公开(公告)号：US06723884B1

公开(公告)日：2004-04-20

申请号：US10049859

申请日：2002-02-19

申请人： Armin Volker Grenacher ,  Hans Stepp

发明人： Armin Volker Grenacher ,  Hans Stepp

IPC分类号： C07C4549

CPC分类号： B01J31/403 ,  B01J31/04 ,  B01J2231/321 ,  C07C29/16 ,  C07C45/50 ,  Y02P20/584 ,  C07C31/125 ,  C07C47/02

摘要： Olefins having from 6 to 20 carbon atoms are hydroformylated by means of a continuous process in which a) an aqueous cobalt(II) salt solution is brought into intimate contact with hydrogen and carbon monoxide to form a hydroformylation-active cobalt catalyst, and the aqueous phase comprising the cobalt catalyst is brought into intimate contact with the olefins and, if desired, an organic solvent and also hydrogen and carbon monoxide in at least one reaction zone where the cobalt catalyst is extracted into the organic phase and the olefins are hydroformylated, b) the output from the reaction zone is treated with oxygen in the presence of acidic aqueous cobalt(II) salt solution, with the cobalt catalyst being decomposed to form cobalt(II) salts and these being backextracted into the aqueous phase; and the phases are subsequently separated, c) the aqueous cobalt(II) salt solution is recirculated in unchanged form to step a), wherein the cobalt(II) salt solution has a concentration of from 1.1 to 1.7% by weight, calculated as cobalt, and is continually maintained under conditions under which the solubility limit of cobalt(II) formate in water is not exceeded. The process allows stable, trouble-free long-term operation.

摘要翻译： 具有6至20个碳原子的烯烃通过连续方法加氢甲酰化，其中a）使钴（II）盐水溶液与氢气和一氧化碳紧密接触以形成加氢甲酰化活性钴催化剂，水相 包括钴催化剂与烯烃紧密接触，并且如果需要，在至少一个反应区中的有机溶剂以及氢和一氧化碳，其中钴催化剂被萃取到有机相中，烯烃被加氢甲酰化，b） 在酸性钴酸钴水溶液的存在下，用氧气处理来自反应区的产物，钴催化剂分解形成钴（II）盐，并将它们反萃取到水相中; 随后分离相，c）将钴水溶液（II）盐溶液以不变形式再循环至步骤a），其中钴（II）盐溶液的浓度为1.1至1.7重量％，计算为钴 ，并且在不超过甲酸钴（II）甲酸盐在水中的溶解度极限的条件下持续保持。该方法允许稳定，无故障的长期操作。

公开(公告)号：US06777503B2

公开(公告)日：2004-08-17

申请号：US10181454

申请日：2002-07-18

申请人： Harald Schwahn ,  Gerhard Borchert ,  Klaus Diehl ,  Armin Volker Grenacher ,  Friedrich Sauer

发明人： Harald Schwahn ,  Gerhard Borchert ,  Klaus Diehl ,  Armin Volker Grenacher ,  Friedrich Sauer

IPC分类号： C08F1000

CPC分类号： C07C45/50 ,  C07C45/80 ,  C07C47/21

摘要： A process for the hydroformylation of olefins having from 20 to 400 carbon atoms by reaction of the olefins with synthesis gas in the presence of a cobalt carbonyl catalyst and recovery of the cobalt catalyst by extraction of the reaction product with an aqueous acidic solution in the presence of oxygen and separation of the organic and aqueous phases, wherein (a) the aqueous phase is separated from the organic phase by means of gravitational forces to the extent that the proportion of aqueous phase dispersed in the organic phase is 2% by weight or less, based on the organic phase, and (b) the organic phase obtained in step (a) is exposed to an electric field to coalesce the remaining dispersed aqueous phase, is described. In this way, the residual cobalt content of the hydroformylation product can be reduced to less than 1 ppm.

摘要翻译： 在羰基钴催化剂存在下，通过烯烃与合成气的反应，通过在酸存在下用酸性水溶液萃取反应产物来回收钴催化剂，从而使具有20至400个碳原子的烯烃加氢甲酰化的方法 的氧气和有机相和水相的分离，其中（a）通过重力将水相与有机相分离，使得分散在有机相中的水相的比例为2重量％以下 ，（b）将步骤（a）中获得的有机相暴露于电场以使剩余的分散的水相结合，这样，加氢甲酰化产物的残余钴含量可以 减少到1 ppm以下。

公开(公告)号：US06849769B2

公开(公告)日：2005-02-01

申请号：US10363660

申请日：2001-09-11

申请人： Michael Röper ,  Heinrich-Josef Blankertz ,  Armin Volker Grenacher ,  Roland Krokoszinski ,  Willi Schönmann

发明人： Michael Röper ,  Heinrich-Josef Blankertz ,  Armin Volker Grenacher ,  Roland Krokoszinski ,  Willi Schönmann

IPC分类号： B01J31/20 ,  C08F8/00 ,  C07C45/50

CPC分类号： C08F8/00 ,  Y02P20/584 ,  Y10S585/901 ,  C08F110/10

摘要： Essentially monounsaturated polyalkylenes having from 30 to 700 carbon atoms are continuously hydroformylated by a process in which i) a hydroformylation-active cobalt carbonyl catalyst is prepared from a catalyst precursor dissolved in an aqueous phase in the absence of the polyalkylenes, ii) the polyalkylenes are hydroformylated by means of synthesis gas in the presence of the cobalt carbonyl catalyst in a reaction zone, iii) the cobalt carbonyl catalyst is separated from the output from the reaction zone with at least partial reformation of the catalyst precursor and the catalyst precursor is recirculated to step i).

摘要翻译： 具有30至700个碳原子的基本单不饱和聚亚烷基通过以下方法连续加氢甲酰化，其中i）在不存在聚亚烷基的情况下由溶解在水相中的催化剂前体制备加氢甲酰化 - 活性钴羰基催化剂，ii）聚亚烷基 在羰基催化剂存在下，通过合成气在反应区中加氢甲酰化，iii）将钴羰基催化剂与反应区的输出分离，至少部分重新形成催化剂前体，催化剂前体再循环至 步骤i）。

公开(公告)号：US06444856B2

公开(公告)日：2002-09-03

申请号：US09867574

申请日：2001-05-31

申请人： Armin Volker Grenacher ,  Hans-Georg Hein ,  Hans Stepp ,  Hans-Jürgen Fröhlich ,  Willi Schönmann ,  Gerhard Borchert

发明人： Armin Volker Grenacher ,  Hans-Georg Hein ,  Hans Stepp ,  Hans-Jürgen Fröhlich ,  Willi Schönmann ,  Gerhard Borchert

IPC分类号： C07C4550

CPC分类号： C07C45/50 ,  B01J3/042 ,  B01J4/002 ,  B01J4/007 ,  B01J10/00 ,  B01J19/006 ,  B01J19/26 ,  B01J2219/00051 ,  B01J2219/00162 ,  C07C29/141 ,  C07C47/02 ,  C07C31/125

摘要： In a process for preparing aldehydes and/or alcohols having from 6 to 30 carbon atoms by hydroformylation of olefins by means of synthesis gas in the presence of a catalyst at from 120° C. to 210° C. and pressures of from 100 to 400 bar, a reaction mixture comprising olefins, synthesis gas and catalyst or catalyst precursor is, according to the present invention, introduced at high velocity into a high-pressure reactor via a nozzle having an adjustable flow cross section.

摘要翻译： 在通过在120℃至210℃的催化剂存在下通过合成气进行烯烃加氢甲酰化制备具有6至30个碳原子的醛和/或醇的方法和压力为100-400 根据本发明，包含烯烃，合成气和催化剂或催化剂前体的反应混合物通过具有可调流动横截面的喷嘴以高速引入高压反应器。

公开(公告)号：US06331656B1

公开(公告)日：2001-12-18

申请号：US09269421

申请日：1999-03-04

申请人： Heinrich-Josef Blankertz ,  Armin Volker Grenacher ,  Friedrich Sauer ,  Harald Schwahn ,  Willi Schönmann ,  Michael Röper

发明人： Heinrich-Josef Blankertz ,  Armin Volker Grenacher ,  Friedrich Sauer ,  Harald Schwahn ,  Willi Schönmann ,  Michael Röper

IPC分类号： C07C4500

CPC分类号： C07C29/16 ,  C07C45/50 ,  C08F8/00 ,  C07C31/18 ,  C08F110/10 ,  C07C47/02

摘要： In a process for the hydroformylation of olefins having from 12 to 100 carbon atoms in the presence of a cobalt carbonyl catalyst at pressures of from 100 to 400 bar and at from 100 to 200° C., depressurization and recovery of the cobalt catalyst by extraction with an aqueous acid solution in the presence of atmospheric oxygen, (a) the extraction is carried out in the presence of a polymeric emulsion breaker selected from the group consisting of alkoxylated compounds containing amino, imino or OH groups, and (b) to achieve complete phase separation in the organic phase still containing small amounts of aqueous phase, the formation of relatively large droplets of the dispersed aqueous phase is effected in a coalescence stage.

摘要翻译： 在羰基钴催化剂存在下，在100-400巴和100-200℃的压力下，在具有12至100个碳原子的烯烃的加氢甲酰基化方法中，通过萃取法减少和回收钴催化剂 在大气氧存在下用酸水溶液处理，（a）萃取在选自包含氨基，亚氨基或OH基团的烷氧基化合物的聚合物破乳剂存在下进行，和（b）实现 在有机相中仍然含有少量水相的完全相分离，在聚结阶段中实现分散的水相的相对大的液滴的形成。