CN1612850A - 由乙酸甲酯副产物料流生产羰基化乙酸、乙酸酐或联产二者的一体化方法 - Google Patents

由乙酸甲酯副产物料流生产羰基化乙酸、乙酸酐或联产二者的一体化方法 Download PDF

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CN1612850A
CN1612850A CNA038020513A CN03802051A CN1612850A CN 1612850 A CN1612850 A CN 1612850A CN A038020513 A CNA038020513 A CN A038020513A CN 03802051 A CN03802051 A CN 03802051A CN 1612850 A CN1612850 A CN 1612850A
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methyl acetate
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W·D·皮卡德
M·O·斯凯茨
S·C·韦布
D·L·厄斯里
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Abstract

本发明涉及将源自形成基于乙酸乙烯酯或基于乙烯醇或亚乙基醇的聚合物或共聚物过程的乙酸甲酯直接用于甲醇羰基化生产过程以生产乙酸、乙酸酐及每一者的联产物。乙酸甲酯是基于工业生产聚乙烯醇或聚乙烯－乙烯醇共聚物的过程的副产物。通常对该物质进行处理以回收甲醇和乙酸。此处讨论的是一种用于在生产中或在工厂设备中跳过乙酸甲酯加工过程并将乙酸甲酯用于一体化甲醇羰基化单元的节约成本的方案。此处讨论的方案删去了经常与聚合物过程相联系的昂贵的水解过程。

Description

由乙酸甲酯副产物料流生产羰基化乙酸、 乙酸酐或联产二者的一体化方法
发明的背景
在基于乙烯醇或乙酸乙烯酯的聚合物或乙烯-乙烯醇/乙酸乙烯酯共聚物的生产中，乙酸甲酯是形成的副产物。希望回收乙酸甲酯以便再利用。通常生产的乙酸甲酯是不纯的，其具有乙酸甲酯、甲醇、乙酸、水、固体物质和其它轻质杂质的混合物。此处公开的是这样的一种方法，其中乙酸甲酯在使用之前被纯化。
乙酸甲酯具有多种用途，其中包括生产乙酸，乙酸酐或联产二者。以下参考文献提供了关于这些材料的生产的背景。
已有技术
US 4234718-公开了由甲醇、纤维素和一氧化碳生产乙酸纤维素酯的循环一体化方法。
US 4234719-公开了由甲醇、纤维素和一氧化碳生产乙酸纤维素酯的循环一体化方法。
US 4352940-生成乙酸的乙酸甲酯水解。
US 4544511-乙酸酐的生产方法。
US 5144068-Rh催化甲醇羰基化方法。
US 5001259-Rh催化甲醇羰基化方法。
US 5206434-乙酸甲酯的纯化方法。
US 5770770-由乙酸甲酯水解生产乙酸和甲醇的反应蒸馏方法和设备。
US 5831120-Rh或Ir催化甲醇羰基化乙酸的生产以及用选自乙酸甲酯、二甲醚、乙酸酐及其混合物的组分至少部分替换甲醇进料。可以通过用至少一种C1至C3醇进行的反应蒸馏对自以上和其它方法回收的排出物进行提纯以使其不含羧酸。
EP 108437-乙酸甲酯和/或二甲醚与一氧化碳或一氧化碳和氢的混合物形成乙叉二乙酸酯和/或乙酸酐的用途。
EP 087870-在酯化、羰基化和分离步骤的序列中在存在或不存在乙酸净共生产的情况下的生产乙酸酐的方法。
EP 1061063-(方法申请)；通过在酸催化剂存在下的羧酸酯的水解得到反应产物液体并分离所述产物液体生产羧酸和醇的方法。羧酸酯是乙酸甲酯。
JP 60-60107-公开了聚乙烯醇的生产，其包括用一氧化碳皂化副产物乙酸甲酯以形成乙酸酐(仅有英文摘要)。
GB 2013184-乙酸乙烯酯的制备，其中甲醇、乙醛和一氧化碳在循环一体化过程中发生反应，其中在该过程的第一步中乙酸甲酯被羰基化。
Finch，CA，《聚乙烯醇的发展》(Polyvinyl Alcohol Developments)，“聚乙酸乙烯酯到聚乙烯醇的水解”，第3.3.6节-乙酸甲酯的回收和乙酸的生产，John Wiley & Sons(1992年)，第71至73页。
Jones，Jane H.，“生产乙酸的CativaTM方法”，《铂金属评论》(Platinum Metals Review)，第44卷，2000年7月第3期第95至105页。
发明的详述
聚乙烯醇的工业生产是通过乙酸乙烯酯与自由基引发剂和甲醇反应产生聚乙酸乙烯酯进行的。聚乙酸乙烯酯随后在碱的存在下与甲醇反应产生聚乙烯醇和乙酸甲酯。该反应的副产物是乙酸甲酯。所生产的乙酸甲酯通常混合在含有乙酸甲酯、甲醇(上述反应的过量的反应物)、轻质有机杂质、可能的聚合物固体和水的反应料流中。
乙酸甲酯通常通过水解被转化为乙酸。出售乙酸或在乙酸乙烯酯生产中将其循环。
如上所述的包含在料流中的乙酸甲酯的水解方法由于需要大量的设备和能量投入(生产成本)而成本高，这是因为需要多重蒸馏/分离步骤和腐蚀性环境所要求的昂贵的建造材料。
可将乙酸甲酯料流直接送入生产乙酸(或乙酸酐或乙酸和乙酸酐的联产物)的羰基化方法能消除对水解所需的设备和能量。然而乙酸甲酯料流却不适合直接被送入羰基化过程。已有技术通常不能解决不纯的乙酸甲酯极其在循环一体化过程中在循环之前需要进行纯化的问题。如果对杂质不去除或进行处理，乙酸甲酯本身不适合被送入羰基化反应单元。如果不被除去的话，乙酸甲酯杂质将会导致下游使用中的问题。聚合物固体必须除去，因为固体将会妨碍羰基化过程。水的含量必须调节到对于所生产的产物合适的水平。例如，如果通过羰基化反应方法生产乙酸，对于每单位乙酸甲酯，不得有超过一分子单位的水进入反应器。否则，无法生产干燥的乙酸。
本发明涉及乙烯醇或基于乙烯-乙烯醇或基于乙酸乙烯酯的聚合物或共聚物的过程的一体化，例如，聚乙烯醇生产与羰基化过程的一体化，以便在第一过程(例如聚乙烯醇生产)中生产的乙酸甲酯以显著降低的能量成本转化为可售出的产品，或者送入用于乙酸、乙酸酐或以上二者的联产的反应系统中。
另外，本发明涉及作为聚乙烯醇过程中的副产物的乙酸甲酯在生产乙酸、乙酸酐或联产二者的反应中的使用。一个作为例子的一体化过程涉及被用于生产乙酸乙烯酯的乙酸的生产。所生产的乙酸乙烯酯将被用于生产聚乙烯醇的反应中。副产物乙酸甲酯将被纯化，然后被直接送入乙酸、乙酸酐或其联产物的生产中。因此，该方法从乙酸生产直到聚乙烯醇生产(包括在中间反应中的所形成的副产物的使用)被一体化。
为了实现过程的一体化，需要一种合适的乙酸甲酯纯化步骤。此处例举了一种方法，其中来自聚乙烯醇聚合物过程的料流被回收和精制，以便送入甲醇羰基化乙酸步骤。例如：含有乙酸甲酯、甲醇、水、轻质杂质和聚合物固体的料流被通过分离/蒸馏纯化。在含水料流中有机物丢失被保持在低水平上的同时，过量的水和聚合物固体被除去。其它包含以上所列组分的一部分的含水/有机物料流也可以被纯化/处理。纯化步骤的产物是通常含有甲醇、乙酸甲酯、可接受含量的杂质、基本不含聚合物固体并含水量足够低的料流。杂质或其量以及水的浓度可以随着所希望的应用和使用的设备变化。通常对于用于生产乙酸的甲醇羰基化单元所用的乙酸甲酯而言，推荐料流中对于每分子单位的乙酸甲酯存在不超过约一分子单位的水。
以下将更多针对从聚乙烯醇生产乙酸的过程描述本发明，但本领域的技术人员应该认识到，乙酸酐的生产或者乙酸和乙酸酐的联产也可以由所形成的乙酸甲酯进行。乙酸、酸酐或每一者的联产物可以通过本领域中已知的多种方法进行。本发明所关注的不是酸或酸和酐的联产物的制造方式，而是允许使用纯化或处理后的乙酸甲酯的一体化过程。
当用甲醇羰基化的方法使用铑或铱作为催化剂生产酸、酸酐或二者的联产时，乙酸甲酯中水和杂质的含量是一个需要考虑的问题。这是因为在羰基化反应器中通过甲醇和/或反应性衍生物的甲烷化产生水的速率是相对较高的，并且可高于羰基化反应器中通过水煤气轮换反应消耗水的速率。甲醇分解作用可如下表示：
                   
水煤气轮换反应可如下表示：
                    
水可能通过直接或间接进入反应器系统中而在乙酸或乙酸酐或二者联产的连续生产中积累。大量文献讨论了在羰基化反应过程中过量水份的除去或水平衡的控制。然而，与除去水有关的一个问题是同时除去例如甲基碘的组分。甲基碘可以被循环至反应中或作为废弃物处理。如果作为废弃物处理，基于环保方面的考虑，必须使用适当的方法。将用于本方法中的乙酸甲酯的水含量控制在最低是有利的。在羰基化单元制造乙酸时，相对于乙酸甲酯的含量，水的存在量低于化学计量比是关键性的。在制造乙酸酐时，希望没有水或甲醇存在。对于在乙酸生产过程中的甲醇，对甲醇浓度的担心不像水那样强烈。
使用源自基于乙烯醇或乙烯醇或乙酸乙烯酯的过程中产生的乙酸甲酯的另一个担心是料流中的羰基含量。羰基杂质包括乙醛、丙酮、甲乙酮、丁醛、巴豆醛、2-乙基巴豆醛和2-乙基丁醛等以及不饱和醛。在乙酸甲酯料流中需要考虑的其他杂质包括甲苯、苯、丙酮、醛缩二甲醇、3-甲基2-戊酮、丙酸、乙酸乙酯和乙醇。
本发明的一个实施方案涉及在甲醇碳基化过程中使用乙酸甲酯料流的方法，其包括：
a)生产水解的基于乙酸乙烯酯的聚合物或共聚物；或
b)作为另一可选项，生产随后经历甲醇分解反应的乙烯醇的聚合物或共聚物；
c)形成乙酸甲酯副产物；
d)将乙酸甲酯导入纯化过程；
e)将纯化的乙酸甲酯导入甲醇碳基化过程。
以上实施方案也可通过使用烯烃(或更具体而言乙烯)作为共聚单体来实现。
所形成的乙酸甲酯副产物可以是包含甲醇、乙酸、水、轻质有机杂质和一些聚合物固体的混合物。纯化乙酸甲酯的方法包括但不仅限于通过蒸馏、萃取、过滤或结晶分离水、杂质和固体。
本发明的另一个实施方案涉及使用乙酸甲酯的方法，其包括：
a)生产乙酸；
b)在足以形成乙酸乙烯酯的条件下使反应物接触乙酸；
c)在足以形成聚乙酸乙烯酯的条件下接触乙酸乙烯酯；
d)在足以形成聚乙烯醇和作为副产物的乙酸甲酯的条件下使碱和甲醇接触聚乙酸乙烯酯；
e)充分处理乙酸甲酯以除去至少部分杂质；
f)将乙酸甲酯送入乙酸生产过程。
本发明的另一个实施方案是使用乙酸甲酯的方法，其包括：
a)生产乙酸酐；
b)在足以形成乙酸乙烯酯的条件下使反应物接触乙酸酐；
c)在足以形成聚乙酸乙烯酯的条件下接触乙酸乙烯酯；
d)在足以形成聚乙烯醇和作为副产物的乙酸甲酯的条件下使碱和甲醇接触聚乙酸乙烯酯；
e)充分处理乙酸甲酯以除去至少部分杂质；
f)将乙酸甲酯送入乙酸酐生产过程。
本发明的另一个实施方案涉及使用乙酸甲酯的方法，其包括：
a)共生产乙酸和乙酸酐；
b)在足以形成乙酸乙烯酯的条件下使反应物接触乙酸和乙酸酐；
c)在足以形成聚乙酸乙烯酯的条件下接触乙酸乙烯酯；
d)在足以形成聚乙烯醇和作为副产物的乙酸甲酯的条件下使碱和甲醇接触聚乙酸乙烯酯；
e)充分处理乙酸甲酯以除去至少部分杂质；
f)将乙酸甲酯送入乙酸和乙酸酐的共生产过程。
在聚乙烯醇(PVOH)的生产中，所形成的产物乙酸甲酯被当做最终被纯化的母液并被送入甲醇羰基化反应器以生产乙酸。粗乙酸甲酯混合物被导入母液塔中纯化以除去杂质(如轻质有机组分、聚合物固体和水)。塔在增加的压力和加热的条件下操作，从而以纯化的形式在塔顶馏出物料流中除去基本上所有的乙酸甲酯以及从不纯的粗乙酸甲酯混合物中除去超过95％的甲醇。调节塔中的回流以便维持在塔顶馏出物中对应于每摩尔乙酸甲酯只含约1摩尔水。聚合物固体通常由聚乙酸乙烯酯、聚乙烯醇、乙酸钠和从母液塔底部作为残留物排出的排出物组成。
通过在升高的压力下操作母液塔，塔顶馏出物组分或塔顶馏出物可被用作聚乙烯醇生产装置中其它回收塔的热源。在55psig压力下操作可使此反应塔中使用的能量超过50％得到回收。可以将其他料流送入母液塔中进行分离。例如，经常可被用于PVOH过程中的含有来自乙酸乙烯酯和甲醇的萃取蒸馏的水和甲醇的料流也可以被送入母液塔分离。
当使用上述的母液塔时，分离甲醇和水的塔可以被保留在PVOH过程中。来自萃取蒸馏的料流可以被送入甲醇水塔或母液塔。母液塔或萃取蒸馏可以以这样的模式操作，即进料中一部分或全部甲醇被允许与水和固体一起从塔底排出。塔底物或残留物可以被送入甲醇水塔。如果输送母液塔塔顶馏出物料流的成本很高，该操作模式可被用于在工厂的总成本优化中。
实施例
实施例1
用来自PVOH过程的料流进行蒸馏。在实验室中，在提高的压力和温度下，使用40个塔板的Oldershaw塔。含有0.24重量％固体的母液料流在塔的大致中间部位送入，同时含有0.13重量％固体的甲醇含水料流被从距离底部大致三分之一处送入。在进行常压蒸馏时，塔顶和底部的温度分别是68℃和100℃。母液的送入速度是13.7g/min，甲醇含水料流的送入速度是11.5g/min。回流比维持在约0.23。蒸馏过程中再沸器中未观察到起泡和淤塞的问题。在从底部起约15塔板处发现深褐色/黑色的污染物或淤塞。然而，这种轻微的淤塞没有堵塞塔板上的小洞或Oldershaw反应塔的降液管。位于母液送入处以上的塔板是干净的。
进料、塔顶馏出物甲醇/乙酸甲酯产物和废水残留物的分析见下表1。
纯化的乙酸甲酯被用于甲醇羰基化乙酸的生产。生产出的乙酸不含有非典型的杂质或具有非典型的杂质概况。
表1：甲醇/乙酸甲酯混合物进料蒸馏的实验室试验分析
   组分           母液进料    含水甲醇进料   产物    残留物
水(重量％)          21.4          82.5        5.3     100
甲醇(重量％)        55.3          17.5        66.8    0.0656
乙酸甲酯(重量％)    27.1          nd          27.9    nd
乙醇(ppm)           1476          75          1704    nd
丙酮(ppm)           nd            nd          nd      16
乙醛缩二甲醇(ppm)   17            nd          22      nd
乙酸乙酯(ppm)       315           nd          366     nd
乙醛(ppm)           248           nd          313     nd
甲苯(ppm)           nd            nd          74      nd
乙酸(ppm)           45            nd          nd      87
烷烃(ppm)           ＜100         781         3       932
nd＝未检测到；数值未经标准化。
产物＝本发明的乙酸甲酯、甲醇产物
本实施例说明，在废水中具有少于1000ppm的甲醇和少于2600ppm的烷烃的条件下，甲醇/乙酸甲酯料流可以在低回流比下被纯化。
实施例2
实施例1中的甲醇/乙酸甲酯产物以如下方式被送入一个实验羰基化单元：在将源自实施例1的材料送入实验甲醇羰基化单元之前，用195℃的纯甲醇进料、1100ppm Rh、2.2重量％MeOAc(乙酸甲酯)、2.2重量％H2O、6.5重量％MeI使实验单元进入稳定状态。得到的时空产率是20摩尔/升/小时。反应条件固定不变，用实施例1的馏出物替代MeOH作为实验单元的进料。水被加入实验单元以便使在进料中水的总摩尔数与乙酸甲酯相等。将这些条件维持3天。反应速率维持在20摩尔/升/小时不变。来自实验单元的乙酸产物的组成见下表。加入来自实施例1的材料后产物中丙酸(HOPr)的浓度增加了。
                 表2：来自实施例2的产物
                      甲醇       189ppm
                    乙酸甲酯     53ppm
                     巴豆醛      1.4ppm
                      丁醛       6ppm
                   2-乙基巴豆醛  5.2ppm
                      丙酸       1601ppm
                      乙酸       余量

Claims (5)

1、在甲醇羰基化过程中使用乙酸甲酯料流的反应方法，其包括：
a)生产水解的基于乙酸乙烯酯的聚合物或共聚物；
b)形成乙酸甲酯副产物；
c)将乙酸甲酯导入纯化过程；
d)将纯化的乙酸甲酯导入甲醇碳基化过程。
2、在甲醇羰基化过程中使用乙酸甲酯料流的方法，其包括：
a)生产随后经历甲醇分解反应的乙烯醇的聚合物或共聚物；
b)形成乙酸甲酯副产物；
c)将乙酸甲酯导入纯化过程；
将纯化的乙酸甲酯导入甲醇碳基化过程。
3、使用乙酸甲酯的反应方法，其包括：
a)生产乙酸；
b)在足以形成乙酸乙烯酯的条件下使反应物接触乙酸；
c)在足以形成聚乙酸乙烯酯的条件下接触乙酸乙烯酯；
d)在足以形成聚乙烯醇和作为副产物的乙酸甲酯的条件下使碱和甲醇接触聚乙酸乙烯酯；
e)处理乙酸甲酯以除去至少部分杂质；
f)将乙酸甲酯送入乙酸生产过程。
4、使用乙酸甲酯的反应方法，其包括：
a)生产乙酸酐；
b)在足以形成乙酸乙烯酯的条件下使反应物接触乙酸酐；
c)在足以形成聚乙酸乙烯酯的条件下接触乙酸乙烯酯；
d)在足以形成聚乙烯醇和作为副产物的乙酸甲酯的条件下使碱和甲醇接触聚乙酸乙烯酯；
e)处理乙酸甲酯以除去至少部分杂质；
f)将乙酸甲酯送入乙酸酐生产过程。
5、使用乙酸甲酯的反应方法，其包括：
a)共生产乙酸和乙酸酐；
b)在足以形成乙酸乙烯酯的条件下使反应物接触乙酸和乙酸酐；
c)在足以形成聚乙酸乙烯酯的条件下接触乙酸乙烯酯；
d)在足以形成聚乙烯醇和作为副产物的乙酸甲酯的条件下使碱和甲醇接触聚乙酸乙烯酯；
e)处理乙酸甲酯以除去至少部分杂质；
f)将乙酸甲酯送入乙酸和乙酸酐的共生产过程。
CNB038020513A 2002-01-11 2003-01-07 由乙酸甲酯副产物料流生产羰基化乙酸、乙酸酐或联产二者的一体化方法 Expired - Lifetime CN100344599C (zh)

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