CN1346821A - 用于烯烃醛化的铑催化剂的稳定化方法 - Google Patents
用于烯烃醛化的铑催化剂的稳定化方法 Download PDFInfo
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Abstract
本发明涉及到用铑催化剂将相应烯烃醛化而制备有3－21碳原子的醛类的方法,其中将醛化反应器的卸料:a)分离成气相和液相,b)将液相分离成含有未反应的烯烃和醛的塔顶馏份和含有铑催化剂的塔底馏份,c)将塔底馏分冷却到低于醛化反应器卸料的温度,并加入含一氧化碳的气体。
Description
技术领域
本发明涉及一种用于制备醛类的改进型方法，该方法在铑-催化剂处理时通过减少经去活作用下将烯烃醛化而制备醛类。
背景技术
在工业范围中，烯烃的醛化是用钴催化剂或铑催化剂催化进行的。在此应用中铑催化剂的应用是最有利的，因为使用铑催化剂能够达到高选择性和产品收率。然而跟钴相比，铑更昂贵；在用铑催化剂使烯轻醛化成相应的醛类时，催化剂是一个非常重要的成本因素。为了提高经济效益，必须降低单位催化剂消耗量。对催化剂的用量应理解为，为了保证催化剂恒定的活性水平，在长期运行中必须向工艺过程中输入催化剂。
用铑催化的烯轻转化为相应的醛类的催化反应通常是在液相中进行的。对丙烯醛化也已经建立了一种方法，在这个方法中，催化剂被熔解在第二种液相中；但是该方法应用到长链烯烃中是有局限性的。
在均相中醛化时，也就是说催化剂、烯烃、产物、溶剂等都在同一相内，就出现了在反应后将催化剂与产物分开的难题。这个难题可以简单地通过未反应原料从产物中蒸馏出来的办法而解决；在塔底物主要是高沸点成分溶解的催化剂接着被送回反应器中。这种蒸馏可连续的或间断的进行。
在蒸馏分离过程中，常常能发现催化剂的分解或去活。特别是在长链烯烃的醛化时，由于产物的沸点，蒸馏只能在高温下和/或低压下进行。
为了在醛化时反应器卸料的处理中减少铑催化剂的去活，已知各种方法。
在EP 0272608 B1中描述了一种方法，在该方法中，采用含氧化三苯膦-配位体的铑催化剂。对于反应卸料的处理中，在蒸馏以前加入三苯膦(其用量为铑的9倍)。蒸馏剩余物含有带三苯膦配位体的铑络合物以及三苯膦和氧化三苯膦。在这个混合物中，游离的和络合的三苯膦被氧化成氧化三苯膦。该催化剂溶液被送回反应器中。氧或过氧化物被用来氧化三苯膦。已知这种方法的其他方案，并且在JP 63222 139，JP 63 208 540，DE 3 338 340和JP 63 218 640中有描述。
这些方法有如下的缺点：即要不断的消耗三苯膦。从而通过氧化而生成相当量的氧化三苯膦。为了在反应器中限制其浓度，就必须有排出流，由此铑也要排出。还需要附加的氧化装置。对于氧化过程来说，如果不直接用空气，还得考虑氧化剂的费用。
在有关的文献资料(例如US 4 400 547)中描述了采用另一种用磷配位体来稳定铑的方法。
在专利刊物US 5 731 472、US 5 767 321和EP 0 149 894中描述了正丁烯的醛化方法。在该法中所用的铑催化剂含有亚磷酸根配位体，并且加有胺来稳定催化剂。其缺点在于胺可作为羟醛缩合的催化剂，这样就容易形成高沸点物。
在JP-04-164042中描述了C8-烯烃混合物的醛化过程中用铑络合物催化，并用取代的酚来稳定催化剂，通过丁烯的二聚合而制备的。在此，铑化合物、配位体和稳定剂具有的摩尔比为1/10/50。这个方法的缺点是稳定剂的费用高和分离的耗费大。
发明内容
本发明的目的是提供一种烯烃醛化的方法，该方法中铑催化剂的去活作作用被进一步压制。
本发明的目的就是用铑催化剂通过相应的烯烃醛化而制备具有3-21个碳原子的醛的方法，将其醛化反应器的卸料：
a)分离成气相和液相，
b)将液相分离成含有未反应的烯烃和醛的塔顶馏份和含有铑催化剂的塔底馏份，
c)将塔底馏份冷却到低于醛化反应器的卸料温度，并且加入含一氧化碳的气体。
通过按照本发明的方法，在醛化卸料的后处理过程中能极大的减少催化剂的活性损失。令人意外的发现，用一氧化碳稳定的铑催化剂溶液有数周的储存稳定性。
所以本发明的另一个目的是含铑的催化剂溶液，特别是在羰基化过程中产生的催化剂溶液在保持其活性的情况下的储存。按照发明活性的保持按如下达到，即在90℃的温度以下，最好是在60℃，一氧化碳分压为0.1-300bar，最好为5-64bar下储存铑催化剂溶液。
本发明的方法与已知的方法相比有如下的优点：催化剂在后处理过程中几乎未被去活。不需要使成本增加的添加物。催化剂用就在反应器中存在的物质稳定。催化剂溶液在储存时不推动活性是可能的。这一点对于长期存放是特别有利的，例如在大修或检查时，或产品的批量生产时。
醛化根据已知的方法(B.Cornils，W.A.Herrmann，“AppliedHomogeneous Catalysis with Organometallic Compounds”(有机金属化合物应用均相催化)Vol.1&2，VCH，Weinham，New York，1996)在反应器中以均相进行。具有2-20碳原子的烯烃都可考虑作为原料，特别是丁烯、戊烯、己烯和辛烯，特别是通过丁烯低聚合而得到的二丁烯。由醛类、醇类、未反应的烯烃、高沸点物，催化剂系统、副产物和分解产物组成的产物流首先在分离阶段(方法步骤a)分离成气相和液相。气相中含有大部分未反应的合成气和根据温度和压力部分未反应的烯轻、醛类、烃类和其他成分。而液相主要是由醛化产物和未反应的烯烃组成。在这分离阶段的温度为30-180℃，优选为50-150℃。分离在一氧化碳的分压为0.5-100bar，优选为1-35bar下进行。在这样的装置中能保证铑的稳定性。在工业生产中中，该分离过程既可以在醛化反应器的顶部进行，也可以在另一个装置如分离瓶中进行。假如反应器运行压力高于分离阶段的压力时，那么在其之间要进行降压。一氧化碳分压能或者通过在醛化反应器使用的气体混合物保持或者通过加入含一氧化碳的气体而得到保持。
因为催化剂能继续与未反应的烯烃起反应，由于液相中合成气体可能的减少而增加了催化剂分解的危险性，所以在分离阶段力求液相的短停留时间，适宜的停留时间为30分钟以下，优选为15分钟以下。
分离成气体和液体以后，液相以蒸馏分离成塔顶馏份和塔底馏份(分馏阶段，方法步骤b))。在塔底馏份中有溶解在高沸点物中的催化剂，这些高沸点物或者是在反应过程中加入的，或者是反应过程中形成的。在较低沸点的塔顶馏份中主要有氧化产物和未反应的烯烃。
液相在分馏阶段的平均停留时间少于15分钟，优选为5分钟以下，最优选为2分钟以下。分馏阶段b)用于分离的装置可以是闪蒸器、降膜蒸发器、薄膜蒸发器或者类似的装置，这些装置均可进行满意的分离。也能用这些装置的组合装置，例如将降膜蒸发器流出的塔底物输送到薄膜蒸发器中。
在分馏阶段的压力为0.01mbar-1bar，优选为10mbar-1bar。温度为40℃-180℃，优选为80℃-150℃。从分馏阶段分馏出的塔底馏份立刻冷却到大约10℃-120℃，优选为40℃-90℃，并且一氧化碳分压为0.1bar-300bar，优选为5-64bar。作为含一氧化碳的气体可以是纯一氧化碳、合成气体或其他的一氧化碳与惰性气体如氮气、二氧化碳、氢气和/或甲烷的混合气体。
该方法部分的一种可能的实施方案是将从分馏阶段得到高沸点物在冷却器中或者通过与冷却液体，优选是与加入的烯轻的混合而冷却，然后借助于泵将这些高沸点物料泵入有一氧化碳加入的容器中，例如搅拌罐炉、压力容器或者压力管道中。
催化剂的储存温度优选为低于从方法步骤b)的催化剂溶液的流出温度。所以优选的塔底馏份的储存温度是10-120℃，特别优选为40-90℃。所要储存的催化剂溶液可有任选的加入溶剂，所适宜的溶剂是在反应过程中存在的物料，例如原料(烯烃)、产物(醛)或氢化产物(醇)。
催化剂溶液，即方法步骤b)的塔底馏份可完全或部分送回醛化反应器中。在分馏阶段b)所产生的蒸汽混合物即未反应的烯烃和醛化产物将根据已知的方法处理。
附图简介
图1为工业实验装置。
图2为120℃下合成气压力对催化剂活性的影响。
图3为50bar合成气压力下温度对催化剂活性的影响。
实施例
下面的实施例描述了本发明，但并不限制本发明在专利要求书中所要求的保护范围。
实施例1
在工业实验装置(图1)中的醛化如下进行。
在泡罩塔反应器(1)(容积为601)中加入烯烃(10)、合成气(11)和催化剂溶液(21)。醛化卸料(13)在闪蒸器(2)中减压到5bar。所逸出的气体(14)在冷却器(未示出)中冷却，产生的冷凝物与液体(15)合并。在闪蒸器(2)中所产生的液相(15)在薄膜蒸发器(3)中分离成塔顶馏份(17)和塔底馏份(16)。粗产物(17)在冷却器(8)中冷凝，并且收集到容器9中。塔底馏份(16)含有溶解在高沸点物中的催化剂，其在冷却器(4)中冷却(参见表3)，并用泵(5)输送到中间容器(6)中。用合成气(18)将容器(6)中的压力调节到10bar。在容器(6)中的催化剂溶液(16)温度根据表3确定。催化剂溶液能通过排出一部分该溶液(19)和添加一些催化剂原液(20)(铑化合物和配位体)调到反应器(1)中所希望的活性，并用泵以溶液(21)送回反应器(1)中。
表1给出了典型的原料的加入量和催化剂浓度。
| 烯烃 | 二-正-丁烯 | 5kg/h |
| 合成气 | CO/CH2(l/l) | 2kg/h |
| 铑化合物 | 辛酸铑 | (反应器1中30-90ppmRh) |
| 配位体 | 三(2，4-二-叔-丁苯)亚磷酸盐 | (20mol配位体/molRh) |
表2给出了实验参数，这些参数在整个实验过程中保持不变。
| 反应器1中的压力 | 50bar |
| 反应器1中的温度 | 130℃ |
| 薄膜蒸发器3中的压力 | 60mbar |
| 薄膜蒸发器3中的温度(塔底出口温度) | 140℃ |
催化剂的活性通过在反应器所达到的转化率来监控。一旦烯烃的转化率低于95％时，马上就要从容器(6)排出部分催化剂溶液，并且加入新的催化剂原液(铑盐和配位体)，以使转化率重新达到95％以上。由于高沸点物排料而导致的较少的催化剂损失也要加以补充。
对于冷却器(4)的不同温度(催化剂溶液的流出温度)必须加入下列的铑量(以金属铑计算)，以便利转化率保持在一定水平(表3)：
| 冷却器4的温度 | 容器6的温度 | 铑(g)/每吨转化的烯轻 |
| 不冷却 | 70-90℃ | 2.1 |
| 60℃ | 40-55℃ | 0.9 |
实施例2
与合成气压力相关的催化剂活性的下降。
在3升的高压釜中(Büchi)将350g甲苯、3.03g的三(2，4-二-叔-丁苯)亚磷酸盐和0.096g辛酸铑在50bar的合成气体(1/1CO/H2)的压力、120℃温度下预处理一小时。然后取出一些试样，通过环辛烯(120℃，50bar合成气压力)在第二个高压釜中进行醛化反应而确定催化剂的活性。接着催化剂在第一个高压釜中继续热处理数小时，在此期间取出试样，像确定催化剂的起始活性那样而测试催化剂的活性。这种试验在不同的温度和合成气压力下重复进行。
在图1中给出合成气压力对催化剂的活性的影响(归一化活性，新催化剂的活性为100％或1)。在合成气压力为50bar时，经过100小时催化剂的活性还有原活性的80％以上。而对于合成气压力为20bar时，经65小时其活性已经下降到不到原活性的40％。
在图2中给出在恒定的50bar的合成气体压力下温度对催化剂稳定性的影响。温度从120℃提高到140℃将导致催化剂的分解急剧加速。
Claims (11)
1.一种利用铑催化剂将相应烯烃醛化而制备有3-21碳原子的醛类的方法，其特征在于，将醛化反应器的卸料：
a)分离成气相和液相，
b)将液相分离成含有未反应的烯烃和醛的塔顶馏份和含有铑催化剂的塔底馏份，
c)将塔底馏份冷却到低于醛化反应器的卸料温度，并加入含一氧化碳的气体。
2.根据权利要求1的方法，其特征在于，在方法步骤a)中一氧化碳的分压被调节到0.5-100bar。
3.根据权利要求1或2之一的方法，其特征在于，在方法步骤b)具有降膜蒸发器、薄膜蒸发器、闪蒸器或它们的组合装置。
4.根据权利要求1-3之一的方法，其特征在于，在方法步骤b)中液相的平均停留时间少于15分钟。
5.根据权利要求1-4之一的方法，其特征在于，在方法步骤b)的塔底馏份的平均停留时间少于2分钟。
6.根据权利要求1-5之一的方法，其特征在于，在方法步骤b)中的温度为40-180℃。
7.根据权利要求1-6之一的方法，其特征在于，在方法步骤b)中的压力为0.01-1bar。
8.根据权利要求1-7之一的方法，其特征在于，在方法步骤c)的塔底馏份中施加分压为0.1-300bar的一氧化碳。
9.根据权利要求1-8之一的方法，其特征在于，合成气、纯的一氧化碳或一氧化碳与氮气、甲烷、氢气和/或二氧化碳的混合物作为含一氧化碳的气体。
10.根据权利要求1-9之一的方法，其特征在于，将方法步骤c)的塔底馏份冷却到10-120℃。
11.根据权利要求1-10之一的方法，其特征在于，将方法步骤c)的塔底馏份完全或部分地送回醛化反应器中。
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| CN113351249B (zh) * | 2021-04-29 | 2023-02-03 | 四川大学 | 一种催化内烯烃氢甲酰化制醛的催化体系 |
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| JPS5638576B2 (zh) * | 1974-07-25 | 1981-09-08 | ||
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| US4400547A (en) * | 1981-04-10 | 1983-08-23 | Eastman Kodak Company | Hydroformylation process utilizing an unmodified rhodium catalyst and the stabilization and regeneration thereof |
| US4446074A (en) * | 1981-12-24 | 1984-05-01 | Union Carbide Corporation | Preparation of rhodium complex compounds |
| US4528403A (en) | 1982-10-21 | 1985-07-09 | Mitsubishi Chemical Industries Ltd. | Hydroformylation process for preparation of aldehydes and alcohols |
| GB8334359D0 (en) | 1983-12-23 | 1984-02-01 | Davy Mckee Ltd | Process |
| EP0272608B1 (en) | 1986-12-23 | 1992-03-04 | Mitsubishi Kasei Corporation | Process for the hydroformylation of an olefin |
| JP2687960B2 (ja) | 1987-02-25 | 1997-12-08 | 三菱化学株式会社 | オレフインのヒドロホルミル化方法 |
| JPH0764772B2 (ja) | 1987-03-09 | 1995-07-12 | 三菱化学株式会社 | オレフインのヒドロホルミル化法 |
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| KR0134494B1 (ko) * | 1993-10-20 | 1998-04-20 | 성재갑 | 하이드리도카르보닐트리스(트리오가노포스포러스)로듐의 제조방법 |
| US5731472A (en) * | 1995-12-06 | 1998-03-24 | Union Carbide Chemicals & Plastics Technology Corporation | Metal-ligand complex catalyzed processes |
| US5767321A (en) * | 1995-12-06 | 1998-06-16 | Union Carbide Chemicals & Plastics Technology Corporation | Metal-ligand complex catalyzed processes |
| DE19605435A1 (de) * | 1996-02-14 | 1997-08-21 | Basf Ag | Verfahren zur Herstellung von Aldehyden durch Hydroformylierung mit einem Rhodiumkatalysator und Wiedergewinnung des Rhodiumkatalysators durch Extraktion |
-
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- 2000-09-29 DE DE10048301A patent/DE10048301A1/de not_active Withdrawn
-
2001
- 2001-08-10 DE DE2001504749 patent/DE50104749D1/de not_active Expired - Lifetime
- 2001-08-10 AT AT01119282T patent/ATE284375T1/de not_active IP Right Cessation
- 2001-08-10 EP EP01119282A patent/EP1193239B1/de not_active Expired - Lifetime
- 2001-08-10 ES ES01119282T patent/ES2231358T3/es not_active Expired - Lifetime
- 2001-09-12 SG SG200105593A patent/SG94863A1/en unknown
- 2001-09-25 PL PL349832A patent/PL201587B1/pl unknown
- 2001-09-25 TW TW090123565A patent/TWI224094B/zh not_active IP Right Cessation
- 2001-09-25 US US09/960,936 patent/US6500991B2/en not_active Expired - Lifetime
- 2001-09-27 BR BR0104335-8A patent/BR0104335A/pt not_active Application Discontinuation
- 2001-09-27 KR KR1020010059894A patent/KR100717984B1/ko not_active IP Right Cessation
- 2001-09-27 CA CA002357856A patent/CA2357856A1/en not_active Abandoned
- 2001-09-27 MY MYPI20014532A patent/MY121533A/en unknown
- 2001-09-27 MX MXPA01009756A patent/MXPA01009756A/es unknown
- 2001-09-28 RU RU2001126325/04A patent/RU2270829C2/ru not_active IP Right Cessation
- 2001-09-28 ZA ZA200107977A patent/ZA200107977B/xx unknown
- 2001-09-28 CN CNB011411198A patent/CN1200923C/zh not_active Expired - Fee Related
- 2001-09-28 JP JP2001300783A patent/JP5226922B2/ja not_active Expired - Fee Related
- 2001-09-28 AR ARP010104573A patent/AR030811A1/es unknown
- 2001-11-13 SA SA01220521A patent/SA01220521B1/ar unknown
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI586644B (zh) * | 2014-12-04 | 2017-06-11 | 陶氏科技投資有限公司 | 氫甲醯化方法 |
| CN107138182A (zh) * | 2016-03-01 | 2017-09-08 | 约翰逊·马泰·戴维技术有限公司 | 设备和方法 |
| CN107138182B (zh) * | 2016-03-01 | 2022-08-23 | 庄信万丰戴维技术有限公司 | 设备和方法 |
| CN108395370A (zh) * | 2017-02-08 | 2018-08-14 | 中国石化扬子石油化工有限公司 | 一种氧化苯乙烯制备苯甲醛的方法 |
| CN108395370B (zh) * | 2017-02-08 | 2021-04-06 | 中国石化扬子石油化工有限公司 | 一种氧化苯乙烯制备苯甲醛的方法 |
| CN112479841A (zh) * | 2020-11-26 | 2021-03-12 | 万华化学集团股份有限公司 | 一种丙烯氢甲酰化合成丁醛的工艺 |
Also Published As
| Publication number | Publication date |
|---|---|
| ZA200107977B (en) | 2002-05-29 |
| KR100717984B1 (ko) | 2007-05-16 |
| DE10048301A1 (de) | 2002-04-11 |
| BR0104335A (pt) | 2002-05-07 |
| JP2002161063A (ja) | 2002-06-04 |
| SG94863A1 (en) | 2003-03-18 |
| JP5226922B2 (ja) | 2013-07-03 |
| ES2231358T3 (es) | 2005-05-16 |
| EP1193239A1 (de) | 2002-04-03 |
| AR030811A1 (es) | 2003-09-03 |
| PL349832A1 (en) | 2002-04-08 |
| SA01220521B1 (ar) | 2006-05-23 |
| DE50104749D1 (de) | 2005-01-13 |
| US20020065437A1 (en) | 2002-05-30 |
| RU2270829C2 (ru) | 2006-02-27 |
| PL201587B1 (pl) | 2009-04-30 |
| ATE284375T1 (de) | 2004-12-15 |
| MY121533A (en) | 2006-01-28 |
| KR20020025747A (ko) | 2002-04-04 |
| CA2357856A1 (en) | 2002-03-29 |
| EP1193239B1 (de) | 2004-12-08 |
| CN1200923C (zh) | 2005-05-11 |
| US6500991B2 (en) | 2002-12-31 |
| MXPA01009756A (es) | 2002-04-15 |
| TWI224094B (en) | 2004-11-21 |
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