1295990 ⑴ 玖、發明說明 (發明說明應敛明·發明所屬之技術領域、先前技術、内容、貫施方式及圖式簡單養明) 拮術領域 本發明係關於將來自乙酸乙烯酯為基礎或是乙埽或乙二 醇為基礎之聚合物或是共聚物方法之乙酸甲酯直接用於甲 醇羰基化生產方法以製造乙酸，乙酸酐或共製造兩者。 先前技術 在製造乙烯醇、或乙酸乙烯酯-為基礎之聚合物或是乙二 -乙烯-醇/乙酸乙二-乙烯-酯共聚物時，乙酸甲酯以副產物 的形式形成。希望能夠取得乙酸甲酯而再利用之。典型產 出之乙酸甲酯含有乙酸甲酯、甲醇、乙酸、水、固體與其 他輕不純物等混合之雜質。此處揭示之方法，其中在使用 之前，乙酸甲酯先經純化。 乙酸曱酯可用於多種不同之用途中，其中，用來生產乙 酸，乙酸酐或共製造兩者。以下之參考資料提供關於製造 該等物料之背景。 US 4,234,718-揭示一種迴圈式整合系統，自甲醇、纖維素 與一乳化碳來製造纖維素醋酸酿。 US 4,234,719-揭示一種環式整合系統，自甲醇、纖維素與 一氧化碳來製造纖維素醋酸g旨。 US 4,352,940-將乙酸甲酯水解為乙酸。 US 4,544,511-製造乙酸奸之方法。 US 5，144,068-Rh催化之甲醇羰基化反應。 US 5,001，259-Rh催化之甲醇羰基化反應。 US 5,206,434-乙酸甲酯之純化方法。 O:\82\82940.DOC\ 6 -6- 1295990 (2) 杳與諫明、♦頁： US 5,770,770-來自乙酸甲酯之水解用於生產乙酸及甲醇之 反應性蒸餾方法及設備。 US 5,381，120-生產經Rh與Ir催化之曱醇羰基化乙酸，與將至 少一部分的甲醇進料以選自由乙酸甲酯、二甲醚、乙酸酐 或其混合物所組成之群經之成分來取代。於此及其它方法 所取得之流出可以經由以至少一種C1至C3醇之反應性蒸餾 以純化羧酸。 EP 108437-使用乙酸甲酯及/或二甲醚與一氧化碳或是一 氧化碳與氫之混合物以形成二乙酸亞乙酯及/或乙酸酐。 EP 087870-可生產或不生產乙酸為淨共產物之一係列酯化 、羰基化與分離步騾以生產乙酸酐方法。 EP 1061063-(製程應用）：在酸催化劑之存在下，以水解羧 酸酯類而得到反應產物液而製造羧酸與醇之方法。 JP 60-60107-揭示一種製造包含副產物乙酸甲酯與一氧化 碳之皂化之聚乙婦醇以形成乙酸酐方法。（只有英文摘要） GB 2013184-製備乙酸乙婦酯，其中甲醇、乙醛與一氧化碳 在環式整合方法中反應，其中乙酸甲酯在該方法之第一步 驟中被羰基化。1295990 (1) 玖, invention description (invention description should be condensed · the technical field, prior art, content, mode of implementation and graphic simplicity of the invention) Ethyl acetate or ethylene glycol based polymers or copolymerized methyl acetate are used directly in the methanol carbonylation process to produce acetic acid, acetic anhydride or co-manufacture. Prior Art Methyl acetate is formed as a by-product in the manufacture of a vinyl alcohol, or a vinyl acetate-based polymer or a ethylene-ethylene-alcohol/ethylene di-ethylene-ester copolymer. It is desirable to be able to obtain methyl acetate and reuse it. Typical methyl acetate produced contains impurities such as methyl acetate, methanol, acetic acid, water, solids and other light impurities. The process disclosed herein wherein methyl acetate is first purified prior to use. Ethyl acetate can be used in a variety of different applications, where it is used to produce acetic acid, acetic anhydride or co-manufacture. The following references provide background on the manufacture of such materials. U.S. Patent No. 4,234,718, the disclosure of which is incorporated herein incorporated by its entirety in its entirety in its entire entire entire entire entire entire entire entire entire entire entire entire portion No. 4,234,719 discloses a cyclic integrated system for the manufacture of cellulose acetate from methanol, cellulose and carbon monoxide. US 4,352,940 - Hydrolysis of methyl acetate to acetic acid. US 4,544,511 - Method of making acetic acid. Methanol carbonylation catalyzed by US 5,144,068-Rh. Methanol carbonylation catalyzed by US 5,001,259-Rh. US 5,206,434 - Purification of methyl acetate. O:\82\82940.DOC\ 6 -6- 1295990 (2) 杳 and 、, ♦ Page: US 5,770,770 - Reactive distillation method and equipment for the production of acetic acid and methanol from hydrolysis of methyl acetate. US 5,381,120 - production of Rhenium and Ir catalyzed sterol carbonylation of acetic acid with at least a portion of the methanol feed selected from the group consisting of methyl acetate, dimethyl ether, acetic anhydride or mixtures thereof Replace. The effluent obtained by this and other processes can be purified via reactive distillation with at least one C1 to C3 alcohol. EP 108437 - The use of methyl acetate and / or dimethyl ether with carbon monoxide or a mixture of carbon monoxide and hydrogen to form ethylene diacetate and / or acetic anhydride. EP 087870 - Process for the production of acetic anhydride by a series of esterification, carbonylation and separation steps of acetic acid as a net co-product. EP 1061063- (Process application): A method of producing a carboxylic acid and an alcohol by hydrolyzing a carboxylic acid ester in the presence of an acid catalyst to obtain a reaction product liquid. JP 60-60107- discloses a process for producing a saponified polyephthyl alcohol comprising by-product methyl acetate and carbon monoxide to form acetic anhydride. (English only) GB 2013184 - Preparation of ethyl acetate, in which methanol, acetaldehyde and carbon monoxide are reacted in a cyclic integration process in which methyl acetate is carbonylated in the first step of the process.
Finch, CA，Polyvingyl Alcohol Developments, "Hydrolysis of Polyvinyl Acetate to Polyvinyl Alcohol，n Section 3·3·6-乙酸甲酉旨回 收及乙酸之生產。】〇1111\^47&8〇113，？71-73，（1992)·Finch, CA, Polyvingyl Alcohol Developments, "Hydrolysis of Polyvinyl Acetate to Polyvinyl Alcohol, n Section 3·3·6-acetate for recovery and production of acetic acid. 】〇1111\^47&8〇113,? 71-73, (1992)·
Jones, Jane H.5 The Cative™ Process for the Manufacture of Acetic Acid，Platinum Metals Review，V 44, July 2000, No· 3, 95-105. 聚乙晞醇在商業上係以乙酸乙晞酯與自由基起始劑和甲 O:\82\82940.DOC\ 7 (3) 1295990 醇反應以製造聚乙酸乙烯酯。而後，聚乙酸乙埽酯與甲醇 在鹼的存在下反應，以製造聚乙烯醇與乙酸曱酯。該反應 <產物即為乙酸甲酯。所製得之乙酸甲酯典型地混合在含 有乙酸甲醋、甲醇（為上述反應之過量反應物）、輕有機不 、、’屯物、與潛在的聚合物固體及水之物流中。 乙酸甲酯典型地經由水解轉換為乙酸。乙酸可以出售或 是回收入乙酸乙晞酯製程中。 由糸夕步必要的蒸餘/分離步驟與腐蚀性環境所必須的 昂貴建築材料所致之資金設備與能量（操作成本），包含在 月’J述物流中之水解乙酸甲酯方法的代價是很高的。乙酸曱 酉日况右是能直接送入羰基化方法中來製造乙酸（或是乙酸 奸或是乙酸與乙酸酐之共製），這種方法就能免除操作水解 <必要性設備與能量之需要。 然而’乙酸甲酯流並不適合直接飼入羰基化方法中。本 領域通常不會明指乙酸甲酯中不純物的課題與回收進入環 式整合方法前純化的必要。在沒有移除或是處理不純物之 前’乙酸甲酯本身並不適合作為羰基化單元的進料。若是 沒有移除的話，乙酸甲酯不純物就造成了下游使用時的問 題。必須移走聚合物固體，因為該固體會玷污羰基化方法 水含量必須要調整至適合所生產的產品。舉例來說，若 是用羰基化方法製造乙酸，則每一單元乙酸甲酯就不能有 超過一分子單元的水進入反應器中。否則，就得不到乾乙 酸。 O:\82\82940.DOC\ 7 1295990 (4) 本發明係 乙烯·醋為基 法整合於羰 中生產之乙 銷售之產品 製之反應系 另外，本 式產出之乙 一實例化之 乙酸乙烯酯 反應中。副 因此該方法 使用形成於 要讓方法 步騾是必須 醇聚合物方 酸方法。例 、與聚合物 水與聚合物 。其他包含 化/處理之。 可接受量之 物流。不純 發明說:明磕頁； 發明内容 關於將乙烯醇或是乙二乙晞醇為基礎或是乙酸 礎之聚合物或是共聚物（例如聚乙烯醇）生產方 基化方法’使得在第一方法（例如聚乙埽醇生產） 酸甲酯以顯著降低能量成本的方式下轉換為可 ，或是飼入用於生產乙酸、乙酸酐或兩者之共 統中。 發明係關於使用在聚乙埽醇方法中以副產物形 酸甲酯於反應中以生產乙酸、乙酸酐或兩者。 整合性方法將涉及乙酸的生產，其可用來生產 。而得到的乙酸乙烯酯可用於生產聚乙埽醇之 產物乙酸甲酉曰純化後直接飼入乙酸的生產中。 係由乙酸的生產整合至聚乙埽醇的生產，包本 間歇反應中之副產物。 整合有效，對於乙酸甲酯而言，一適當之純化 的。已經示範過了一種方法，其中來自聚乙晞 法之物流被回收與精練後，嗣入甲醇羰基化乙 如，含有乙酸甲酯、甲醇、水、輕有機不純物 固體之物流經由分離/蒸餾來純化。移除彡餘的 固體，同時水相流中有機損失則是維持低水平 上述列出成分之次群之水相/有機流亦可一併純 純化步驟之產物為通常含有甲醇、乙酸甲酯、 不純物、實質上無聚合物固體，與夠低量水之 物與其量，以及水的濃度會依據所希之用途及 -9- O:\82\82940.DOC\ 7 (5) 1295990 所使用之設備而有所不同。典型地。對於要 化單元以製造乙酸之乙酸甲酯而言，建議是 之乙酸甲酯，不要有超過大約一分子單元的 中。 將描述本發明，特別是，關於從聚乙烯醇 热習遠項技藝者亦能認知，從形成之乙酸甲 酸奸或乙酸與乙酸肝之共製。乙酸、酐或兩 以本技藝中所熟知之各式方法製得。本發明 酸與共製之製造方法，而是能夠使用經純 之乙酸T醋之整合性方法。 當酸、酐或兩者共製係由甲醇羰基化方法 採用Rh就是採用上當作催化劑，在乙酸甲酿中 多少是要顧及的。這是因為在羰基化反應器 及/或反應物之甲醇轉換化所產生的水的速 的，而且有可能比起在羰基化反應器中經由 應所消耗水的速率還要大。甲醇解反應為： CH3OH + H2 CH4 + H2O 水煤氣轉化反應為： co + h2o — co2 + h2 水有可能累積在乙酸或乙酸酐或其共製之連 經由直接或是間接方式進入反應系統中。移 是在羰基化反應中水的平衡控製是許多參考 然而，在移除水之時，同時還有移除例如甲 問題。甲基碘可以再迴圈至反應中，或是丢 O:\82\82940.DOC\ 7 -10- 舞明妩明讀ϋ 用於甲醇羰基 每一分子單元 水存在於物流 製造乙酸，但 酯亦可製得乙 者之共製可以 並非關於酸或 化或是處理過 製得時，不是 水與不純物的 中，經由甲醇 率是相對地高 水煤氣轉化反 續式生產中， 除過量的水或 文獻的主題。 基蛾等成分的 棄。若是要丟 1295990 ⑹ 發明說明續頁 棄的話’基於環境考慮，必 心、要適春步g ^5 應中之乙酸甲酯具有最少晷2 、两處置。希望用於本反 I的水。六 酸時，所存在水的量係低於相。在羰基化單元中製造乙 量是很關鍵的。若是製造7 A 1於乙酸甲酯含量的化學計 G酸_時， 、 是甲醇。關於在製造乙酸的過。、，不希望存在有水，或 並不如水濃度的顧慮一樣的高^中的甲醇，其濃度的顧慮 使用來自乙婦-或是乙-$ 哲了》^ Έί 方法的乙酸甲酉旨的另一個顧/疋乙酸乙婦酉旨-為基礎之 不純物包含乙•、丙嗣、甲‘;為物流中羰基的含量。羰基 乙酿*、丁醛、巴豆醛、2-乙美 巴豆醛、與2-乙基丁醛、 二收 2乙基 ^ r ψ δ- ^ φ - 九似之等等者，以及未飽和醛 類。乙鉍甲酯泥中需要额外 ^ m ^ 慮到的不純物可能為甲苯、 丰、丙酮、二甲基縮醛、3 、 土 戊酮、丙酸、乙酸乙酯 與乙醇。 本發明之一具體實施例 ^ 種在甲醇羰基化方法中使 用乙酸甲酯流方法，其係包括： 1 a) 生產一種經水解之以乙醢 吸乙埽酯-為基礎之聚合物或 是共聚物； & b) 要不然生產一種經後墙取含 二便增甲醉解之乙烯醇之聚合物 共聚物； 疋 c) 形成乙酸甲酯副產物； d) 將乙酸甲酯引入純化方法中； e) 將經純化之乙酸甲舻λ浓# T S曰引入甲醇羰基化方法中。 上述之具體實施例換你咕a π 侏作時也可以使用烯類、或特士 乙晞，作為共單體。 0 為 O:\82\82940.DOC、 7 -11 - 1295990 ⑺ 「#明叙啥 、、V;〆、、ΪΤ、/〆，^ 所形成之乙酸甲酯副產物可能為甲醇、乙酸、水、輕質 有機不純物與一些聚合物固體群。純化乙酸甲酯之方法包 括’但不限於，經由蒸餾、萃取、過濾或結晶來分離水、 不純物與固體群。 本發明艾另一具體實施例涉使用乙酸甲酯之方法，其係 包括： a) 生產乙酸； b) 在足以形成乙酸乙烯酯之條件下將乙酸與反應物相接 觸； c)在足以形成聚乙酸乙缔酯之條件下接觸乙酸乙烯酯； 〇在足以形成聚乙烯醇之條件下將聚乙酸乙烯醋與鹼及 甲醇相接觸而乙酸甲酯則為副產物·， 中至少一部分之不純物 e)處理乙酸甲酯使其足以移除其 f)將乙酸甲酯引入乙酸製造方法中 乙酸甲酯之方法，其 乙酸酐與反應物相 而本發明之另一具體實施例涉使用 係包括： a) 生產乙酸酐； 乙埽酯之條件下將 b) 在足以形成乙酸 接觸； c)在足以形成聚 d)A >? ,α ^ ^ - 、酯之條件下接觸乙酸乙婦酯 d) 在足以形成聚乙埽醇 ^ 甲醇相i立鎚品r 、 下將聚乙酸乙埽酯與鹼 甲％相接觸而乙酸甲醋則為副產物； e) 處理乙酸甲酯使其足以， 〇將乙酸甲酿引入乙酸奸製：其中至少-部分之不純物 W I造万法中。 O:\82\82940.DOC\ 7 -12- (8) 1295990 而本發明> 酯之方法，其 係包括： 一 ^實施例涉使用乙酸甲 ,a)共製乙酸與乙酸酐； b) 在足以 开> 成乙酸乙埽酯之條件下 應物相接觸· 、 ^與乙酸肝與反 c) 在足以 取 a 乂成水乙故乙晞酯之條件 d) 在足以形士取 卞1干下接觸乙酸乙婦酯，· 甲醇相接觸π α 等聚乙馱乙埽酯與鹼及 要觸而乙酸甲酯則為副產物； e) 處理乙酸甲酯使其足以 f) 將乙酸甲妒弓丨入制、止 #分<不純物； -曰j 製k乙酸與乙酸旬1之共Μ A Μ ^ ^ 表万法中。 為最！：：乙缔醇(PV〇H)中，所形成而得到之乙酸甲酿被 。：屯化而飼入甲醇羰基化反應器中以製造乙酸之母 展、'且1 <乙酸甲醋混合物被引入用作純化之母液管柱中 以移除像是輕質有機成分、聚固物固體與水之不純物。管 枉在升壓，與加熱，下操作以實質上在頂端流中以純化形 式移除所有的乙酸甲酯，而超過95%的甲醇來自粗製之乙酸 y酯混合物之不純物中。管柱之回流要調整到維持大約在 管柱頂端每一莫耳之乙酸甲酯有一莫耳之水。聚合物固體 典型地由聚乙酸乙缔酯，聚乙埽醇與醋酸鈉所組成，並以 殘餘物的形式自母液管柱的底部離開。 藉由在升壓下操作母液管柱，頂部成份或是頂部可以用 作為聚乙婦醇工廠中其餘回收管柱之熱源。在大約55 psig 的壓力下可以回收使用於塔中5〇%的能量。其他物流也可以 額外送入母液管柱中來分離。例如，來自乙酸乙婦酯與甲 -13- O:\82\82940.DOC\ 7 (9) 1295990 發明說明續頁 醇萃取性蒸餾之含有水與甲醇之 由 、. b 其通常用於PVOH方法 ’亦可送入母液管柱中來作分離。 當使用所建議之母液管柱時，一 ^ 根用來分離甲醇與水的 吕枉疋可以保留在PV0H方法中的。 i PM、 J用作卒取性蒸餾之物流 以進一步轉送至甲醇水管柱，或 ， 一 Λ疋母现管柱。母液管柱 或^取性蒸館’可以以允許在進科中之—部分或是所 《知與水和固體離開管柱底部之方式來操作。管柱底 ;心是殘餘物’ Τ以轉送至甲醇水管柱。當運送母液管 ::、邵泥^成本大時，㈣操作方式就可以為尋求全廠成 本取佳化之用。 實施方式Jones, Jane H.5 The CativeTM Process for the Manufacture of Acetic Acid, Platinum Metals Review, V 44, July 2000, No. 3, 95-105. Polyethylene sterol is commercially available with ethyl acetate and free The base initiator and the O:\82\82940.DOC\7 (3) 1295990 alcohol react to produce polyvinyl acetate. Then, polyvinyl acetate and methanol are reacted in the presence of a base to produce polyvinyl alcohol and decyl acetate. The reaction <product is methyl acetate. The methyl acetate produced is typically mixed in a stream containing methyl acetate, methanol (excess reactants for the above reaction), light organic, > sputum, and potential polymer solids and water. Methyl acetate is typically converted to acetic acid via hydrolysis. Acetic acid can be sold or recycled back into the ethyl acetate process. The cost of equipment and energy (operating costs) due to the necessary steaming/separation steps and the expensive building materials necessary for corrosive environments, the cost of the method of hydrolyzing methyl acetate contained in the monthly flow is very high. The hydrazine acetate can be directly fed into the carbonylation process to produce acetic acid (either acetic acid or acetic acid and acetic anhydride), which eliminates the need to operate hydrolysis &equipment; need. However, the methyl acetate stream is not suitable for direct feeding into the carbonylation process. The subject matter of impurities in methyl acetate is generally not indicated in the art and is necessary for purification prior to recovery into the cyclo-integration process. The methyl acetate itself is not suitable as a feed to the carbonylation unit until it has been removed or treated with impurities. If it is not removed, methyl acetate impurities cause problems in downstream use. The polymer solid must be removed because the solid will smear the carbonylation process. The water content must be adjusted to suit the product being produced. For example, if acetic acid is produced by a carbonylation process, then each unit of methyl acetate cannot have more than one unit of water entering the reactor. Otherwise, dry acetic acid will not be obtained. O:\82\82940.DOC\ 7 1295990 (4) The present invention is a reaction system prepared by the product of the product of the ethylene and vinegar-based synthesis integrated in the carbonyl production. In the ester reaction. The method is therefore used in order to make the method step by step is necessary alcohol polymer sulphuric acid method. For example, with polymer water and polymers. Other inclusion/processing. An acceptable amount of logistics. The invention of the invention is based on the invention of a vinyl alcohol or a diethyl hydrazine-based or acetic acid-based polymer or a copolymer (for example, polyvinyl alcohol). Methods (e.g., production of polyacetate) Methyl esters can be converted to a significant reduction in energy cost, or fed to the common system for the production of acetic acid, acetic anhydride or both. The invention relates to the use of a by-product methyl ester in a polyethylene glycol process to produce acetic acid, acetic anhydride or both. The integrated approach will involve the production of acetic acid, which can be used for production. The obtained vinyl acetate can be used for the production of polyethylene glycol, the product of formazan acetate, which is directly fed into the production of acetic acid. It is integrated into the production of polyacetate by the production of acetic acid, and it is a by-product of the batch reaction. The integration is effective and is suitably purified for methyl acetate. A process has been demonstrated in which the stream from the polyethyl hydrazine process is recovered and scoured, and the methanol is carbonylated, and the stream containing methyl acetate, methanol, water, light organic impurities solids is purified by separation/distillation. . The remaining solids are removed, while the organic loss in the aqueous phase is maintained at a low level. The aqueous phase/organic stream of the subgroup of the listed components may also be purely purified. The product usually contains methanol, methyl acetate, Impure, substantially no polymer solids, and a low amount of water and its amount, and the concentration of water will be used according to the intended use and -9- O:\82\82940.DOC\ 7 (5) 1295990 The equipment varies. Typically. For the methylation unit to produce methyl acetate, it is recommended that it be methyl acetate, not more than about one molecule. The present invention will be described, and in particular, it will be recognized by those skilled in the art from the practice of polyvinyl alcohol, from the formation of acetic acid or the co-production of acetic acid and acetic acid liver. Acetic acid, anhydride or two are prepared by various methods well known in the art. The acid of the present invention and the co-fabrication method can be used, but an integrated method of pure acetic acid T-vinegar can be used. When the acid, anhydride or both are co-made by the methanol carbonylation process, the use of Rh is the use of the catalyst as a catalyst, which is considered in the acetic acid brewing. This is because the rate of water produced by the methanol conversion of the carbonylation reactor and/or the reactants is greater and may be greater than the rate of water consumed by the reaction in the carbonylation reactor. The methanolysis reaction is: CH3OH + H2 CH4 + H2O The water gas shift reaction is: co + h2o - co2 + h2 Water may accumulate in acetic acid or acetic anhydride or its co-processed system and enter the reaction system directly or indirectly. Shift is the balance control of water in the carbonylation reaction is a number of references. However, when water is removed, there is also the problem of removing, for example, A. Methyl iodide can be recycled back to the reaction, or O:\82\82940.DOC\ 7 -10- 妩明妩明ϋ Used in methanol carbonyl per molecule of water present in the stream to produce acetic acid, but ester It can also be obtained that the conjugated system of B can be produced not in the case of acid or chemical treatment or in the case of water and impurities, and the methanol rate is relatively high in water gas conversion in the reverse production, except for excess water or The subject of the literature. Abandonment of components such as moths. If you want to lose 1295990 (6) Inventor's Note Continued Page Abandoned' Based on environmental considerations, it is necessary to have a minimum of 晷2 and two treatments. I hope to use the water for this anti-I. In the case of hexahydrate, the amount of water present is lower than the phase. It is critical to make a quantity in the carbonylation unit. If it is a chemical meter G acid _ 7 A 1 in the methyl acetate content, it is methanol. About the production of acetic acid. , it is not desirable to have water, or methanol that is not as high as the concentration of water, the concentration of which is considered to be different from the use of acetic acid for the purpose of using the method of ethyl acetate - or B - Z 哲 ^ ^ ^ Έί A non-purified substance based on a sulphuric acid-containing acetaminophen contains B, propyl ketone, and A'; the content of carbonyl in the stream. Carbonyl bromide*, butyraldehyde, crotonaldehyde, 2-ethyl crotonaldehyde, 2-ethylbutanal, diethyl 2-ethyl^r ψ δ-^ φ - IX, and unsaturated aldehydes class. The impurities that require additional ^ m ^ in the methyl methacrylate sludge may be toluene, abundance, acetone, dimethyl acetal, 3, pentylene ketone, propionic acid, ethyl acetate and ethanol. DETAILED DESCRIPTION OF THE INVENTION One embodiment of the present invention utilizes a methyl acetate stream process in a methanol carbonylation process, which comprises: 1 a) producing a hydrolyzed ethyl acetonate-based polymer or copolymerization & b) otherwise produce a polymer copolymer containing vinyl alcohol which is dehydrated by the second wall; 疋c) forming a methyl acetate by-product; d) introducing methyl acetate into the purification method e) The purified acetic acid formamidine λ concentration # TS曰 is introduced into the methanol carbonylation process. The above specific examples may also use an olefin or a stearyl oxime as a comonomer in the case of 咕a π 侏. 0 is O:\82\82940.DOC, 7 -11 - 1295990 (7) "#明叙啥, V; 〆, ΪΤ, /〆, ^ The methyl acetate by-product formed may be methanol, acetic acid, water Light organic impurities and some polymer solids. Methods for purifying methyl acetate include, but are not limited to, separating water, impurities, and solid groups via distillation, extraction, filtration, or crystallization. Another embodiment of the present invention relates to A method of using methyl acetate, which comprises: a) producing acetic acid; b) contacting acetic acid with a reactant under conditions sufficient to form vinyl acetate; c) contacting acetic acid under conditions sufficient to form polyethylene acetate Vinyl ester; hydrazine is contacted with a base and methanol under conditions sufficient to form polyvinyl alcohol and methyl acetate is a by-product, at least a portion of the impurities e) treatment of methyl acetate is sufficient to remove And f) a method of introducing methyl acetate into methyl acetate in a process for producing acetic acid, the acetic anhydride and the reactant phase, and another embodiment of the present invention includes: a) producing acetic anhydride; conditions of acetamidine Next b) Contacting ethyl acetate in a condition sufficient to form polyd) A >?, α ^ ^ - , ester, d) sufficient to form polyethylene glycol ^ methanol phase i vertical hammer The polyethylene acetate is contacted with the alkali methyl methacrylate and the acetic acid methyl vinegar is a by-product; e) the methyl acetate is treated to make it sufficient, and the acetic acid is introduced into the acetic acid: at least - part of the impurity WI O.\82\82940.DOC\7 -12- (8) 1295990 The method of the present invention is characterized in that: the embodiment involves the use of acetic acid, a) the co-production of acetic acid and Acetic anhydride; b) in the condition of being sufficient to open the acetate to be contacted with ·, ^ and acetic acid and anti-c) in a condition sufficient to take a 乂 乂 水 晞 晞 在 在形士取卞1 dry contact with ethyl acetate, · methanol contact π α and other acetamidine esters and alkali and methyl acetate is a by-product; e) treatment of methyl acetate makes it enough ) 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸 乙酸In the alcohol (PV〇H), the resulting acetic acid is brewed.: It is fermented and fed into a methanol carbonylation reactor to produce a master of acetic acid, and the mixture of acetic acid and methyl acetate is introduced for use. Purifying the mother liquor column to remove impurities such as light organic components, solid solids and water. The tube is pressurized, heated, and operated to remove virtually all of the purified form in the top stream. Methyl acetate, and more than 95% of the methanol is derived from the crude y ester mixture of crude acetate. The reflux of the column is adjusted to maintain a molar amount of water per mole of methyl acetate at the top of the column. The polymer solid typically consists of polyethylene acetate, polyethylene glycol and sodium acetate and exits from the bottom of the mother liquor column as a residue. By operating the mother liquor column under elevated pressure, the top component or top can be used as a heat source for the remaining recovery columns in the polyethylene glycol plant. The energy used in the tower can be recovered at a pressure of about 55 psig. Other streams can also be added to the mother liquor column for separation. For example, from Ethyl acetate and A-13-O:\82\82940.DOC\7 (9) 1295990 Description of the invention: The extraction of alcohol and methanol from alcohol extractive distillation, b. It is usually used in PVOH process. 'Can also be sent to the mother liquor column for separation. When using the proposed mother liquor column, one of the ruthenium used to separate methanol from water can be retained in the PVOH process. i PM, J is used as a stream of stroke distillation for further transfer to the methanol water column, or a mother column. The mother liquor column or the vaporizer can be operated in such a way as to allow the portion or the water and solids to leave the bottom of the column. The bottom of the column; the heart is the residue' Τ to be transferred to the methanol water pipe column. When transporting the mother liquid pipe ::, Shao Mu ^ cost, (4) operation mode can be used for seeking the whole plant cost. Implementation
貴例I 使用來自PVOH方法中的物流以執行蒸餾。在實驗室中， ^。升溫與升壓下採用一種4〇盤之Oldershaw管柱。含有〇·24重 夏％固體之母液流在大約管中央被飼入，同時含有〇·13重量 0固把之水性甲醇液流由自底部起算大約三分之一的地方 被飼入。在大氣壓下蒸餾時，頂部與基部的溫度分別為68 Λ 100 C °母液進料速率為13.7克/分鐘而水性甲醇液進料 速率為11.5克/分鐘。回流比維持在約〇·23。在蒸餾過程中並 未觀τ、到再/弗爐中有起泡或是會壞事的結垢問題。從大約 1 5盤至一直至底部觀察到有深棕/黑色之污潰或是污垢。然 而’這種播關痛癢的結垢並未堵塞Oldershaw管柱的小盤眼或 是降流管。母液進料處以上之盤均無污染。 進料’頂部甲醇/乙酸甲酯產物，與廢水殘餘物之分析如 O:\82\82940.DOC\ η -14- 1295990 (10) 發明說明磺頁: 表1 0 經純化之乙酸甲酯用於甲醇羰基化乙酸之生產中。在無 非典型不純物或是不純物侧寫的情形下製造乙酸。 表1 :甲醇/乙酸甲酯聚合物進料之蒸餾之實驗室試驗分析 成份 母液進料 水性甲醇進料 產物 殘餘物 水(Wt%) 21.4 82.5 5.3 100 甲醇(Wt%) 55.3 17.5 66.8 0.0656 乙酸甲S旨(wt%) 27.1 未測出 27.9 未測出 乙醇(ppm) 1476 75 1704 未測出 丙酮(ppm) 未測出 未測出 未測出 16 二甲縮酮(ppm) 17 未測出 22 未測出 乙酸乙酉旨(ppm) 315 未測出 366 未測出 乙酸(ppm) 248 未測出 313 未測出 甲苯(ppm) 未測出 未測出 74 未測出 乙酸(ppm) 45 未測出 未測出 87 燒類(ppm) <100 781 3 932 表中值未經正交化。 產物==乙酸甲醋，發明之甲醇產物 實例中例示了甲醇/乙酸甲酯流可以以在廢水中低於1000 ppm之甲醇與低於2600 ppm之燒類下以低回流比純化。 實例2 實例1中之甲醇/乙酸甲酯產物以下述之方式飼入實驗性 羰基化單元中：在來自實例1中之材料進料至甲醇羰基化實 驗性單元前，實驗性單元使用於195°C純甲醇進料、1100 ppm 之Rh、2.2重量％MeOAc、2.2重量％水與6.5重量％MeI而維持於 穩態。最終之空間時間產率為20莫耳/升/小時。反應條件維 -15- O:\82\82940.DOQ 7 1295990 _Example I uses a stream from the PVOH process to perform the distillation. In the lab, ^. An Oldershaw column with 4 turns is used for heating and boosting. The mother liquor stream containing 〇·24 weights of summer% solids was fed at about the center of the tube, while the aqueous methanol stream containing 〇·13 weight 0 solids was fed from about one third of the bottom. When distilled at atmospheric pressure, the top and base temperatures were 68 Λ 100 C °, the mother liquor feed rate was 13.7 g/min, and the aqueous methanol feed rate was 11.5 g/min. The reflux ratio was maintained at about 〇·23. During the distillation process, there is no τ, there is blistering in the re-furnace furnace or scaling problems that can cause bad things. Dark brown/black stains or dirt were observed from about 15 to the bottom. However, this kind of fouling fouling did not block the small disk or the downcomer of the Oldershaw column. There is no pollution on the tray above the mother liquor feed. Feeding 'top methanol/methyl acetate product, and analysis of wastewater residue such as O:\82\82940.DOC\ η -14-1295990 (10) Description of the invention: Table 1 0 Purified methyl acetate In the production of methanol carbonylation of acetic acid. Acetic acid is produced without atypical impurities or impurities. Table 1: Laboratory test analysis of methanol/methyl acetate polymer feed distillation. Ingredient mother liquor feed aqueous methanol feed product residue water (Wt%) 21.4 82.5 5.3 100 methanol (Wt%) 55.3 17.5 66.8 0.0656 acetic acid S (wt%) 27.1 Not detected 27.9 Undetected ethanol (ppm) 1476 75 1704 No acetone detected (ppm) No undetected 16 dimethyl ketal (ppm) not detected 17 Not detected 22 No acetic acid was detected (ppm) 315 Not detected 366 Undetected acetic acid (ppm) 248 Not detected 313 Undetected toluene (ppm) Not detected Undetected 74 Undetected acetic acid (ppm) 45 Not tested Not detected 87 Burning (ppm) <100 781 3 932 The value in the table is not orthogonalized. Product = = methyl acetate, the methanol product of the invention It is exemplified in the examples that the methanol/methyl acetate stream can be purified at a low reflux ratio with less than 1000 ppm methanol and less than 2600 ppm in waste water. Example 2 The methanol/methyl acetate product of Example 1 was fed to an experimental carbonylation unit in the following manner: The experimental unit was used at 195 ° before the material from Example 1 was fed to the methanol carbonylation experimental unit. C pure methanol feed, 1100 ppm Rh, 2.2 wt% MeOAc, 2.2 wt% water and 6.5% wt MeI were maintained at steady state. The final space time yield is 20 moles per liter per hour. Reaction condition dimension -15- O:\82\82940.DOQ 7 1295990 _
(Π) 番明說初續I 持固定，來自實例1之蒸餾物取代MeOH作為進入實驗性單 元之進料。將水加入實驗性單元中使得進料中之總水量與 總乙酸甲酯量為等莫耳。上述之條件維持三天。反應速率 不變地維持在20莫耳/升/小時。來自實驗性單元中乙酸產物 的組成列於下表。產物中丙酸（HOPr)之濃度在將來自實例1 之材料進料後增加。 表2 : 甲醇 189 ppm 乙酸甲酯 53 ppm 巴豆醛 1.4 ppm 丁醛 6 ppm 2-乙基巴豆醛 5.2 ppm 丙酸 1601 ppm 乙酸 餘量 O:\82\82940.DOC\ -16·(Π) Fan Ming said that the initial I was fixed, and the distillate from Example 1 replaced MeOH as the feed to the experimental unit. Water was added to the experimental unit such that the total amount of water in the feed and the amount of total methyl acetate were equal to one mole. The above conditions are maintained for three days. The reaction rate was maintained constant at 20 mol/l/hr. The composition of the acetic acid product from the experimental unit is listed in the table below. The concentration of propionic acid (HOPr) in the product increased after the feed from Example 1 was fed. Table 2: Methanol 189 ppm methyl acetate 53 ppm crotonaldehyde 1.4 ppm butyraldehyde 6 ppm 2-ethyl crotonaldehyde 5.2 ppm propionic acid 1601 ppm acetic acid balance O:\82\82940.DOC\ -16·