公开(公告)号：US07115540B2

公开(公告)日：2006-10-03

申请号：US10669485

申请日：2003-09-24

申请人： Joseph Broun Powell ,  Paul Richard Weider ,  John Frederick Knifton ,  Kevin Dale Allen ,  Lynn Henry Slaugh ,  Juan Pedro Arhancet

发明人： Joseph Broun Powell ,  Paul Richard Weider ,  John Frederick Knifton ,  Kevin Dale Allen ,  Lynn Henry Slaugh ,  Juan Pedro Arhancet

IPC分类号： B01J31/20 ,  B01J31/28 ,  B01J31/16

CPC分类号： B01J31/2471 ,  B01J31/1805 ,  B01J31/1815 ,  B01J31/183 ,  B01J31/20 ,  B01J31/24 ,  B01J31/28 ,  B01J2231/321 ,  B01J2531/025 ,  B01J2531/16 ,  B01J2531/80 ,  B01J2531/82 ,  B01J2531/821 ,  B01J2531/824 ,  B01J2531/828 ,  B01J2531/845 ,  C07C29/16 ,  Y02P20/584 ,  C07C31/205

摘要： This invention is a process for synthesizing aliphatic 1,3-diols in one step by hydroformylation and hydrogenation of oxirane, carbon monoxide, and hydrogen employing a catalyst comprising a cobalt carbonyl compound and a cocatalyst metal compound ligated with a ligand in a ligand to cocatalyst metal atom molar ratio in the range of 0.2:1.0 to 0.6:1.0, optionally in the presence of a promoter, where recovery of product is preferably accomplished via water extraction of a diol rich phase from the bulk reaction mixture. The process modifications can, particularly in combination, be beneficial with respect to product recovery, catalyst recycle, and overall economics of a one-step process for producing aliphatic 1,3-diols.

公开(公告)号：US06660892B2

公开(公告)日：2003-12-09

申请号：US10360302

申请日：2003-02-07

申请人： Joseph Broun Powell ,  Paul Richard Weider ,  John Frederick Knifton ,  Kevin Dale Allen ,  Lynn Henry Slaugh ,  Juan Pedro Arhancet

发明人： Joseph Broun Powell ,  Paul Richard Weider ,  John Frederick Knifton ,  Kevin Dale Allen ,  Lynn Henry Slaugh ,  Juan Pedro Arhancet

IPC分类号： C07C2700

CPC分类号： B01J31/2471 ,  B01J31/1805 ,  B01J31/1815 ,  B01J31/183 ,  B01J31/20 ,  B01J31/24 ,  B01J31/28 ,  B01J2231/321 ,  B01J2531/025 ,  B01J2531/16 ,  B01J2531/80 ,  B01J2531/82 ,  B01J2531/821 ,  B01J2531/824 ,  B01J2531/828 ,  B01J2531/845 ,  C07C29/16 ,  Y02P20/584 ,  C07C31/205

摘要： This invention is a process for synthesizing aliphatic 1,3-diols in one step by hydroformylation and hydrogenation of oxirane, carbon monoxide, and hydrogen employing a catalyst comprising a cobalt carbonyl compound and a cocatalyst metal compound ligated with a ligand in a ligand to cocatalyst metal atom molar ratio in the range of 0.2:1.0 to 0.6:1.0, optionally in the presence of a promoter, where recovery of product is preferably accomplished via water extraction of a diol rich phase from the bulk reaction mixture. The process modifications can, particularly in combination, be beneficial with respect to product recovery, catalyst recycle, and overall economics of a one-step process for producing aliphatic 1,3-diols.

摘要翻译： 本发明是通过使用包含羰基钴化合物的催化剂和与配位体中的配体连接的助催化剂金属化合物进行助催化剂的环氧乙烷，一氧化碳和氢气的加氢甲酰化和氢化来合成脂肪族1,3-二醇的方法 金属原子摩尔比在0.2:1.0至0.6:1.0的范围内，任选地在助催化剂存在下，其中产物的回收优选通过从本体反应混合物中萃取富含二醇的相来完成。 关于产物回收，催化剂再循环以及用于生产脂族1,3-二醇的一步法的总体经济性，方法修饰尤其可以组合地是有益的。

公开(公告)号：US5777182A

公开(公告)日：1998-07-07

申请号：US703295

申请日：1996-08-26

申请人： Joseph Broun Powell ,  Lynn Henry Slaugh ,  Thomas Clayton Forschner ,  Jiang-Jen Lin ,  Terry Blane Thomason ,  Paul Richard Weider ,  Thomas Carl Semple ,  Juan Pedro Arhancet ,  Howard Lam-Ho Fong ,  Stephen Blake Mullin ,  Kevin Dale Allen ,  David Cleve Eubanks ,  David William Johnson

发明人： Joseph Broun Powell ,  Lynn Henry Slaugh ,  Thomas Clayton Forschner ,  Jiang-Jen Lin ,  Terry Blane Thomason ,  Paul Richard Weider ,  Thomas Carl Semple ,  Juan Pedro Arhancet ,  Howard Lam-Ho Fong ,  Stephen Blake Mullin ,  Kevin Dale Allen ,  David Cleve Eubanks ,  David William Johnson

IPC分类号： C07C29/141 ,  C07C45/58 ,  C07C45/80 ,  C07C27/04

CPC分类号： C07C45/58 ,  C07C29/141 ,  C07C45/80

摘要： 1,3-propanediol is prepared in a process which involves hydroformylating ethylene oxide: (a) in an essentially non-water-miscible solvent in the presence of a non-ligated cobalt catalyst and a catalyst promoter at a temperature within the range of about 50.degree. to about 100.degree. C. and a pressure within the range of about 500 to about 5000 psig, to produce an intermediate product mixture comprising less than about 15 wt % 3-hydroxypropanal; (b) adding an aqueous liquid and extracting at a temperature less than about 100.degree. C. the 3-hydroxypropanal to provide an aqueous phase comprising 3-hydroxypropanal in greater concentration than the concentration of 3-hydroxypropanal in said intermediate product mixture, and an organic phase comprising the cobalt catalyst; (c) separating the aqueous phase from the organic phase; (d) hydrogenating the 3-hydroxypropanal to provide a hydrogenation product mixture comprising 1,3-propanediol; and (e) recovering 1,3-propanediol from said hydrogenation product mixture. The process enables the production of 1,3-propanediol in high yields and selectivity without the use of a phosphine ligand-modified cobalt catalyst.

摘要翻译： 1,3-丙二醇的制备方法包括在环氧乙烷中加氢甲酰化：（a）在非连接的钴催化剂和催化剂助催化剂存在下，在基本上与水不混溶的溶剂中，温度范围为约 50℃至约100℃，压力范围为约500至约5000psig，以产生包含小于约15重量％的3-羟基丙醛的中间产物混合物; （b）加入水性液体并在低于约100℃的温度下提取3-羟基丙醛，以提供比所述中间产物混合物中3-羟基丙醛浓度更高浓度的3-羟基丙醛的水相，以及 包含钴催化剂的有机相; （c）将水相与有机相分离; （d）氢化3-羟基丙醛以提供包含1,3-丙二醇的氢化产物混合物; 和（e）从所述氢化产物混合物中回收1,3-丙二醇。 该方法能够以高产率和选择性生产1,3-丙二醇，而不需要使用膦配体改性的钴催化剂。

公开(公告)号：US07538061B2

公开(公告)日：2009-05-26

申请号：US10790598

申请日：2004-03-01

申请人： John Frederick Knifton ,  Talmadge Gail James ,  Lynn Henry Slaugh ,  Paul Richard Weider ,  Kevin Dale Allen ,  Joseph Broun Powell

发明人： John Frederick Knifton ,  Talmadge Gail James ,  Lynn Henry Slaugh ,  Paul Richard Weider ,  Kevin Dale Allen ,  Joseph Broun Powell

IPC分类号： B01J31/12 ,  B01J31/20 ,  B01J31/22 ,  B01J31/24 ,  B01J31/18

CPC分类号： B01J31/24 ,  B01J31/1805 ,  B01J31/1815 ,  B01J31/183 ,  B01J31/20 ,  B01J31/28 ,  B01J2231/321 ,  B01J2231/48 ,  B01J2531/0241 ,  B01J2531/842 ,  B01J2531/845 ,  C07C29/16 ,  Y02P20/52 ,  C07C31/205

摘要： Disclosed is a new catalyst composition comprising a bimetallic Co—Fe catalyst, optionally complexed with a ligand selected from a N-heterocycle, phosphine, or porphorine ligand, that provides a lower cost alternative for the one step synthesis of 1,3-propanediol (1,3-PDO) from ethylene oxide and synthesis gas. For example, a catalyst containing cobalt carbonyl: iron carbonyl with no ligand, or a catalyst containing a cobalt carbonyl: octaethylporphine iron acetate provide moderate yields of 1,3-PDO in a one step synthesis under mild conditions.

摘要翻译： 公开了一种新的催化剂组合物，其包含任选与选自N-杂环，膦或卟吩配体的配体络合的双金属Co-Fe催化剂，其为1,3-丙二醇的一步合成提供了较低成本的替代方案（ 1,3-PDO）和环氧乙烷和合成气。 例如，在温和条件下，在一步合成中含有羰基羰基羰基，不含配体的羰基催化剂或含有羰基钴：八乙基卟吩乙酸铁的乙酸铁的催化剂提供了适量的1,3-PDO产率。

公开(公告)号：US06576802B2

公开(公告)日：2003-06-10

申请号：US10158452

申请日：2002-05-30

申请人： John Frederick Knifton ,  Talmadge Gail James ,  Kevin Dale Allen ,  Paul Richard Weider ,  Joseph Broun Powell ,  Lynn Henry Slaugh

发明人： John Frederick Knifton ,  Talmadge Gail James ,  Kevin Dale Allen ,  Paul Richard Weider ,  Joseph Broun Powell ,  Lynn Henry Slaugh

IPC分类号： C07C2700

CPC分类号： B01J31/2433 ,  B01J31/20 ,  B01J31/2208 ,  B01J2231/48 ,  B01J2531/0211 ,  B01J2531/0258 ,  B01J2531/821 ,  B01J2531/845

摘要： Disclosed is a novel class of modified ruthenium catalysts useful in the one step synthesis of 1,3-PDO comprising (a) a cobalt component comprising one or more non-ligated cobalt compounds; and (b) a ruthenium component comprising in major part a ruthenium carbonyl compound ligated with a phospholanoalkane ligand, solubilized in an ether solvent, that provides potential improvements in cost and performance in one step hydroformylation/hydrogenation. For example, cobalt-ruthenium-bidentate, bis(phospholano)alkane catalyst precursors in ether solvents provide good yields of 1,3-PDO in a one step synthesis.

公开(公告)号：US06469222B2

公开(公告)日：2002-10-22

申请号：US09808974

申请日：2001-03-15

申请人： John Frederick Knifton ,  Lynn Henry Slaugh ,  Paul Richard Weider ,  Talmadge Gail James ,  Joseph Broun Powell ,  Kevin Dale Allen ,  Timothy Scott Williams

发明人： John Frederick Knifton ,  Lynn Henry Slaugh ,  Paul Richard Weider ,  Talmadge Gail James ,  Joseph Broun Powell ,  Kevin Dale Allen ,  Timothy Scott Williams

IPC分类号： C07C2700

CPC分类号： B01J31/2409 ,  B01J31/20 ,  B01J31/24 ,  B01J31/2414 ,  B01J31/248 ,  B01J2231/48 ,  B01J2531/821 ,  B01J2531/845 ,  C07C29/16 ,  Y02P20/52 ,  Y02P20/584 ,  C07C31/205

摘要： The invention provides a process for an improved oxirane hydroformylation catalyst, the improved oxirane hydroformylation catalyst, and a one step process for preparing a 1,3-diol in the presence of such a catalyst. One process for preparing the hydroformylation catalyst involves: a) forming a complex (A) by contacting a ruthenium(0) compound with a ditertiary phosphine ligand; and b) forming a complex (B) by subjecting complex (A) to a redox reaction with a cobalt(0) carbonyl compound. This catalyst is used in a one step hydroformylation process for preparing a 1,3-diol, comprising the reaction of an oxirane with syngas at hydroformylation conditions in an inert solvent in the presence of the above hydroformylation catalyst where recovery of product is preferably accomplished via phase separation of a diol rich phase from the bulk reaction liquor.

摘要翻译： 本发明提供改进的环氧乙烷加氢甲酰化催化剂，改进的环氧乙烷加氢甲酰化催化剂的方法，以及在这种催化剂存在下制备1,3-二醇的一步法。 制备加氢甲酰化催化剂的一个方法包括：a）通过使钌（O）化合物与二膦配体接触形成络合物（A）; 和b）通过使复合物（A）与羰基钴（O）化合物进行氧化还原反应形成络合物（B）。 该催化剂用于制备1,3-二醇的一步加氢甲酰化方法，其包括在上述加氢甲酰化催化剂存在下，在惰性溶剂中，在加氢甲酰化条件下使环氧乙烷与合成气反应，其中产物的回收优选通过 富二醇相与本体反应液相分离。

公开(公告)号：US06903044B2

公开(公告)日：2005-06-07

申请号：US10298866

申请日：2002-11-18

申请人： John Frederick Knifton ,  Talmadge Gail James ,  Kevin Dale Allen ,  Paul Richard Weider ,  Joseph Broun Powell ,  Lynn Henry Slaugh ,  Timothy Williams

发明人： John Frederick Knifton ,  Talmadge Gail James ,  Kevin Dale Allen ,  Paul Richard Weider ,  Joseph Broun Powell ,  Lynn Henry Slaugh ,  Timothy Williams

IPC分类号： B01J31/28 ,  B01J31/18 ,  B01J31/20 ,  C07B61/00 ,  C07C29/16 ,  C07C29/44 ,  C07C31/20 ,  B01J31/00

CPC分类号： C07C29/16 ,  B01J31/181 ,  B01J31/1815 ,  B01J31/183 ,  B01J31/20 ,  B01J31/28 ,  B01J2231/48 ,  B01J2531/0208 ,  B01J2531/025 ,  B01J2531/821 ,  B01J2531/845 ,  Y02P20/52 ,  C07C31/205

摘要： Disclosed is a new catalyst composition comprising a bimetallic Co—Ru catalyst complexed with a N-heterocylcic ligand that is effective, economical, and provides improvements in oxidative stability in the one step synthesis of 1,3-propanediol (1,3-PDO) from ethylene oxide and synthesis gas. For example, cobalt-ruthenium-2,2′-bipyrimidine, 2,2′-dipyridyl, or 2,4,6-tripridyl-s-triazine catalyst precursors in cyclic ether solvents, such as 1,3-dioxolane, 1,4-dioxolane, 1,4-dioxane, and 2-ethyl-2-methyl-1,3-dioxolane, provide good yields of 1,3-PDO in a one step synthesis.

摘要翻译： 公开了一种新的催化剂组合物，其包含与N-杂环配体络合的双金属Co-Ru催化剂，该双金属Co-Ru催化剂有效，经济，并且在一步合成1,3-丙二醇（1,3-PDO）中提供氧化稳定性的改善， 来自环氧乙烷和合成气。 例如，在环醚溶剂中的钴 - 钌-2,2'-联嘧啶，2,2'-二吡啶基或2,4,6-三苯基-s-三嗪催化剂前体，如1,3-二氧戊环， 4-二氧戊环，1,4-二恶烷和2-乙基-2-甲基-1,3-二氧戊环，在一步合成中可提供1,3-PDO的良好产率。

公开(公告)号：US06753289B2

公开(公告)日：2004-06-22

申请号：US10371462

申请日：2003-02-21

申请人： John Frederick Knifton ,  Talmadge Gail James ,  Kevin Dale Allen ,  Paul Richard Weider ,  Joseph Broun Powell ,  Lynn Henry Slaugh

发明人： John Frederick Knifton ,  Talmadge Gail James ,  Kevin Dale Allen ,  Paul Richard Weider ,  Joseph Broun Powell ,  Lynn Henry Slaugh

IPC分类号： B01J3100

CPC分类号： B01J31/2433 ,  B01J31/20 ,  B01J31/2208 ,  B01J2231/48 ,  B01J2531/0211 ,  B01J2531/0258 ,  B01J2531/821 ,  B01J2531/845

摘要： Disclosed is a novel class of modified ruthenium catalysts useful in the one step synthesis of 1,3-PDO comprising (a) a cobalt component comprising one or more non-ligated cobalt compounds; and (b) a ruthenium component comprising in major part a ruthenium carbonyl compound ligated with a phospholanoalkane ligand, solubilized in an ether solvent, that provides potential improvements in cost and performance in one step hydroformylation/hydrogenation. For example, cobalt-ruthenium-bidentate, bis(phospholano)alkane catalyst precursors in ether solvents provide good yields of 1,3-PDO in a one step synthesis.

摘要翻译： 公开了一种新型的改性钌催化剂，其用于一步合成1,3-PDO，其包含（a）包含一种或多种非连接的钴化合物的钴组分; 和（b）主要部分包含与溶于醚溶剂中的磷酸烷烃配体连接的钌羰基化合物的钌组分，其在一步加氢甲酰化/氢化中提供成本和性能的潜在改进。 例如，在醚溶剂中的钴 - 钌二齿，双（磷酸）烷烃催化剂前体在一步合成中提供了1,3-PDO的良好产率。

公开(公告)号：US06750373B2

公开(公告)日：2004-06-15

申请号：US10146675

申请日：2002-05-15

申请人： John Frederick Knifton ,  Talmadge Gail James ,  Lynn Henry Slaugh ,  Kevin Dale Allen ,  Paul Richard Weider ,  Joseph Broun Powell

发明人： John Frederick Knifton ,  Talmadge Gail James ,  Lynn Henry Slaugh ,  Kevin Dale Allen ,  Paul Richard Weider ,  Joseph Broun Powell

IPC分类号： C07C2700

CPC分类号： B01J31/24 ,  B01J31/1805 ,  B01J31/1815 ,  B01J31/183 ,  B01J31/20 ,  B01J31/28 ,  B01J2231/321 ,  B01J2231/48 ,  B01J2531/0241 ,  B01J2531/842 ,  B01J2531/845 ,  C07C29/16 ,  Y02P20/52 ,  C07C31/205

摘要： Disclosed is a new catalyst composition comprising a bimetallic Co—Fe catalyst, optionally complexed with a ligand selected from a N-heterocycle, phosphine, or porphorine ligand, that provides a lower cost alternative for the one step synthesis of 1,3-propanediol (1,3-PDO) from ethylene oxide and synthesis gas. For example, a catalyst containing cobalt carbonyl: iron carbonyl with no ligand, or a catalyst containing a cobalt carbonyl: octaethylporphine iron acetate provide moderate yields of 1,3-PDO in a one step synthesis under mild conditions.

摘要翻译： 公开了一种新的催化剂组合物，其包含任选与选自N-杂环，膦或卟吩配体的配体络合的双金属Co-Fe催化剂，其为1,3-丙二醇的一步合成提供了较低成本的替代方案（ 1,3-PDO）和环氧乙烷和合成气。 例如，在温和条件下，在一步合成中含有羰基羰基羰基，不含配体的羰基催化剂或含有羰基钴：八乙基卟吩乙酸铁的乙酸铁的催化剂提供了适量的1,3-PDO产率。

公开(公告)号：US06706656B2

公开(公告)日：2004-03-16

申请号：US10127957

申请日：2002-04-23

申请人： John Frederick Knifton ,  Lynn Henry Slaugh ,  Paul Richard Weider ,  Talmadge Gail James ,  Joseph Broun Powell ,  Kevin Dale Allen ,  Timothy Scott Williams

发明人： John Frederick Knifton ,  Lynn Henry Slaugh ,  Paul Richard Weider ,  Talmadge Gail James ,  Joseph Broun Powell ,  Kevin Dale Allen ,  Timothy Scott Williams

IPC分类号： B01J3100

CPC分类号： B01J31/2409 ,  B01J31/20 ,  B01J31/24 ,  B01J31/2414 ,  B01J31/248 ,  B01J2231/48 ,  B01J2531/821 ,  B01J2531/845 ,  C07C29/16 ,  Y02P20/52 ,  Y02P20/584 ,  C07C31/205

摘要： The invention provides a process for an improved oxirane hydroformylation catalyst, the improved oxirane hydroformylation catalyst, and a one step process for preparing a 1,3-diol in the presence of such a catalyst. One process for preparing the hydroformylation catalyst involves: a) forming a complex (A) by contacting a ruthenium(0) compound with a ditertiary phosphine ligand; and b) forming a complex (B) by subjecting complex (A) to a redox reaction with a cobalt(0) carbonyl compound. This catalyst is used in a one step hydroformylation process for preparing a 1,3-diol, comprising the reaction of an oxirane with syngas at hydroformylation conditions in an inert solvent in the presence of the above hydroformylation catalyst where recovery of product is preferably accomplished via phase separation of a diol rich phase from the bulk reaction liquor.

摘要翻译： 本发明提供改进的环氧乙烷加氢甲酰化催化剂，改进的环氧乙烷加氢甲酰化催化剂的方法，以及在这种催化剂存在下制备1,3-二醇的一步法。 制备加氢甲酰化催化剂的一个方法包括：a）通过使钌（O）化合物与二膦配体接触形成络合物（A）; 和b）通过使复合物（A）与羰基钴（O）化合物进行氧化还原反应形成络合物（B）。 该催化剂用于制备1,3-二醇的一步加氢甲酰化方法，其包括在上述加氢甲酰化催化剂存在下，在惰性溶剂中，在加氢甲酰化条件下使环氧乙烷与合成气反应，其中产物的回收优选通过 富二醇相与本体反应液相分离。