CN1171774A - 从乙酸甲酯水解生产乙酸及甲醇用的反应蒸馏方法和装置 - Google Patents
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Abstract
本发明是一种乙酸甲酯水解用的反应蒸馏方法,包括精馏区(2)、反应区(3)和汽提区(4)。将水流供入精馏区(2)或反应区(3)的上部,并将乙酸甲酯流供进反应区(3)的下部,反应区(3)含有离子交换树脂填料,从该装置的底部连续不断地生产出乙酸和甲醇产品。
Description
本发明背景
本发明领域
本发明涉及用离子交换树脂作催化剂，通过反应蒸馏法将乙酸甲酯水解成乙酸及甲醇的方法。本发明特别适用限平衡反应，如共沸混合物的水解、酯化和分离。
背景技术说明
乙酸甲酯(MA)，本发明的原料流之一，作为高纯度对苯二酸(PTA)工厂及聚乙烯醇(PVA)工厂的副产物被大量生产。来自PVA工厂的乙酸甲酯混合物是一种含有乙酸甲酯和甲醇的共沸组合物，而来自PTA工厂的乙酸甲酯混合物则是乙酸甲酯和水的混合物。在本发明中，上述两种混合物以及乙酸甲酯含量超过50％的其它混合物被称为乙酸甲酯混合物。
由于乙酸甲酯是一种低值溶剂，所以它被以低价出售，或者通过水解反应及随后的常规蒸馏过程，将其水解成甲醇和乙酸，两者都是高价值溶剂。但是，水解反应后的常规蒸馏具有很多缺点。首先，由于控制水解反应的平衡常数很小，该复合反应过程得率低；第二个缺点是固定投资大且生产成本高，这是由于分离水解反应器及四级蒸馏塔所致，四级蒸馏塔包括萃取蒸馏柱及两个脱水柱。
还有，水解或酯化反应用的催化剂一般为液体酸性催化剂如硫酸及盐酸，会引起设备腐蚀问题和产品与催化剂之间分离。
作为乙酸甲酯的反应蒸馏的第一项专利是U.S.4,435,595。与本发明不同，在该方法中，顶部产品乙酸甲酯由甲醇和乙酸合成，反应蒸馏用液体催化剂硫酸进行。
本发明的重要目的是设计和优化通过反应蒸馏方法水解乙酸甲酯用的操作条件。
本发明概述
本发明的主要目的是设计一种反应蒸馏方法，该方法消除了由分离反应和蒸馏过程而引起的许多固有问题，如反应得率低、产品纯度低、设备腐蚀、固定投资大和生产成本高。
反应蒸馏是一种在同一个反应柱中将反应和蒸馏结合在一起的方法，尽管自本世纪20年代起反应蒸馏已经被认为是一种单元操作，但是，大部分反应和蒸馏过程一直是独立进行的。
反应蒸馏的优点是有可能开发工业反应蒸馏过程，例如生产MTBE(甲基叔丁基醚)，它是洁净辛烷增强剂，以及合成乙酸甲酯。
乙酸甲酯水解用反应蒸馏法的优点是比常规方法的优点更有吸引力，因为从技术上将反应和蒸馏结合在同一个反应柱大大地降低设备投资和操作成本。大部分水解或酯化反应受化学平衡所限制，但是，通过连续地从反应物乙酸甲酯和水中除去乙酸和甲醇产物，反应蒸馏法能够使平衡反应向前移。当在反应柱中形成共沸混合物时，反应蒸馏打破共沸组合物，使反应得率和选择性增加。
所以，本发明提供一种用新的反应蒸馏法将乙酸甲酯水解和反应产品与反应物分离结合在一起的方法。
更具体地讲，本发明提供一种从含有50％以上乙酸甲酯的副产品组合物中生产水解产品乙酸和甲醇的反应蒸馏方法，包括以下步骤：
(a)在反应区将含有乙酸甲酯的混合物水解成乙酸和甲醇，反应区内装有作为催化剂的离子交换树脂填料，将水向下供给离子交换树脂填料，并将乙酸甲酯混合物向上供给离子交换树脂填料；
(b)收集位于反应区上部的未反应乙酸甲酯和水蒸汽，并将其冷凝后，再供给反应区；以及
(c)在进行(b)步操作的同时，收集位于反应区下部的(a)步反应混合物，通过再沸将反应混合物分离成水解产物和不纯物，再向反应区供给不纯物，并且回收水解产物。
除了反应蒸馏方法以外，本发明还提供了一种乙酸甲酯水解用的反应蒸馏装置，包括使蒸汽流冷凝成液体的冷凝器、反应蒸馏柱和再沸器。
本发明的反应蒸馏柱有三个新区，它们是再蒸馏用的精留区、反应区以及汽提区，在汽提区内将产品从反应混合物中分离出来。
在本发明中，反应蒸馏柱有两个进料位置，即分别为供水用的上进料位置和供乙酸甲酯混合物用的下进料位置。
本发明的反应区填充有离子交换树脂，是一种最廉价的固体催化剂，该固体催化剂排除了设备腐蚀问题，同时避免了产品分离，离子交换树脂主要用水处理进行使用，按着功能分组的类型可以分成四类，作为该四类之一的强酸性离子交换树脂适用于本发明，作为水解和酯化反应的催化剂材料。但是，常规离子交换树脂的小珠粒(0.4-1.1mm)会产生很高的压降，小珠粒树脂不被优选地直接用作本发明的填充材料。在本发明中，优选的方法是在离子交换树脂中加入作为粘合剂的惰性聚合物，将其压成薄环。
结合说明本发明之方法的附图，从以下详细说明中，可以更加清楚地了解本发明其它一些特征及其优点。但是，应当理解，所说的这种详细说明及特别实施例在说明本发明优选实施例的同时，只是以说明的目的而给出的。因为对于本技术领域里普通技术人员而言，从这些详细说明中很容易了解属于本发明精神及范围内的各种变化及改动。本发明详细说明
附图说明本发明，在附图中：
图1示意说明带有精馏区的反应蒸馏过程，在精馏区要进行进一步的分离过程。
图2示意说明不带精馏区的反应蒸馏过程，在反应区内不需要进行上述的进一步分离过程。
优选实施例的详细说明
如实施例附图所示，反应蒸馏装置有五个主要部分，从柱的顶部起：冷凝器(1)、精馏区(2)、反应区(3)、汽提区(4)及再沸区(5)。
本发明的特征之一是向反应蒸馏柱提供有双供料流，位于反应区上部的上进料管向反应区(3)或精馏区(2)的上部供给水流，从反应区下部进入的下进料管向反应区下部供给乙酸甲酯或含有乙酸甲酯的组合物。在离子交换树脂的内侧和表面上进行着向上移动之乙酸甲酯和向下流动之水的水解反应，水与乙酸甲酯的摩尔比为1∶1-1∶20，当摩尔比小于1时，由于太多乙酸甲酯蒸汽造成的夹带会溢出反应柱，当摩尔比超过20时，由大水流作用会产生向下溢流现象。
本发明的另一个特征是乙酸甲酯水解用的催化剂，这是一种强酸性离子交换树脂催化剂，任何常用的强酸性离子交换树脂都可以用于本发明。
合适的强酸性离子交换树脂是具有连结在不溶性苯乙烯或丙烯酸聚合物基体上之硫酸基(-SO3H)的苯乙烯树脂和丙烯酸树脂。但是，一般地讲，常规树脂的珠粒很小，以致于需要用常规模压方法将树脂和惰性聚合物模压在一起，形成常用填充形状，例如薄环状、弧鞍形填料状、英驼洛克斯鞍形填料状或带孔环形填料状。然后将填料置于或嵌于反应区(3)内。
一般地讲，要将3-30％(wt)的惰性聚合物加到离子交换树脂内，如果该重量百分比小于3％，则惰性聚合物不能有效地与离子交换树脂粘合在一起，当该重量百分比大于30％，则会大大地减少离子交换树脂的活性部位。如上所述，本发明的阳离子交换树脂避免了腐蚀和分离问题，而且促进气液传质。
理论板数是蒸馏柱中最重要的因素之一，考虑到反应和蒸馏效率以及柱的经济性，本发明中理论板数优选的是对于精馏区(2)为0-10块板、反应区(3)为5-25块板以及汽提区(4)为5-40块板。精馏区(2)中的零块理论板是指在柱布置中没有精馏区(2)，所以，本发明包括不含精馏区(2)的反应蒸馏方法。
回流比也是蒸馏塔设计和操作的重要因素，为了提高反应得率和选择性，要将冷凝液体全部或大部分循环回到柱内。
本发明的重要操作因素之一是再沸器(5)的温度，本发明的温度为40℃-150℃，当温度低于40℃时，在汽提区(4)会出现乙酸甲酯的不充分分离，在温度超过150℃时，会产生由乙酸甲酯蒸汽而引起的夹带溢流。
在汽提区(4)分离乙酸和甲醇产品，然后从再沸器(5)制得该产品。未反应物、水和乙酸甲酯向上移至精馏区(2)和冷凝器(1)，形成共沸混合物，将所有的或大部分的冷凝液体返回到柱内，以便促进水解反应。
如图2所示，除了带有精馏区(2)的反应蒸馏方法之外，该方法在没有精馏区(2)的情况下也能进行操作。
实施例
在下述实施例中，所用的催化剂是Diaion PK 208H，由日本三井化成株式会社生产，惰性聚合物可以从韩国Yukong公司购得。实施例1
MA进料＝纯乙酸甲酯
再沸器温度＝70.8℃
反应区温度＝57℃
回流比＝50
实施例2
| 进 料 流 | |
| 水流量(毫升/分钟) | 1.2 |
| MA流量(毫升/分钟) | 2.2 |
| 摩尔比 | 2.5 |
| 理论板数 | |
| 精流区 | 2 |
| 反应区 | 10 |
| 汽提区 | 30 |
| 底 部 | |
| 反应率(％) | 99.2 |
| 乙酸甲酯(wt％) | 0.81 |
| 乙酸(wt％) | 28.3 |
MA进料＝乙酸甲酯与水的共沸混合物
再沸器温度＝95.2℃
反应区温度＝57℃
回流比＝50
实施例3
| 进 料 流 | |
| 水流量(毫升/分钟) | 3.0 |
| MA流量(毫升/分钟) | 2.2 |
| 摩尔比 | 6.0 |
| 理论板数 | |
| 精流区 | 2 |
| 反应区 | 10 |
| 汽提区 | 20 |
| 底 部 | |
| 反应率(％) | 99.5 |
| 乙酸甲酯(wt％) | 0.47 |
| 乙酸(wt％) | 25.6 |
MA进料＝乙酸甲酯与甲醇的共沸混合物
再沸器温度＝130.6℃
反应区温度＝57℃
回流比＝∞
| 进 料 流 | |
| 水流量(毫升/分钟) | 7.4 |
| MA流量(毫升/分钟) | 2.2 |
| 摩尔比 | 15.0 |
| 理论板数 | |
| 精流区 | 5 |
| 反应区 | 15 |
| 汽提区 | 20 |
| 底 部 | |
| 反应率(％) | 99.9 |
| 乙酸甲酯(wt％) | 0.12 |
| 乙酸(wt％) | 20.1 |
显然，根据上述说明，可以进行本发明的另外一些改进和变动。所以，应当理解，在所附的权利要求范围之内，本发明除了按以下具体说明的方法实施以外，也有其它的实施方法。
优先权文本韩国专利申请第1994/38355号(申请日为1994年12月29日)全部内容在此并入供参考。
Claims (11)
1.一种从含有50％以上乙酸甲酯组合物中生产水解产品乙酸和甲醇的反应蒸馏方法，包括步骤：
(a)在带有上部和下部的反应区内将所说的组合物水解成乙酸和甲醇，所说的反应区含有酸性离子交换树脂催化剂，将水向下供给所说的离子交换树脂催化剂，并且将所说的组合物向上供给所说的离子交换树脂催化剂，形成反应混合物；
(b)收集位于所说反应区上部的未反应乙酸甲酯和水蒸汽，并且将所说的收集到的乙酸甲酯和水蒸汽冷凝，形成冷凝物，将所说的该冷凝物再供给所说的反应区；以及
(c)在进行(b)步操作的同时，从所说的反应区下部收集所说的反应混合物，通过再沸将所说的反应混合物分离成乙酸、甲醇和不纯物，再向所说的反应区供给所说的不纯物，并且回收所说的乙酸和甲醇。
2.根据权利要求1的方法，其中所说的组合物是纯的乙酸甲酯、乙酸甲酯与水的混合物或乙酸甲酯与甲醇的混合物。
3.根据权利要求1的方法，还包括在所说的(b)步中于所说的冷凝之前精馏未反应乙酸甲酯和水。
4.根据权利要求1的方法，还包括在所说的向(a)步再供给料之前精馏未反应乙酸甲酯和水。
5.根据权利要求3的方法，还包括在所说的向(a)步再供给料之前精馏未反应乙酸甲酯和水。
6.根据权利要求1的方法，其中所说的反应区的温度为40-150℃。
7.根据权利要求1的方法，其中所说的组合物和所说的水按组合物与水摩尔比为1∶1～1∶20提供。
8.一种用于将乙酸甲酯水解成乙酸和甲醇的反应蒸馏装置，包括：
冷凝器，在其中将蒸汽流冷凝成液体；
用于将乙酸甲酯水解成乙酸和甲醇的反应区，在反应区内含有离子交换树脂催化剂，其中所说的反应区以流体与所说的冷凝器相通，并且从所说的冷凝器接受液体；
以流体与所说的反应区相通的汽提区，其中所说的乙酸和甲醇从所说的反应区分离出来；以及
以流体与所说的汽提区相通的再沸器。
9.根据权利要求1的装置，还包括位于所说的冷凝器和所说的反应区之间的用于蒸馏所说的蒸汽流的精馏区。
10.根据权利要求9的方法，其中所说的精馏区有0-10块理论板，所说的反应区有5-25块理论板，以及所说的汽提区有5-40块理论板。
11.根据权利要求1的方法，其中所说的反应区有上部和下部，所说的该装置还包括进入所说的反应区上部的用于向所说的反应区供水的供水管道，以及进入所说的反应区下部的用于向所说的反应区供给乙酸甲酯的乙酸甲酯进料管道。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1994/38355 | 1994-12-29 | ||
| KR19940038355 | 1994-12-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1171774A true CN1171774A (zh) | 1998-01-28 |
| CN1067048C CN1067048C (zh) | 2001-06-13 |
Family
ID=19404608
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95197208A Expired - Lifetime CN1067048C (zh) | 1994-12-29 | 1995-12-27 | 从乙酸甲酯水解生产乙酸及甲醇用的反应蒸馏方法和装置 |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5770770A (zh) |
| EP (1) | EP0800502B1 (zh) |
| JP (1) | JP3848679B2 (zh) |
| KR (1) | KR960022419A (zh) |
| CN (1) | CN1067048C (zh) |
| DE (1) | DE69517198T2 (zh) |
| ES (1) | ES2148588T3 (zh) |
| WO (1) | WO1996020912A1 (zh) |
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| CN102249851A (zh) * | 1999-07-02 | 2011-11-23 | 纳特拉斯维特公司 | 3,3－二甲基丁醛的制备方法 |
| CN104230664A (zh) * | 2013-06-05 | 2014-12-24 | 大连化学工业股份有限公司 | 烯丙醇的制造方法 |
| CN111606797A (zh) * | 2020-06-12 | 2020-09-01 | 天津大学 | 一种隔壁塔分离乙酸甲酯水解产物的反应精馏新工艺 |
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- 1995-07-03 KR KR1019950019291A patent/KR960022419A/ko not_active Application Discontinuation
- 1995-12-21 US US08/576,485 patent/US5770770A/en not_active Expired - Lifetime
- 1995-12-27 CN CN95197208A patent/CN1067048C/zh not_active Expired - Lifetime
- 1995-12-27 DE DE69517198T patent/DE69517198T2/de not_active Expired - Lifetime
- 1995-12-27 WO PCT/KR1995/000178 patent/WO1996020912A1/en active IP Right Grant
- 1995-12-27 EP EP95941916A patent/EP0800502B1/en not_active Expired - Lifetime
- 1995-12-27 ES ES95941916T patent/ES2148588T3/es not_active Expired - Lifetime
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249851A (zh) * | 1999-07-02 | 2011-11-23 | 纳特拉斯维特公司 | 3,3－二甲基丁醛的制备方法 |
| CN100402481C (zh) * | 2002-11-28 | 2008-07-16 | 瓦克化学股份公司 | 由对应的羧酸酯水解制造羧酸和醇的方法及装置 |
| CN104230664A (zh) * | 2013-06-05 | 2014-12-24 | 大连化学工业股份有限公司 | 烯丙醇的制造方法 |
| CN104230664B (zh) * | 2013-06-05 | 2016-03-02 | 大连化学工业股份有限公司 | 烯丙醇的制造方法 |
| CN111606797A (zh) * | 2020-06-12 | 2020-09-01 | 天津大学 | 一种隔壁塔分离乙酸甲酯水解产物的反应精馏新工艺 |
Also Published As
| Publication number | Publication date |
|---|---|
| US5770770A (en) | 1998-06-23 |
| WO1996020912A1 (en) | 1996-07-11 |
| EP0800502B1 (en) | 2000-05-24 |
| ES2148588T3 (es) | 2000-10-16 |
| CN1067048C (zh) | 2001-06-13 |
| JPH10511675A (ja) | 1998-11-10 |
| KR960022419A (ko) | 1996-07-18 |
| JP3848679B2 (ja) | 2006-11-22 |
| EP0800502A1 (en) | 1997-10-15 |
| DE69517198T2 (de) | 2000-11-23 |
| DE69517198D1 (de) | 2000-06-29 |
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