CN100341836C - 用于高乙酸生产率和用于水平衡控制的低水甲醇羰基化法 - Google Patents
用于高乙酸生产率和用于水平衡控制的低水甲醇羰基化法 Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/50—Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/08—Acetic acid
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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Abstract
本发明涉及一种通过甲醇和其反应性衍生物在使用铑基催化剂的反应混合物中在低水条件下的羰基化来制造乙酸的方法。使用该方法是用于实现至少15克摩尔/升/小时的反应速率。这种高速反应在低于2.0wt%的水浓度下进行。在某些条件下，通过包括在反应体系中加入例如乙酸甲酯、二甲醚、乙酸酐之类的化合物或这些化合物的混合物在内的至少一个工艺步骤来使本方法的反应混合物中的水浓度保持在所需浓度。在反应混合物中加入这些组分的工艺步骤可以与用于控制甲醇的羰基化反应混合物中水浓度的其它工艺步骤相结合。
Description
发明背景
发明领域
本发明涉及改进的制造乙酸的方法。
相关技术
制造乙酸的一种重要的方法是使用一氧化碳在液体反应介质中对烷基醇，尤其是甲醇，及其反应衍生物进行羰基化。这些羰基化反应通常在存在催化剂(例如铑和铱之类的第VIII族金属催化剂)、含卤素的助催化剂(例如甲基碘)和水的情况下进行的。美国专利3,769,329号公开了溶于或分散于液体介质中或负载在惰性固体上的铑基羰基化催化剂的使用，该催化剂与含卤素助催化剂(以甲基碘为例)一起使用。不过，要了解的是，各种催化剂体系，特别是含有第VIII族金属的催化剂体系，都可用于通过甲醇的羰基化来制造乙酸。通常，用溶于液体反应介质的催化剂进行羰基化反应，其中一氧化碳气体连续鼓泡通过该液体介质。美国专利3,769,329公开了可以在反应混合物中加入水以便对反应速率产生有益影响，而且通常使用大约14重量百分比(wt％)-15wt％之间的水浓度。这有时称作“高水”羰基化法。
“高水”羰基化法的一种替代方案是如美国专利5,001,259、美国专利5,026,908和美国专利5,144,068中所述的“低水”羰基化法。在“低水”羰基化法中可以使用浓度低于14wt％的水。采用低水浓度简化了将所需羧酸变成其冰状形式的下游处理。反应流中的水越多，从产品乙酸中去除水的操作成本就越高，而且在产品回收和提纯设备上的资本投入就越高。以非常低的水浓度进行操作时达到的效率使得以尽可能最低的水浓度进行操作具有吸引力。然而，如美国专利5,026,908中所解释的那样，减少反应器中的水以使操作和固定成本最小化时，就更难在良好的催化剂稳定性下保持可以接受的高速度的乙酸生产，因为当反应器水减少时，反应速率会降低。
与低水制造有关的问题之一是当水浓度降低时，尤其是在低于14wt％的浓度下，催化剂体系，尤其是铑基催化剂易于从反应混合物中沉淀出来。严重的催化剂沉淀当然会导致反应速率降低、单元操作中断甚至完全停止运转。已知可以使用催化剂稳定剂，例如可溶金属碘化物或碘化季盐，来使催化剂稳定性问题减小到最低程度。如美国专利5,218,143中所述，尤其适宜的盐是碱金属碘化物，例如碘化锂，因为它们在反应介质中的可溶性和热稳定性最好。EP-A-0161874描述了下述反应体系：在使用具有低水含量的液体反应介质的同时，以甲醇为例的醇被羰基化成乙酸之类的羧酸衍生物。该公开描述了这是如下实现的：在液体反应介质中使用特定浓度的碘化物盐、烷基碘和相应的烷基酯以保持铑催化剂稳定性和系统生产率。
与较低水浓度下的羰基化反应有关的另一问题在于，即使在催化剂体系稳定时，也会不利地降低生产率。例如，美国专利5,760,279公开了在低水条件下操作时，实现的反应速率低于在给定条件组合下正常预期的反应速率的一半。
已经提出了各种在低水羰基化反应条件下提高生产率的技术。生产率通常以时空产率(STY)进行界定，它是以羰基化反应器中所含的每升反应介质每小时产生的乙酸的克-摩尔数(克-摩尔/升/小时)表示的。在环境温度下测定未充气状态下的反应介质体积。美国专利5,218,143公开了如果以乙酸甲酯在反应混合物中的最佳浓度操作反应器就可以提高低水含量下的生产水平。EP 0-250189提出在加入反应混合物中的一氧化碳进料中加入氢气以提高生产率。美国专利5,939,585公开了使用钌或锇作助催化剂以提高生产率。该专利公开的内容指出，使用这些助催化剂可以在水浓度低于1.0wt％的低水条件下获得最高可达大约11克-摩尔/升/小时的STY。美国专利5,218,143公开了使用VIB族金属催化剂共稳定剂将低水条件下的STY提高至在2.0wt％水浓度下高达9.2克-摩尔/升/小时。美国专利5,760,279指出与铑催化剂一起加入锰稳定剂可以在4.5wt％的水浓度下将STY提高至大约8克-摩尔/升/小时。美国专利5,488,153和GB 2,336,154 A提出使用与铑催化剂配合的二齿磷-硫配体提高低水条件下的反应速率。美国专利5,488,153的实施例公开了可实现最高达19.6克-摩尔/升/小时的STY的生产率。GB 2,336,154A公开了高达21.9克-摩尔/升/小时的反应速率。这些参考文献中公开的这些反应是在高水条件下进行的。
尽管上述参考文献中的一些提出了高达5000ppm的铑催化剂浓度，但这些参考文献的实施例通常公开的是大约1000ppm或更低的铑催化剂浓度。
美国专利5,144,068号公开了在低水浓度下，在羰基化反应器中的乙酸甲酯和碘化物盐稳定剂之间具有增强甲醇羰基化的协合作用。该专利还公开了使反应器在高乙酸甲酯浓度下运作的优点是减少了不需要的反应产物的生成。特别地，将丙酸减少了相当多。还减少了水煤气转换反应生成的二氧化碳和氢。
由于反应的羰基化速率强烈地依赖于水的浓度，因而在乙酸制造过程中将反应混合物中的水含量保持在受控范围内对于保持高反应速率是重要的。Hjortkjaer和Jensen[Ind.Eng.Chem.，Prod.Res.Dev.16，281-285(1997)]通过论证当水浓度最高提高至14wt％时反应速率的增加来揭示反应速率对水含量的强烈依赖性。通过反应混合物中的两个关键反应可以至少部分实现对反应混合物中水的控制。第一个反应按照下列化学式通过甲烷化生成水：
CH3OH+H2→CH4+H2O
消耗水的第二个反应已知为下式所示的前述水煤气转换反应：
CO+H2O→CO2+H2
为了有效控制反应介质中的水，重要的是了解哪个反应占优势以便确定是供应水还是从反应段去除水的操作，从而保持反应段中精确的水平衡，以最大程度地降低由反应器水浓度的变化引起的反应羰基化速率的变化。
美国专利5,831,120公开了在铱催化的羰基化反应中，甲烷化反应生成水的速率相对较高而且可以高于水煤气转化反应消耗水的速率。在这种情况下，需要去除这种不平衡产生的过量的水。相反，美国专利5,831,120还公开了在铑催化的羰基化反应中，甲烷化反应与水煤气转换反应的速率相比相对较慢，因此在该反应体系中消耗水。通常需要向铑催化的体系提供水以保持水在反应混合物中的稳态浓度。
已经提出了各种从羰基化反应体系生成的粗产物流中去除过量水的方法。美国专利3,769,177和3,791,935公开了通过一系列蒸馏从反应体系中去除水。美国专利4,008,131公开了通过使用侧流从蒸馏塔中去除水来对这些系统进行的改进。据称这种系统的优点在于从来自蒸馏塔的塔顶馏出物中去除水时，将有价值的甲基碘随水的去除降至最低。这些专利中公开的工艺系统针对的是从这些工艺系统的后反应段部分的粗产物流中去除水的方法。因此，公开的系统没有解决在羰基化工艺系统的反应段中控制水的问题。
美国专利5,831,120公开了如下去除铱催化的体系中过量的水：从轻端蒸馏塔的塔顶馏出物中去除水并加以处理，并将一部分加入反应混合物中的甲醇进料替换成选自由乙酸甲酯、二甲醚、乙酸酐及其混合物组成的组的组分。该专利公开了将二甲醚和乙酸甲酯羰基化以制造乙酸，同时水被净消耗，而乙酸酐通过生成乙酸的反应从反应混合物中去除水。在该方法中，水被认为按照下列化学式消耗：
美国专利5,001,259和相关的美国专利5,026,908和5,144,068公开了铑催化的低水羰基化法，其中实现了高的甲醇羰基化速率，同时将反应段的水浓度保持在从有限(≤0.1wt％)的水浓度至高水浓度的非常低的水平。这些专利公开了通过控制一氧化碳、水、甲醇和甲基碘的流动来保持反应介质的浓度。在这些专利中公开的最高的乙酸生产反应速率是在2wt％水浓度下大约32的STY。然而，在低于2wt％的水浓度下，公开的最高乙酸STY是大约12。这些专利的图10证明了在低于2.0wt％的水浓度下保持合意的反应速率的难度。从图10中可以看出，当水浓度降到2.0wt％以下时，反应速率急剧降低。
总之，羰基化技术的技术状况仍然缺乏一种可用于在低于2wt％的水浓度下实现15克-摩尔/升/小时或更高的反应速率STY的、在可控低水条件下保持高度稳定催化体系的方法。
发明概要
本发明涉及通过烷基醇、烷基醇的反应衍生物、和烷基醇及其反应衍生物的混合物在具有低水含量的反应混合物中羰基化来制造乙酸的方法。除了在低水条件下制造乙酸，本发明还提供了高的乙酸生产率。本发明的另一特征是在高生产率下运作的同时使低水浓度保持在受控范围内。本发明在反应混合物中低于2.0wt％的水浓度下实现了15克-摩尔/升/小时和更高的乙酸生产率。本发明的方法使用具有高乙酸甲酯含量的高水平铑和/铑/铱催化剂体系。在某些条件下，通过包括在该方法中加入耗水组分(例如二甲醚、乙酸甲酯、乙酸酐和这些化合物的混合物)在内的至少一个工艺步骤来使本方法的反应混合物中的水浓度保持在所需浓度。在反应混合物中加入耗水组分的步骤可以与用于控制羰基化反应混合物中水浓度的其它工艺步骤结合。
附图的简要说明
图1是本发明的一个实施方案的示意图。
发明详述
从成本角度考虑，在反应器中以低水条件运作羰基化法是合意的，如美国专利5,144,068中所述，众所周知的是，在其它条件类似的情况下，在低水条件下这些方法的产率远低于在高水浓度下运作时预期的产率。然而，本发明能够出人意料地实现高的反应速率，同时在低于2wt％的反应混合物中的水浓度下运作并获得其成本优势。本发明能够通过使铑基或铑/铱基催化剂体系的关键反应组分最优化来获得这些高生产率，同时将非常低的水浓度保持在有效范围内。
本发明涉及具有高生产率的低水羰基化法。与之前所了解的不同，已经发现，通过使用高浓度催化剂，利用碘化物盐共助催化剂与乙酸甲酯的协合作用，特别是它们在高乙酸甲酯浓度与高催化剂浓度下的协合作用，可以使反应速率达到并保持在非常高的水平。在某些条件下，这些方法可能在羰基化反应过程中生成水。也就是说，通过上述甲烷化反应生成的水超过通过上述水煤气反应消耗的水。本发明识别出这些条件，并提供了一种在保持高反应速率的同时在这些条件下保持反应混合物中水平衡的方法。
通过甲醇与一氧化碳的催化羰基化作用合成乙酸的方法是本领域内公知的，以前面列举的参考文献公开的内容为例。一氧化碳与甲醇和/或其反应衍生物在存在催化体系的条件下反应，该催化体系可以包括，例如族VIII金属元素，特别是Rh、Ir、Co、Ni、Ru、Pd或Pt，最通常是Rh或Ir；卤素助催化剂，最通常是卤化氢或有机卤化物，特别是烷基碘，例如甲基碘；稳定剂/共助催化剂，其是元素周期表族IA或IIA的金属的盐，或季铵或鏻盐，特别是碘化物或盐乙酸盐，最通常是碘化锂或乙酸锂。活性催化剂可以是族VIII金属的络合物，在某些情况下可以作为预制成的络合物而非上述独立的催化剂组分加入反应段中。该催化剂体系溶于或分散在含乙酸甲酯、乙酸、有限量的水(例如至少大约0.1wt％)和任何其它与存在的其它化合物相容的溶剂组分的液体介质中。适合用于羰基化反应的甲醇衍生物包括乙酸甲酯、二甲醚和甲基碘。
适于本发明方法的催化剂体系含有铑和铑/铱金属和化合物作为族VIII金属并含有烷基碘作为卤素助催化剂。烷基碘，通常是甲基碘，在反应介质中的浓度通常为大约2.0至大约30wt％，在一个实施方案中为大约5.0至大约15wt％，在另一实施方案中为大约5至大约10wt％。也可以使用催化剂稳定剂/共助催化剂。该稳定剂/共助催化剂可以是来自碱金属或碱土金属或季铵或鏻盐的可溶盐的形式，其在反应溶液中生成上述有效量的碘离子。催化剂稳定剂/共助催化剂优选为碘化锂、乙酸锂或它们的混合物。催化剂体系可进一步含有选自由钌、钨、锇、镍、钴、铂、钯、锰、钛、钒、铜、铝、锡和锑组成的组的过渡金属盐作为共助催化剂。碘离子在反应介质中的浓度通常为大约2.0至大约20wt％。在一个实施方案中，其存在量为大约5.0至大约20wt％，在另一实施方案中，碘离子的存在量为大约10至大约20wt％。所有这些反应组分都溶于或分散在含乙酸甲酯、乙酸和低浓度水的介质中。乙酸甲酯在反应介质中的浓度通常为大约1.0至大约30wt％，在一个实施方案中为大约2.0至大约15wt％，在另一实施方案中乙酸甲酯的存在量为大约3.0至大约10wt％。铑催化剂体系是公知的。在美国专利3,769,329中举例说明了适宜的含铑作为族VIII金属的催化剂体系。结合使用铑盐与铱盐的催化剂体系同样是已知的。在美国专利6,211,405中举例说明了适宜的铑/铱催化剂体系。铑基催化剂体系和铑/铱基催化剂体系下文称作铑基催化剂体系。就本申请而言，族VIII金属应当指指明的族VIII金属和含有指明的族VIII金属的化学化合物。
在活性反应期间，将甲醇和一氧化碳连续加入含反应液体的反应器中，在该反应器中维持所需的一氧化碳分压。如以上所提及以及以下所论述的，除了所需的上述组分外，反应液体可含有少量不需要的杂质，例如乙醛和其它含羰基的可还原高锰酸盐的化合物(“PRC”)和丙酸。PRC在此定义为羰基化合物，例如乙醛，其生成不饱和醛类和其它羰基杂质，例如丙酮、甲基乙基铜、丁醛、巴豆醛、2-乙基巴豆醛、2-乙基丁醛等，和它们的羟醛缩合产物。其它PRC包括烷基碘，例如乙基碘、丙基碘、丁基碘、戊基碘、己基碘等。
为防止惰性化合物或试剂的蓄积，从反应器顶部抽取吹扫气体并在燃烧之前处理以回收有价值的可冷凝物，例如甲基碘和乙酸甲酯。从反应器中抽取反应液体并加入闪蒸器中，在闪蒸器中，压力的降低使得出自反应混合物中的较轻组分和产物乙酸蒸发出来，主要含有乙酸和催化剂的反应混合物残余部分可再循环到反应器中。将出自闪蒸器的蒸气送入轻馏分塔或者分流塔，如美国专利5,144,068中所述，从这里提取粗制乙酸产品作为液体侧馏分或蒸馏塔底，并送去进行进一步提纯，并将塔顶馏出蒸气冷凝并分离成轻水相和重有机相。轻水相主要含有水、还含有较低但是显著量的乙酸、量小得多的甲醇、甲基碘和乙酸甲酯。还存在乙醛和其它PCR，它们是最初反应的副产品或者在随后由乙醛的进一步反应形成。重有机相主要含有甲基碘和一些乙酸甲酯，还含有较少量的水，和通常比轻水相中的百分比小的乙醛。重有机相或者直接循环到反应段或者在进一步加工后再循环。
轻馏分塔的塔顶冷凝物的轻水相通常用作回流物，一部分直接循环到反应段。此处所用的术语“反应段”是指该系统的反应器以及闪蒸器组件。在一些方法中，如例如美国专利第6,143,930号和美国专利第3,769,329号所述，首先将轻水相加入乙醛去除系统。在乙醛去除系统的一个变型中，将轻馏分塔塔顶冷凝物的轻水相加入称作“乙醛浓缩器”的第一蒸馏塔，其用于将大部分乙醛、甲基碘和乙酸甲酯作为塔顶馏出物与含有乙酸和水的较重馏分分离，较重馏分再循环到提纯段。然后将后一塔顶馏出物加入称作“乙醛汽提塔”的第二蒸馏塔中，其用于将该物流中的大部分乙醛与含有甲基碘和乙酸甲酯的较重馏分分离，较重馏分再循环到提纯段。然后将含有浓度增大的乙醛和例如甲基碘之类的一些较重组分的后一塔顶馏出物用水进行萃取，以获得含有大部分乙醛的水性萃取物和包含例如甲基碘之类的该物流中水溶性较差的组分的有机萃余液，有机萃余液再循环到提纯段。将水性乙醛流作为废物处置。此处所用的术语“提纯段”是指该系统的蒸馏塔以及分离器/倾析器组件。
可以认为连续羰基化法包括三个基本区段：反应段、提纯段和废气处理段。参照图1，将烷基醇和/或其反应衍生物和一氧化碳的连续流分别通过管线1和2加入搅拌反应器3或其它适宜的反应器中，该反应器装有包含铑基催化剂体系的乙酸溶液、卤素助催化剂、共助催化剂/稳定剂、水、未反应的烷基醇和/或其反应衍生物和一氧化碳、以及例如乙醛和其它PRC之类的杂质和较高级烷基碘的反应液体。通过管线4提取反应段中生成的气体，并送去进行排气回收以分离适合再循环到反应中的组分。通过管线5从反应器3中连续提取反应液体并加入闪蒸器6中，在此，压力的降低使得一部分乙酸和大部分低沸点化合物作为蒸气闪蒸出来，留下催化剂体系的较重组分的溶液。残余在闪蒸器6中的液体通过管线7再循环到反应器3中，同时闪蒸器6中的蒸气通过管线8进入轻馏分塔或“分流器”塔9中，在此，包括甲基碘、乙酸甲酯和乙醛在内的大部分低沸点组分和一部分水从塔顶除去。通过管线10从轻馏分塔9中提取粗制水性乙酸液体并送入乙酸回收系统(未标示)。通过管线11从轻馏分塔9中提取含有一些乙酸和高沸点组分的底部馏分并再循环到反应段。将出自轻馏分塔的塔顶蒸气流冷凝并通过管线12送去按照各种已知的额外处理步骤进一步处理。一部分含有甲基碘、乙酸甲酯和一些乙酸的这种进一步处理过的物流(未标示)再循环到反应器或提纯段。
在一些化学工艺中，必须监控化学反应的进程并调整反应物的供应以确保反应按要求进行。乙酸的生产就是这样的化学工艺之一。一种通过甲醇或其衍生物(例如乙酸甲酯或甲基碘)的羰基化制造乙酸的方法包括由上述催化剂体系引发的化学反应。羰基化已经成为制造乙酸的优选途径。然而，有一些影响实施该方法的负面考虑。首先，其基本的反应化学错综复杂，包括许多相互联系的反应、副产品和平衡条件，所有这些都必须互相适当地进行平衡，以使该方法可实行并使原材料利用效率最大化。此外，羰基化所需的催化剂体系通常很昂贵。而且羰基化催化剂体系对许多反应参数的变化格外敏感，这些又会对催化剂稳定性和活性产生不利影响。
最好在反应混合物中的低水浓度下制造乙酸以提供更高的系统效率和生产率。采用低水浓度简化了将所需羧酸制成其冰状(也就是高纯)形式的下游处理。已认识到水是粗制乙酸中不合意的组分，而且粗制产品流中的水越多，操作成本和在反应及产品回收提纯系统中所需的资本投入就越高。在高水处理法中，提供被水占据的系统体积和去除水是主要的资金和能量支出以，也是系统容量的限制。然而，通常发现，水浓度越低，羰基化速率就会降低。例如，在接近5.0wt％的水浓度下，羰基化反应速率会明显降低，因为反应速率高度依赖于反应器水，尤其是在非常低的水浓度下。在反应系统周围保持严格的水平衡是关键的，而且就此而言在反应段内保持高反应器活性并由此保持高生产率是关键的。
本发明提供了一种方法，通过该方法，即使当反应混合物中的水含量保持在2.0wt％以下时也能使反应速率保持在非常高的水平。本发明提供了STY为至少15克-摩尔/升/小时的稳定的反应速率，反应混合物中的水浓度低于2.0wt％，且可归因于铑基催化剂体系的铑浓度为至少1000ppm。在本发明的一个实施方案中，在低于2.0wt％的反应混合物水含量下反应速率为大约20至大约40克-摩尔/升/小时的STY。在另一实施方案中，在低于2.0wt％的反应混合物水含量下STY为25至40克摩尔/升/小时。在又一实施方案中，按照本发明在低于2.0wt％的反应混合物水含量下STY为大约35至40克-摩尔/升/小时。
本发明通过使催化剂浓度、乙酸甲酯浓度和反应温度等反应参数最优化同时保持反应混合物中的严格水平衡，从而在这样低的水浓度下实现这些之前无法获得的反应速率。已经发现，非常高的铑基催化剂浓度与高乙酸甲酯浓度结合可用于实现这种高反应速率。
通常，反应混合物中的铑基催化剂浓度越高，可以实现的反应速率就越高，在低水浓度下尤为如此。在本发明的一个实施方案中，水浓度低于2.0wt％，铑或铑/铱浓度为至少1000ppm且STY为15至大约20克-摩尔/升/小时。在本发明的另一实施方案中，水浓度低于0.7wt％，铑/铱浓度为至少1500ppm且STY为大约20至30克-摩尔/升/小时。在本发明的又一实施方案中，水浓度低于0.5wt％，铑/铱浓度为至少1800ppm，且STY为大约30至大约40克摩尔/升/小时。
可用于本发明的铑基催化剂体系与可溶金属碘化物或碘化季盐之类的催化剂稳定剂结合使用。适宜的助催化剂是以大约2wt％至大约30wt％的浓度存在的甲基碘。在一个实施方案中，甲基碘浓度为大约5wt％至大约15wt％。在另一实施方案中，甲基碘浓度为大约5wt％至大约10wt％。
在一个实施方案重，反应混合物中的乙酸甲酯浓度为大约1wt％至大约20wt％。在另一实施方案中，乙酸甲酯浓度为大约2wt％至大约15wt％。在本发明的又一实施方案中，乙酸甲酯浓度的范围为大约3wt％至大约10wt％。
按照本发明以高反应速率运作的一个重要因素是按照本发明能够通过在非常低的水浓度下使水浓度保持在严格或窄范围内来保持稳定的反应混合物组成。已经意外地发现，在某些情况下，当以按照本发明的反应速率进行羰基化时，反应体系的水平衡可能偏离预期的水平衡机制。为了保持按照本发明的高羰基化反应速率，重要的是识别特定反应何时是生成水的或消耗水的。如前述美国专利5,831,120中所公开的，本领域技术人员认为铑催化剂体系在用于羰基化反应时会导致催化剂反应混合物中水的净消耗。为了保持铑基反应混合物中稳定的水浓度，之前认为必须在反应混合物中加入水，因为水煤气转换反应强于甲烷化反应。然而，已经发现，在某些情况下，铑基催化剂体系产生净生成水的羰基化反应，因为甲烷化反应强于水煤气反应。在这些情况下，为了保持反应混合物中稳定的水浓度以实现稳定和有生产效能的反应，必须除去过量的水。这可以如下实现：通过机械或物理方法或通过化学方法从反应混合物中去除水，或通过化学途径消耗水。
为了检测水的净生成发生的时间，必须监控反应器中二氧化碳和甲烷的SYT。监控这些生产率可以估计反应混合物中正在进行的净生成水机制。在低反应器水条件下在具有高催化剂浓度和高乙酸甲酯浓度的铑基催化剂羰基化反应中，反应中甲烷的生成可能超过二氧化碳的生成，该反应体系成为生成水的而非消耗水的。这种向整体生成水的反应体系的改变是意外的且令人吃惊的。其产生原因是在某些条件下，反应式CH3OH+H2→CH4+H2O所示的甲烷化反应超过(反应强于)反应式CO+H2O→CO2+H2所示的水煤气转换反应。
如上所述，这些发现是意料外的，而且与美国专利5,831,120中提出的结果相反，该专利提出在仅用铑催化的反应体系中，通常需要在该体系中加入水。据发现，改变水、乙酸甲酯和铑浓度，可以在大约0.1wt％至4.0wt％的水浓度范围内发生生成水的羰基化反应。
实施例
下表和相关论述所列的实施例提供了对本发明的羰基化反应的示范性说明，其中在低于2.0wt％的水浓度下反应速率超过15克-摩尔/升/小时。使用一实验装置并使其达到稳定状态。条件如表I所注。
表I
| 反应条件 | 工艺速率 | |||||||
| 实施例 | H2Owt％ | MeOAcwt％ | MeIwt％ | Rhppm | H2psi | 酸STY | CO2STY | CH4STY |
| 1 | 0.4 | 3.7 | 6.4 | 1613 | 11 | 28 | 0.01 | 0.03 |
| 2 | 0.5 | 5.6 | 6.7 | 1897 | 12 | 40 | 0.01 | 0.01 |
| 3 | 0.7 | 5.8 | 6.1 | 1793 | 12 | 36 | 0.01 | 0.03 |
| 4 | 0.7 | 6.0 | 6.7 | 1387 | 14 | 24 | 0.01 | 0.02 |
1.实施例1-4的反应器条件是195℃，400psig。
2.所有STY值的单位都是克-摩尔/升/小时。
3.实施例中所有反应都是在10wt％碘化锂下进行。
这些实施例论证了使甲烷化反应的速率超过水煤气反应的速率或速率相同的条件。通过审查实施例的CH4和CO2的STY，参看实施例2，在该反应中既不是净生成水也不是净消耗水，因为CO2的STY等于CH4的STY。相反，在实施例1、3和4中，由CH4的STY表示的甲烷化反应速率超过由CO2的STY表示的水煤气转换反应速率。重要的是记住，取决于在低于2wt％的水浓度下的反应浓度，这两个反应中的一个会占据优势，从而影响反应水浓度，这又会影响该方法的乙酸生产率。在实施例1、3和4种，在反应混合物中净生成水，该水必须去除以按照本发明在高反应速率下保持低水浓度。
在某一水浓度、铑基催化剂浓度和例如乙酸甲酯和甲基碘之类的其它组分的浓度范围内，可能抑制水煤气反应有利于甲烷化反应，从而导致水生成的净平衡。例如，在低于2.0wt％的低水条件下同时以至少15克摩尔/升/小时的反应速率和至少1000ppm的铑基催化剂浓度操作时，可以逐渐产生水的净生成。水的净生成更可能在低于1.0wt％的水浓度、至少大约1200的铑基催化剂浓度下以至少大约25克摩尔/升/小时的反应速率发生。水的净生成还更可能在低于大约0.5wt％、至少大约1500ppm的铑基催化剂浓度下以至少大约30克摩尔/升/小时的反应速率进行。
当在净生成水的条件下制造乙酸时，需要除去生成的过量水以保持所需的低反应水浓度。按照本发明，水可以通过机械或化学途径去除。如果选择机械去除水，可以通过本领域已知的各种从运行于与本发明不同的条件下的反应体系中去除水的技术去除水。在美国专利4,008,131、美国专利3,791,935、美国专利3,769,117中公开了去除过量水的各种技术中的一些技术，在美国专利5,831,120中公开或提到了其它方法。
然而，机械去除水的方法具有一些缺点，包括需要额外的资本支出。尽管在本发明中可以使用这些机械的水去除系统，但已经发现，以按照本发明的低水条件下的高反应速率，过量的水可以全部由化学途径去除。也可以在本发明中结合使用机械的水去除法和通过化学途径去除水的方法。
在通过化学途径去除水的方法中，可以通过在反应段中加入乙酸甲酯、二甲醚、乙酸酐或这些化合物的混合物来去除过量的水。在反应段中加入这些化合物中的一种降低了反应段中的水浓度。在该方法中二甲醚和乙酸甲酯被羰基化生成乙酸，同时净消耗水。通过如前述反应式中所列的乙酸酐与水生成两摩尔乙酸的反应，加入的乙酸酐降低了反应段中水的浓度。反应区和闪蒸器区中的催化剂溶液的温度和性质足以迅速使乙酸酐水解。
加入反应段的耗水剂的量取决于净生成水的速率，而净生成水的速率是由反应器区中的甲烷化反应与水煤气转换反应的相对速率确定的。然而，通常，耗水剂的加入量应该至少等于按照上示反应式的羰基化反应中生成的水的化学计量。耗水剂可以在本方法的各种位置加入。例如，耗水剂可以加入反应器区、闪蒸器区、或提纯区，只要它最终再循环到反应器中即可。然而，也可以将耗水剂加入甲醇进料中以方便地实现耗水剂的加入。要理解的是，所述向反应段中加入耗水剂包括加入最终再循环到反应段的工艺流中以及直接加入反应区或闪蒸器区中。
已经发现，按照本发明在反应段中加入耗水剂可用于水浓度高于2.0wt％的铑基催化剂反应。该水平衡控制法在反应混合物最高达5.0wt％的水浓度下在使用铑基催化剂体系的反应体系中令人满意。
参考的所有专利和出版物都完整地经此引用并入本文。
尽管已经详细描述了本发明及其优点，但应该理解的是，可以在不脱离下述权利要求所界定的本发明的实质和保护范围的情况下对其进行各种改变、替换和变动。
Claims (22)
1.一种通过催化的羰基化反应以至少15克-摩尔/升/小时的时空产率制造乙酸的方法，该方法包括使选自由甲醇、甲基碘、乙酸甲酯、二甲醚或其组合组成的组的化合物在存在一氧化碳和铑基催化剂体系的条件下在反应混合物中反应，其中该反应混合物包含低于2.0wt％的水、浓度至少1000ppm的选自由铑、铑和铱的组合组成的组的金属、浓度为2至20wt％的碘离子、以及浓度为2.0wt％至30.0wt％的卤素助催化剂。
2.按照权利要求1的方法，其中所述卤素助催化剂的存在浓度为反应混合物的5.0wt％至15.0wt％。
3.按照权利要求1的方法，其中所述反应混合物含有1.0wt％至30wt％的乙酸甲酯。
4.权利要求3的方法，其中所述卤素助催化剂是甲基碘。
5.权利要求1至4任一项的方法，其中所述反应混合物含有低于0.7wt％的水和至少1500ppm的铑基催化剂体系。
6.权利要求1至4任一项的方法，其中所述反应混合物含有低于0.5wt％的水和至少1800ppm的族VIII金属。
7.权利要求1至4任一项的方法，其中乙酸生产的时空产率为15克-摩尔/升/小时至20克-摩尔/升/小时。
8.权利要求5的方法，其中乙酸生产的时空产率为30克-摩尔/升/小时至40克-摩尔/升/小时。
9.权利要求6的方法，其中乙酸生产的时空产率为30克-摩尔/升/小时至40克-摩尔/升/小时。
10.权利要求7的方法，其中甲基碘的存在量为反应混合物的5wt％至10wt％。
11.一种在包括反应段和提纯段的系统中通过羰基化反应制造乙酸的方法，该方法包括下列步骤：
(a)在含有低于2wt％的水、浓度为2至20wt％的碘离子、和浓度为2.0wt％至30.0wt％的卤素助催化剂、浓度至少1000ppm的选自由铑、铑和铱的组合组成的组的金属的反应混合物中，在存在铑基催化剂体系的条件下，使甲醇、甲基碘、乙酸甲酯、二甲醚或其组合与一氧化碳反应，和
(b)在反应段中加入选自由乙酸甲酯、二甲醚、乙酸酐及其混合物组成的组的化合物。
12.权利要求11的方法，其中所述卤素助催化剂的存在浓度为反应混合物的5.0wt％至15.0wt％。
13.按照权利要求12的方法，其中所述反应混合物含有1.0wt％至30wt％的乙酸甲酯。
14.权利要求13的方法，其中所述卤素助催化剂是甲基碘。
15.权利要求14的方法，其中铑基催化剂体系在反应混合物中的存在浓度足以产生至少1000ppm的选自由铑、铱及其掺合物组成的组的族VIII金属。
16.权利要求14的方法，其中铑基催化剂体系在反应混合物中的存在浓度足以产生至少1500ppm选自由铑、铱及其掺合物组成的组的族VIII金属。
17.权利要求14的方法，其中铑基催化剂体系在反应混合物中的存在浓度足以产生至少1800ppm选自由铑、铱及其掺合物组成的组的族VIII金属。
18.权利要求15的方法，其中乙酸生产的时空产率为至少15克-摩尔/升/小时。
19.权利要求16的方法，其中乙酸生产的时空产率为至少20克-摩尔/升/小时。
20.权利要求17的方法，其中乙酸生产的时空产率为至少30克-摩尔/升/小时。
21.权利要求20的方法，其中甲基碘的存在量为反应混合物的5.0wt％至10.0wt％。
22.权利要求18的方法，其中反应混合物中水的浓度为0.1wt％至2.0wt％。
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