公开(公告)号：US06433220B1

公开(公告)日：2002-08-13

申请号：US09345572

申请日：1999-06-30

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

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

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 extracting the catalyst from the reaction mixture, outside the reaction zone. Substantially all the unreacted cyclohexane, the majority of adipic acid, and preferably substantially all the monobasic acid solvent are removed from the reaction product. In the case that substantially all the monobasic acid solvent is removed, protic solvent, is added intermittently or continuously in the reaction mixture during the removal of the monobasic acid solvent, preferably by distillation, thus preventing solids precipitation. Dipolar aprotic solvent is then added in the presence of an adequate amount of the protic solvent (the total of dipolar aprotic solvent and the protic solvent constituting a novel combination solvent) to maintain a single liquid phase, followed by a step of extracting substantially all the catalyst in protic solvent. The catalyst extract is preferably recycled to the reaction zone, where the cyclohexane is oxidized to adipic acid. Thus, the novel combination solvent, which is preferably a combination of cyclohexanone with water, allows the dissolution of the reaction product, preferably after removal of the majority of the adipic acid, followed by a substantially complete extraction of the catalyst in water. No catalyst precipitation takes place, and all disadvantages and costs of solids handling are prevented.

摘要翻译： 本发明涉及在一元酸溶剂存在下，通过在反应区外反萃取催化剂，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，优选基本上全部的一元酸溶剂从反应产物中除去。 在去除基本上所有的一元酸溶剂的情况下，优选通过蒸馏除去一元酸溶剂，在反应混合物中间歇地或连续地添加质子性溶剂，从而防止固体沉淀。 然后在足够量的质子溶剂（总计偶极非质子溶剂和构成新的组合溶剂的质子溶剂）的存在下加入偶极非质子溶剂以维持单一的液相，随后将基本上所有的 催化剂在质子溶剂中。 催化剂提取物优选循环至反应区，其中环己烷被氧化成己二酸。 因此，优选环己酮与水的组合的新型组合溶剂允许反应产物溶解，优选在除去大部分己二酸之后，然后在水中基本上完全提取催化剂。 没有发生催化剂沉淀，并且防止了固体处理的所有缺点和成本。

公开(公告)号：US6129875A

公开(公告)日：2000-10-10

申请号：US245156

申请日：1999-02-04

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

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

IPC分类号： C07C51/43 ,  C07C51/16 ,  C07C51/31 ,  C07C55/02 ,  C07C55/14 ,  D01D1/02 ,  D01D5/08 ,  D01F13/00

CPC分类号： C07C51/313

摘要： This invention relates to methods for controlling the oxidation of hydrocarbons to dibasic acids, in the presence of a catalyst and a monobasic acid, by removing the catalyst from the reaction mixture, outside the oxidation zone, after the oxidation has taken place at least partially. Initially, the catalyst is partially precipitated and removed by reducing the water level in the reaction mixture and/or subjecting the reaction mixture to a temperature, at which or over which catalyst precipitates. After the initial partial precipitation of the catalyst, the remaining catalyst is subjected to a thermal treatment, during which at least part of the monobasic acid is removed leaving behind molten dibasic acids, in which, at least a major part of the remaining catalyst is precipitated, and it is removed. A minor part of remaining catalyst is removed by methods, which include but are not limited to ion exchange, precipitation with a base or appropriate salt, and electrodialysis. The precipitated catalyst in the three removal stages may be recycled in miscellaneous ways. The dibasic acid(s) may be removed at least partially before or after any catalyst precipitation stage.

摘要翻译： 本发明涉及在催化剂和一元酸的存在下，通过在至少部分氧化发生氧化区之后从反应混合物外部除去催化剂来控制烃类二元酸的氧化的方法。 最初，通过降低反应混合物中的水位和/或使反应混合物达到催化剂沉淀的温度，部分沉淀和除去催化剂。 在催化剂的初始部分沉淀之后，对剩余的催化剂进行热处理，其中除去至少部分一元酸，留下熔融二元酸，其中至少大部分剩余的催化剂沉淀 ，并被删除。 通过方法除去剩余催化剂的一小部分，其包括但不限于离子交换，用碱或适当的盐沉淀和电渗析。 三个去除阶段中的沉淀催化剂可以以各种方式回收。 在任何催化剂沉淀阶段之前或之后，可以至少部分去除二元酸。

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：US06417128B1

公开(公告)日：2002-07-09

申请号：US09551938

申请日：2000-04-19

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

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

IPC分类号： B01J2034

CPC分类号： C07C51/313 ,  C07C55/14

摘要： This invention relates to methods of replacing water and cyclohexanone with acetic acid in an aqueous solution of catalyst, preferably a cobalt compound. Such an aqueous solution is produced by extracting catalyst with water from a cyclohexanone/water solution of reaction products made by the direct oxidation of cyclohexane to adipic acid. The replacement of both water and cyclohexanone are conducted in a solvent exchange column, wherein acetic acid dissolves the catalyst, while water vapors force the cyclohexanone into a condenser, followed by a decanter wherein two liquid phases may be formed and separated; an upper liquid phase containing a majority of cyclohexanone and a lower liquid phase containing a majority of water. The cyclohexanone may be removed in a pretreatment zone, wherein also part of the water may be removed, before the concentrated catalyst extract enters the solvent exchange column.

摘要翻译： 本发明涉及在催化剂，优选钴化合物的水溶液中用乙酸代替水和环己酮的方法。 通过用环己酮/环己酮/水溶液将环己酮直接氧化成己二酸制成的反应产物的水提取催化剂来制备这种水溶液。 水和环己酮两者的替代物在溶剂交换柱中进行，其中乙酸溶解催化剂，而水蒸汽迫使环己酮进入冷凝器，接着是沉淀器，其中可以形成和分离两个液相; 含有大部分环己酮的上部液相和含有大部分水的较低液相。 在浓缩的催化剂萃取物进入溶剂交换塔之前，可以在预处理区中除去环己酮，其中也可以除去部分水。

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：US06326455B2

公开(公告)日：2001-12-04

申请号：US09827656

申请日：2001-04-05

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： C08G6302

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，催化剂优选主要地，更优选地基本上被还原为化合价 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：US06218573B1

公开(公告)日：2001-04-17

申请号：US09345876

申请日：1999-06-30

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： C07L5131

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 removing the catalyst from the reaction mixture, outside the reaction zone. Substantially all the unreacted cyclohexane along with at least the majority of the monobasic acid solvent are removed. A substantially non-solvent for the catalyst (first constituent), and water are added into the resulting mixture, in such amounts as to maintain one solids-free single liquid phase. This process is highly facilitated in the presence of considerable amounts of adipic acid. The catalyst may then be extracted with water from the solids-free single liquid phase. A water phase containing dissolved catalyst may also be formed by addition of small amounts of a solvent which is substantially non-solvent for the catalyst and substantially non-solvent for the dibasic acids (second constituent), and/or dropping the temperature. Adipic acid may be precipitated after catalyst removal with further addition of second constituent and/or dropping the temperature.

摘要翻译： 本发明涉及通过在反应区外除去反应混合物中的催化剂，在一元酸溶剂存在下，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以及至少大部分一元酸溶剂被除去。 用于催化剂（第一组分）的基本上非溶剂，并且将水加入到所得混合物中，其量保持一个无固体的单液相。 在大量己二酸的存在下，该方法被极大地促进。 然后可以用无水的单一液相的水萃取催化剂。 含有溶解催化剂的水相也可以通过加入少量用于催化剂的基本上非溶剂的溶剂和用于二元酸（第二组分）的基本上非溶剂和/或降低温度来形成。 在除去催化剂后，己二酸可以进一步添加第二成分和/或降低温度而沉淀。

公开(公告)号：US5908589A

公开(公告)日：1999-06-01

申请号：US986505

申请日：1997-12-08

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

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

IPC分类号： C07C51/31 ,  C07C51/42 ,  C07C55/14 ,  C08G63/90 ,  C08G69/46 ,  C08G73/10 ,  D01D1/02 ,  D01D5/08 ,  D01F13/00

CPC分类号： C07C51/313

摘要： This invention relates to methods and reactor devices for controlling the oxidation of hydrocarbons to dibasic acids, in the presence of a catalyst and a monobasic acid, by removing the catalyst from the reaction mixture, outside the oxidation zone, after the oxidation has taken place at least partially. Initially, the catalyst is partially precipitated and removed by reducing the water level in the reaction mixture and/or subjecting the reaction mixture to a temperature, at which or over which catalyst precipitates. After the initial partial precipitation of the catalyst, the mother liquor remaining is subjected to a thermal treatment during which at least the major part of the monobasic acid is removed leaving behind molten dibasic acids, in which the remaining catalyst precipitates substantially in its totality, and it is removed. The precipitated catalyst in the two precipitation stages may be recycled in miscellaneous ways. From the foregoing it will be appreciated that, although specific embodiments of the invention have been described herein for purposes of illustration, various modifications may be made without deviating from the spirit and scope of the invention. Accordingly, the invention is not limited except as by the appended claims.

摘要翻译： 本发明涉及在催化剂和一元酸存在下，通过在氧化区之外从反应混合物中除去催化剂，在氧化发生之后，将烃氧化成二元酸来控制二元酸的方法和反应器装置 最少部分。 最初，通过降低反应混合物中的水位和/或使反应混合物达到催化剂沉淀的温度，部分沉淀和除去催化剂。 在催化剂的初始部分沉淀之后，对剩余的母液进行热处理，在此期间，至少大部分一元酸被除去，留下熔融二元酸，其中剩余的催化剂基本上全部沉淀，以及 它被删除。 两个沉淀阶段中的沉淀催化剂可以以各种方式回收。 从上述可以理解，虽然为了说明的目的在本文中描述了本发明的具体实施例，但是可以在不脱离本发明的精神和范围的情况下进行各种修改。 因此，除了所附权利要求之外，本发明不受限制。

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：US6103933A

公开(公告)日：2000-08-15

申请号：US861180

申请日：1997-05-21

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

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

IPC分类号： B01J10/00 ,  B01J19/00 ,  B01J19/26 ,  C07C51/31 ,  C07C55/14 ,  C07C61/09

CPC分类号： B01J19/26 ,  B01J19/0006 ,  C07C51/313 ,  B01J2219/00058 ,  B01J2219/00065 ,  B01J2219/00069 ,  B01J2219/00164

摘要： Methods for controlling the oxidation rate of a hydrocarbon to an acid by adjusting addition of a rate-modulator are disclosed. In order to control oxidation rate, the ratio of hydrocarbon to rate modulator is appropriately adjusted. Preferably, this ratio is adjusted continually based on feedback relative to oxidation progress parameters. It may be kept substantially constant at steady state conditions of the oxidation, or it may take a path of predetermined values. The rate-modulator preferably comprises a hydrocarbon oxidation initiator.

摘要翻译： 公开了通过调节速率调制器的添加来控制烃与酸的氧化速率的方法。 为了控制氧化速率，适当地调节烃与速率调节剂的比例。 优选地，基于相对于氧化进程参数的反馈来连续地调节该比率。 在氧化的稳态条件下，其可以保持基本恒定，或者可以采取预定值的路径。 速率调节剂优选包含烃氧化引发剂。