公开(公告)号：US08552238B2

公开(公告)日：2013-10-08

申请号：US13863722

申请日：2013-04-16

Applicant: James R. Butler ,  Xin Xiao ,  James T. Merrill

Inventor： James R. Butler ,  Xin Xiao ,  James T. Merrill

IPC: C07C2/66

CPC classification number: C07C2/66 ,  B01J29/06 ,  B01J29/7057 ,  B01J2219/00006 ,  C07C6/126 ,  C07C7/12 ,  C07C15/073 ,  C07C2529/08 ,  C07C2529/70 ,  Y02P20/52 ,  Y02P20/584 ,  Y02P20/588 ,  C07C15/04

Abstract: Alkylation systems and methods of minimizing alkylation catalyst regeneration are described herein. The alkylation systems generally include a preliminary alkylation system adapted to receive an input stream including an alkyl aromatic hydrocarbon and contact the input stream with a preliminary alkylation catalyst disposed therein to form a first output stream. The preliminary alkylation catalyst generally includes a zeolite catalyst having a SiO2/Al2O3 ratio of less than about 25. The alkylation systems further include a first alkylation system adapted to receive the first output stream and contact the first output stream with a first alkylation catalyst disposed therein and an alkylating agent to form a second output stream.

Abstract translation: 本文描述了使烷基化催化剂再生最小化的烷基化系统和方法。 烷基化系统通常包括适于接收包含烷基芳族烃的输入流并将输入流与设置在其中的预置烷基化催化剂接触以形成第一输出流的初步烷基化系统。 初步烷基化催化剂通常包括SiO 2 / Al 2 O 3比小于约25的沸石催化剂。烷基化系统还包括适于接收第一输出流并将第一输出流与置于其中的第一烷基化催化剂接触的第一烷基化系统 和烷基化剂以形成第二输出流。

公开(公告)号：US07507385B2

公开(公告)日：2009-03-24

申请号：US10874887

申请日：2004-06-23

Applicant: James R. Butler ,  James T. Merrill ,  Adrian M. Jacobsen

Inventor： James R. Butler ,  James T. Merrill ,  Adrian M. Jacobsen

IPC: B01J1/00

CPC classification number: C07C5/333 ,  B01F5/06 ,  B01J8/0292 ,  B01J8/0453 ,  B01J8/065 ,  B01J2208/00061 ,  B01J2208/00212 ,  B01J2208/00548 ,  B01J2208/0084 ,  B01J2208/00849 ,  Y10S585/922 ,  Y10S585/923 ,  Y10S585/924 ,  C07C15/44 ,  C07C15/46

Abstract: Process for the catalytic dehydrogenation of a C2 or C3 alkyl aromatic in which a feedstock containing the alkyl aromatic and steam is supplied into the inlet of a tubular reactor containing a dehydrogenation catalyst. Within the reactor, the feedstock flows through at least a portion of the reactor along a spiral flow path extending longitudinally of the reactor. The resulting vinyl aromatic product is then recovered from a downstream or outlet section of the reactor. The spiral flow path through which the feedstock is passed is located at least adjacent the inlet side of the reactor and at least a portion of the spiral flow path contains a particulate dehydrogenation catalyst. The spiral flow path may extend throughout a major portion of the elongated tubular reactor and may contain a particulate dehydrogenation catalyst in a substantial portion there. The feedstock containing the alkyl aromatic and steam is supplied into a plurality of tubular reactors located within the interior of a dehydrogenation reactor vessel and is arranged in a parallel relationship in which the tubular reactors are spaced laterally from one another and from the interior wall of the reaction vessel.

公开(公告)号：US06864399B2

公开(公告)日：2005-03-08

申请号：US10193792

申请日：2002-07-12

Applicant: James T. Merrill ,  James R. Butler

Inventor： James T. Merrill ,  James R. Butler

IPC: B01J29/70 ,  C07C2/66

CPC classification number: B01J29/7007 ,  B01J2229/42 ,  C07C2/66 ,  C07C2521/08 ,  C07C2529/70 ,  Y02P20/544 ,  Y02P20/584 ,  C07C15/073

Abstract: The alkylation of benzene-containing feedstock over a zeolite beta alkylation catalyst which is formulated with a silica binder and has an average regeneration coefficient of at least 95% for at least three regenerations. The alkylation reaction is carried out in the liquid phase or supercritical region with a C2-C4 alkylating agent, specifically ethylene. The catalyst exhibits a regeneration coefficient of at least 95% after ethylation of the benzene with ethylene at a benzene/ethylene mole ratio of less than 10. The ethylation of benzene occurs at an initial designated primary activity. The operation of the reaction zone is continued until the activity of the catalyst for the ethylation of benzene decreases by a value of at least 0.1% and not more 1% from the initial designated primary activity. The operation of the reaction for alkylation is terminated and a regeneration procedure is instituted in which the catalyst is regenerated in an oxidizing environment at an average temperature of no more than 500° C. At the conclusion of the regeneration procedure, the operation of the alkylation zone is reinstituted with the reaction zone again operated under conditions as described above followed by regeneration.

Abstract translation: 在沸石β烷基化催化剂上的含苯原料的烷基化，其用二氧化硅粘合剂配制，并且对至少三次再生具有至少95％的平均再生系数。 烷基化反应在液相或超临界区域用C2-C4烷基化剂，特别是乙烯进行。 苯与乙烯在苯/乙烯摩尔比小于10的乙醚化后，催化剂表现出至少95％的再生系数。苯的乙基化发生在初始指定的主要活性。 反应区的操作继续进行，直到苯的乙基化催化剂的活性从初始指定的主要活性降低至少0.1％且不超过1％的值。 终止烷基化反应的操作，并且在不超过500℃的平均温度下在氧化环境中再生催化剂的再生步骤。在再生过程结束时，烷基化操作 区域被重新配置，反应区域再次在如上所述的条件下操作，随后再生。

公开(公告)号：US06222084B1

公开(公告)日：2001-04-24

申请号：US09289488

申请日：1999-04-09

Applicant: Ashim Kumar Ghosh ,  James T. Merrill ,  James R. Butler

Inventor： Ashim Kumar Ghosh ,  James T. Merrill ,  James R. Butler

IPC: C07C266

CPC classification number: C07C15/073 ,  C07C2/66 ,  C07C2529/08 ,  C07C2529/40

Abstract: Process for the production of ethylbenzene by alkylation over a silicalite alkylation catalyst with subsequent transalkylation of diethylbenzene with the alkylation catalyst and conditions selected to retard xylene production and also heavies production. Benzene and ethylene are applied to a multi-stage alkylation reaction zone having a plurality of series-connected catalyst beds containing silicalite of a predominantly monoclinic symmetry having a silica/alumina ratio of at least 275. Gas-phase ethylation of benzene is at a flow rate to provide a space velocity of benzene over the catalyst to produce a xylene concentration of about 600 ppm or less of the ethylbenzene content. Periodically the space velocity may be increased to a value which is greater than the space velocity associated with a minimum concentration of diethylbenzene in the alkylation product such that diethylbenzene production is enhanced while minimizing any attendant transalkylation reactions within the alkylation reaction zone. The alkylation reactor output is applied to an intermediate recovery zone for the separation and recovery of ethylbenzene with the recovery of a polyalkylated aromatic component which is supplied along with benzene to a transalkylation reaction zone for disproportionation to provide a reduced diethylbenzene content and an enhanced ethylbenzene content. A specific monoclinic silicalite alkylation catalyst has a silica/alumina ratio of at least 300 and has a crystal size of less than one micron.

Abstract translation: 通过在硅沸石烷基化催化剂上烷基化生产乙苯的方法，随后用烷基化催化剂对二乙基苯进行烷基转移和选择用于延迟二甲苯生产和重质生产的条件。 苯和乙烯被施加到多级烷基化反应区，该多级烷基化反应区具有多个串联连接的催化剂床，该催化剂床含有主要单斜对称的硅沸石，其二氧化硅/氧化铝比至少为275.苯的气相乙基化处于流动 速率以提供苯在催化剂上的空速，以产生约600ppm或更少的乙苯含量的二甲苯浓度。 定期地，空间速度可以增加到大于与烷基化产物中的二乙基苯的最小浓度相关联的空间速度的值，使得二苯基产生增强，同时最小化在烷基化反应区内的任何伴随的烷基转移反应。 将烷基化反应器输出应用于中间回收区，用于分离和回收乙苯，回收与苯一起供应的多烷基化芳族组分至用于歧化的烷基转移反应区，以提供还原的二乙苯含量和增强的乙苯含量 。 特定的单斜硅沸石烷基化催化剂具有至少300的二氧化硅/氧化铝比例，其晶体尺寸小于1微米。

公开(公告)号：US6057485A

公开(公告)日：2000-05-02

申请号：US193310

申请日：1998-11-17

Applicant: James T. Merrill ,  James R. Butler ,  Ashim Kumar Ghosh

Inventor： James T. Merrill ,  James R. Butler ,  Ashim Kumar Ghosh

IPC: B01J29/06 ,  C07B61/00 ,  C07C2/66 ,  C07C15/073 ,  C07C1/00 ,  C07C2/64 ,  C07C2/68

CPC classification number: C07C15/073 ,  C07C2/66 ,  C07C2529/035 ,  C07C2529/08

Abstract: Ethylbenzene is produced by alkylation over a split load of monoclinic silicalite alkylation catalysts having different silica/alumina ratios. A feedstock containing benzene and ethylene is applied to a multi-stage alkylation reaction zone having a plurality of series-connected catalyst beds. At least one catalyst bed contains a first monoclinic silicalite catalyst having a silica/alumina ratio of at least 275. At least one other catalyst bed contains a second monoclinic silicalite catalyst having a silica/alumina ratio of less than about 275. The alkylation reaction zone is operated at temperature and pressure conditions in which the benzene is in a gaseous phase to cause gas-phase alkylation of the aromatic substrate in the presence of the monoclinic silicalite catalysts to produce an alkylation product. The alkylation product is then withdrawn from the reaction zone for separation and recovery. The use of the split load of catalyst allows a higher purity ethylbenzene product to be produced at improved efficiencies than if only one of the catalysts were used by itself.

Abstract translation: 通过在具有不同二氧化硅/氧化铝比的单斜晶硅沸石烷基化催化剂的分裂负载下烷基化来制备乙苯。 将含有苯和乙烯的原料施加到具有多个串联催化剂床的多级烷基化反应区。 至少一个催化剂床含有二氧化硅/氧化铝比至少为275的第一单斜晶硅沸石催化剂。至少一个其它催化剂床含有二氧化硅/氧化铝比小于约275的第二单斜硅沸石催化剂。烷基化反应区 在其中苯处于气相的温度和压力条件下操作，以在单斜硅沸石催化剂的存在下引起芳族底物的气相烷基化以产生烷基化产物。 然后将烷基化产物从反应区取出以进行分离和回收。 与仅使用一种催化剂本身一起使用的催化剂的分离负载的使用允许以提高的效率生产更高纯度的乙苯产物。

公开(公告)号：US06897346B1

公开(公告)日：2005-05-24

申请号：US09329502

申请日：1999-06-10

Applicant: James T. Merrill ,  James R. Butler

Inventor： James T. Merrill ,  James R. Butler

IPC: C07C2/66 ,  C07B61/00 ,  C07C6/12 ,  C07C15/073 ,  C07C15/107

CPC classification number: C07C6/126 ,  C07C15/073 ,  C07C2529/40

Abstract: A process for the transalkylation of polyalkylated aromatic compounds over a high porosity zeolite-Y molecular sieve having a surface area of no more than 500 m2/g. A feedstock comprising a polyalkylated aromatic component, including polyalkylbenzenes in which the predominant alkyl substituents contain from 2 to 4 carbon atoms, is supplied to a transalkylation reaction zone containing the high porosity zeolite-Y catalyst. Benzene is also supplied to the transalkylation zone, and the reaction zone is operated under temperature and pressure conditions to maintain the polyalkylated aromatic component in the liquid phase and which are effective to cause disproportionation of the polyalkylated aromatic component to arrive a disproportionation product having a reduced polyalkylbenzene content and an enhanced monoalkylbenzene content. An alkylation reaction zone is provided which contains a molecular sieve aromatic alkylation catalyst having an average pore size which is less than the average pore size of the average pore size of the high porosity zeolite-Y. A feedstock comprising benzene in a C2-C4 alkylating agent is supplied to the alkylation reaction zone which is operated under conditions to produce alkylation of the benzene by the alkylating agent in the presence of the molecular sieve alkylation catalyst. The alkylation product from the alkylation reaction zone is supplied to an intermediate recovery zone for the separation and recovery of a monoalkylbenzene, e.g. ethylbenzene, from the alkylation product; together with the recovery of a polyalkylated aromatic component employing a dialkylbenzene, e.g. diethylbenzene. The polyalkylated aromatic component is employed in at least a portion of the feedstream supplied to the transalkylation reactor.

Abstract translation: 在多孔烷基化芳族化合物在表面积不超过500m 2 / g的高孔隙率沸石-Y分子筛上烷基转移的方法。 包含多烷基化芳族组分的原料被供应到包含高孔隙率沸石-Y催化剂的烷基转移反应区，包括其中主要烷基取代基含有2至4个碳原子的聚烷基苯。 苯也被供应到烷基转移区，并且反应区在温度和压力条件下操作以将多烷基化芳族组分保持在液相中，并且有效地引起多烷基化芳族组分的歧化，以得到具有减少的歧化产物 多烷基苯含量和增强的单烷基苯含量。 提供烷基化反应区，其含有平均孔径小于高孔隙率沸石-Y的平均孔径的平均孔径的分子筛芳族烷基化催化剂。 将包含C 2 -C 4烷基化剂中的苯的原料供给到烷基化反应区，该烷基化反应区在烷基化试剂生成苯烷基化的条件下操作 存在分子筛烷基化催化剂。 来自烷基化反应区的烷基化产物被供应到中间回收区，用于分离和回收单烷基苯，例如。 乙基苯，来自烷基化产物; 以及采用二烷基苯的多烷基化芳族组分的回收。 二乙基苯。 多烷基化芳族组分用于供应至烷基转移反应器的进料流的至少一部分。

公开(公告)号：US06376729B1

公开(公告)日：2002-04-23

申请号：US09729032

申请日：2000-12-04

Applicant: James T. Merrill ,  James R. Butler

Inventor： James T. Merrill ,  James R. Butler

IPC: C07C266

CPC classification number: C07C15/073 ,  C07C2/66 ,  C07C2529/035 ,  C07C2529/08 ,  C07C2529/70 ,  Y02P20/544

Abstract: A process for the production of ethylbenzene by the gas phase alkylation of benzene over a molecular sieve aromatic alkylation catalyst followed by liquid phase alkylation of the product of the gas phase alkylation. A feedstock containing benzene and ethylene is supplied to a first alkylation reaction zone containing a molecular sieve aromatic alkylation catalyst. The reaction zone is operated at temperature and pressure conditions to cause gas phase ethylation of the benzene with the production of an alkylation product comprising a mixture of ethylbenzene and polyalkylated aromatic components including diethylbenzene. The output from the first alkylation reaction zone is supplied, at least in part, to a second alkylation zone which is operated in the liquid phase or in the supercritical region followed by supply to an intermediate recovery zone for the separation and recovery of ethylbenzene and a polyalkylated aromatic compound component including diethylbenzene.

Abstract translation: 通过在分子筛芳族烷基化催化剂上苯气相烷基化生产乙苯的方法，随后气相烷基化产物的液相烷基化。 将含有苯和乙烯的原料供给到含有分子筛芳烃烷基化催化剂的第一烷基化反应区。 反应区在温度和压力条件下操作，以产生包含乙苯和多烷基化芳族组分（包括二乙基苯）的混合物的烷基化产物的苯气相乙基化。 第一烷基化反应区的输出至少部分地供应到在液相或超临界区域中操作的第二烷基化区，然后供应到用于分离和回收乙苯的中间回收区和 多烷基化芳族化合物组分，包括二乙基苯。

公开(公告)号：US06268542B1

公开(公告)日：2001-07-31

申请号：US09378819

申请日：1999-08-23

Applicant: James T. Merrill ,  James R. Butler

Inventor： James T. Merrill ,  James R. Butler

IPC: C07C266

CPC classification number: C07C15/073 ,  C07C2529/035 ,  C07C2529/08 ,  C07C2529/70 ,  Y02P20/52

Abstract: A process for the production of ethylbenzene by the alkylation of benzene over a molecular sieve aromatic alkylation catalyst followed by transalkylation of polyalkylated aromatic components and then liquid phase alkylation. A feedstock containing benzene and ethylene is supplied to a first alkylation reaction zone containing a molecular sieve aromatic alkylation catalyst. The reaction zone is operated at temperature and pressure conditions to cause gas phase ethylation of the benzene with the production of an alkylation product comprising a mixture of ethylbenzene and polyalkylated aromatic components including diethylbenzene with xylene present in only small amounts. The output from the alkylation reaction zone is supplied to an intermediate recovery zone for the separation and recovery of ethybenzene, a polyalkylated aromatic compound component including diethylbenzene. At least a portion of the polyalkylated component is supplied along with benzene to a transalkylation reaction zone operated in the liquid phase. Disproportionation product from the transalkylaton reaction zone is supplied to a second alkylation zone containing a molecular sieve aromatic alkylation catalyst. Ethylene is also supplied to the second alkylation zone which is operated under temperature and pressure conditions to cause liquid phase ethylation of the benzene. The alkylation product from the second alkylation zone is supplied to the aforementioned intermediate recovery zone.

Abstract translation: 一种通过在分子筛芳族烷基化催化剂上烷基化苯然后经多烷基化芳族组分的烷基转移然后进行液相烷基化来生产乙苯的方法。 将含有苯和乙烯的原料供给到含有分子筛芳族烷基化催化剂的第一烷基化反应区。 反应区在温度和压力条件下操作，以产生包含乙苯和多烷基化芳族组分（包括二乙基苯）与二甲苯的混合物的烷基化产物的气相乙基化，其中二甲苯仅以少量存在。 将烷基化反应区的输出物供应到中间回收区，用于分离和回收乙苯，包括二乙基苯的多烷基化芳族化合物组分。 至少一部分多烷基化组分与苯一起供应到在液相中操作的烷基转移反应区。 来自转烷基转移反应区的歧化产物供给含有分子筛芳族烷基化催化剂的第二烷基化区。 乙烯也被供给到在温度和压力条件下操作以引起苯的液相乙基化的第二烷基化区。 将来自第二烷基化区的烷基化产物供给到上述中间回收区。

公开(公告)号：US5847255A

公开(公告)日：1998-12-08

申请号：US861206

申请日：1997-05-21

Applicant: Ashim Kumar Ghosh ,  James T. Merrill ,  James R. Butler

Inventor： Ashim Kumar Ghosh ,  James T. Merrill ,  James R. Butler

IPC: B01J29/40 ,  B01J29/08 ,  C07B61/00 ,  C07C2/66 ,  C07C6/12 ,  C07C15/073

CPC classification number: C07C15/073 ,  B01J29/084 ,  C07C2/66 ,  C07C2529/035 ,  C07C2529/08 ,  C07C2529/40 ,  Y02P20/52

Abstract: Process for the production of ethylbenzene by alkylation over a silicalite alkylation catalyst with the subsequent transalkylation of diethylbenzene with the alkylation catalyst and conditions selected to retard xylene production and also heavies production. A feedstock containing benzene and ethylene is applied to a multi-stage alkylation reaction zone having a plurality of series-connected catalyst beds containing a pentasil molecular sieve alkylation catalyst which is silicalite of a predominantly monoclinic symmetry having a silica/alumina ratio of at least 275. The feedstock is supplied to the alkylation reaction zone to cause gas-phase ethylation of benzene at a flow rate to provide a space velocity of benzene over the catalyst to produce a xylene concentration in the product of about 600 ppm or less based upon the ethylbenzene content. Periodically the space velocity may be increased to a value which is greater than the space velocity associated with a minimum concentration of diethylbenzene in the alkylation product such that diethylbenzene production is enhanced while minimizing any attendant transalkylation reactions within the alkylation reaction zone. This is accompanied by a relatively low xylene content in the product, specifically no more than 600 ppm based upon the ethylbenzene in the product. The output from the alkylation reactor is applied to an intermediate recovery zone for the separation and recovery of ethylbenzene with the recovery of a polyalkylated aromatic component which is supplied along with benzene to a transalkylation reaction zone where the polyalkylated aromatic fraction is subject to disproportionation to provide a reduced diethylbenzene content and an enhanced ethylbenzene content.

Abstract translation: 通过在硅沸石烷基化催化剂上烷基化制备乙苯的方法，随后使用烷基化催化剂对二乙基苯进行烷基转移和选择用于延迟二甲苯生产和重质生产的条件。 将含有苯和乙烯的原料施加到多级烷基化反应区，该多段烷基化反应区具有多个串联连接的催化剂床，该催化剂床含有pentasil分子筛烷基化催化剂，其为主要单斜对称的硅沸石，二氧化硅/氧化铝比为至少275 将原料供应到烷基化反应区，以使流速进行苯的气相乙基化，以提供苯在催化剂上的空速，以产生基于乙苯约600ppm或更低的产物中的二甲苯浓度 内容。 定期地，空间速度可以增加到大于与烷基化产物中的二乙基苯的最小浓度相关联的空间速度的值，使得二苯基产生增强，同时最小化在烷基化反应区内的任何伴随的烷基转移反应。 这伴随产物中相对较低的二甲苯含量，特别是不超过600ppm，基于产物中的乙苯。 将烷基化反应器的输出应用于中间回收区，用于分离和回收乙苯，回收与苯一起供给的烷基化芳族组分到烷基转移反应区，其中多烷基化芳族部分经过歧化以提供 二乙苯含量降低，乙苯含量增加。

公开(公告)号：US20130225888A1

公开(公告)日：2013-08-29

申请号：US13863722

申请日：2013-04-16

Applicant: James R. Butler ,  Xin Xiao ,  James T. Merrill

Inventor： James R. Butler ,  Xin Xiao ,  James T. Merrill

IPC: C07C2/66

CPC classification number: C07C2/66 ,  B01J29/06 ,  B01J29/7057 ,  B01J2219/00006 ,  C07C6/126 ,  C07C7/12 ,  C07C15/073 ,  C07C2529/08 ,  C07C2529/70 ,  Y02P20/52 ,  Y02P20/584 ,  Y02P20/588 ,  C07C15/04

Abstract: Alkylation systems and methods of minimizing alkylation catalyst regeneration are described herein. The alkylation systems generally include a preliminary alkylation system adapted to receive an input stream including an alkyl aromatic hydrocarbon and contact the input stream with a preliminary alkylation catalyst disposed therein to form a first output stream. The preliminary alkylation catalyst generally includes a zeolite catalyst having a SiO2/Al2O3 ratio of less than about 25. The alkylation systems further include a first alkylation system adapted to receive the first output stream and contact the first output stream with a first alkylation catalyst disposed therein and an alkylating agent to form a second output stream.

Abstract translation: 本文描述了使烷基化催化剂再生最小化的烷基化系统和方法。 烷基化系统通常包括适于接收包含烷基芳族烃的输入流并将输入流与设置在其中的预置烷基化催化剂接触以形成第一输出流的初步烷基化系统。 初步烷基化催化剂通常包括SiO 2 / Al 2 O 3比小于约25的沸石催化剂。烷基化系统还包括适于接收第一输出流并将第一输出流与置于其中的第一烷基化催化剂接触的第一烷基化系统 和烷基化剂以形成第二输出流。