CN101061100A - 使用薄膜将膦和/或氧化膦助催化剂与产品分离的丙烯环氧化方法 - Google Patents
使用薄膜将膦和/或氧化膦助催化剂与产品分离的丙烯环氧化方法 Download PDFInfo
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Abstract
一种丙烯、氧和氢在液体溶剂中催化反应生产环氧丙烷的方法，其中使用膦和/或氧化膦助催化剂，改进包括用有效保留所述膦和/或氧化膦助催化剂的薄膜来分离膦和/或氧化膦助催化剂，而使环氧丙烷和溶剂通过。优选所述助催化剂为三苯基膦，所述薄膜为亲水纳米过滤薄膜或反渗透薄膜。
Description
发明领域
本发明的方法涉及一种将例如用于环氧丙烷生产的溶剂与有机膦和/或氧化膦分离的方法，以及特别涉及在环氧丙烷生产方法中回收和循环有机膦和/或氧化膦。
发明背景
已对用于环氧丙烷生产的无副产物的直接氧化法的研制花费了巨大的努力。USP 6005123是已达得令人鼓舞结果的说明。
正如在USP 6005123中公开的，可通过丙烯、氧和氢在贵金属/硅酸钛催化剂例如Pd/TS-1存在下反应来制备环氧丙烷。通常，在反应过程中，将固体催化剂浆化在适合的溶剂例如甲醇和水混合物中。
在生成环氧丙烷的反应混合物中还存在膦或氧化膦类型反应助催化剂例如三苯基膦的场合下，得到特别有利的结果。
为了能使膦或氧化膦用于连续的化学过程，必需将它们循环。如果膦或氧化膦不能方便地循环再利用，那么膦或氧化膦的使用是费用极高的。遗憾的是，甲醇和/或水用作溶剂的方法使大多数典型的装置操作不能使用。当甲醇从反应混合物中蒸馏或汽提时，膦或氧化膦从溶液中沉积，从而使蒸馏釜污染。而且，膦或氧化膦不足够稳定或挥发性很高，从而从蒸馏塔顶蒸出。即使水以某种方式从蒸馏塔顶蒸出，而使膦或氧化膦保留在PEG和其它环氧丙烷开环产物的溶液中，开环产物从膦或氧化膦中的分离也不能用蒸馏法实现。因此，蒸馏不起作用。
蒸馏不是一种选择方案的事实是，萃取技术也不能有效地起作用。即使人们可制得在开环产物溶液中的膦或氧化膦，溶解膦或氧化膦的溶剂与开环部分也是混溶的。即使可找到可从开环的溶液中选择性萃取膦或氧化膦的溶剂，这种方法也需要更多的蒸馏操作，以便使萃取溶剂循环。
发明概述
本发明提供这样一种方法，用这一方法可将含有环氧丙烷和膦和/或氧化膦助催化剂的反应混合物(例如按USP 6005123生产的)分离成用于循环的溶剂和助催化剂馏分以及用于产物回收的环氧丙烷馏分。使用薄膜分离来实现这一分离，薄膜的功能是允许溶剂和环氧丙烷流到渗透液中，而将用于循环的膦和/或氧化膦助催化剂保留在渗余液中。
附图简介
附图图示说明本发明的实施。
发明详述
在附图中描述了本发明一个特别优选的实施。参考附图，反应器1为一个适用于丙烯、氧和氢在固体贵金属/硅酸钛催化剂的浆液中反应生成环氧丙烷的传统反应器。将丙烯、氧和氢分别通过管线2、3和4送入。溶剂和催化剂通过管线5送入。补充溶剂也可通过管线5加入(未示出)。将反应器1保持在有效生成环氧丙烷的已知条件下，含环氧丙烷的反应混合物通过管线6取出。
一个关键的特点是在环氧化反应混合物中提供膦和/或氧化膦助催化剂。在循环物流7中含有这些助催化剂，如果需要还可通过管线8补充。
反应混合物通过管线6从反应器1送入分离段9，在那里分离固体催化剂，并通过管线5与溶剂和一些反应物和反应产物一起循环到反应器1。过滤、离心分离等是适合用于这一分离的步骤。
含有溶剂、环氧丙烷和其它反应材料的液体物流与膦和/或氧化膦助催化剂通过管线10从分离段9送入蒸馏段11，其中(在一个优选的实施方案中)，各种轻质材料例如丙烯和丙烷作为塔顶产物通过管线12从反应液体中分离。
在一个优选的实施中，含有环氧丙烷、开环的有机产物、溶剂、膦和/或氧化膦助催化剂的塔11的塔底物流通过管线20送入蒸馏段21，其中环氧丙烷产物作为塔顶产物通过管线22回收。含有膦和/或氧化膦助催化剂的塔底物流通过管线23送入段14，在其中这一物流与适合的薄膜15接触，有效地将渗透液与膦和/或氧化膦助催化剂渗余液分离，所述的渗透液含有溶剂和开环的材料。
膦和/或氧化膦渗余液通过管线7返回反应器1，以便再用于所述的方法，而助催化剂通过管线16送入传统的分离设备，以便回收环氧丙烷产物以及分离和循环溶剂(未示出)。
本发明使用的薄膜分离涉及使用亲水性纳米过滤薄膜和反渗透薄膜。在现有技术中许多这样的薄膜是大家熟悉的，最好的例子是聚(酰胺)，例如Dow’s Film Tec薄膜以及其它化学上更稳定的聚合物薄膜，例如Koch’s SelRO薄膜等。在本方法中，这些薄膜可用于反应器后的任何地方，并包括在分离序列(train)中。一个可方便使用薄膜的地方是在反应器流出物处理的过程中，在除去固体浆液催化剂以后或在反应器以后(如果催化剂用作填充床)。特别优选的是，正如在附图中说明的，在从混合物中除去轻质气体、丙烯和丙烷以后使用薄膜。薄膜允许甲醇、水、环氧丙烷和开环的物类渗透，而作为渗余液在溶液中留下膦和氧化膦。渗透溶液送去本方法的蒸馏和精制部分，而将膦和氧化膦在甲醇、环氧丙烷、水和开环产物的溶液中的浓缩溶液循环回反应器再利用。正如上述，使用薄膜的优选方法是在轻质气体、丙烯、丙烷和环氧丙烷从物流中除去以后。在这种情况下，几乎没有环氧丙烷循环回反应器。
在现有技术中，用于本发明分离的薄膜是大家熟悉的。根据本发明，为了将环氧丙烷和溶剂溶液与膦和/或氧化膦分离，使用纳米多孔薄膜或反渗透薄膜，它们在有机溶剂例如甲醇和环氧丙烷存在下是稳定的。适合薄膜的说明性例子是Koch Membrane Systems得到的SelRO薄膜。适用的各向同性微孔薄膜在Kirk-Othmer，“Encyclopedia ofChemical Technology”，Fourth Edition，Vol.16，pages137-153(1995)中描述。也可使用例如在USP 5681473第23栏中公开的那些薄膜。
薄膜分离在这样一些条件下进行，以致大部分优选至少90％膦和/或氧化膦保留在用于循环的渗余液中，而大部分环氧丙烷和溶剂作为渗透液送去随后的分离。
在本发明的薄膜分离中，使用耐有机溶剂的薄膜复合材料，它能使主要部分例如60％或更多的环氧丙烷和有机溶剂和水通过，而使至少90wt％膦和/或氧化膦不渗透。薄膜分离是一种压力推动的过程，一般来说进料物流的压力可为约50lb/in2的低压至约1500lb/in2的高压。更优选的是，本发明进料物流的压力为约100至约600psi。“渗透液”为渗透过薄膜的物流，与进料物流相比，渗透液处于低得多的压力下。通常，渗透液接近大气压至50psi。渗透液含有少量的膦和/或氧化膦，溶于大量有机溶剂和环氧丙烷产物中。所述的渗透液可用任何传统的方法回收，例如简单地将它作为液体收集。渗余液物流(也称为“浓缩液”或“非渗透液”物流)为未渗透过薄膜的物流。渗余液含有大量溶于有机溶剂中的膦和/或氧化膦。渗余液物流通常比进料物流的压力仅仅稍低，可循环回氧化反应器再利用。
以下举例说明本发明的实施。
实施例
根据US 6005123中公开的方法，丙烯在反应器1中以连续反应的方式与氧和氢在甲醇/水溶剂混合物中反应，使用浆化的钯/TS-1(1.5wt％Pd)催化剂。反应混合物约0.1wt％的三苯基膦用作助催化剂。
含有浆化催化剂的液体反应混合物通过管线6从反应器1中取出，并送入分离器9。将催化剂和溶剂与分离器14通过管线7循环的循环物流一起通过管线5循环到反应器1。
分离器9的液体反应混合物物流通过管线10送入蒸馏塔11，轻质物流作为塔顶产物通过管线12分离。处于170℃和275psig的塔11的塔底产物通过管线20送入蒸馏塔21，在120℃和100psig下通过管线22回收环氧丙烷产物物流。
塔21的塔底产物通过管线23送入123℃和100psig下的分离器14。用泵将压力升至300psig，将温度调节到30℃。分离器14内安装有亲水的纳米过滤薄膜Koch SELRO MPS-44，它主要保留三苯基膦促进剂，而使大量开环有机物、水和甲醇渗透。
在30℃和290psig下通过管线7除去渗余液，并循环到反应器1，而在30℃和20psig下通过管线16除去渗透液，用于进一步分离。
下表1给出以lb/hr表示的各种物流中各组分的流速。
表1
| 组分 | 物流 | ||||||
| 10 | 12 | 20 | 22 | 23 | 7 | 16 | |
| H2O | 173.2 | 173.2 | 173.2 | 33.8 | 139.4 | ||
| TPP(1) | 0.01 | 0.01 | 0.01 | 0.0099 | 0.0001 | ||
| C3H6 | 18.8 | 18.8 | |||||
| O2 | - | ||||||
| H2 | - | ||||||
| 压舱物 | - | ||||||
| 甲醇 | 447.3 | 447.3 | 40 | 407.3 | 79.5 | 327.8 | |
| RO(2) | 8.3 | 8.3 | 8.3 | 1.6 | 6.7 | ||
| PO(3) | 69.9 | 69.9 | 69.9 | ||||
| C3H8 | 3.1 | 3.1 | |||||
| 催化剂 | |||||||
(1)三苯基膦
(2)开环有机物
(3)环氧丙烷
从这一实施例可以看出，本发明的方法有效地分离用于循环的三苯基膦。
Claims (3)
1.一种通过丙烯、氧和氢在液体溶剂中的催化反应生产环氧丙烷的方法，其中使用膦和/或氧化膦助催化剂，改进包括用有效保留所述膦和/或氧化膦助催化剂的薄膜来分离膦和/或氧化膦助催化剂，而使环氧丙烷和溶剂通过。
2.根据权利要求1的方法，其中所述助催化剂为三苯基膦。
3.根据权利要求1的方法，其中所述薄膜为亲水纳米过滤薄膜或反渗透薄膜。
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| Application Number | Priority Date | Filing Date | Title |
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| US10/990,028 | 2004-11-16 | ||
| US10/990,028 US7084284B2 (en) | 2004-11-16 | 2004-11-16 | Separation process |
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| CN101061100A true CN101061100A (zh) | 2007-10-24 |
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| CNA200580039205XA Pending CN101061100A (zh) | 2004-11-16 | 2005-09-09 | 使用薄膜将膦和/或氧化膦助催化剂与产品分离的丙烯环氧化方法 |
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| US (1) | US7084284B2 (zh) |
| EP (1) | EP1812415B1 (zh) |
| JP (1) | JP2008520663A (zh) |
| CN (1) | CN101061100A (zh) |
| AT (1) | ATE386731T1 (zh) |
| DE (1) | DE602005004939T2 (zh) |
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| RU2452731C2 (ru) * | 2006-12-20 | 2012-06-10 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. | Способ удаления поли(пропиленоксида) из пропиленоксида путем мембранного разделения |
| US8981012B2 (en) * | 2008-07-09 | 2015-03-17 | University Of Iowa Research Foundation | Modified polydicyclopentadienes |
| US8207360B2 (en) * | 2010-01-29 | 2012-06-26 | Lyondell Chemical Technology, L.P. | Propylene oxide process |
| US8778186B2 (en) * | 2011-07-11 | 2014-07-15 | University Of Iowa Research Foundation | High-density polydicyclopentadiene |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5248794A (en) * | 1993-02-16 | 1993-09-28 | The Dow Chemical Company | Process for purifying propylene oxide |
| US5440058A (en) * | 1994-06-07 | 1995-08-08 | Union Carbide Chemicals & Plastics Technology Corporation | Method for separating compounds in process streams |
| KR970703805A (ko) * | 1995-05-01 | 1997-08-09 | 유니온 카바이드 케미칼즈 앤드 플라스틱스 테크놀러지 코포레이션 | 막 분리방법(Membrane Separation) |
| DE19605683A1 (de) * | 1996-02-16 | 1997-09-11 | Forschungszentrum Juelich Gmbh | Verfahren zur Trennung von Substanzen mittels einer geeigneten Membran |
| DE19632530C1 (de) * | 1996-08-13 | 1998-02-05 | Hoechst Ag | Verfahren zur Abtrennung von Phosphinoxiden und Alkylarylphosphinen aus Reaktionsgemischen einer homogenen Hydroformylierung |
| US6005123A (en) * | 1998-04-16 | 1999-12-21 | Arco Chemical Technology, L.P. | Epoxidation process |
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- 2005-09-09 AT AT05795530T patent/ATE386731T1/de not_active IP Right Cessation
- 2005-09-09 JP JP2007543024A patent/JP2008520663A/ja not_active Withdrawn
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| Publication number | Publication date |
|---|---|
| JP2008520663A (ja) | 2008-06-19 |
| US20060106237A1 (en) | 2006-05-18 |
| EP1812415B1 (en) | 2008-02-20 |
| US7084284B2 (en) | 2006-08-01 |
| WO2006055071A1 (en) | 2006-05-26 |
| EP1812415A1 (en) | 2007-08-01 |
| DE602005004939T2 (de) | 2009-02-19 |
| ATE386731T1 (de) | 2008-03-15 |
| DE602005004939D1 (de) | 2008-04-03 |
| ES2299093T3 (es) | 2008-05-16 |
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