  Sreeramagiri Siva Kumar

发明人： Sanjib Mall ,  Sreeramagiri Siva Kumar

IPC分类号： C07C5131

CPC分类号： C07C51/44 ,  C07C51/313 ,  C07C51/43 ,  C07C51/48 ,  C07C55/14

摘要： The present invention relates to one-step oxidation process for preparation of cyclohexane to adipic acid, using molecular oxygen, in liquid phase, in the presence of catalyst, containing either cobalt or cobalt and iron. The catalyst is activated outside the reactor and molecular oxygen is used as an oxidant. The use of molecular oxygen as oxidant along with preactivated catalyst in the reactor and also by restricting the conversion of cyclohexane between 20-30% with catalyst in the reactor results in enhanced selectivity to adipic acid. The reaction mixture of cyclohexane and preactivated catalyst is subjected to oxidation by bubbling pure molecular oxygen while stirring the homogenous mixture while bubbling the oxygen at a predetermined temperature, pressure and space velocity conditions. The product selectivity to form adipic acid is found to be at least 5% better than the maximum attainable using the conventional processes.

摘要翻译： 本发明涉及在含有钴或钴和铁的催化剂存在下，使用分子氧在液相中制备环己烷至己二酸的一步氧化方法。 催化剂在反应器外活化，分子氧用作氧化剂。 在反应器中使用分子氧作为氧化剂以及预活化催化剂，并且通过限制反应器中催化剂与环己烷在20-30％之间的转化率可以提高对己二酸的选择性。 通过在预定的温度，压力和空间速度条件下鼓泡氧气同时搅拌均匀混合物，鼓泡纯分子氧，使环己烷和预活化催化剂的反应混合物进行氧化。 发现形成己二酸的产物选择性比使用常规方法可达到的最大值至少高5％。

公开(公告)号：US06787669B1

公开(公告)日：2004-09-07

申请号：US09623414

申请日：2000-11-08

申请人： Michel Costantini ,  Eric Fache ,  Philippe Leconte

发明人： Michel Costantini ,  Eric Fache ,  Philippe Leconte

IPC分类号： C07C5131

CPC分类号： C07C51/44 ,  C07C51/42 ,  C07C51/43 ,  C07C51/487 ,  C07C55/14

摘要： The present invention relates to the treatment of the reaction mixtures resulting from an oxidation reaction of cyclohexane to adipic acid and more particlarly to the separation of the various constituents of the said mixtures and to the purification of the adipic acid.

摘要翻译： 本发明涉及由环己烷与己二酸的氧化反应产生的反应混合物的处理，更特别涉及分离所述混合物的各种成分和己二酸的纯化。