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：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：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：US06545190B2

公开(公告)日：2003-04-08

申请号：US09963068

申请日：2001-09-25

申请人： Kevin Dale Allen ,  Joseph Broun Powell ,  Paul Richard Weider ,  John Frederick Knifton

发明人： Kevin Dale Allen ,  Joseph Broun Powell ,  Paul Richard Weider ,  John Frederick Knifton

IPC分类号： C07C2700

CPC分类号： C07C29/16 ,  Y02P20/582 ,  Y02P20/584 ,  C07C31/205

摘要： Disclosed is 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 a hydroformylation catalyst comprising a ruthenium (+1)-phosphine bidentate: cobalt (−1) complex, wherein the ligated metal is ruthenium, under conditions which preferably upon completion of the oxirane/syngas reaction cause a phase separation of the reaction mixture into a solvent phase which is rich in catalyst and a second phase which is rich in the 1,3-diol, recycling the phase rich in catalyst directly to the hydroformylation reaction for further reaction with previously unreacted starting materials, thus permitting valuable hydroformylation catalyst to be recycled without degradation or exposure to downstream processing and recovering the 1,3-diol from the second phase rich in 1,3-diol.

摘要翻译： 公开了一种用于制备1,3-二醇的一步加氢甲酰化方法，其包括在加氢甲酰化条件下，在惰性溶剂中，在加氢甲酰化催化剂存在下，环氧乙烷与合成气的反应，所述加氢甲酰化催化剂包含钌（+1） - 膦二齿：钴 （-1）络合物，其中连接的金属是钌，在优选在完成环氧乙烷/合成气反应的条件下，使反应混合物相分离成富含催化剂的溶剂相和富含 该1,3-二醇将富含催化剂的相直接再循环到加氢甲酰化反应中以进一步与先前未反应的起始原料反应，从而允许有价值的加氢甲酰化催化剂再循环而不降解或暴露于下游加工并回收1,3-二醇 从第二阶段富含1,3-二醇。

公开(公告)号：US06518466B2

公开(公告)日：2003-02-11

申请号：US09957279

申请日：2001-09-20

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.

公开(公告)号：US06468940B1

公开(公告)日：2002-10-22

申请号：US09957561

申请日：2001-09-20

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。

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。