CN100344599C - 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 PDFInfo
- Publication number
- CN100344599C CN100344599C CNB038020513A CN03802051A CN100344599C CN 100344599 C CN100344599 C CN 100344599C CN B038020513 A CNB038020513 A CN B038020513A CN 03802051 A CN03802051 A CN 03802051A CN 100344599 C CN100344599 C CN 100344599C
- Authority
- CN
- China
- Prior art keywords
- methyl acetate
- acetate
- methyl
- materials flow
- alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- 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
- C07C51/54—Preparation of carboxylic acid anhydrides
- C07C51/56—Preparation of carboxylic acid anhydrides from organic acids, their salts, their esters or their halides, e.g. by carboxylation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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
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:
CH3OH+H2→CH4+H2O
水煤气轮换反应可如下表示:
CO+H2O→CO2+H2
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羰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羰基化过程。
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足够量的杂质;
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足够量的杂质;
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足够量的杂质;
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 (25)
1.在甲醇羰基化过程中使用乙酸甲酯料流的方法,其包括:
a)生产基于乙酸乙烯酯的聚合物或共聚物;
b)在足以形成乙烯醇的聚合物或共聚物和乙酸甲酯副产物料流的条件下使碱和甲醇接触基于乙酸乙烯酯的聚合物或共聚物;
c)将乙酸甲酯副产物料流导入包括萃取蒸馏的纯化过程;
d)对乙酸甲酯副产物料流进行纯化以形成纯化的乙酸甲酯料流;和
e)将纯化的乙酸甲酯料流导入甲醇羰基化过程中。
2.如权利要求1的方法,其中乙酸甲酯副产物料流包含乙酸甲酯、乙酸、甲醇、轻质有机物、聚合物固体和水。
3.如权利要求1的方法,其中纯化的乙酸甲酯料流包含乙酸甲酯、甲醇和水。
4.如权利要求1的方法,其中纯化的乙酸甲酯料流包含乙酸甲酯和水,在纯化的乙酸甲酯料流中水的浓度被限制为与乙酸甲酯的摩尔比不高于1。
5.如权利要求1的方法,其中纯化处理的操作使纯化的乙酸甲酯料流中每摩尔乙酸甲酯对应的水被维持在1摩尔。
6.如权利要求1的方法,其中使用烯烃作为共聚单体。
7.如权利要求6的方法,作为共聚单体的烯烃为乙烯。
8.在甲醇羰基化过程中使用乙酸甲酯料流的方法,其包括;
a)提供一种乙烯醇聚合物或乙烯醇共聚物;
b)对乙烯醇聚合物或乙烯醇共聚物进行甲醇分解反应以形成乙酸甲酯副产物料流;
c)将乙酸甲酯副产物料流导入包括萃取蒸馏的纯化过程;
d)对乙酸甲酯副产物料流进行纯化以产生纯化的乙酸甲酯料流;和
e)将纯化的乙酸甲酯料流导入甲醇羰基化过程中。
9.如权利要求8的方法,其中乙酸甲酯副产物料流包含乙酸甲酯、乙酸、甲醇、轻质有机物、聚合物固体和水。
10.如权利要求8的方法,其中纯化的乙酸甲酯料流包含乙酸甲酯、甲醇和水。
11.如权利要求8的方法,其中纯化的乙酸甲酯料流包含乙酸甲酯和水,在纯化的乙酸甲酯料流中水的浓度被限制为与乙酸甲酯的摩尔比不高于1。
12.如权利要求8的方法,其中纯化处理的操作使纯化的乙酸甲酯料流中每摩尔乙酸甲酯对应的水被维持在1摩尔。
13.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乙酸甲酯副产物料流的条件下使碱和甲醇接触聚乙酸乙烯酯;
e)通过萃取蒸馏纯化乙酸甲酯副产物料流以形成乙酸甲酯料流,其中纯化步骤从得到的乙酸甲酯副产物料流中除去足够量的杂质,以使乙酸甲酯料流适合被送入乙酸生产过程中;和
f)将乙酸甲酯料流导入乙酸的生产过程中。
14.如权利要求13的的方法,其中乙酸甲酯副产物料流包含乙酸甲酯、乙酸、甲醇、轻质有机物、聚合物固体和水。
15.如权利要求13的方法,其中乙酸甲酯料流包含乙酸甲酯、甲醇和水。
16.如权利要求13的方法,其中乙酸甲酯料流包含乙酸甲酯和水,在乙酸甲酯料流中水的浓度被限制为与乙酸甲酯的摩尔比不高于1。
17.如权利要求13的方法,其中纯化处理的操作使乙酸甲酯料流中每摩尔乙酸甲酯对应的水被维持在1摩尔。
18.如权利要求13的方法,其中乙酸生产过程是甲醇羰基化过程。
19.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使反应物接触乙酸乙烯酯;
d)在足以形成聚乙烯醇和乙酸甲酯副产物料流的条件下使碱和甲醇接触聚乙酸乙烯酯;
e)通过萃取蒸馏纯化乙酸甲酯副产物料流以形成乙酸甲酯料流,其中纯化步骤从得到的乙酸甲酯副产物料流中除去足够量的杂质,以使乙酸甲酯适合被送入乙酸酐生产过程中;和
f)将乙酸甲酯料流导入乙酸酐的生产过程中。
20.如权利要求19的方法,其中乙酸甲酯副产物料流包含乙酸甲酯、乙酸、甲醇、轻质有机物、聚合物固体和水。
21.如权利要求19的方法,其中乙酸甲酯料流包含相对于每摩尔乙酸甲酯不多于1摩尔的水。
22.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乙酸甲酯副产物料流的条件下使碱和甲醇接触聚乙酸乙烯酯;
e)通过萃取蒸馏纯化乙酸甲酯副产物料流以形成乙酸甲酯料流,其中纯化步骤从得到的乙酸甲酯副产物料流中除去足够量的杂质,以使乙酸甲酯适合被送入生产乙酸和乙酸酐的共生产过程中;和
f)将乙酸甲酯料流导入生产乙酸和乙酸酐的共生产过程中。
23.如权利要求20的方法,其中乙酸甲酯副产物料流包含乙酸甲酯、乙酸、甲醇、轻质有机物、聚合物固体和水。
24.如权利要求20的方法,其中乙酸甲酯料流包含乙酸甲酯、甲醇和水。
25.如权利要求20的方法,其中乙酸甲酯料流包含相对于每摩尔乙酸甲酯不多于1摩尔的水。
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US34753202P | 2002-01-11 | 2002-01-11 | |
US60/347,532 | 2002-01-11 | ||
US10/324,648 US7115772B2 (en) | 2002-01-11 | 2002-12-19 | Integrated process for producing carbonylation acetic acid, acetic anhydride, or coproduction of each from a methyl acetate by-product stream |
US10/324,648 | 2002-12-19 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1612850A CN1612850A (zh) | 2005-05-04 |
CN100344599C true CN100344599C (zh) | 2007-10-24 |
Family
ID=26984554
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB038020513A Expired - Lifetime CN100344599C (zh) | 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 |
Country Status (13)
Country | Link |
---|---|
US (5) | US7115772B2 (zh) |
EP (1) | EP1463705B1 (zh) |
JP (2) | JP2005515227A (zh) |
KR (1) | KR100958482B1 (zh) |
CN (1) | CN100344599C (zh) |
AT (1) | ATE397577T1 (zh) |
BR (1) | BR0306691B1 (zh) |
CA (1) | CA2472172C (zh) |
DE (1) | DE60321442D1 (zh) |
ES (1) | ES2307894T3 (zh) |
MX (1) | MXPA04006706A (zh) |
MY (1) | MY129853A (zh) |
WO (1) | WO2003059860A2 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103946205A (zh) * | 2011-11-28 | 2014-07-23 | 国际人造丝公司 | 生产聚乙烯醇或其共聚物以及乙醇的集成方法 |
Families Citing this family (210)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7115772B2 (en) * | 2002-01-11 | 2006-10-03 | Celanese International Corporation | Integrated process for producing carbonylation acetic acid, acetic anhydride, or coproduction of each from a methyl acetate by-product stream |
US7989659B2 (en) * | 2007-05-17 | 2011-08-02 | Celanese International Corporation | Method and apparatus for making acetic acid with improved light ends column productivity |
US7390919B1 (en) * | 2007-10-01 | 2008-06-24 | Lyondell Chemical Technology, L.P. | Methyl acetate purification and carbonylation |
US8062482B2 (en) * | 2007-10-30 | 2011-11-22 | Celanese International Corporation | Acetaldehyde removal from methyl acetate by distillation at elevated pressure |
US8304586B2 (en) | 2010-02-02 | 2012-11-06 | Celanese International Corporation | Process for purifying ethanol |
US8546622B2 (en) | 2008-07-31 | 2013-10-01 | Celanese International Corporation | Process for making ethanol from acetic acid using acidic catalysts |
US8309773B2 (en) | 2010-02-02 | 2012-11-13 | Calanese International Corporation | Process for recovering ethanol |
US20110137080A1 (en) * | 2008-08-13 | 2011-06-09 | Wu Kuang-Yeu | Process and apparatus for recovery of acetic acid from a feed stream containing the corresponding ester |
BR112012009824A2 (pt) | 2009-10-26 | 2016-11-22 | Celanese Int Corp | processo para a fabricação de etanol a partir do ácido acético com a utilização de catalisadores de ácidos |
EP2531292A2 (en) | 2010-02-02 | 2012-12-12 | Celanese International Corporation | Processes for producing ethanol from acetaldehyde |
US8318988B2 (en) | 2010-05-07 | 2012-11-27 | Celanese International Corporation | Process for purifying a crude ethanol product |
US8680343B2 (en) | 2010-02-02 | 2014-03-25 | Celanese International Corporation | Process for purifying ethanol |
US8314272B2 (en) | 2010-02-02 | 2012-11-20 | Celanese International Corporation | Process for recovering ethanol with vapor separation |
US8394984B2 (en) * | 2010-02-02 | 2013-03-12 | Celanese International Corporation | Process for producing an ethyl acetate solvent and co-production of ethanol |
US8747492B2 (en) | 2010-02-02 | 2014-06-10 | Celanese International Corporation | Ethanol/fuel blends for use as motor fuels |
WO2012039840A2 (en) | 2010-02-02 | 2012-03-29 | Celanese International Corporation | Processes for producing alcohols from a mixed acid feed |
US8552225B2 (en) | 2010-02-02 | 2013-10-08 | Celanese International Corporation | Process for vaporizing acetic acid for hydrogenation processes to produce ethanol |
US8394985B2 (en) | 2010-02-02 | 2013-03-12 | Celanese International Corporation | Process for producing an ester feed stream for esters production and co-production of ethanol |
US8575403B2 (en) | 2010-05-07 | 2013-11-05 | Celanese International Corporation | Hydrolysis of ethyl acetate in ethanol separation process |
US8541633B2 (en) | 2010-02-02 | 2013-09-24 | Celanese International Corporation | Processes for producing anhydrous ethanol compositions |
WO2011097193A2 (en) | 2010-02-02 | 2011-08-11 | Celanese International Corporation | Hydrolysis of ethyl acetate in ethanol separation process |
US8728179B2 (en) | 2010-02-02 | 2014-05-20 | Celanese International Corporation | Ethanol compositions |
BR112012019406A2 (pt) | 2010-02-02 | 2018-03-20 | Celanese Int Corp | processo para purificacao de um produto de etanol bruto |
US8932372B2 (en) | 2010-02-02 | 2015-01-13 | Celanese International Corporation | Integrated process for producing alcohols from a mixed acid feed |
WO2011097220A2 (en) | 2010-02-02 | 2011-08-11 | Celanese International Corporation | Process for producing ethanol using an extractive distillation column |
AU2011213125B2 (en) | 2010-02-02 | 2014-07-17 | Celanese International Corporation | Process for purifying ethanol |
US8552226B2 (en) | 2010-02-02 | 2013-10-08 | Celanese International Corporation | Process for heat integration for ethanol production and purification process |
US8858659B2 (en) | 2010-02-02 | 2014-10-14 | Celanese International Corporation | Processes for producing denatured ethanol |
US8344186B2 (en) | 2010-02-02 | 2013-01-01 | Celanese International Corporation | Processes for producing ethanol from acetaldehyde |
US8222466B2 (en) | 2010-02-02 | 2012-07-17 | Celanese International Corporation | Process for producing a water stream from ethanol production |
US8460405B2 (en) | 2010-02-02 | 2013-06-11 | Celanese International Corporation | Ethanol compositions |
US8668750B2 (en) | 2010-02-02 | 2014-03-11 | Celanese International Corporation | Denatured fuel ethanol compositions for blending with gasoline or diesel fuel for use as motor fuels |
US8552224B2 (en) | 2010-05-07 | 2013-10-08 | Celanese International Corporation | Processes for maximizing ethanol formation in the hydrogenation of acetic acid |
JP2013518819A (ja) | 2010-02-02 | 2013-05-23 | セラニーズ・インターナショナル・コーポレーション | 変性エタノールの製造方法 |
WO2012039841A1 (en) | 2010-02-02 | 2012-03-29 | Celanese International Corporation | Integrated process for producing alcohols from a mixed acid feed |
US8680342B2 (en) | 2010-05-07 | 2014-03-25 | Celanese International Corporation | Process for recovering alcohol produced by hydrogenating an acetic acid feed stream comprising water |
EP2566837A2 (en) | 2010-05-07 | 2013-03-13 | Celanese International Corporation | Process for purifying ethanol |
US8604255B2 (en) | 2010-05-07 | 2013-12-10 | Celanese International Corporation | Process for recovering ethanol with sidedraws to regulate C3+ alcohols concentrations |
US8704011B2 (en) | 2010-05-07 | 2014-04-22 | Celanese International Corporation | Separating ethanol and ethyl acetate under low pressure conditions |
US8569551B2 (en) | 2010-05-07 | 2013-10-29 | Celanese International Corporation | Alcohol production process integrating acetic acid feed stream comprising water from carbonylation process |
US8754267B2 (en) | 2010-05-07 | 2014-06-17 | Celanese International Corporation | Process for separating acetaldehyde from ethanol-containing mixtures |
US8575404B2 (en) | 2010-05-07 | 2013-11-05 | Celanese International Corporation | Process for recycling gas from acetic acid hydrogenation |
US8704010B2 (en) | 2010-05-07 | 2014-04-22 | Celanese International Corporation | Alcohol production process with impurity removal |
US8846988B2 (en) | 2010-07-09 | 2014-09-30 | Celanese International Corporation | Liquid esterification for the production of alcohols |
CA2800319A1 (en) | 2010-07-09 | 2012-01-12 | Celanese International Corporation | Finishing reactor for purifying ethanol |
US8664454B2 (en) | 2010-07-09 | 2014-03-04 | Celanese International Corporation | Process for production of ethanol using a mixed feed using copper containing catalyst |
US8884080B2 (en) | 2010-07-09 | 2014-11-11 | Celanese International Corporation | Reduced energy alcohol separation process |
US8710279B2 (en) | 2010-07-09 | 2014-04-29 | Celanese International Corporation | Hydrogenolysis of ethyl acetate in alcohol separation processes |
US9272970B2 (en) | 2010-07-09 | 2016-03-01 | Celanese International Corporation | Hydrogenolysis of ethyl acetate in alcohol separation processes |
US8901358B2 (en) | 2010-07-09 | 2014-12-02 | Celanese International Corporation | Esterification of vapor crude product in the production of alcohols |
US8710280B2 (en) | 2010-07-09 | 2014-04-29 | Celanese International Corporation | Weak acid recovery system for ethanol separation processes |
US9150474B2 (en) | 2010-07-09 | 2015-10-06 | Celanese International Corporation | Reduction of acid within column through esterification during the production of alcohols |
US8846986B2 (en) | 2011-04-26 | 2014-09-30 | Celanese International Corporation | Water separation from crude alcohol product |
US20120010445A1 (en) | 2010-07-09 | 2012-01-12 | Celanese International Corporation | Low Energy Alcohol Recovery Processes |
US8809597B2 (en) | 2010-07-09 | 2014-08-19 | Celanese International Corporation | Separation of vapor crude alcohol product |
US8859827B2 (en) | 2011-11-18 | 2014-10-14 | Celanese International Corporation | Esterifying acetic acid to produce ester feed for hydrogenolysis |
CA2798750A1 (en) | 2010-08-06 | 2012-02-09 | Celanese International Corporation | Denatured fuel ethanol compositions for blending with gasoline or diesel fuel for use as motor fuels |
EP2601165A2 (en) | 2010-08-06 | 2013-06-12 | Celanese International Corporation | Ethanol/fuel blends for use as motor fuels |
US8877963B2 (en) | 2010-09-28 | 2014-11-04 | Celanese International Corporation | Production of acetic acid with high conversion rate |
US8394988B2 (en) | 2010-09-28 | 2013-03-12 | Celanese International Corporation | Production of acetic acid with high conversion rate |
US8678715B2 (en) | 2010-11-15 | 2014-03-25 | B&J Rocket America, Inc. | Air cooled spacer for multi-blade abrading wheel |
USRE46999E1 (en) | 2010-12-15 | 2018-08-21 | Daicel Corporation | Process for producing acetic acid |
US20120253084A1 (en) | 2011-04-01 | 2012-10-04 | Celanese International Corporation | Vent scrubbers for use in production of ethanol |
US8933278B2 (en) | 2011-04-26 | 2015-01-13 | Celanese International Corporation | Process for producing ethanol and reducing acetic acid concentration |
US9024085B2 (en) | 2011-04-26 | 2015-05-05 | Celanese International Corporation | Process to reduce ethanol recycled to hydrogenation reactor |
US8907141B2 (en) | 2011-04-26 | 2014-12-09 | Celanese International Corporation | Process to recover alcohol with secondary reactors for esterification of acid |
AR086128A1 (es) | 2011-04-26 | 2013-11-20 | Celanese Int Corp | Proceso para producir etanol que emplea una corriente de acido diluido como agente extractivo |
US9024082B2 (en) | 2011-04-26 | 2015-05-05 | Celanese International Corporation | Using a dilute acid stream as an extractive agent |
CN103119010B (zh) | 2011-04-26 | 2015-07-29 | 国际人造丝公司 | 通过分离来自加氢过程的粗产物回收乙醇侧线馏分 |
US8748675B2 (en) | 2011-06-16 | 2014-06-10 | Celanese International Corporation | Extractive distillation of crude alcohol product |
US8927788B2 (en) | 2011-04-26 | 2015-01-06 | Celanese International Corporation | Process to recover alcohol with reduced water from overhead of acid column |
AR086136A1 (es) | 2011-04-26 | 2013-11-20 | Celanese Int Corp | Reduccion del acido dentro de la columna por medio de la esterificacion durante la produccion de alcoholes |
WO2012149146A2 (en) | 2011-04-26 | 2012-11-01 | Celanese International Corporation | Reduced energy alcohol separation process having controlled pressure |
US9000233B2 (en) | 2011-04-26 | 2015-04-07 | Celanese International Corporation | Process to recover alcohol with secondary reactors for hydrolysis of acetal |
WO2012149137A1 (en) | 2011-04-26 | 2012-11-01 | Celanese International Corporation | Process for the production of ethanol from an acetic acid feed and a recycled ethyl acetate feed |
US20120277482A1 (en) | 2011-04-26 | 2012-11-01 | Celanese International Corporation | Removing Water from an Acetic Acid Stream in the Production of Alcohols |
US8686199B2 (en) | 2011-04-26 | 2014-04-01 | Celanese International Corporation | Process for reducing the concentration of acetic acid in a crude alcohol product |
US8592635B2 (en) | 2011-04-26 | 2013-11-26 | Celanese International Corporation | Integrated ethanol production by extracting halides from acetic acid |
WO2012148465A1 (en) | 2011-04-26 | 2012-11-01 | Celanese International Corporation | Recovering ethanol with sidestreams to regulate c3+ alcohols concentrations |
US8927780B2 (en) | 2011-04-26 | 2015-01-06 | Celanese International Corporation | Process for removing aldehydes from ethanol reaction mixture |
US8461399B2 (en) | 2011-04-26 | 2013-06-11 | Celanese International Corporation | Separation process having an alcohol sidestream |
US9073816B2 (en) | 2011-04-26 | 2015-07-07 | Celanese International Corporation | Reducing ethyl acetate concentration in recycle streams for ethanol production processes |
US8686200B2 (en) | 2011-04-26 | 2014-04-01 | Celanese International Corporation | Process to recover alcohol from an acidic residue stream |
WO2012149199A2 (en) | 2011-04-26 | 2012-11-01 | Celanese International Corporation | Process for producing ethanol and reducing acetic acid concentration |
US8927783B2 (en) | 2011-04-26 | 2015-01-06 | Celanese International Corporation | Recovering ethanol with sidestreams to regulate C3+ alcohols concentrations |
BR112013027348A2 (pt) | 2011-04-26 | 2017-01-17 | Celanese Int Corp | extração por destilação de álcool bruto |
US8754268B2 (en) | 2011-04-26 | 2014-06-17 | Celanese International Corporation | Process for removing water from alcohol mixtures |
US9000232B2 (en) | 2011-04-26 | 2015-04-07 | Celanese International Corporation | Extractive distillation of crude alcohol product |
WO2012149140A1 (en) | 2011-04-26 | 2012-11-01 | Celanese International Corporation | Reduced energy alcohol separation process having water removal |
CN103080053B (zh) | 2011-04-26 | 2015-08-12 | 国际人造丝公司 | 使用叠置床反应器生产乙醇的方法 |
US9024084B2 (en) | 2011-04-26 | 2015-05-05 | Celanese International Corporation | Reduced energy alcohol separation process having controlled pressure |
US8927787B2 (en) | 2011-04-26 | 2015-01-06 | Celanese International Corporation | Process for controlling a reboiler during alcohol recovery and reduced ester formation |
US8927784B2 (en) | 2011-04-26 | 2015-01-06 | Celanese International Corporation | Process to recover alcohol from an ethyl acetate residue stream |
WO2012149164A1 (en) | 2011-04-26 | 2012-11-01 | Celanese International Corporation | Process for controlling a reboiler during alcohol recovery and reduced ester formation |
US8884081B2 (en) | 2011-04-26 | 2014-11-11 | Celanese International Corporation | Integrated process for producing acetic acid and alcohol |
EP2702027B1 (en) | 2011-04-26 | 2014-12-24 | Celanese International Corporation | Process to recover alcohol with secondary reactors for esterification of acid |
US8652988B2 (en) | 2011-04-27 | 2014-02-18 | Celanese International Corporation | Catalyst for producing acrylic acids and acrylates |
US8642498B2 (en) | 2011-05-11 | 2014-02-04 | Celanese International Corporation | Catalysts for producing acrylic acids and acrylates |
US8704012B2 (en) | 2011-06-16 | 2014-04-22 | Celanese International Corporation | Distillation of crude alcohol product using entrainer |
WO2013019232A1 (en) | 2011-08-03 | 2013-02-07 | Celanese International Corporation | Reducing acetals during ethanol separation process |
WO2013019230A1 (en) | 2011-08-03 | 2013-02-07 | Celanese International Corporation | Process for separating ethanol having low acid |
US8846987B2 (en) | 2011-08-03 | 2014-09-30 | Celanese International Corporation | Ethanol separation process having stripping section for reducing acetals |
US8481792B2 (en) | 2011-08-03 | 2013-07-09 | Celanese International Corporation | Reducing acetals and/or esters during ethanol separation process |
US8927782B2 (en) | 2011-08-03 | 2015-01-06 | Celanese International Corporation | Vapor separation in alcohol production |
US8575405B2 (en) | 2011-08-03 | 2013-11-05 | Celanese International Corporation | Reducing acetals during ethanol separation process |
WO2013019237A1 (en) | 2011-08-03 | 2013-02-07 | Celanese International Corporation | Reducing acetals and/or esters during ethanol separation process |
US8440866B2 (en) | 2011-08-03 | 2013-05-14 | Celanese International Corporation | Process for separating ethanol having low acid |
US8877987B2 (en) | 2011-08-03 | 2014-11-04 | Celanese International Corportation | Process for producing anhydrous ethanol using extractive distillation column |
WO2013019233A1 (en) | 2011-08-03 | 2013-02-07 | Celanese International Corporation | Process for producing anhydrous ethanol using extractive distillation column |
US8558034B2 (en) | 2011-08-03 | 2013-10-15 | Celanese International Corporation | Reducing acetals during ethanol separation process using high pressure distillation column |
US8884079B2 (en) | 2011-08-03 | 2014-11-11 | Celanese International Corporation | Reducing impurities in hydrogenation processes with multiple reaction zones |
US8895786B2 (en) | 2011-08-03 | 2014-11-25 | Celanese International Corporation | Processes for increasing alcohol production |
WO2013019229A1 (en) | 2011-08-03 | 2013-02-07 | Celanese International Corporation | Reducing impurities in ethanol in hydrogenation processes with multiple reaction zones |
US8748676B2 (en) | 2011-08-03 | 2014-06-10 | Celanese International Corporation | Process for purifying a crude ethanol product |
WO2013019238A1 (en) | 2011-08-03 | 2013-02-07 | Celanese International Corporation | Reducing acetals during ethanol separation process using high pressure distillation column |
CN103930392A (zh) | 2011-08-03 | 2014-07-16 | 国际人造丝公司 | 用于通过酯污染物的水解改善乙醇生产的方法 |
WO2013019231A1 (en) | 2011-08-03 | 2013-02-07 | Celanese International Corporation | Vapor separation in ethanol production |
WO2013019239A1 (en) | 2011-08-03 | 2013-02-07 | Celanese International Corporation | Ethanol separation process having stripping section for reducing acetals |
US8877986B2 (en) | 2011-08-03 | 2014-11-04 | Celanese International Corporation | Process for recovering alcohol |
WO2013019235A1 (en) | 2011-08-03 | 2013-02-07 | Celanese International Corporation | Process for purifying a crude ethanol product |
WO2013019236A1 (en) | 2011-08-03 | 2013-02-07 | Celanese International Corporation | Process for recovering ethanol in a side draw distillation column |
US8853467B2 (en) | 2011-08-19 | 2014-10-07 | Celanese International Corporation | Integrated process for producing ethanol |
US8829253B2 (en) | 2011-08-19 | 2014-09-09 | Celanese International Corporation | Integrated process for producing ethanol from methanol |
US8853466B2 (en) | 2011-08-19 | 2014-10-07 | Celanese International Corporation | Integrated process for producing ethanol from methanol |
US20130053599A1 (en) | 2011-08-22 | 2013-02-28 | Celanese International Corporation | Catalysts for producing acrylic acids and acrylates |
CN102381956B (zh) * | 2011-09-06 | 2013-08-21 | 安徽皖维高新材料股份有限公司 | 醋酸甲酯和甲醇共沸物羰基合成醋酐、醋酸及分离方法 |
US9663437B2 (en) | 2011-09-13 | 2017-05-30 | Celanese International Corporation | Production of acetic acid with high conversion rate |
US8802585B2 (en) | 2011-09-22 | 2014-08-12 | Celanese International Corporation | Catalysts for producing acrylic acids and acrylates |
US8735314B2 (en) | 2011-09-29 | 2014-05-27 | Celanese International Corporation | Catalysts for producing acrylic acids and acrylates |
US8536368B2 (en) | 2011-10-03 | 2013-09-17 | Celanese International Corporation | Processes for the production of acrylic acids and acrylates from a trioxane feed |
US20130085297A1 (en) | 2011-10-03 | 2013-04-04 | Celanese International Corporation | Processes for Producing Acrylic Acids and Acrylates with Pre- and Post-Reactor Dilution |
US20130253224A1 (en) | 2012-03-20 | 2013-09-26 | Celanese International Corporation | Process for Producing Acrylic Acids and Acrylates |
US20130085299A1 (en) | 2011-10-03 | 2013-04-04 | Celanese International Corporation | Processes for Producing Acrylic Acids and Acrylate with Diluted Crude Acrylate Stream |
US8658823B2 (en) | 2011-10-03 | 2014-02-25 | Celanese International Corporation | Processes for producing acrylic acids and acrylates |
US9487466B2 (en) | 2011-12-16 | 2016-11-08 | Celanese International Corporation | Process for producing acrylic acids and acrylates |
US20130085295A1 (en) | 2011-10-03 | 2013-04-04 | Celanese International Corporation | Processes for producing acrylic acids and acrylates |
US20130085298A1 (en) | 2011-10-03 | 2013-04-04 | Celanese International Corporation | Processes for Producing Acrylic Acids and Acrylates with Liquid Product Dilution |
US8658824B2 (en) | 2011-10-03 | 2014-02-25 | Celanese International Corporation | Processes for producing acrylic acids and acrylates |
US20130267736A1 (en) | 2011-10-03 | 2013-10-10 | Celanese International Corporation | Processes for Producing Acrylic Acids and Acrylates with Diluted Reaction Mixture and By-Product Recycle |
US8864950B2 (en) | 2011-10-03 | 2014-10-21 | Celanese International Corporation | Processes for producing acrylic acids and acrylates |
US8729299B2 (en) | 2011-10-03 | 2014-05-20 | Celanese International Corporation | Processes for the production of acrylic acids and acrylates |
US20130085302A1 (en) | 2011-10-03 | 2013-04-04 | Celanese International Corporation | Processes for Producing Acrylic Acids and Acrylates |
US20130085303A1 (en) | 2011-10-03 | 2013-04-04 | Celanese International Corporation | Processes for Producing Acrylic Acids and Acrylates |
US8658822B2 (en) | 2011-10-03 | 2014-02-25 | Celanese International Corporation | Processes for producing acrylic acids and acrylates |
US8536382B2 (en) | 2011-10-06 | 2013-09-17 | Celanese International Corporation | Processes for hydrogenating alkanoic acids using catalyst comprising tungsten |
WO2013056268A2 (en) | 2011-10-06 | 2013-04-18 | Celanese International Corporation | Hydrogenation catalysts prepared from polyoxometalate precursors and process for using same to produce ethanol |
US8658843B2 (en) | 2011-10-06 | 2014-02-25 | Celanese International Corporation | Hydrogenation catalysts prepared from polyoxometalate precursors and process for using same to produce ethanol while minimizing diethyl ether formation |
US8648220B2 (en) | 2011-10-11 | 2014-02-11 | Celanese International Corporation | Process for producing ethanol using a crude vinyl acetate feed |
US8809599B2 (en) | 2011-11-09 | 2014-08-19 | Celanese International Corporation | Integrated process for producing ethanol and water balance control |
US8809598B2 (en) | 2011-11-09 | 2014-08-19 | Celanese International Corporation | Producing ethanol using two different streams from acetic acid carbonylation process |
US8614359B2 (en) | 2011-11-09 | 2013-12-24 | Celanese International Corporation | Integrated acid and alcohol production process |
US8704013B2 (en) | 2011-11-09 | 2014-04-22 | Celanese International Corporation | Integrated process for producing ethanol |
US8686201B2 (en) | 2011-11-09 | 2014-04-01 | Celanese International Corporation | Integrated acid and alcohol production process having flashing to recover acid production catalyst |
US8748673B2 (en) | 2011-11-18 | 2014-06-10 | Celanese International Corporation | Process of recovery of ethanol from hydrogenolysis process |
CN104024192A (zh) | 2011-11-22 | 2014-09-03 | 国际人造丝公司 | 将乙酸加氢生产乙酸乙酯和将乙酸乙酯还原为乙醇 |
EP2782890A1 (en) | 2011-11-22 | 2014-10-01 | Celanese International Corporation | Esterifying an ethanol and acetic acid mixture to produce an ester feed for hydrogenolysis |
US20130131399A1 (en) | 2011-11-23 | 2013-05-23 | Celanese International Corporation | Catalyst Preparations for High Conversion Catalysts for Producing Ethanol |
US20130137903A1 (en) * | 2011-11-28 | 2013-05-30 | Celanese International Corporation | Integrated process for producing polyvinyl alcohol or a copolymer thereof and ethanol |
US20130137905A1 (en) * | 2011-11-28 | 2013-05-30 | Celanese International Corporation | Integrated process for producing polyvinyl alcohol or a copolymer thereof and ethanol |
US20130137904A1 (en) * | 2011-11-28 | 2013-05-30 | Celanese International Corporation | Integrated process for producing polyvinyl alcohol or a copolymer thereof and ethanol |
US8697802B2 (en) | 2011-11-28 | 2014-04-15 | Celanese International Corporation | Process for producing polyvinyl alcohol or a copolymer thereof |
US8927785B2 (en) | 2011-11-29 | 2015-01-06 | Celanese International Corporation | Treatment of recycle gas from acid hydrogenation |
WO2013089990A1 (en) | 2011-12-14 | 2013-06-20 | Celanese International Corporation | Phasing reactor product from hydrogenating acetic acid into ethyl acetate feed to produce ethanol |
US8927790B2 (en) | 2011-12-15 | 2015-01-06 | Celanese International Corporation | Multiple vapor feeds for hydrogenation process to produce alcohol |
US9249081B2 (en) | 2011-12-16 | 2016-02-02 | Celanese International Corporation | Processes for the production of acrylic acids and acrylates |
US20130165704A1 (en) | 2011-12-21 | 2013-06-27 | Celanese International Corporation | Process for producing ethanol in a reactor having a constant temperature |
US20130165695A1 (en) | 2011-12-22 | 2013-06-27 | Celanese International Corporation | Process conditions for producing acrylic acid |
WO2013095963A1 (en) | 2011-12-22 | 2013-06-27 | Celanese International Corporation | Ethanol process using hydrogenation catalysts having an amorphous support |
US20130172633A1 (en) | 2011-12-29 | 2013-07-04 | Celanese International Corporation | Process For Producing Ethanol From Impure Methanol |
US8907142B2 (en) | 2011-12-29 | 2014-12-09 | Celanese International Corporation | Process for promoting catalyst activity for ethyl acetate conversion |
US8802902B2 (en) | 2011-12-30 | 2014-08-12 | Celanese International Corporation | Pressure driven distillation for ethanol production and recovery from hydrogenation process |
US8937203B2 (en) | 2012-01-06 | 2015-01-20 | Celanese International Corporation | Multifunctional hydrogenation catalysts |
MX2014008270A (es) | 2012-01-06 | 2014-10-06 | Celanese Int Corp | Catalizadores de hidrogenacion que contienen cobalto y procesos para la preparacion de los mismos. |
WO2013103398A1 (en) | 2012-01-06 | 2013-07-11 | Celanese International Corporation | Modified catalyst supports and process for producing ethanol using the catalyst |
US8815768B2 (en) | 2012-01-06 | 2014-08-26 | Celanese International Corporation | Processes for making catalysts with acidic precursors |
US8975200B2 (en) | 2012-01-06 | 2015-03-10 | Celanese International Corporation | Hydrogenation catalysts with cobalt-modified supports |
US20130178667A1 (en) | 2012-01-06 | 2013-07-11 | Celanese International Corporation | Processes for Making Catalysts |
WO2013103394A1 (en) | 2012-01-06 | 2013-07-11 | Celanese International Corporation | Processes for making catalysts with metal halide precursors |
US20130197278A1 (en) | 2012-01-27 | 2013-08-01 | Celanese International Corporation | Process For Manufacturing Ethanol Using A Metallic Catalyst Supported on Titania |
US9353034B2 (en) | 2012-02-07 | 2016-05-31 | Celanese International Corporation | Hydrogenation process with reduced residence time for vapor phase reactants |
US9051235B2 (en) | 2012-02-07 | 2015-06-09 | Celanese International Corporation | Process for producing ethanol using a molar excess of hydrogen |
US9050585B2 (en) | 2012-02-10 | 2015-06-09 | Celanese International Corporation | Chemisorption of ethyl acetate during hydrogenation of acetic acid to ethanol |
US8729311B2 (en) | 2012-02-10 | 2014-05-20 | Celanese International Corporaton | Catalysts for converting acetic acid to acetone |
US8729317B2 (en) | 2012-02-15 | 2014-05-20 | Celanese International Corporation | Ethanol manufacturing process over catalyst with cesium and support comprising tungsten or oxides thereof |
US9126194B2 (en) | 2012-02-29 | 2015-09-08 | Celanese International Corporation | Catalyst having support containing tin and process for manufacturing ethanol |
US20130225876A1 (en) | 2012-02-29 | 2013-08-29 | Celanese International Corporation | Hydrogenation Catalyst Using Multiple Impregnations of an Active Metal Solution |
US8927786B2 (en) | 2012-03-13 | 2015-01-06 | Celanese International Corporation | Ethanol manufacturing process over catalyst having improved radial crush strength |
WO2013137934A1 (en) | 2012-03-13 | 2013-09-19 | Celanese International Corporation | Catalyst for producing acrylic acids and acrylates |
CN107497418B (zh) | 2012-03-13 | 2021-02-23 | 国际人造丝公司 | 用于产生丙烯酸和丙烯酸类的包含钒、铋和钨的催化剂 |
US20130245310A1 (en) | 2012-03-13 | 2013-09-19 | Celanese International Corporation | Catalyst for producing acrylic acids and acrylates |
US8802903B2 (en) | 2012-03-13 | 2014-08-12 | Celanese International Corporation | Stacked bed reactor with diluents for producing ethanol |
WO2013137935A1 (en) | 2012-03-13 | 2013-09-19 | Celanese International Corporation | Catalyst for producing acrylic acids and acrylates comprising vanadium, titanium and tungsten |
US20130245131A1 (en) | 2012-03-14 | 2013-09-19 | Celanese International Corporation | Hydrogenation of Mixed Oxygenate Stream to Produce Alcohol |
US8536383B1 (en) | 2012-03-14 | 2013-09-17 | Celanese International Corporation | Rhodium/tin catalysts and processes for producing ethanol |
US20130261349A1 (en) | 2012-03-28 | 2013-10-03 | Celanese International Corporation | Hydrogenation Catalysts and Processes for Making Same |
WO2013191399A1 (ko) * | 2012-06-18 | 2013-12-27 | 삼성비피화학(주) | 초산, 초산비닐 및 폴리비닐알코올의 통합 제조방법 |
KR101413495B1 (ko) * | 2012-06-18 | 2014-08-07 | 삼성비피화학(주) | 초산, 초산비닐 및 폴리비닐알코올의 통합 제조공정에서의 에너지 회수방법 |
CN103570492B (zh) * | 2012-07-26 | 2015-09-09 | 亚申科技研发中心(上海)有限公司 | 一种聚乙烯醇生产过程中副产的醋酸甲酯粗产品加氢制乙醇的工艺和系统 |
RS58692B1 (sr) | 2012-09-06 | 2019-06-28 | Celanese Int Corp | Postupci za proizvodnju vinil acetata |
US8759576B2 (en) | 2012-09-06 | 2014-06-24 | Celanese International Corporation | Processes for purifying acetic anhydride |
US20140121410A1 (en) | 2012-10-31 | 2014-05-01 | Celanese International Corporation | Processes for Regenerating Catalyst for Producing Acrylic Acids and Acrylates |
US8729318B1 (en) | 2012-11-20 | 2014-05-20 | Celanese International Corporation | Process for producing ethanol from methyl acetate |
US9000237B2 (en) | 2012-12-20 | 2015-04-07 | Celanese International Corporation | Ethanol refining process using intermediate reboiler |
TWI508942B (zh) * | 2012-12-24 | 2015-11-21 | Chang Chun Petrochemical Co | Process and reaction system for the continuous preparation of acetic acid and / or acetic anhydride |
US8975450B2 (en) | 2013-03-15 | 2015-03-10 | Celanese International Corporation | Ethanol and ethyl acetate production using an acetic acid and acetic anhydride mixed feed |
US9073846B2 (en) | 2013-06-05 | 2015-07-07 | Celanese International Corporation | Integrated process for the production of acrylic acids and acrylates |
US9120743B2 (en) | 2013-06-27 | 2015-09-01 | Celanese International Corporation | Integrated process for the production of acrylic acids and acrylates |
US9150475B2 (en) | 2013-11-08 | 2015-10-06 | Celanese International Corporation | Process for producing ethanol by hydrogenation with carbon monoxide controls |
CN111065617B (zh) | 2017-09-15 | 2022-11-29 | 国际人造丝公司 | 生产丙烯酸和丙烯酸酯的方法 |
CN109721484A (zh) * | 2019-01-21 | 2019-05-07 | 中国石化长城能源化工(宁夏)有限公司 | 一种利用聚乙烯醇副产醋酸甲酯生产醋酸的系统装置及其制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US35860A (en) * | 1862-07-08 | Improved lamp-burner | ||
JPS6060107A (ja) * | 1983-09-13 | 1985-04-06 | Shinetsu Sakusan Vinyl Kk | ポリビニルアルコ−ル系合成樹脂の製造方法 |
US4843170A (en) * | 1979-10-18 | 1989-06-27 | Mitsubishi Gas Chemical Company, Inc. | Process for producing vinyl acetate |
CN1061590A (zh) * | 1990-11-19 | 1992-06-03 | 赫希斯特人造丝公司 | 乙酸甲酯的提纯方法 |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2671052A (en) * | 1951-11-13 | 1954-03-02 | Celanese Corp | Methyl acetate distillation |
NL7812485A (nl) | 1977-12-30 | 1979-07-03 | Halcon Res & Dev | Werkwijze voor de bereiding van vinylacetaat. |
US4252741A (en) * | 1978-10-06 | 1981-02-24 | Halcon Research & Development Corp. | Carbonylation with Group VIII noble metal catalysts |
US4234718A (en) * | 1979-06-29 | 1980-11-18 | Halcon Research And Development Corp. | Process for preparing cellulose acetate |
US4234719A (en) * | 1979-06-29 | 1980-11-18 | Halcon Research And Development Corp. | Preparation of cellulose acetate |
JPS567731A (en) * | 1979-06-29 | 1981-01-27 | Denki Kagaku Kogyo Kk | Separation of methyl acetate, methanol, and water |
JPS5934164B2 (ja) * | 1980-03-06 | 1984-08-21 | 三菱瓦斯化学株式会社 | エチリデンジアセテ−トの製造法 |
US4352940A (en) * | 1980-04-28 | 1982-10-05 | E. I. Du Pont De Nemours And Company | Hydrolysis of methyl acetate |
DE3170782D1 (en) * | 1980-12-26 | 1985-07-04 | Mitsubishi Gas Chemical Co | Process for producing acetic anhydride |
NZ203226A (en) | 1982-02-13 | 1985-08-30 | Bp Chemical Ltd | Production of acetic anhydride from methanol and carbon monoxide |
JPS5953440A (ja) * | 1982-09-17 | 1984-03-28 | Kuraray Co Ltd | 無水酢酸と酢酸の同時的製造法 |
DE3363531D1 (en) | 1982-11-01 | 1986-06-19 | Shell Int Research | Process for the preparation of ethylidene diacetate and/or acetic acid anhydride |
JPS59152336A (ja) * | 1983-02-16 | 1984-08-31 | Nippon Synthetic Chem Ind Co Ltd:The | 酢酸メチル・メタノ−ル混合液の分離方法 |
US5001259A (en) * | 1984-05-03 | 1991-03-19 | Hoechst Celanese Corporation | Methanol carbonylation process |
US5144068A (en) * | 1984-05-03 | 1992-09-01 | Hoechst Celanese Corporation | Methanol carbonylation process |
JP3066167B2 (ja) * | 1991-01-18 | 2000-07-17 | 株式会社クラレ | エチレン−ビニルアルコール共重合体の製造方法 |
KR960022419A (ko) * | 1994-12-29 | 1996-07-18 | 김준웅 | 반응증류를 이용하여 메틸아세테이트로부터 초산과 메탄올을 제조하는 방법 및 장치 |
US5831120A (en) * | 1996-11-19 | 1998-11-03 | Watson; Derrick John | Process for the production of acetic acid |
JP4282829B2 (ja) | 1999-06-16 | 2009-06-24 | 株式会社クラレ | カルボン酸及びアルコールの製造方法 |
US7115772B2 (en) * | 2002-01-11 | 2006-10-03 | Celanese International Corporation | Integrated process for producing carbonylation acetic acid, acetic anhydride, or coproduction of each from a methyl acetate by-product stream |
-
2002
- 2002-12-19 US US10/324,648 patent/US7115772B2/en not_active Expired - Lifetime
-
2003
- 2003-01-07 CA CA2472172A patent/CA2472172C/en not_active Expired - Fee Related
- 2003-01-07 MX MXPA04006706A patent/MXPA04006706A/es active IP Right Grant
- 2003-01-07 WO PCT/US2003/000416 patent/WO2003059860A2/en active Application Filing
- 2003-01-07 JP JP2003559967A patent/JP2005515227A/ja not_active Withdrawn
- 2003-01-07 KR KR1020047010715A patent/KR100958482B1/ko active IP Right Grant
- 2003-01-07 DE DE60321442T patent/DE60321442D1/de not_active Expired - Lifetime
- 2003-01-07 ES ES03702027T patent/ES2307894T3/es not_active Expired - Lifetime
- 2003-01-07 BR BRPI0306691-6A patent/BR0306691B1/pt not_active IP Right Cessation
- 2003-01-07 EP EP03702027A patent/EP1463705B1/en not_active Expired - Lifetime
- 2003-01-07 CN CNB038020513A patent/CN100344599C/zh not_active Expired - Lifetime
- 2003-01-07 AT AT03702027T patent/ATE397577T1/de not_active IP Right Cessation
- 2003-01-09 MY MYPI20030065A patent/MY129853A/en unknown
-
2006
- 2006-08-23 US US11/508,776 patent/US7906680B2/en not_active Expired - Fee Related
- 2006-08-23 US US11/508,775 patent/US7812192B2/en not_active Expired - Fee Related
- 2006-11-22 US US11/508,778 patent/US7772422B2/en not_active Expired - Fee Related
- 2006-11-22 US US11/508,777 patent/US7767849B2/en not_active Expired - Fee Related
-
2010
- 2010-01-04 JP JP2010000256A patent/JP5369002B2/ja not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US35860A (en) * | 1862-07-08 | Improved lamp-burner | ||
US4843170A (en) * | 1979-10-18 | 1989-06-27 | Mitsubishi Gas Chemical Company, Inc. | Process for producing vinyl acetate |
JPS6060107A (ja) * | 1983-09-13 | 1985-04-06 | Shinetsu Sakusan Vinyl Kk | ポリビニルアルコ−ル系合成樹脂の製造方法 |
CN1061590A (zh) * | 1990-11-19 | 1992-06-03 | 赫希斯特人造丝公司 | 乙酸甲酯的提纯方法 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103946205A (zh) * | 2011-11-28 | 2014-07-23 | 国际人造丝公司 | 生产聚乙烯醇或其共聚物以及乙醇的集成方法 |
Also Published As
Publication number | Publication date |
---|---|
US20070191625A1 (en) | 2007-08-16 |
KR20040079413A (ko) | 2004-09-14 |
CA2472172A1 (en) | 2003-07-24 |
CN1612850A (zh) | 2005-05-04 |
ATE397577T1 (de) | 2008-06-15 |
DE60321442D1 (de) | 2008-07-17 |
US7767849B2 (en) | 2010-08-03 |
US20080221352A1 (en) | 2008-09-11 |
KR100958482B1 (ko) | 2010-05-17 |
US7115772B2 (en) | 2006-10-03 |
WO2003059860A2 (en) | 2003-07-24 |
BR0306691B1 (pt) | 2013-05-07 |
US20030135070A1 (en) | 2003-07-17 |
CA2472172C (en) | 2010-03-16 |
US20070197822A1 (en) | 2007-08-23 |
MXPA04006706A (es) | 2004-10-04 |
JP2005515227A (ja) | 2005-05-26 |
JP5369002B2 (ja) | 2013-12-18 |
JP2010132667A (ja) | 2010-06-17 |
BR0306691A (pt) | 2004-12-07 |
US20080234512A1 (en) | 2008-09-25 |
US7772422B2 (en) | 2010-08-10 |
MY129853A (en) | 2007-05-31 |
WO2003059860A3 (en) | 2003-11-13 |
EP1463705B1 (en) | 2008-06-04 |
US7906680B2 (en) | 2011-03-15 |
ES2307894T3 (es) | 2008-12-01 |
EP1463705A2 (en) | 2004-10-06 |
US7812192B2 (en) | 2010-10-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN100344599C (zh) | 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 | |
CN1035175C (zh) | 丙烯酸制造中高纯度地精制丙烯酸的方法 | |
JP2005515227A5 (zh) | ||
US7524988B2 (en) | Preparation of acetic acid | |
CN102307841B (zh) | 乙酸的制备 | |
CN1244856A (zh) | 制备乙酸的方法 | |
CN1183761A (zh) | 从羧基化过程产生的含水稀液流中回收乙酸 | |
CN1071411A (zh) | 羧酸和/或其酸酐的纯化方法 | |
CN1484630A (zh) | 乙酸乙酯和乙酸异丙酯的同时共同生产和纯化的方法 | |
CN1656053A (zh) | 乙酸生产方法 | |
CN1226884A (zh) | 酯的联产方法 | |
CN1251084A (zh) | 制备羧酸乙烯酯的方法 | |
CN1379746A (zh) | 同时生产马来酸酐和其氢化衍生物的方法 | |
CN1357545A (zh) | α-乙酰基-γ-丁内酯的制造方法 | |
CN1207260C (zh) | 两种酯的联合生产 | |
CN1030909C (zh) | 丙酮脱除方法 | |
TWI295990B (en) | Integrated process for producing carbonylation acetic acid, acetic anhydride, or coproduction of each from a methyl acetate by-product stream | |
JP3805178B2 (ja) | メタクリル酸の回収方法 | |
JPS63156737A (ja) | エタノ−ルの精製法 | |
CN1169421A (zh) | 对苯二甲酸二甲酯工艺中的粗酯分离方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CX01 | Expiry of patent term | ||
CX01 | Expiry of patent term |
Granted publication date: 20071024 |