CN1210514A - 烯烃加氢甲酰化制醛的工艺 - Google Patents
烯烃加氢甲酰化制醛的工艺 Download PDFInfo
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- CN1210514A CN1210514A CN97191973A CN97191973A CN1210514A CN 1210514 A CN1210514 A CN 1210514A CN 97191973 A CN97191973 A CN 97191973A CN 97191973 A CN97191973 A CN 97191973A CN 1210514 A CN1210514 A CN 1210514A
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- hydroformylation
- rhodium
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- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 229910003450 rhodium oxide Inorganic materials 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- YWFDDXXMOPZFFM-UHFFFAOYSA-H rhodium(3+);trisulfate Chemical compound [Rh+3].[Rh+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YWFDDXXMOPZFFM-UHFFFAOYSA-H 0.000 description 1
- 230000001020 rhythmical effect Effects 0.000 description 1
- WBHHMMIMDMUBKC-QJWNTBNXSA-M ricinoleate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O WBHHMMIMDMUBKC-QJWNTBNXSA-M 0.000 description 1
- 229940066675 ricinoleate Drugs 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
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Abstract
一种由含3个以上碳原子的烯烃加氢甲酰化制醛或者制醛和醇的工艺,包括一个压力为50—1000巴,温度为50℃—180℃,使用一种溶解在均相反应介质中的铑催化剂将烯烃加氢甲酰化的加氢甲酰化步骤,和一个通过铑催化剂萃取的催化剂回收步骤,其中:(a)加氢甲酰化在铑络合物存在下进行,铑络合物具有一个多齿的、不含磷的能与第八族金属生成络合物的有机氮化合物作配位体,它还含至少一个能在弱酸中被质子化的叔氮基,(b)在将加氢甲酰化步骤的流出物中的醛和醇根据需要加以分离或部分分离之后,用一种可蒸馏酸的水溶液对流出物进行萃取,(c)在加氢甲酰化条件下是惰性的一种有机溶剂或溶剂混合物存在下,对含水酸萃取液进行热处理,蒸出含水酸,使络合物去质子化并转移到有机相中,(d)将含催化剂络合物的有机相循环到加氢甲酰化步骤中。
Description
本发明涉及一种由含3个以上碳原子的烯烃加氢甲酰化制醛或者制醛和醇的工艺以及催化剂的回收工艺,其中催化剂的回收通过下面两步达到:(1)在蒸馏出烯烃加氢甲酰化产物后将蒸馏塔釜物循环和(2)用弱酸水溶液萃取催化剂络合物,该弱酸的多齿含氮配位体还含有至少一个可用弱酸质子化的叔氮基。
在过渡金属催化剂存在下烯烃与一氧化碳和氢发生加氢甲酰化反应是众所周知的。尽管使用含铑的膦改性催化剂(参看J.Falbe的论著“采用一氧化碳的新合成方法”Springer出版社,1980年,柏林,自第55页以后)可以使α烯烃达到很高的加氢甲酰化程度,但这种催化剂体系不太适合于内内支链烯烃和含7个碳以上的烯烃(参看J.Falbe的论著,自第95页以后)。因为使用这种催化剂内部碳-碳双键加氢甲酰化的速度很慢。由于常常通过蒸馏将加氢甲酰化产物与溶解在反应系统中的均相催化剂分离,加氢甲酰化生成的醛的沸点随碳数和链长的增加而增高,以至达到铑催化剂的分解温度,这种加氢甲酰化方法对含7个碳以上的烯烃是不经济的。在聚合烯烃例如聚异丁烯的加氢甲酰化过程中,贵金属催化剂不能被恢复到可以重新使用的形式。
与此相反,用所谓的“裸露”铑,即溶解在加氢甲酰化介质中的、未用诸如膦类或亚磷酸盐类的含磷配位体改性的均相铑化合物有利于内内支链烯烃的加氢甲酰化。这种未用磷类或亚磷酸盐类改性的铑催化剂及其对前面提到的各类烯烃加氢甲酰化的适应性是公知的(参看J.Falbe的论著,自第38页以后)。本申请中的术语“裸露铑”或“裸露铑催化剂”是指在加氢甲酰化条件下未用配位体、尤其是如膦类或亚磷酸盐类的含磷配位体改性的、不同于传统的铑加氢甲酰化催化剂。本文中的配位体不考虑羰基或氢化配位体。在技术文献中假定(参看J.Falbe的论著,自第38页以后)铑化合物HRh(CO)4是使用“裸露铑催化剂”的加氢甲酰化反应中的催化活性的铑化合物,虽然许多同时发生在加氢甲酰化反应区中的化学机理并未绝对地证明这一点。仅仅为了简化起见,我们在本申请中也依据这一假定,如果未来某个时候另一种非所述的铑化合物证明是实际有催化活性的,不应当认为是对本发明的限制。“裸露铑催化剂”是在加氢甲酰化条件下由铑化合物如铑盐,如氯化铑(Ⅲ)、硝酸铑(Ⅲ)、醋酸铑(Ⅲ)、乙酰丙酮铑(Ⅱ)、硫酸铑(Ⅲ)、氯化铵铑(Ⅲ);由硫属铑化合物如氧化铑(Ⅲ)或硫化铑(Ⅲ);由铑羟基酸盐如铑酸盐;由羰基铑化合物如Rh4(CO)12和Rh6(CO)16或由有机铑化合物,例如二羰基乙酰丙酮铑、环辛二烯醋酸铑或氯化铑在通常被称为合成气的CO/H2混合物存在下反应生成的。有关本文所指的用“裸露”铑进行的加氢甲酰化过程可参考下列文献:USA4400547;DE-A3338340;DE-A2604545;WO82/03856;Chem.Ber.(化学报告)102,2238(1969);Tetrahedron Lett.(四面体通讯)29,3261(1968);Hydrocarbon Process.(烃加工)85-86(1975)。
即使用“裸露”铑进行的加氢甲酰化过程也存在热不稳定的铑催化剂(参见US-A4400547)因蒸馏提纯加氢甲酰化产物过程的热负荷作用而部分分解为金属铑这样的缺点,这些金属铑沉积在反应器壁或管壁上。这些沉积的金属铑不能再用于加氢甲酰化反应,因为在加氢甲酰化反应条件下它不能被转化为有催化活性的铑化合物。由于“裸露铑催化剂”的这种化学行为导致的铑损失至今妨碍着这一工艺的大规模实施。
DE-A3338340和US-A4400547描述了使用“裸露铑催化剂”进行的加氢甲酰化过程,其中将一种膦或亚磷酸盐添加到加氢甲酰化流出物中,以防止铑的沉淀和通过生成膦或亚磷酸盐络合物防止铑催化剂在蒸馏精制加氢甲酰化产物过程中的热分解。蒸馏结束后,用氧化剂处理含铑的蒸馏塔釜产物,从而使铑从相应的膦或亚磷酸盐络合物中释放出来,恢复催化活性,膦或亚磷酸盐配位体被氧化成在加氢甲酰化条件下不能形成铑络合物的相应的氧化膦或磷酸盐。氧化的蒸馏塔釜产物再被用做加氢甲酰化催化剂。在氧化中生成的氧化的磷化合物通常不影响加氢甲酰化反应,本工艺的特殊性在于,因氧化的磷化合物在加氢甲酰化循环过程中积累,需要被不断地将一部分催化剂溶液从加氢甲酰化循环过程中移出,同时补充新鲜的催化剂溶液。移出的催化剂溶液必须经过特别的工序将其中的铑回收。
WO82/03856涉及使用一种未改性的、被称为“裸露铑催化剂”的热稳定工艺,其中用含氧气体处理加氢甲酰化反应的流出物,这意味着生成的醛被部分地氧化为相应的羧酸,它与铑催化剂在蒸馏精制过程中生成耐热的羧酸铑,它可以重新作为加氢甲酰化催化剂使用。这一工艺的缺点是:由于产品醛被部分地氧化为羧酸导致产量下降。而且此工艺只限于生成可蒸馏产品的加氢甲酰化。例如,在这个工艺中,不能将铑催化剂从聚异丁烯这种加氢甲酰化产物中分离出来。
US3594425描述了另一种在多齿的、含至少两个氮原子的配位体如联吡啶和N,N,N’,N’-四甲基亚乙二胺存在下的特别是用钴和铑的加氢甲酰化工艺。这些配位体在蒸馏精制及其随后的催化剂循环过程中以所谓的“滞留方式”保持催化剂的稳定性。蒸馏结束后含铑的塔釜物被再次用做加氢甲酰化的催化剂。在加氢甲酰化中和蒸馏精制中生成的高沸物通常不影响加氢甲酰化反应,而是受工艺控制积累在加氢甲酰化循环过程中,因此一部分催化剂溶液须被不断地从加氢甲酰化循环过程中移出,同时补充新鲜的催化剂溶液。移出的催化剂溶液必须经过特别的工序将其中的铑回收。然而此工艺只限于生成可蒸馏产品的加氢甲酰化。例如,在这个工艺中,不能将铑催化剂从聚异丁烯这种加氢甲酰化产物中分离出来。
JP-A262086描述了作为加氢甲酰化催化剂的含多齿的、含氮配位体的铑络合物。据报导这种体系的特殊性在于对生成支链产物具有高度的选择性。
US4298499描述了向羰基合成产物引入诸如联吡啶类的含氮配位体,目的是防止蒸馏精制过程中铑沉淀。在叔胺存在下进行的加氢甲酰化用于有目的地生成醇类。在胺的萃取之后,特别地引入配位体用于分离铑而不会引起沉淀。然后将塔釜物循环用做加氢甲酰化区的催化剂。然而,这种方法仍有上述“滞留方式”的缺点,即有必要移出部分残留物并精制将其中的铑回收。
最后,EP621075透露了使用一种叔胺取代的三芳基膦的可逆萃取法。该文献特别描述了采用一种含碳酸水溶液的萃取法。将溶液减压后又产生一种溶于有机介质的催化剂。使用叔胺取代的三芳基膦的方案有以下缺点,首先,在CO2存在下发生例如用铑催化剂使三芳基膦氧化为三芳基膦氧化物的副反应是公知的,第二,由于双键异构化引起的产物损失是在预料之中的。最后,铑/膦催化剂对内部双键的加氢甲酰化的催化速度很慢。而且制备叔胺取代的膦类很困难。
因此本发明的目标是找到一种使用“裸露铑催化剂”由内和/或支链烯烃生产醛的工艺,它没有上述缺点,使用它可以令人满意地解决加氢甲酰化产物蒸馏精制中的金属铑沉淀和将铑与不可蒸馏醛或反应中特有的高沸物的分离的问题。
本发明通过下述工艺解决问题:一种由含3个以上碳原子的烯烃加氢甲酰化制醛或者制醛和醇的工艺,包括一个在压力为50-1000巴、温度为50℃-180℃下、使用一种溶解在均相反应介质中的铑催化剂将烯烃加氢甲酰化的加氢甲酰化步骤,和一个涉及铑催化剂萃取的催化剂回收的步骤,(a)加氢甲酰化在铑络合物的存在下进行,铑络合物具有一个多齿的、不含磷的能与第八族金属生成络合物的有机氮化合物作配位体,它还含至少一个能在弱酸中质子化的叔氮基,(b)将加氢甲酰化步骤的流出物中的醛和醇根据需要加以分离或部分分离之后,用一种可蒸馏的酸的水溶液对流出物进行萃取,(c)在一种在加氢甲酰化条件下惰性的有机溶剂或溶剂混合物存在下,对含水酸萃取液进行热处理,蒸出含水酸,使络合物去质子化并转移到有机相中,(d)将含催化剂络合物的有机相循环到加氢甲酰化步骤中。
此种新奇方法产生的惊人佳绩不仅在于催化剂回收方法的简单,而且即使在加氢甲酰化温度低的情况下,与醇相比醛仍达到很高的产量,反之,根据US4298499和Chem.Ing.Techn.(化学工程技术)44,708,(1972)的预计,在含叔胺基的配位体存在时醛产量较少,不足以实现大规模生产。
根据本发明,所用的配位体主要是含至少两个氮原子的双功能多齿有机氮化物,它能与第八族过渡金属生成的络合物,还含至少一个能被质子化的叔氨基。
由于这些配位体的作用,他们与铑催化剂的铑中心原子形成配价键-据推测是经氮原子的自由电子对形成的。已知这种化合物是络合剂。存在至少一个可质子化的并且不与铑催化剂的铑中心原子相连的叔氨基,是使本发明工艺具有可行性的决定性因素。
本发明特别采用了结构式1所示的新型化合物:
其中X代表从共价键、亚甲基、亚乙基、氧代基、硫基、烷亚胺基和芳亚胺基选出的桥成分,基团R独立地代表氢、含1-18个碳原子的烷基、或是含1-18个碳原子的烷氧基,这些基团可以是饱和或不饱和环的组成部分,其中至少一个基团R或任选的由烷基或烷氧基形成的环上的取代基是下式的基团:
其中n是一个0-20之间的整数,R’代表一个含18个碳以下的烷基、环烷基、芳烷基、或芳基,R’基可以是桥连的。
其中R”代表氢、烷基、环烷基、芳基、或芳烷基,它还能携带一个二烷基氨基,m是2-35000之间的一个整数,其条件是R”代表氢,至少一些氢原子被来自仲胺基与1-10摩尔环氧乙烷或环氧丙烷反应生成的含2-18个碳原子的烷羰基或者羟基(烷氧基)烷基取代,而且假设聚胺含至少3个能被质子化的叔氮原子。
其中n和R’的含义同前。
为了说明本发明使用的大量配位体,下面列举一批在本发明的工艺中引入叔胺基团之后使用的含氮络合剂。
1,10-菲咯啉,2,9-二甲基菲咯啉,4,7-二苯基-1,10-菲咯啉如配位体5(红菲绕啉)2,9-二甲基-4,7-二苯基-1,10-菲咯啉如配位体6(浴铜灵)4,5-重氮芴如配位体7联吡啶并-(3,2-a∶2’,3’-c)吩嗪如配位体8
(配位体7和8可根据Aust.J.Chem.(澳大利亚化学杂志),23,1023,(1970)中描述的方法制得)
其它适用的含氮多齿配位体是联吡咯、联吡唑、双咪唑、联三唑、联四唑、联哒嗪、联嘧啶、联吡嗪、联三嗪、以及卟吩。需要的话,配位体可以是不对称的,例如将咪唑与吡啶连接。使用含多齿合氮配位体的铑络合物的加氢甲酰化反应的条件是公知的。通常的温度范围在60-180℃,优选80℃-140℃,特别优选90℃-130℃,压力范围在50-1000巴,优选70-500巴,特别优选100-400巴。其它的加氢甲酰化反应条件如通常在使用“裸露铑”的加氢甲酰化和上述有关使用“裸露铑”的加氢甲酰化的文献提到的相同。
在加氢甲酰化阶段采用的压力、温度和合成气组成的变化对加氢甲酰化产品物流中醇/醛比有不同的影响。例如:给定不同的合成气组成-CO∶H2的摩尔比分别为50∶50,40∶60,和60∶40,三聚丙烯的加氢甲酰化在温度130℃,压力280巴的条件下得到的醛/醇比均为93∶7。当温度由130℃增加到150℃时,加氢甲酰化产品物流中的醛/醇比根据合成气组成-CO∶H2的摩尔比50∶50,40∶60,和60∶40-分别变为76∶24,67∶33,和82∶18。
无论有机溶剂存在与否,加氢甲酰化反应均可以进行。使用有机溶剂十分有利,尤其是对长链的或者聚合的烯烃。常用于加氢甲酰化反应的有机溶剂有如:高沸点芳烃和脂肪烃,或是在加氢甲酰化反应中由于产品醛的缩合生成的高沸点缩合醛副产物。
在用酸性水相萃取加氢甲酰化阶段的产物之前要适当地减压。加氢甲酰化阶段产物的萃取通常采用下列条件:温度20-140℃,优选70℃-130℃,特别优选90℃-120℃,压力范围在1-20巴,优选1-10巴,特别优选1-5巴。萃取可以在空气或如氮气、氢气或氩气等惰气环境中进行。然而,向惰气中加入一氧化碳或合成气,或者在一氧化碳存在下进行萃取是有益的。
萃取时水相与有机相的体积比通常选择0.2∶1-2∶1,优选0.3∶1-1∶1。酸性水相中水溶的弱酸含量通常为0.1-50%,优选1-30%,特别优选3-10%。
在用酸性水相萃取时,在配位体的叔胺基处发生质子化,从而铑络合物变成了水溶性的。
用于本发明工艺中的萃取剂是可蒸馏酸的水溶液,特别是其铵盐在室温至200℃之间能被分解为游离的配位体和游离酸的可蒸馏酸。
特别适用的萃取剂是pKs值为3-6的酸的水溶液。典型的例子是碳酸、甲酸、乙酸、丙酸、正丁酸或者戊酸。在使用碳酸的时候,按照EP0621075的方法将含催化剂的、待萃取的有机液体与水混合,然后压入碳酸气。在相分离之后,按对其它酸的方法提纯所需的相。
适用于酸性水相萃取加氢甲酰化产品物流的设备实际上包括所有的液液萃取器,例如混合分离器、泡罩塔、对流或顺流萃取塔,在其中安装附加部件来改善水相与有机相的混合效率,例如筛板、填料或静态混合器。从加氢甲酰化产品物流中萃取铑催化剂的过程可以采用单级萃取,但最好采用例如两级或三级的多级萃取,在其中使含络合剂的水相相对于有机相顺流或是最好逆流导入。
萃取完成之后,可以用常规的方法,例如蒸馏法精制已同铑催化剂分离的加氢甲酰化产品物流,以便分离所需的终产物醇和/或醛。
为了释放溶解在水萃取液中的铑络合物,并将其转移到能循环进入加氢甲酰化的有机相中,一种适合加氢甲酰化的溶剂,例如一种液态烃或Eastman出售的Texanol烃混合物被加到酸性水萃取液中。加氢甲酰化的产物及其副产物亦适合于作为溶剂。溶剂与水相的体积比通常是0.1∶1-2∶1,优选0.5∶1-1∶1。然后将溶剂和酸性水相的混合物加热到这样一种温度:使弱酸的铵盐分解,去质子化的铑络合物溶解在溶剂中。将有机相与水相(若存在)分离后,将含铑催化剂的有机相送回加氢甲酰化阶段。
去质子化通常随着有机相和水相的充分混合并加热到90℃移出CO2或加热到150℃移出碳酸而发生,在此期间温度一般不得超过200℃。
下面以图1所表示的某一工艺为例对本发明作进一步的详细说明。为了简明起见,将本发明工艺中显而易见的不需要的部分从图1中加以省略。
图1所示的本发明的工艺流程包含使用均匀溶于有机反应介质的铑催化剂的加氢甲酰化阶段,将催化剂从加氢甲酰化反应产物中分离,将移出的铑送回加氢甲酰化阶段。催化剂的分离必要时在部分或完全蒸馏之后通过用酸性水相从反应产物或者塔釜物对催化剂进行可逆萃取进行。萃取之后对酸/配位体加合物进行热分解,将催化剂重新转移到有机相中,从而无须成盐就能保证铑的回收。然后将铑送回加氢甲酰化阶段。过程连续进行时,可以仅通过蒸馏方便地将铑分离,只有当副产物积累到一定程度时才使用萃取方法。
具体地讲,在如图1所示的本发明的工艺的连续实施方案中:由加氢甲酰化反应器H来的烯烃加氢甲酰化产物1经减压、液相与过量合成气分离之后经过管线5进入萃取过程或者首先经过管线2进入一个蒸馏精制(由闪蒸设备和/或塔组成)。在蒸馏精制过程A,易蒸发的醛类4与高沸点的含催化剂的塔底物分离。将塔釜物经管线3间歇地或部分地送回加氢甲酰化阶段和间歇地或部分地经过管线6送入萃取精制阶段。在此萃取精制阶段将含酸水相与有机相在混合器M进行混合。该混合物经过管线7进入相分离阶段P。含醛类和/或高沸点组分的有机相经过管线8被分离并用于进一步精制。水相经过管线9进入混合器M,同与加氢甲酰化反应相容的有机相10,其组成如烯烃、醛、和/或醇、甲苯或其它芳香烃或Texanol混合物、或醚类如乙醚混合。然后将混合物经过管线11送入热分解阶段T。它可以用蒸馏塔的方式分离水/羧酸混合物,也可以用纯粹的热处理方式去除CO2。根据需要,可以将水相经过管线12送回到萃取阶段或移出反应系统。含催化剂的有机相经过管线13返回加氢甲酰化阶段。
本发明的工艺非常适用于含3个以上,最好是7个以上碳原子的烯烃的加氢甲酰化,特别适用于C7-C20烯烃的加氢甲酰化,这些烯烃可以是直链的或最好支链的、含α-烯属和/或内部双键,例如辛烯-1、十二碳烯-1、三聚或四聚丙烯、或二聚、三聚或四聚丁烯。同样地,其它烯烃的不饱和低聚物以及不同烯烃的共聚低聚物也可用于加氢甲酰化。由这些烯烃生成的醛作为中间体,可以通过加氢的方法方便地制造增塑剂醇和表面活性剂。用于加氢甲酰化的烯烃可以通过将相应的脂肪醇进行酸催化脱水或根据大量报道的技术工艺获得,例如Wissermel,Arpe:Industrielle OrganischeChemie(工业有机化学),pp67-86,Verlag Chemie,Weinheim,1978中报道的方法。
本发明的工艺还非常适用于聚合烯烃的加氢甲酰化,例如低分子量聚异丁烯、低分子量聚丁二烯或低分子量1,3-丁二烯-异丁烯共聚物或1,3-丁二烯-丁烯共聚物。我们所指的低分子量聚合物是特指分子量为280-5000道尔顿的聚合物。然而,具有高分子量的,即分子量在5000以上的不饱和聚合物的加氢甲酰化也是可能的。唯一的前提是它们必须溶于介质。
因此本工艺事实上适用于可经烯烃加氢甲酰化获得的所有醛类的制备。本发明的工艺特别对于带有1个或2个取代基的烯烃,最好是带有1个取代基的烯烃进行加氢甲酰化。本发明的工艺能对例如不饱和脂族羧酸酯、乙缩醛、醇、醚、醛、酮以及胺和酰胺进行加氢甲酰化。那些有关的、被取代的原料烯烃是:甲基丙烯酸酯、二环戊二烯、乙烯醚和烯丙醚,特别是不饱和脂肪酸的相应取代衍生物:例如油酸的、亚油酸的、亚麻酸的、蓖麻酸的、或芥酸的酯类。由这些烯属原料加氢甲酰化获得的醛类同样可以作为生产可生物降解的、洗涤活性的物质的原料。
实施例A)催化剂母体的合成:由β-甲基吡啶分三步制备5,5’-双(二甲氨甲基)-2,2’联吡啶(配位体1)第一步:J.Chem.Soc.(化学会志),Dalton trans.,1985,pp.2247描述了将4-甲基吡啶氧化键合成4,4’-二甲基-2,2’-联吡啶的方法。β-甲基吡啶键合成5,5’-二甲基-2,2’-联吡啶的方法与之很类似,按照该文献所述的历程进行:第二步:Helv.Chim.Acta.(瑞士化学学报),Vol.67,pp.2264,1984中描述了在自由基引发剂如过氧化苯甲酰存在下6,6’-二甲基-2,2’-联吡啶在CCl4中的自由基溴化反应。在2,2-偶氮二异丁腈引发剂的存在下5,5’-二甲基-2,2’-联吡啶与N-溴丁二酰亚胺的溴化反应与之很类似,按照该文献所述的历程进行:第三步:在THF中5,5’-双(溴甲基)-2,2’联吡啶与LiNMe2反应生成5,5’-双(二甲氨甲基)-2,2’联吡啶。用1%的碳酸氢钠溶液对产物溶液进行急冷,并加入乙醚直到形成第二个相。有机相经过精制生成配位体1:与步骤1相似的可能的替换反应是4-二甲氨基吡啶键合成4,4’-双(二甲氨基)-2,2’联吡啶:B)间歇反应过程的一般条件:所有的间歇加氢甲酰化反应在压力为70巴的100毫升高压釜中进行(高碳钢材料)。将反应混合物在反应温度加热10分钟,同时用一个气/液搅拌器剧烈搅拌溶液。所有的间歇加氢甲酰化反应在压力为280巴的300毫升高压釜中进行(高碳钢材料)。将反应混合物在反应温度加热45分钟,同时用一个磁力搅拌器剧烈搅拌溶液。用通入CO/H2(1∶1)的方法调节两种情况所需的压力,经压力调节器压入气体使反应期间的反应器压力保持在恒定水平。反应结束后冷却反应器,减压和排空。用气相色谱仪分析反应混合物-使用内标法和校正因子。实施例1)用铑/配位体1进行加氢甲酰化,用醋酸溶液萃取分离和催化剂回收a)已知用铑/配位体1进行辛烯-N(异辛烯的混合物,支化度1.3,98克)的加氢甲酰化反应(13ppm铑,配位体/铑=10,150℃,CO/H2(1∶1)280巴,5小时,用5克Texanol作为溶剂),获得98%的辛烯转化率,产出76%的壬醛和19%的壬醇,物料损失3%(以辛烯-N为基计)。b)在20毫巴下蒸馏分离氧代产物直至釜温达150℃为止。c)重复步骤1(12ppm铑),使用b)项的铑催化剂/塔釜溶液。辛烯转化率99%,产出66%的壬醛和15%的壬醇,物料损失16%(以辛烯-N为基计;包括物理损失,高沸物生成和石蜡生成)。d)在20毫巴下蒸馏分离氧代产物(99克)直到釜温达到150℃(16克)为止,用5%醋酸(体积比1∶1)萃取塔釜物,然后进行相分离。经过硅藻土床层和一个纸过滤器的过滤使相分离得到加速。从有机相中检测到铑15ppm,即铑的萃取率达80%。接着向水相中加入Texanol,在标准压力下蒸馏醋酸/水溶液直至釜温达150℃,获得一种均匀溶液。e)重复步骤1(12ppm铑),使用d)项的铑催化剂/Texanol溶液。辛烯转化率97%,产出67%的壬醛和10.5%的壬醇,物料损失19%(以辛烯-N为基计)。对在釜温150℃、压力20毫巴下蒸馏分离的氧代产物直接分析,其高沸物含量仅为5%。f)用5%醋酸(3×50ml)直接萃取反应流出物,接着进行相分离,从有机相中检测出3ppm铑,即铑的萃取率达94%。接着向水相中加入Texanol,在标准压力下蒸馏精制直至釜温达150℃,使配位体去质子化。g)使用f)项的铑催化剂/Texanol溶液进行C12-C14的α-烯烃混合物(94克)的加氢甲酰化(2ppm铑,100℃,CO/H2(1∶1)280巴,4小时),烯烃转化率98%,产出81%的醛,线性异构体的选择性为47%,物料损失6.5%(以α-烯烃为基计;包括物理损失,高沸物生成和石蜡生成)。实施例2)使用铑/配位体1进行加氢甲酰化和使用CO2/H2O溶液萃取分离a)使用铑/配位体1进行辛烯-N(异辛烯的混合物,支化度1.3;95克)的加氢甲酰化反应(13ppm铑,配位体/铑=10,150℃,CO/H2(1∶1)280巴,5小时,用5克Texanol作为溶剂),获得辛烯转化率98%,产出79%的壬醛和壬醇,物料损失18%(以辛烯-N为基计)。b)向由1排出的反应产物(23克)加入20克水,压入1巴的CO2进行萃取并接着进行相分离,有机相中检测出4ppm铑,水相中7ppm,铑的萃取率达85%。c)按实施例1的方法将铑络合物循环使用。
Claims (10)
1.一种由含3个以上碳原子的烯烃加氢甲酰化制醛或者制醛和醇的工艺,包括一个压力为50-1000巴,温度为50℃-180℃,使用一种溶解在均相反应介质中的铑催化剂将烯烃加氢甲酰化的加氢甲酰化步骤,和一个通过铑催化剂萃取的催化剂回收步骤,其中:(a)加氢甲酰化在铑络合物的存在下进行,铑络合物具有一个多齿的、不合磷的能与第八族金属生成络合物的有机氮化合物作配位体,它还含至少一个能在弱酸中质子化的叔氮基,(b)将加氢甲酰化步骤的流出物中的醛和醇根据需要加以分离或部分分离之后,用一种可蒸馏酸的水溶液对流出物进行萃取,(c)在加氢甲酰化条件下是惰性的一种有机溶剂或溶剂混合物存在下,对含水酸萃取液进行热处理,蒸出含水酸,使络合物去质子化并转移到有机相中,(d)将含催化剂络合物的有机相循环到加氢甲酰化步骤中。
2.权利要求1的工艺,其特征在于,所用的可蒸馏酸的铵盐能在室温-200℃下被解离为游离配位体和游离酸。
4.权利要求1的工艺,其特征在于,所用的配位体是结构式Ⅲ表示的聚胺:
其中R”代表氢、烷基、环烷基、芳基、或芳烷基,它还能携带一个二烷基氨基,m是一个2-35000之间的整数,其条件是R”代表氢,至少一些氢原子被来自仲胺基与1-10摩尔环氧乙烷或环氧丙烷反应生成的含2-18个碳原子的烷羰基或者羟基(烷氧基)烷基取代,而且假设聚胺含至少3个能被质子化的叔氮原子。
7.权利要求1的工艺,其特征在于,使用一种pK值为3-6的酸进行萃取。
8.权利要求1的工艺,其特征在于,使用碳酸、甲酸、乙酸、丙酸、正丁酸、或正戊酸的水溶液进行萃取。
9.权利要求1的工艺,其特征在于,使含有7-20个碳原子的烯烃或聚异丁烯加氢甲酰化。
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DE19603201A DE19603201A1 (de) | 1996-01-30 | 1996-01-30 | Verfahren zur Herstellung von Aldehyden durch Hydroformylierung von Olefinen |
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KR (1) | KR19990082119A (zh) |
CN (1) | CN1210514A (zh) |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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CN100339158C (zh) * | 2003-11-20 | 2007-09-26 | 三菱化学株式会社 | 铑络合物催化剂的回收方法 |
CN102649718A (zh) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | 烯烃进行氢甲酰化的方法 |
CN101497561B (zh) * | 2008-01-29 | 2015-03-18 | 财团法人工业技术研究院 | 氢甲酰化制程 |
CN111278560A (zh) * | 2017-11-13 | 2020-06-12 | 陶氏技术投资有限责任公司 | 从氢甲酰化方法回收铑的方法 |
CN114426469A (zh) * | 2020-09-28 | 2022-05-03 | 中国石油化工股份有限公司 | 一种烯烃氢甲酰化制备醇和醛的方法 |
CN116408147A (zh) * | 2023-04-10 | 2023-07-11 | 中国科学院兰州化学物理研究所 | 一种共价三嗪有机聚合物负载铑催化材料的制备及其应用 |
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DE19801437A1 (de) * | 1998-01-16 | 1999-07-22 | Basf Ag | Verfahren zur Herstellung von Aldehyden |
DE19908462A1 (de) * | 1999-02-26 | 2000-08-31 | Basf Ag | Verfahren zur Hydroformylierung von Olefinen |
CN100595180C (zh) * | 2003-12-18 | 2010-03-24 | 埃克森美孚化学专利公司 | 加氢甲酰化或相关方面的改进 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1530136A (fr) * | 1966-07-07 | 1968-06-21 | Jeferson Chemical Company | Procédé d'hydroformylation des oléfines et produits obtenus |
US3594425A (en) * | 1966-07-07 | 1971-07-20 | Jefferson Chem Co Inc | Hydroformylation process |
DE1902460C3 (de) * | 1969-01-18 | 1974-06-12 | Basf Ag, 6700 Ludwigshafen | Verfahren zur Herstellung von Aldehyden und Alkoholen durch Oxo-Synthese |
US3857895A (en) * | 1969-05-12 | 1974-12-31 | Union Oil Co | Recovery of catalyst complexes |
DE2604545C3 (de) * | 1976-02-06 | 1978-08-17 | Basf Ag, 6700 Ludwigshafen | Verfahren zur Herstellung von Alkylcarbonsäuren |
US4400547A (en) * | 1981-04-10 | 1983-08-23 | Eastman Kodak Company | Hydroformylation process utilizing an unmodified rhodium catalyst and the stabilization and regeneration thereof |
US4388476A (en) * | 1981-05-01 | 1983-06-14 | Eastman Kodak Company | Hydroformylation process with rhodium catalyst and oxygen stabilization thereof |
US4528403A (en) * | 1982-10-21 | 1985-07-09 | Mitsubishi Chemical Industries Ltd. | Hydroformylation process for preparation of aldehydes and alcohols |
DE4316180A1 (de) * | 1992-09-16 | 1994-11-17 | Basf Ag | Verfahren zur Herstellung von Aldehyden |
JPH06252086A (ja) * | 1993-02-24 | 1994-09-09 | Hitachi Ltd | 半導体製造装置 |
CA2121308C (en) * | 1993-04-19 | 2001-07-24 | Toshihiro Omatsu | Rhodium-containing catalyst |
DE4408950A1 (de) * | 1994-03-16 | 1995-09-21 | Basf Ag | Verfahren zur Herstellung von Alkoholen und/oder Aldehyden |
-
1996
- 1996-01-30 DE DE19603201A patent/DE19603201A1/de not_active Withdrawn
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- 1997-01-28 KR KR1019980705841A patent/KR19990082119A/ko not_active Application Discontinuation
- 1997-01-28 DE DE59703863T patent/DE59703863D1/de not_active Expired - Lifetime
- 1997-01-28 CN CN97191973A patent/CN1210514A/zh active Pending
- 1997-01-28 JP JP9527290A patent/JP2000504001A/ja active Pending
- 1997-01-28 ES ES97902245T patent/ES2158488T3/es not_active Expired - Lifetime
- 1997-01-28 US US09/101,692 patent/US6107524A/en not_active Expired - Fee Related
- 1997-01-28 WO PCT/EP1997/000372 patent/WO1997028113A1/de not_active Application Discontinuation
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Cited By (10)
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CN100339158C (zh) * | 2003-11-20 | 2007-09-26 | 三菱化学株式会社 | 铑络合物催化剂的回收方法 |
CN101497561B (zh) * | 2008-01-29 | 2015-03-18 | 财团法人工业技术研究院 | 氢甲酰化制程 |
CN102649718A (zh) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | 烯烃进行氢甲酰化的方法 |
CN102649718B (zh) * | 2011-02-25 | 2014-05-28 | 中国石油化工股份有限公司 | 烯烃进行氢甲酰化的方法 |
CN111278560A (zh) * | 2017-11-13 | 2020-06-12 | 陶氏技术投资有限责任公司 | 从氢甲酰化方法回收铑的方法 |
CN111278560B (zh) * | 2017-11-13 | 2023-07-21 | 陶氏技术投资有限责任公司 | 从氢甲酰化方法回收铑的方法 |
CN114426469A (zh) * | 2020-09-28 | 2022-05-03 | 中国石油化工股份有限公司 | 一种烯烃氢甲酰化制备醇和醛的方法 |
CN114426469B (zh) * | 2020-09-28 | 2024-07-09 | 中国石油化工股份有限公司 | 一种烯烃氢甲酰化制备醇和醛的方法 |
CN116408147A (zh) * | 2023-04-10 | 2023-07-11 | 中国科学院兰州化学物理研究所 | 一种共价三嗪有机聚合物负载铑催化材料的制备及其应用 |
CN116408147B (zh) * | 2023-04-10 | 2023-09-29 | 中国科学院兰州化学物理研究所 | 一种共价三嗪有机聚合物负载铑催化材料的制备及其应用 |
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EP0885183B1 (de) | 2001-06-20 |
EP0885183A1 (de) | 1998-12-23 |
JP2000504001A (ja) | 2000-04-04 |
ES2158488T3 (es) | 2001-09-01 |
US6107524A (en) | 2000-08-22 |
WO1997028113A1 (de) | 1997-08-07 |
DE19603201A1 (de) | 1997-07-31 |
KR19990082119A (ko) | 1999-11-15 |
DE59703863D1 (de) | 2001-07-26 |
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