TW487700B

TW487700B - Method for purifying crude terephthalic acid from a liquid dispersion produced from the oxidation of mixed xylenes

Info

Publication number: TW487700B
Application number: TW88108301A
Authority: TW
Inventors: Fu-Ming Lee; Wiston Lamshing; Randi Wright Wytcherley
Original assignee: Hfm Int Inc
Priority date: 1999-05-20
Filing date: 1999-05-20
Publication date: 2002-05-21

Description

7 7 8 4 經濟部智慧財產局員工消費合作社印製 A7 ___B7_ 五、發明說明（1 ) 相關申請案本申請案係1998年5月7日提出申請之共同申請中之美國申請案序號09/074,251，標題爲「製備純化對酞酸之方法及裝置（Method and Apparatus for Preparing Purified Terephthalic Acid)」之部分延續，此美國申請案序號09/074,251係1995年 6月7日提出申請之共同申請中之美國申請案號數08/477,898 ，標題爲「製備純化對酞酸之方法及裝置」，現爲美國專利號數5,767,311之部分，且亦爲1997年10月3 1日提出申請之美國申請案序號08/962,030，標題爲「製備純化對酞酸之方法及裝置」之部分延續，此美國申請案序號08/962,030係 1996年12月6日提出申請之美國申請案序號08/760,890，標題爲「製備純化對酞酸之方法及裝置」之部分延續，此美國申請案序號08/760,890依序爲1995年6月7日提出申請之共同申請中之美國申請案序號〇8/477,898，標題爲「製備純化對酞酸之方法及裝置」，現爲美國專利號數5,767,311之部分延續，此四篇專利皆係受讓給與本申請案相同之受讓人，將其全部之揭示内容以提及的方式併入本文中供所有用途用。緒論本發明係關於對酞酸及異酞酸之製造，及更明確言之，係關於自混合二曱苯製備純化對酞酸及異酞酸之方法及裝置。背景習知的對酞酸（TPA)製造方法需要相當高的對二甲苯純度 (請先閱讀背面之注意事項寫本頁) Μ 裝訂： -I線· -4- 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐）經濟部智慧財產局員工消費合作社印製 487700 A7 ___ B7 五、發明說明（2 ) (99.7+。/。），以改良產品品質及降低製造成本。此係由於此等先如技藝方法使用氮化爲主要方法，以純化在該方法之氧化段中所產生之粗製對酞酸。雖然氫化方法對於經由將主要的不純物-4-叛基苯甲酸（4-CBA)-轉變成對甲苯酸而將其除去非常具選擇性，但此方法僅可在非常少量之4 _ CBA(以低於3,000 ppm較佳）的存在下操作。並且，習知的 TP A裝方法典法自其異構物，諸如異酜酸（ip a)及目太酸 (PA)中分離出TPA。發明總結相對於前述之先前技藝的TPA方法，本發明提供一種自混合二甲苯製備純化對酞酸，及視需要可製備異酞酸之方法及裝置。更重要地爲其可純化含有對g太酸及異自太酸以及少量4 -羧基苯曱醛（4 - CB A)、3 _羧基苯甲醛（3 _ CB A)、及甲苯酸異構物之混合物之氧化反應器流出物，而在整體方法中製造純化對酞酸，及視需要可製造純化異酞酸。此等產物可有用於製造纖維、薄膜、塑膠瓶、及通常經其他材料諸如玻璃纖維強化之聚酯樹脂結構。根據本發明，提供一種在整體方法中自混合二甲苯製造純化對酞酸，及視需要可製造純化異酞酸之方法及裝置。在一具體實例中，本發明之方法包括經由氧化主要含有對二甲苯及較少量間二甲苯及其他異構物之混合二甲苯，而製造粗製混合酸（包括對酞酸及異酞酸）。氧化步驟不僅會產生對酞酸及異酞酸，並且會經由不完全氧化而產生4_ CBA、3-CBA、對甲苯酸、間甲苯酸及其他微量的酸及醛 ------------------- (請先閱讀背面之注意事項|fl|c寫本頁) 一：°JI . -5-7 7 8 4 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ___B7_ V. Description of the Invention (1) Related Applications This application is a US application No. 09 / 074,251 in the joint application filed on May 7, 1998 , Part of which is entitled "Method and Apparatus for Preparing Purified Terephthalic Acid", this U.S. application serial number 09 / 074,251 is part of a joint application filed on June 7, 1995 U.S. Application No. 08 / 477,898, titled "Method and Device for Purifying and Purifying Terephthalic Acid", is now part of U.S. Patent No. 5,767,311, and is also the serial number of the U.S. application filed on October 31, 1997 Partial continuation of 08 / 962,030, entitled "Method and Device for Purifying and Purifying Terephthalic Acid", this US application serial number 08 / 962,030 is US application serial number 08 / 760,890 filed on December 6, 1996, entitled " The method and device for preparing and purifying terephthalic acid are continued. This US application serial number 08 / 760,890 is sequentially the US application in the joint application filed on June 7, 1995. Case No. 08 / 477,898, entitled "Method and Apparatus for Purifying and Purifying Terephthalic Acid", which is a continuation of U.S. Patent No. 5,767,311, all of which are assigned to the same assignee as the present application , The entire disclosure of which is incorporated herein by reference for all purposes. Introduction The present invention relates to the production of terephthalic acid and isophthalic acid, and more specifically, to a method and apparatus for preparing and purifying terephthalic acid and isophthalic acid from mixed xylene. Background The conventional manufacturing method of terephthalic acid (TPA) requires a relatively high purity of p-xylene (please read the notes on the back to write this page first) Binding: -I line · -4- This paper size applies to Chinese national standards ( CNS) A4 specification (210 x 297 mm) Printed 487700 A7 ___ B7 by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (2) (99.7 +. /) To improve product quality and reduce manufacturing costs. This is because these prior art methods use nitridation as the main method to purify the crude terephthalic acid produced in the oxidation section of the method. Although the hydrogenation method is very selective in removing 4- Impurylbenzoic acid (4-CBA) -to-p-toluic acid by converting the main impurity, this method can only be used in very small amounts of 4-CBA (to Less than 3,000 ppm is preferred). In addition, the conventional method for packing TPA isolates TPA from its isomers, such as isophosphonic acid (ip a) and mesh acid (PA). Summary of the Invention Compared to the TPA method of the prior art, the present invention provides a method and apparatus for preparing and purifying terephthalic acid from mixed xylene, and preparing isophthalic acid as needed. More importantly, it can be purified to contain p-g citric acid and iso-caproic acid, and a small amount of 4-carboxybenzaldehyde (4-CB A), 3-carboxybenzaldehyde (3-CB A), and toluic acid isomers. The mixture is oxidized to the reactor effluent, and purified terephthalic acid is produced in the overall process, and purified isophthalic acid can be produced if necessary. These products can be used to make fibers, films, plastic bottles, and polyester resin structures often reinforced with other materials such as glass fibers. According to the present invention, there is provided a method and apparatus for producing purified terephthalic acid from mixed xylene in a monolithic method, and if necessary, for producing purified isophthalic acid. In a specific example, the method of the present invention includes the production of crude mixed acids (including terephthalic acid and isophthalic acid) by oxidizing mixed xylenes mainly containing para-xylene and a small amount of meta-xylene and other isomers. . The oxidation step will not only generate terephthalic acid and isophthalic acid, but also produce 4_ CBA, 3-CBA, p-toluic acid, m-toluic acid and other trace acids and aldehydes through incomplete oxidation -------- ----------- (Please read the precautions on the back | fl | c to write this page) 1: ° JI. -5-

487700 A7 B7 五、發明說明（3 ) ------一----------- (請先閱讀背面之注意事項寫本頁) 異構物°由氧化步驟所產生之產物係包含未反應起始物料 ’若有使用之任何溶劑，副反應之產物，尤其係方才提及 t產物’及在所企望之純化對酞酸及純化異g太酸中不期望之其他物料的液體分散物。將反應器流出物供應至一系列的結晶器，其經由減壓使反應溶劑蒸發，此反應溶劑以醋酸較佳，而使固體得以成長。過濾、及洗滌來自最後一個結晶器之淤漿。然後將經過濾、的晶體乾燥，以將溶劑移除至在所產生之粗製混合酸晶體中低於0.25%之量値。將經由過濾而得之母液供應至溶劑脱水單兀，以自水回收溶劑（醋酸），而再循環至氧化器。再根據本發明，將來自氧化段之乾燥器之粗製混合酸再 /合解於選擇性結晶溶劑中，然後在一個結晶段中，或以兩個車又佳’使對g太酸（TPA)自選擇性結晶溶劑結晶而出。準備將經結晶及逐漸純化的TPA自本發明之溶劑（有或沒有共溶劑）分離出。以水洗滌及浸泡最終製得之純化τρΑ的濾餅，以自TPA產物移除顏色及最終微量的選擇性結晶溶劑。線！經濟部智慧財產局員工消費合作社印制衣爲自結晶器母液回收異酞酸（IP A)(於經由過濾移除TPA固體加入反溶劑，以使τρΑ實質上完全地自母液沈澱。將實質上不含TPA之母液經由使選擇性結晶溶劑及反溶劑自母液瘵發而濃縮，並經冷卻而使粗製IpA結晶。接著經由在另一選擇性結晶溶劑中再結晶，而將粗製IPA進一步純化。本發明亦考慮將在各段結晶及洗滌，及最終浸泡中之本發明/谷劑回收及再循環之步驟。亦採取步驟，以嚴密地控制任何不受歡迎物料之輸送至環境。 487700 J# il A7 ! ·. Bf 五、發明說明（4) ——一一——— (請先閱讀背面之注意事項再填寫本頁) 本發明之一重要態樣係發現可經由結晶及分離步騾，而有效地自粗製混合物（含有TPA、直至2 0 % IPA、較少量之 3-CBA、4-CBA、間甲苯酸、對曱苯酸等等）純化TPA以及 IPA之溶劑。此等發現可概述如下。關於TPA純化，有用於實施本發明之選擇性結晶溶劑包括，其中（a)期望自TPA分離之不純物（包括IPA)在要用來處理含TPA之溶劑之期望溫度範圍内之實質上的所有溫度下，在溶劑中皆較TPA甚可溶解，及（b)TPA在高溫下更可溶解及在較低或降低溫度下較不可溶解。應明暸術語「選擇性結晶溶劑」係意指包括可有用於如前所述之TPA之選擇性結晶的任何溶劑。關於IPA純化，要加至母液（來自TPA結晶流出物）中之反溶劑應可實質上地使TPA完全自母液沈澱（或結晶），但仍可使大部分的IPA保留於母液中。經由蒸發（或蒸餾）使實質上不含TPA之母液濃縮而使粗製IPA結晶，其接著再經由過濾分離，及再溶解於第二選擇性結晶中，而產生純化IP A。經濟部智慧財產局員工消費合作社印製根據本發明，基於論述於下之數項理由及基於其優良性能，用於純化TPA之主要較佳的選擇性結晶溶劑為N -甲基吡咯啶酮（NMP)。其為非水性、熱安定、無毒（對環境安全）、非腐蝕性、且可於市面購得。TPA在高溫下可溶解於NMP 中，及在較低溫度下可自NMP沈澱或結晶。主要的不純物諸如4 - CBA、3 - CBA、對甲苯酸、間甲苯酸以及IPA，在所有溫度下在NMP中皆較TPA具有甚高的溶解度。因此，經由降低溫度，僅有TPA傾向於自溶液結晶或沈澱，而生成純本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 487700 A7 五、發明說明（5 ) 化TPA晶體。雖然NMP爲最佳的選擇性結晶溶劑，但應明瞭根據本發明，用於純化粗製TP A之其他較佳的選擇性結晶溶劑可選自各種極性有機溶劑，其包括，但不限於，N，N-二甲基乙醯胺、N，N-二甲基甲醯胺、N_甲醯基六氫吡啶、N-烷基-2 - p比p各淀明（諸如N -乙基p比咯淀酮）、N -硫醇貌基-2 - p比洛淀酮（諸如N -硫醇乙基-2 -吨p各淀酮）、N -纟完基-2 -硫峨咯咬酮（諸如N -甲基-2 -硫ρ比咯淀酮）、N-藉燒基_ 2 - p比咯淀酮（諸如N -經乙基-2 - ρ比p各淀酮）、嗎琳（諸如嗎淋、及N -甲驢基嗎淋）、卡必醇（carbitols)、Ci至C12醇、醚、胺、醯胺、及酯、及其混合物。主要較佳的反溶劑爲甲醇，雖然用於使TPA實質上完全自母液沈澱之反溶劑亦可選自各種極性有機溶劑，其包括，但並不限於，甲基乙基酮、丙酮、^至^】醇、卡必醇、酯、醚、C 1至C12複酸、水、及其混合物。供IPA純化用之主要較佳的選擇性結晶溶劑爲甲醇，雖然溶劑亦可選自，但不限於，甲基乙基酮、丙酮、CisCi2 醇、卡必醇、酯、醚、^至^2羧酸、水、及其混合物。爲移除陷於TPA終產物晶體中之殘留溶劑（例如，NMp)，將經洗滌的TPA晶體供應至高溫浸泡器，其中使用水於使 TPA晶體部分或完全溶解較佳。陷於最終ipA晶體中之殘留落劑（甲醇），可經由乾燥而移除至低於〇 25%之量値。在一具體實例中，本發明之自由氧化混合二甲苯所產生之液體分散物純化粗製對g太酸（TPA)之方法包括下列步驟： χ 297公釐） &氏張尺度咖鮮（CNS)A4規格“ -8- 487700 A7 五、發明說明（6 ) (a)知粗製TPA在自約5〇°C至約250°C之溫度下溶解於選擇性結晶溶劑中，而形成溶液；（b)經由降低溫度及/或壓力，而使純化酸自該溶液結晶；（c)自該溶液分離出該結晶的純化TPA ; (d)將該分離出的純化τρΑ再溶解於選擇性結晶溶劑中，而形成第二溶液；（e )經由充分地降低溫度及壓力以使溶劑自該第二溶液之該TPA急速蒸發，但不將該溶液冷卻至低於5 0 °C，而使第二段純化Tp a自該第二溶液結晶； (f)自該第二溶液分離出該第二段純化TPA ; (g)以水洗滌該分離出之第二段純化TPA ; (h)在約150°C及約30(TC之間的 /皿度下’以水浸泡該經洗滌之分離出之第二段純化TPA ; (i)將該經浸泡水的第二段純化TPA過濾及乾燥；（j)將反溶劑加至在（c)中之該經過濾溶液，以使實質上所有的TpA沈殿’（k)自步驟（j)中之該溶液分離出該沈澱的TpA，並將該沈澱的TPA與該原始的粗製TPa結合，以於步驟（a)中處理 ;(1)使溶劑自步驟（k)中之該經過濾之不含TPA的溶液蒸發，以使IPA在自約5 °C及約10(TC之溫度下結晶；（m)自步驟（1)中之該溶液分離出該結晶的粗製IPA ; 在自約5〇至 250°C之溫度下，將粗製卩八再溶解於選擇性結晶溶劑中，而形成第二溶液；（〇)經由充分地降低溫度及壓力以使溶劑自该第二溶液之該IP A急速蒸發，但不將該溶液冷卻至低於約5 0 °C，而使純化IP A自步驟（η)中之該第二溶液結晶；及 (Ρ)將來自該第二溶液之該第二段純化IP Α分離並乾燥。在此具體實例中，分散物包含至少0至2 0 %之異酞酸 (IPA)、及少量的4-羧基苯甲醛（4-CBA)、3-羧基苯甲醛 .9 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ---,------------裝--- (請先閱讀背面之注意事項me寫本頁) 訂：線. 經濟部智慧財產局員工消費合作社印制衣 487700 A7487700 A7 B7 V. Description of the invention (3) ------ 1 ----------- (Please read the notes on the back to write this page) Isomers ° Produced by the oxidation step The product contains unreacted starting materials 'if any solvents are used, the products of side reactions, especially the product t mentioned above', and other materials which are not desirable in the desired purification of terephthalic acid and purification of iso-g-acid Liquid dispersion. The reactor effluent is supplied to a series of crystallizers which evaporate the reaction solvent under reduced pressure. This reaction solvent is preferably acetic acid to allow the solid to grow. Filter and wash the slurry from the last crystallizer. The filtered crystals are then dried to remove the solvent to an amount of less than 0.25% in the resulting crude mixed acid crystals. The mother liquor obtained by filtration is supplied to a solvent dehydration unit to recover the solvent (acetic acid) from water and recycle it to the oxidizer. According to the present invention, the crude mixed acid from the dryer in the oxidation section is re-combined in a selective crystallization solvent, and then in one crystallization section, or two cars, it is better to make p-g too acid (TPA) Crystallized from a selective crystallization solvent. Preparation The crystallized and gradually purified TPA is separated from the solvent (with or without co-solvent) of the present invention. The final purified τρΑ filter cake was washed and soaked with water to remove color and the final trace amount of selective crystallization solvent from the TPA product. line! The clothing printed by the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs collects isophthalic acid (IP A) from the mother liquor of the crystallizer (adding an antisolvent to remove the TPA solids by filtration, so that τρΑ is substantially completely precipitated from the mother liquor. The TPA-free mother liquor was concentrated by evolving the selective crystallization solvent and antisolvent from the mother liquor, and cooled to crystallize the crude IpA. The crude IPA was then further purified by recrystallization in another selective crystallization solvent. The present invention also considers the steps of the invention / cereal recovery and recycling which will be crystallized and washed in various stages, and in the final immersion. Steps are also taken to tightly control the transportation of any unwanted materials to the environment. 487700 J # il A7! ·. Bf V. Description of the invention (4) ——One by one ———— (Please read the notes on the back before filling this page) An important aspect of the present invention is that it can be found through crystallization and separation steps, and Efficient purification of solvents for TPA and IPA from crude mixtures (containing TPA, up to 20% IPA, smaller amounts of 3-CBA, 4-CBA, m-toluic acid, p-benzoic acid, etc.). These findings can be summarized Such as With regard to TPA purification, selective crystallization solvents useful in the practice of the present invention include, where (a) the impurities (including IPA) that are desired to be separated from TPA are substantially within the desired temperature range to be used to process the solvent containing TPA It is even more soluble in solvents than TPA at all temperatures, and (b) TPA is more soluble at high temperatures and less soluble at lower or lower temperatures. It should be understood that the term "selective crystallization solvent" is meant to include There may be any solvent used for the selective crystallization of TPA as previously described. With regard to IPA purification, the antisolvent to be added to the mother liquor (from the TPA crystallization effluent) should substantially allow the TPA to completely precipitate (or crystallize) from the mother liquor ), But still can keep most of the IPA in the mother liquor. The crude IPA is crystallized by concentrating the mother liquor that is substantially free of TPA by evaporation (or distillation), which is then separated by filtration and redissolved in the second option. In the crystallization, the purified IP A is produced. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs According to the present invention, it is used to purify TPA based on several reasons discussed below and based on its excellent performance. The main preferred selective crystallization solvent is N-methylpyrrolidone (NMP). It is non-aqueous, heat stable, non-toxic (environmentally safe), non-corrosive, and commercially available. TPA is at high temperature Soluble in NMP, and precipitate or crystallize from NMP at lower temperature. The main impurities such as 4-CBA, 3-CBA, p-toluic acid, m-toluic acid and IPA are better in NMP at all temperatures. TPA has a very high solubility. Therefore, by reducing the temperature, only TPA tends to crystallize or precipitate from the solution, and the pure paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 487700 A7 V. Description of the invention (5) TPA crystal. Although NMP is the best selective crystallization solvent, it should be clear that according to the present invention, other preferred selective crystallization solvents for purifying crude TP A may be selected from various polar organic solvents, including, but not limited to, N, N-dimethylacetamide, N, N-dimethylformamide, N-formamyl hexahydropyridine, N-alkyl-2-p ratio p each (such as N-ethyl p ratio Pyrrolidone), N-thiol-methyl-2 -p-biloxone (such as N-thiol ethyl-2 -t-pyridone), N-fluorenyl-2 -thiopyrrolidone (Such as N-methyl-2 -sulfo-pyrrolidone), N-boryl group 2- 2-p-pyrrolidone (such as N-ethyl-2-p-pyridone), morphine (Such as morphine and N-methymorphyl), carbitols, Ci to C12 alcohols, ethers, amines, amidines, and esters, and mixtures thereof. The main preferred anti-solvent is methanol. Although the anti-solvent used to substantially completely precipitate the TPA from the mother liquor can also be selected from various polar organic solvents, including, but not limited to, methyl ethyl ketone, acetone, ^] Alcohols, carbitol, esters, ethers, C1-C12 polyacids, water, and mixtures thereof. The main preferred selective crystallization solvent for IPA purification is methanol. Although the solvent can also be selected from, but is not limited to, methyl ethyl ketone, acetone, CisCi2 alcohol, carbitol, ester, ether, ^ to ^ 2 Carboxylic acids, water, and mixtures thereof. In order to remove the residual solvent (for example, NMp) trapped in the crystals of the final TPA product, the washed TPA crystals are supplied to a high-temperature soaker, wherein water is preferably used to partially or completely dissolve the TPA crystals. The residual solvent (methanol) trapped in the final ipA crystals can be removed by drying to an amount of less than 25%. In a specific example, the method for purifying the crude p-g-acid (TPA) produced by the free oxidation of mixed xylene produced by the present invention includes the following steps: χ 297 mm) & Zhang's scale coffee (CNS) A4 specification "-8- 487700 A7 V. Description of the invention (6) (a) It is known that the crude TPA is dissolved in a selective crystallization solvent at a temperature from about 50 ° C to about 250 ° C to form a solution; (b) ) Crystallizing the purified acid from the solution by reducing the temperature and / or pressure; (c) separating the purified TPA from the solution; (d) re-dissolving the isolated purified τρΑ in a selective crystallization solvent To form a second solution; (e) by sufficiently reducing the temperature and pressure to rapidly evaporate the solvent from the TPA of the second solution, but not to cool the solution to less than 50 ° C, so that the second stage Purified Tp a crystallized from the second solution; (f) separating the second stage of purified TPA from the second solution; (g) washing the separated second stage of purified TPA with water; (h) at about 150 ° C and about 30 ° C / dish 'soak the washed and separated second purified TPA with water; (i) place Purify the TPA by soaking in the second stage of filtration and dry; (j) add the anti-solvent to the filtered solution in (c) so that substantially all TpA Shen Dian '(k) from step (j) The solution was used to separate the precipitated TpA, and the precipitated TPA was combined with the original crude TPa for processing in step (a); (1) the solvent was removed from the filtered solution in step (k). The TPA-containing solution was evaporated to crystallize IPA at a temperature from about 5 ° C and about 10 ° C; (m) the crystallized crude IPA was separated from the solution in step (1); At a temperature of up to 250 ° C, the crude lutea is redissolved in a selective crystallization solvent to form a second solution; (0) The solvent is rapidly removed from the IP A of the second solution by sufficiently reducing the temperature and pressure. Evaporate, but do not cool the solution below about 50 ° C, so that purified IP A crystallizes from the second solution in step (η); and (P) the second stage from the second solution Purified IP A is separated and dried. In this specific example, the dispersion contains at least 0 to 20% isophthalic acid (IPA), and a small amount of 4-carboxybenzaldehyde (4-C BA), 3-carboxybenzaldehyde. 9-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ---, ------------ Packing --- (Please read the note on the back first to write this page) Order: Line. Printed clothing 487700 A7 for the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

五、發明說明（7 ) (3 - CBA)及選自未反應起始物料、溶劑、副反應之產物及 /或其他不期望物料之不純物。供TPA純化用之選擇性於晶溶劑係選自由N -甲基吡咯啶酮（NMP)、N，N -二甲基乙酉蘇胺、N，N-二甲基甲醯胺、N-甲醯基六氫吡啶、N-烷基_2_ 说洛淀酮（諸如N-乙基吡咯啶酮）、N-硫醇烷基-2-吨哈淀酮（諸如N-硫醇乙基-2-吡咯啶酮）、N-烷基-2-硫吡洛咬酮 (諸如N-甲基-2-硫吡咯啶酮）、N-羥烷基-2-吡咯啶酮（諸如N-羥乙基-2-吡咯啶酮）、嗎啉（諸如嗎啉、及N-甲醯基嗎琳）、卡必醇、C!至C!2醇、醚、胺、醯胺、及酯、及其混合物所組成之群。在此具體實例中供Tpa純化用之選擇性結晶溶劑爲N-甲基吡咯啶酮*N，n-二甲基乙醯胺或N_ 甲基吡咯啶酮。使TPA自TPA/IPA溶液沈澱之反溶劑係選自由甲醇、水、甲基乙基酮、丙酮、c i至Cu醇、卡必醇、酯、醚、（^至心2羧酸、水、及其混合物所組成之群。使lpA 再結晶之選擇性結晶溶劑係選自由甲醇、水、甲基乙基酮、丙酮、（^至心〗醇、卡必醇、酯、醚、CisCi2羧酸:水、及其混合物所組成之群。反溶劑係以〇1至1〇之反溶劑V. Description of the invention (7) (3-CBA) and impurities selected from unreacted starting materials, solvents, products of side reactions and / or other undesired materials. Selective crystalline solvents for TPA purification are selected from the group consisting of N-methylpyrrolidone (NMP), N, N-dimethylacetamidine, N, N-dimethylformamide, and N-formamidine Hexahydropyridine, N-alkyl_2_ Said Luodianone (such as N-ethylpyrrolidone), N-thiol alkyl-2-ton Hardidone (such as N-thiol ethyl-2- Pyrrolidone), N-alkyl-2-thiopyrrolidone (such as N-methyl-2-thiopyrrolidone), N-hydroxyalkyl-2-pyrrolidone (such as N-hydroxyethyl -2-pyrrolidone), morpholine (such as morpholine, and N-formylmorpholin), carbitol, C! To C! 2 alcohols, ethers, amines, amidines, and esters, and mixtures thereof Group of people. The selective crystallization solvent for Tpa purification in this specific example is N-methylpyrrolidone * N, n-dimethylacetamide or N-methylpyrrolidone. The antisolvent that precipitates TPA from the TPA / IPA solution is selected from the group consisting of methanol, water, methyl ethyl ketone, acetone, ci to Cu alcohol, carbitol, esters, ethers, (2 to 2 carboxylic acids, water, and A group consisting of a mixture thereof. The selective crystallization solvent for recrystallizing lpA is selected from the group consisting of methanol, water, methyl ethyl ketone, acetone, ^ alcohol, carbitol, ester, ether, CisCi2 carboxylic acid: A group of water and mixtures thereof. The antisolvent is an antisolvent of 0 to 10

/落液比使用較佳，及在〇 . 5至3之間的比更佳，以使τρ A 沈澱。經濟部智慧財產局員工消費合作社印製 -II-— — ΙΊΙ — — — — — — - I I (請先閱讀背面之注意事項me寫本頁) 在另一具體實例中，分散物包含至少〇至2〇%之異酞酸 (IPA)、及少量的4-羧基苯甲醛（4-Cba)、3•羧基苯甲醛 (^ - CBA)、及選自未反應起始物料、溶劑、副反應之產物及/或其他不期望物料之不純物。供Tp A純化用之選擇性結晶落劑係選自由N-甲基吡咯啶酮（NMp)、N，N_二曱美乙 -10- 487700 A7 B7 五、發明說明（8 ) 醯胺、N，N-二甲基曱醯胺、N -甲醯基六氫吡啶、N-烷基-2 _吡咯啶酮（諸如N-乙基吡咯啶酮）、N-硫醇烷基-2 -吡洛啶酮（諸如N -硫醇乙基-2 -吡咯啶酮）、N -烷基-2 -硫吡咯淀酮（諸如N -甲基-2 -硫吡咯啶酮）、N-羥烷基-2 -吡咯啶酮（諸如N -羥乙基-2 _吡咯啶酮）、嗎啉（諸如嗎啉、及N -甲醯基嗎啉）、卡必醇、C 1至C12醇、醚、胺、醯胺、及酯、及其混合物所組成之群。供TPA純化用之選擇性結晶溶劑爲N-甲基吡咯啶酮或N, N -二甲基乙醯胺。以下之實施例説明選擇性結晶溶劑於分離TPA及IPA之效用，其係本發明之原理及特色：實施例1 經濟部智慧財產局員工消費合作社印製、(請先閱讀背面之·事項HI寫本頁) 此實施例説明TPA以及IPA在大氣壓力在三個不同溫度下，在作爲選擇性結晶溶劑之NMP中之溶解度的實驗數據。此實驗係在浸於保持在預定溫度下之恆溫槽中之實驗室燒瓶内進行。利用溫度計測量燒瓶中之液相溫度。對於高溫測量，使用全迴流冷凝器於回收由於蒸發所造成的溶劑損耗。在實驗過程中，將少量的固體逐量加至燒瓶中之不斷攪摔的溶劑中，直至不再有固體溶解爲止，然後將此溶液視爲在該溫度下與固體飽和。根據溶劑之重量及加入固體之總重量計算溶解度。表1概述在15、40、70、及160°C下，TPA及IPA於NMP中之溶解度。 -11 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 487700 A7 B7 五、發明說明（9 ) 表1 固體溶劑溶解度（固體克數/100克之溶劑） 15°C 40°C 70°C 160°C TPA NMP 2.8 8.0 14.0 23.0 IPA NMP 10.7 22.2 46.0 62.0 4-CBA NMP * * 18.9 27.4 66.0 125.0*The / fall ratio is preferably used, and a ratio between 0.5 and 3 is preferred to allow τρ A to precipitate. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-II --- — ΙΊΙ — — — — — — — II (Please read the notes on the back first to write this page) In another specific example, the dispersion contains at least 0 to 20% isophthalic acid (IPA), and a small amount of 4-carboxybenzaldehyde (4-Cba), 3 • carboxybenzaldehyde (^-CBA), and selected from unreacted starting materials, solvents, side reactions Impurities in the product and / or other undesirable materials. The selective crystallizing agent for the purification of Tp A is selected from the group consisting of N-methylpyrrolidone (NMp), N, N_diazepam ethyl-10-487700 A7 B7 V. Description of the invention (8) osmamine, N , N-dimethylamidamine, N-methylamidinohexahydropyridine, N-alkyl-2-pyrrolidone (such as N-ethylpyrrolidone), N-thiol alkyl-2 -pyridine Loridone (such as N-thiol ethyl-2-pyrrolidone), N-alkyl-2-thiopyrrolidone (such as N-methyl-2 -thiopyrrolidone), N-hydroxyalkyl -2 -pyrrolidone (such as N-hydroxyethyl-2-pyrrolidone), morpholine (such as morpholine, and N-formylmorpholine), carbitol, C 1 to C12 alcohol, ether, A group of amines, amidines, and esters, and mixtures thereof. Selective crystallization solvents for TPA purification are N-methylpyrrolidone or N, N-dimethylacetamide. The following examples illustrate the effectiveness of selective crystallization solvents in the separation of TPA and IPA, which are the principles and features of the present invention: Example 1 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, (This page) This example illustrates experimental data on the solubility of TPA and IPA in NMP as a selective crystallization solvent at atmospheric pressure at three different temperatures. This experiment was performed in a laboratory flask immersed in a thermostatic bath maintained at a predetermined temperature. The temperature of the liquid phase in the flask was measured with a thermometer. For high temperature measurements, use a full reflux condenser to recover solvent losses due to evaporation. During the experiment, a small amount of solids was added to the continuously stirred solvent in the flask until no more solids were dissolved, and then this solution was considered to be saturated with the solids at this temperature. Calculate solubility based on the weight of the solvent and the total weight of solids added. Table 1 summarizes the solubility of TPA and IPA in NMP at 15, 40, 70, and 160 ° C. -11-This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 487700 A7 B7 V. Description of the invention (9) Table 1 Solid solvent solubility (g / g of solvent) 15 ° C 40 ° C 70 ° C 160 ° C TPA NMP 2.8 8.0 14.0 23.0 IPA NMP 10.7 22.2 46.0 62.0 4-CBA NMP * * 18.9 27.4 66.0 125.0 *

* 在 110〇C * * 在 2 3 °C ------,----------- (請先閱讀背面之注意事項HI寫本頁) 根據表1所示之溶解度數據，其説明TPA可經由結晶而自 TPA、IPA、及4-CBA(3-CBA)之混合物純化，由於IPA及 CBA兩者皆由於其較高的溶解度而傾向於保持於母液中。由母液所產生之TPA晶體應具有相對於母液中所包含之其他成份實質上更高份量的TP A。實施例2 根據TPA在160°C下在NMP中之溶解度，將包含大約9 5重量百分比TP A及5重量百分比IP A之固體混合物加至NMP中。然後將此混合物移至裝設有經特殊設計的混合器以使晶體破裂減至最小、加熱夾套、及蒸氣冷凝器之冷卻結晶器。將結晶器緩慢加熱至160°C，並在此溫度下維持1小時，以確保所有的固體皆溶解。然後在9 0分鐘内使結晶器冷卻至 45°C，以使TPA晶體成長。邊將溫度維持於40至45°C，邊將結晶器之内容物移至夾套過濾器，並快速地過濾。使用適當量的溫熱溶劑（5 0至7 0 °C )洗滌濾餅。在某些情況中， -12- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） .. _線· 經濟部智慧財產局員工消費合作社印製 7 7 8 4 A7 _B7_ 五、發明說明（10 ) -------1-----— — I (請先閱讀背面之注意事項ml寫本頁) 於溫熱溶劑之洗滌後，進行在9 5 °C下之濾餅的熱水洗滌。將經洗鲦的滤餅乾燥，並利用氣相層析術分析，以測定產物組成。表2記述結果之總結。表2 試驗數過濾器溫進料中之產物中之滌洗條件度(。。） IPA IPA 1A 41 4.94 wt% 0.21 wt% 在50°C下使用三次溶劑 2A 41 5.02 wt% 0.16 wt% 在7〇°C下使用三次溶劑 3A 41 5.00 wt% 0.18 wt% 在53°C下使用三次溶劑 1B 41 4.94 wt% 0.15 wt% 同1A加上在95°C下之 10次水洗 2B 41 5.02 wt% 0.13 wt% 同2A加上10次水洗 3B 41 5.00 wt% 0.15 wt% 同3A加上在95°C下之 10次水洗 -線. 經濟部智慧財產局員工消費合作社印製上表2中之數據顯示在TPA中之IPA含量視滌洗條件而驚人地降低（2 3至3 9倍）。當將由結晶而得之TPA濾餅以溶劑在 70°C下滌洗，隨後再在95°C下水洗時（試驗2B)，IPA含量實際上由單段結晶而降低3 9倍。依照相同的步驟，TPA混合物中之IPA含量可經由兩段式結晶，而自5重量百分比降 -13- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 7 7 8 4 A7 _ B7_ 五、發明說明（H ) 至百萬分之33份重量（ppmw)。實施例3 此實施例產生TPA以及IPA在大氣壓力在各種溫度下，在作爲選擇性結晶之甲醇中之溶解度的實驗數據。實驗裝置及步驟係與説明於以上實施例1中者相同，除了蒸氣壓係大於大氣壓之外。根據溶劑之重量及加入固體之總重量計算溶解度。表3概述TPA及IPA在各種溫度下於甲醇中之溶解度0 表3 溫度(°c) 溶解度（固體克數/100克之甲醇) (請先閱讀背面之注意事項寫本頁) 裝 TPA IPA 10 0.03 25 0.09 1.82 50 0.47 4.00 160 2.90 161 15.00 · 經濟部智慧財產局員工消費合作社印製由表3觀察到在自2 5至5 0 °C之溫度範圍内，IP A在甲醇中之溶解度大略較TPA高8至2 0倍。TPA在甲醇中之溶解度只有在較高溫度下，諸如160至200°C在壓力下才會變得顯著。實施例4 由表3可發現IPA在曱醇中之溶解度實質上較TPA在室溫 (2 5 °C至5 0 °C )下之溶解度高。因此，進行實驗以判定是否 -14- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 7 7 8 4 A7 _B7_ 五、發明說明（12 ) 可經由將適當量的甲醇加至溶液中，而使TPA自TPA、IPA 及少量4 - CBA之溶液中沈澱。此溶液可爲來自TPA結晶器，於利用過濾器移除TPA晶體後之母液。母液可具有下列組成：100克之NMP、20克之TPA、10克之IPA、及少量之4-CBA(^L3-CBA) 〇此實施例顯示將甲醇加至母液中基本上可使TPA完全沈澱，但IPA僅有少量沈澱。於100克NMP、4克TPA、及1 . 5克 IPA之混合物中，將大約210克曱醇加至此室溫之混合物中。將全體混合物攪拌約9 0分鐘，以使固體自混合物結晶及沈澱。將晶體過濾、洗滌及乾燥供分析用。經發現回收得母液中之47.5%的TPA，及晶體大略包含99.0重量百分比TPA 及1.0重量百分比IPA。爲增加TPA之回收，經由移除一部分之NMP而將母液濃縮，及混合物包含100克之NMP、20克之TPA及1 0克之IP A。將大約260克之甲醇加至混合物中，以使T P A在室溫下自混合物結晶。當加入甲醇時，在將TPA晶體自淤漿過濾出之前，使混合物攪拌9 0分鐘。經發現自母液回收得直至97.5% TPA，及TPA晶體包含97.3重量百分比TPA及2.7重量百分比 IPA。數據顯示可經由自母液移除更多的NMP(較高濃度），或經由將更多甲醇加至母液中，或兩者之組合，而達到 100%的TPA回收。在典型的母液中，4-CBA之含量應爲0.01克每100克 NMP(0.01%)左右。由於母液中之4-CBA之量非常小，及4-CBA在NMP中在室溫附近之溶解度（示於表1)非常高，因而 -15- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項寫本頁) 裝經濟部智慧財產局員工消費合作社印制衣 487700 第88108301號專利申請案中文說明書修正頁(90年6月 # j£ 五、發明說明（ 13, 加入甲醇應不致使4 _ CB a自母液沈澱。於自母液回收得1.00%之TPA，及經由加入曱醇而再循環後，可將不含TPA之母液作進一步處理，以回收IPA。方法程序之細節呈現於表丨，及稍後說明於下一段中。圖不說明圖1係用於實施本發明之較佳具體實例，以製造TpAi IPA 兩者之工廠的概略流程圖；及圖2係用於貫施本發明之另一較佳具體實例，以僅製造經濟部智慧財產局員工消費合作社印製 TPA之工戚的概略流程圖。圖示之元件符號說明 100 第一溶解器 114 蒸發器 101 第一冷卻結晶器 115 第一 IPA結晶器 102 過濾器I 116 過濾器V 103 第二溶解器 117 IP A溶解器 104 弟一急速結晶器 118 過濾器VI 105 過濾器Π 119 第二IPA結晶器 106 濾餅洗滌 120 過濾器VH 107 浸泡器 121 乾燥器Π 108 過濾器Π 1-35 ’37-39 管線 109 乾燥器I 200 溶解器I 110 蒸餾塔 201 管線 111 氧化器 202 弟一結晶器 112 沈澱器 203 過濾器I 113 過濾器IV 204 溶解器Π 16- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ------------Aw --------^---------. (請先閱讀背面之注意事項再填寫本頁) 487700 經濟部中央標準局員工消費合作社印製五、發明説明（13/ 第88108301號專利申請案中文說明書修正頁(90年6月* At 110 ° C * * At 2 3 ° C ------, ----------- (Please read the note on the back HI first to write this page) Solubility according to Table 1 Data, which shows that TPA can be purified from a mixture of TPA, IPA, and 4-CBA (3-CBA) by crystallization, since both IPA and CBA tend to remain in the mother liquor due to their higher solubility. The TPA crystals produced from the mother liquor should have substantially higher amounts of TPA than the other components contained in the mother liquor. Example 2 Based on the solubility of TPA in NMP at 160 ° C, a solid mixture containing approximately 95 weight percent TPA and 5 weight percent IP A was added to NMP. This mixture was then moved to a cooling crystallizer equipped with a specially designed mixer to minimize crystal breakage, a heating jacket, and a vapor condenser. The crystallizer is slowly heated to 160 ° C and maintained at this temperature for 1 hour to ensure that all solids are dissolved. The crystallizer was then cooled to 45 ° C within 90 minutes to allow TPA crystals to grow. While maintaining the temperature at 40 to 45 ° C, move the contents of the crystallizer to a jacketed filter and quickly filter. Wash the filter cake with a suitable amount of warm solvent (50 to 70 ° C). In some cases, -12- This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm). _Line · Printed by the Employee Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 7 7 8 4 A7 _B7_ 5 、 Explanation of the invention (10) ------- 1 ------- — I (Please read the precautions on the back to write this page) After washing in warm solvent, perform at 9 5 ° C Wash the cake with hot water. The washed filter cake was dried and analyzed by gas chromatography to determine the product composition. Table 2 summarizes the results. Table 2 Tests The degree of cleaning conditions in the product of the filter warm feed (...) IPA IPA 1A 41 4.94 wt% 0.21 wt% Three times solvent at 50 ° C 2A 41 5.02 wt% 0.16 wt% at 7 Three times solvent at 0 ° C 3A 41 5.00 wt% 0.18 wt% Three times solvent at 53 ° C 1B 41 4.94 wt% 0.15 wt% Same as 1A plus 10 water washes at 95 ° C 2B 41 5.02 wt% 0.13 wt% same as 2A plus 10 times of washing 3B 41 5.00 wt% 0.15 wt% same as 3A plus 10 times of washing at 95 ° C-line. The data printed in Table 2 above is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The IPA content in TPA decreases dramatically depending on the washing conditions (23 to 39 times). When the TPA cake obtained from the crystallization was washed with a solvent at 70 ° C and then washed at 95 ° C (Test 2B), the IPA content was actually reduced by 39 times from a single stage of crystallization. According to the same steps, the IPA content in the TPA mixture can be crystallized in two stages and reduced from 5 weight percent to -13- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 7 7 8 4 A7 _ B7_ V. Description of the invention (H) to 33 parts per million by weight (ppmw). Example 3 This example produces experimental data on the solubility of TPA and IPA in methanol as a selective crystallization at atmospheric pressure at various temperatures. The experimental equipment and procedures are the same as those described in Example 1 above, except that the vapor pressure is greater than atmospheric pressure. Calculate solubility based on the weight of the solvent and the total weight of solids added. Table 3 summarizes the solubility of TPA and IPA in methanol at various temperatures. 0 Table 3 Temperature (° c) Solubility (grams of solids / 100 g of methanol) (Please read the precautions on the back first to write this page) Install TPA IPA 10 0.03 25 0.09 1.82 50 0.47 4.00 160 2.90 161 15.00 · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs It is observed from Table 3 that the solubility of IP A in methanol is slightly higher than that of TPA in the temperature range from 25 to 50 ° C 8 to 20 times higher. The solubility of TPA in methanol becomes significant only at higher temperatures, such as 160 to 200 ° C, under pressure. Example 4 It can be found from Table 3 that the solubility of IPA in methanol is substantially higher than the solubility of TPA at room temperature (25 ° C to 50 ° C). Therefore, experiments were performed to determine whether -14- This paper size is in compliance with the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 7 7 8 4 A7 _B7_ V. Description of the invention (12) The amount of methanol can be added by adding Into the solution, and TPA was precipitated from the solution of TPA, IPA and a small amount of 4-CBA. This solution may be a mother liquor from a TPA crystallizer after removing the TPA crystals with a filter. The mother liquor can have the following composition: 100 grams of NMP, 20 grams of TPA, 10 grams of IPA, and a small amount of 4-CBA (^ L3-CBA). This example shows that the addition of methanol to the mother liquor can basically precipitate the TPA completely, but There was only a small amount of IPA precipitation. To a mixture of 100 grams of NMP, 4 grams of TPA, and 1.5 grams of IPA, about 210 grams of methanol was added to the mixture at room temperature. The whole mixture was stirred for about 90 minutes to crystallize and precipitate a solid from the mixture. The crystals were filtered, washed and dried for analysis. It was found that 47.5% of the TPA in the mother liquor was recovered, and the crystals roughly contained 99.0% by weight TPA and 1.0% by weight IPA. To increase the recovery of TPA, the mother liquor was concentrated by removing a portion of the NMP, and the mixture contained 100 grams of NMP, 20 grams of TPA, and 10 grams of IP A. Approximately 260 grams of methanol was added to the mixture to crystallize TPA from the mixture at room temperature. When methanol was added, the mixture was stirred for 90 minutes before filtering the TPA crystals from the slurry. It was found that up to 97.5% TPA was recovered from the mother liquor, and the TPA crystals contained 97.3 weight percent TPA and 2.7 weight percent IPA. The data show that 100% TPA recovery can be achieved by removing more NMP (higher concentration) from the mother liquor, or by adding more methanol to the mother liquor, or a combination of the two. In a typical mother liquor, the content of 4-CBA should be about 0.01 g per 100 g of NMP (0.01%). Because the amount of 4-CBA in the mother liquor is very small, and the solubility of 4-CBA in NMP near room temperature (shown in Table 1) is very high, -15- This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) (Please read the notes on the back to write this page first) Install the printed sheet of clothing of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 487700 No. 88108301 Patent Application Chinese Manual Correction Page (June 90 # j £ V. Explanation of the invention (13) The addition of methanol should not cause 4_CB a to precipitate from the mother liquor. After recovering 1.00% of TPA from the mother liquor and recycling it by adding methanol, the mother liquor without TPA can be further processed. In order to recover the IPA, the details of the method and procedure are presented in Table 丨 and described later in the next paragraph. Figures do not illustrate Figure 1 is a schematic diagram of a preferred embodiment of the present invention for manufacturing TpAi IPA. Flowchart; and Figure 2 is a schematic flowchart for implementing another preferred embodiment of the present invention to print only TPA workers printed in the TCA by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics. First dissolver 114 Evaporator 101 First cooling crystallizer 115 First IPA crystallizer 102 Filter I 116 Filter V 103 Second dissolver 117 IP A dissolver 104 Brother one rapid crystallizer 118 Filter VI 105 Filter Π 119 Second IPA crystallizer 106 filter cake washing 120 filter VH 107 immersion unit 121 dryer Π 108 filter Π 1-35 '37 -39 line 109 dryer I 200 dissolver I 110 distillation column 201 line 111 oxidizer 202 Filter 112 Settler 203 Filter I 113 Filter IV 204 Dissolver Π 16- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ------------ Aw -------- ^ ---------. (Please read the notes on the back before filling out this page) 487700 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs V. Invention Description (13 / Revised Page of Chinese Specification for Patent Application No. 88108301 (June 90

211結晶器瓜 212過濾器IV 213蒸發器Π 214結晶器IV 215過濾器V 220-240 管線 205第二結晶器 206過濾器Π 207逆流接觸器 208浸泡器 209過濾器m 210蒸發器I 較佳具體實例說明用於製造純化TPA及IPA兩者之本發明之一較佳具體實例呈現於圖1。現參照圖1，使來自反應器（未示於圖中）之氧化段，包含大約95% TPA、5% IPA、及少量其他不純物（4-CBA、3-CBA 、對甲苯酸、間甲苯酸等等）之粗製TPA經由管線1供應至第一溶解器100，以與來自過濾器II 1〇5(經由管線7)之母液及來自過濾器IV 113(經由管線19)之淤漿混合。將第一溶解器100中之溫度維持於160至180°C，以使固體完全溶解，及使由管線1 9帶過來之所有甲醇實質上地蒸發。然後將來自第一溶解器100之飽和溶液經由管線2連續供應至第一冷卻結晶器101，以在30至50°C下產生TPA鹽晶體。含有TPA鹽晶體之淤漿經由管線3離開第一冷卻結晶器101 而至過濾器I 102，在此將粗製晶體濾餅移除，並經由管線4 而供應至第二溶解器103。在第二溶解器103中，將濾 -16A- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 487700 A7 B7 五、發明說明（14 ) 餅再溶解於經由管線3 5自溶劑回收系統再循環之乾淨的 NMP中。再次將第二溶解器103中之溫度維持於160至180°C ，以使TPA鹽晶體完全溶解。經由管線5將來自第二溶解器 103之飽和溶液連續供應至第二急速結晶器104，在此將溫度維持於6 0 °C之最小値，以防止生成TPA鹽晶體。在結晶器中之溫度降低程度係由經由降低壓力而自結晶器急速蒸發之NMP之量控制。經由管線3 6將急速蒸發的NMP再循環至第一溶解器100。經由管線6將來自第二結晶器104之淤漿供應至過濾器II 105，在此回收得純化TPA固體濾餅，並將其送至濾餅洗滌 106，同時經由管線7將母液再循環至第一溶解器1〇〇。在濾、餅洗滌單元106中，經由以水逆流洗滌而移除濾餅中之大量的殘留NMP，及經由管線1 0將經洗滌的濾餅供應至浸泡器 107，以經由在160至280°C之間的溫度下浸泡水，而將TPA 固體中之最終微量的NMP移除。將不含NMP之濾餅在過滤器 III 108中過濾，並在乾燥器I 109中乾燥，而得TPA終產物。經由管線15將來自過濾器I 102之母液輸送至沈澱器112 。在此過程中，其通過氧化器111，此氧化器係可有用於實施在由本申請案之受讓人所持有之共同申請中之美國申請案序號09/098,060，標題爲「降低對酞酸或異酞酸中之羧基苯甲酸異構物之方法（Method to Reduce Carboxybenzaldehyde211 Crystallizer Melon 212 Filter IV 213 Evaporator 214 Crystallizer IV 215 Filter V 220-240 Line 205 Second Crystallizer 206 Filter Π 207 Countercurrent Contactor 208 Soaker 209 Filter m 210 Evaporator I Better DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A preferred embodiment of the present invention for manufacturing both purified TPA and IPA is shown in FIG. 1. Referring now to FIG. 1, the oxidation section from the reactor (not shown) contains approximately 95% TPA, 5% IPA, and a small amount of other impurities (4-CBA, 3-CBA, p-toluic acid, m-toluic acid) Etc.) The crude TPA was supplied to the first dissolver 100 via line 1 to mix with the mother liquor from filter II 105 (via line 7) and the slurry from filter IV 113 (via line 19). The temperature in the first dissolver 100 was maintained at 160 to 180 ° C to completely dissolve the solids, and to substantially evaporate all the methanol carried over from the line 19. The saturated solution from the first dissolver 100 is then continuously supplied to the first cooling crystallizer 101 via line 2 to generate TPA salt crystals at 30 to 50 ° C. The slurry containing TPA salt crystals leaves the first cooling crystallizer 101 via line 3 to filter I 102, where the crude crystal cake is removed and supplied to the second dissolver 103 via line 4. In the second dissolver 103, the filter-16A- This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page) Consumption of employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Cooperative printed 487700 A7 B7 V. Description of the invention (14) The cake was redissolved in clean NMP recycled from the solvent recovery system via line 35. The temperature in the second dissolver 103 was maintained at 160 to 180 ° C again to completely dissolve the TPA salt crystals. The saturated solution from the second dissolver 103 was continuously supplied to the second rapid crystallizer 104 via line 5, and the temperature was maintained at a minimum temperature of 60 ° C to prevent the formation of TPA salt crystals. The degree of temperature reduction in the crystallizer is controlled by the amount of NMP that is rapidly evaporated from the crystallizer by reducing the pressure. The rapidly evaporated NMP is recycled to the first dissolver 100 via a line 36. The slurry from the second crystallizer 104 is supplied to the filter II 105 via the line 6, where a purified TPA solid filter cake is recovered and sent to the cake wash 106, while the mother liquor is recycled to the first via the line 7 A dissolver 100. In the filter and cake washing unit 106, a large amount of residual NMP in the filter cake is removed by counter-current washing with water, and the washed filter cake is supplied to the infuser 107 through line 10 to pass through 160 to 280 ° Water was immersed at a temperature between C and the final trace of NMP in the TPA solids was removed. The filter cake without NMP was filtered in filter III 108 and dried in dryer I 109 to obtain the final TPA product. The mother liquor from the filter I 102 is transferred to the settler 112 via line 15. In the process, it passes through an oxidizer 111, which may be used to implement US application serial number 09 / 098,060 in a joint application held by the assignee of this application, entitled "Reducing Terephthalic Acid 2. Method to Reduce Carboxybenzaldehyde

Isomers in Terephthalic Acid or Isophthalic Acid)」中所揭示及提出專利申請之相關發明，將此篇專利之揭示内容以提及的方式併入本文中供所有用途用。經由管線1 6將甲醇加至 -17- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） I - ϋ— —Βϋ ϋ·· emmMm —.1 —Bi iaiv I · n HI (請先閱讀背面之注意事項HI寫本頁) 訂· 487700 A7"Isomers in Terephthalic Acid or Isophthalic Acid)" and related patent applications, the disclosure of this patent is incorporated herein by reference for all purposes. Add methanol to -17 via line 16- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) I-ϋ— —Βϋ ϋ ·· emmMm —.1 —Bi iaiv I · n HI (Please read the note on the back first to write this page) Order · 487700 A7

7 7 8 4 A7 _B7_ 五、發明說明（16 ) 120之母液再循環至蒸發器114。僅用於製造純化TPA之本發明之另一較佳具體實例説明於圖2。經由管線201將粗製TPA(大略包含9 0至9 9 % TPA及1 至1 0 % IPA)供應至溶解器I 200，使與來自過濾器II 206(經由管線220再循環）之母液M/L-2及來自過濾器V 215(經由管線221再循環）之再循環濾餅混合。將溶解器中之溫度維持於140至200°C，以使所有固體實質上地溶解。然後經由管線222將飽和溶液供應至第一結晶器202，在此經由冷卻或溶劑蒸發（降低壓力）將溫度降至3 0至6 0 °C，而使TPA晶體成長。經由管線223連續或逐批地將來自第一結晶器202之淤漿輸送至過濾器I 203，以回收固體濾餅。在過濾器I 203需要洗滌貧乏或飽和的NMP，以在經由管線2 2 4將濾餅輸送至溶解器II 204之前自濾餅置換母液，使濾餅在溶解器II 204中與來自管線225之急速蒸發的NMP及來自管線226及227之經蒸發的NMP混合。再次將溶解器II 204中之溫度維持於140 至200°C，以使所有固體實質上地溶解。經由管線228將飽和溶液供應至第二結晶器205，在此經由冷卻或溶劑蒸發（降低壓力）將溫度降至3 0至6 0 °C，而使純化TPA晶體成長。再次經由管線229將來自第二結晶器205之淤漿供應至過濾器II 206以回收濾餅，然後經由管線230將其輸送至逆流接觸器207，以經水洗游：，而自濾、餅移除大量的自由NMP。經由管線231將經水洗滌的固體送至浸泡器208，以經由在 150至280°C之溫度下使固體部分或完全溶解於浸泡器208中 -19- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ----------------裝--- (請先閱讀背面之注意事項寫本頁) 一. 經濟部智慧財產局員工消費合作社印制衣 487700 A7 B7_ 五、發明說明（17 ) ，而自純化TPA固體移除微量的陷入NMP。經由管線233將不含NMP之固體送至過濾器III 209，在此經由管線232將水移除，及經由管線234將TPA濾餅送至乾燥器中乾燥，而得純化TPA終產物。經由管線235將來自過濾器I 203之母液Μ/L-l送至蒸發器I 210，以移除實質量的NMP。經由管線236將濃縮溶液輸送至結晶器III 211，以使低純度的TPA晶體成長。接著自過濾器IV 212回收晶體，並經由管線237將其再循環至溶解器I 200。經由管線238將來自過濾器IV 212之母液M/L-3輸送至蒸發器Π 213，然後再至結晶器IV 214及過濾器V 215，以回收殘留的低純度TPA，而經由管線239再循環至溶解器I 200。使來自過濾器V 215，主要包含IPA、NMP及少量TPA 之最終母液M/L-4通過管線240，並在處置之前經由與水混合而經處理，以進一步回收NMP。 ------------------- (請先閱讀背面之注意事項HI寫本頁) -tr°J.. Ϊ線· 經濟部智慧財產局員工消費合作社印製 -20- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）7 7 8 4 A7 _B7_ V. Description of the invention (16) The mother liquor of 120 is recycled to the evaporator 114. Another preferred embodiment of the present invention which is used only for the production of purified TPA is illustrated in FIG. Crude TPA (approximately 90 to 99% TPA and 1 to 10% IPA) is supplied to dissolver I 200 via line 201, and the mother liquor M / L from filter II 206 (recirculated via line 220) is supplied -2 and recycle filter cake from filter V 215 (recycled via line 221). Maintain the temperature in the dissolver at 140 to 200 ° C so that all solids dissolve substantially. The saturated solution is then supplied to the first crystallizer 202 via line 222, where the temperature is reduced to 30 to 60 ° C by cooling or solvent evaporation (reducing pressure) to grow the TPA crystal. The slurry from the first crystallizer 202 is continuously or batch-wise fed to the filter I 203 via the line 223 to recover the solid filter cake. The filter I 203 needs to wash the lean or saturated NMP to replace the mother liquor from the filter cake before it is transported to the dissolver II 204 via line 2 2 4 so that the filter cake in dissolver II 204 and The rapidly evaporated NMP is mixed with the evaporated NMP from lines 226 and 227. The temperature in Dissolver II 204 was again maintained at 140 to 200 ° C so that all solids were substantially dissolved. The saturated solution is supplied to the second crystallizer 205 via line 228, where the temperature is reduced to 30 to 60 ° C by cooling or solvent evaporation (reducing the pressure), thereby growing the purified TPA crystals. The slurry from the second crystallizer 205 is again supplied to the filter II 206 via the line 229 to recover the filter cake, and then it is conveyed to the countercurrent contactor 207 via the line 230 to be washed with water: Remove a lot of free NMP. The water-washed solid is sent to the infuser 208 via line 231 to partially or completely dissolve the solid in the infuser 208 at a temperature of 150 to 280 ° C. -19- This paper applies Chinese National Standards (CNS) A4 size (210 X 297 mm) ------------- (Please read the precautions on the back to write this page) 1. Consumption by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Cooperative printed clothing 487700 A7 B7_ 5. Description of the invention (17), and the trace amount of trapped NMP was removed from the purified TPA solids. The NMP-free solid is sent to filter III 209 via line 233, where water is removed via line 232, and the TPA filter cake is sent to a dryer via line 234 to be dried to obtain a purified final TPA product. The mother liquid M / L-1 from the filter I 203 is sent to the evaporator I 210 via the line 235 to remove the solid NMP. The concentrated solution is transferred to crystallizer III 211 via line 236 to grow low-purity TPA crystals. Crystals were then recovered from filter IV 212 and recycled to dissolver I 200 via line 237. The mother liquid M / L-3 from the filter IV 212 is transferred to the evaporator Π 213 via the line 238, and then to the crystallizer IV 214 and the filter V 215 to recover the remaining low-purity TPA, and is recycled through the line 239 To Dissolver I 200. The final mother liquor M / L-4 from the filter V 215, which mainly contains IPA, NMP, and a small amount of TPA, was passed through line 240 and treated by mixing with water before disposal to further recover NMP. ------------------- (Please read the note on the back first to write this page) -tr ° J .. -20- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Claims

487700 No. 881〇83〇1 Patent Application Case 8 Chinese Patent Application Scope Amendment (June ^ June) g88 I Announcement JJ m ... 1 I ....., one ~, one ... ~ L_1 二A method for purifying crude terephthalic acid (TPA) from a mixed xylene-derived liquid dispersion, including: (a) dissolving crude TPA in a selective crystallization solvent at a temperature from 50 ° C to 250 ° C ' A solution is formed; (b) the purified acid is separated from the solution by reducing the temperature and / or pressure; (c) the purified Tp a is separated from the solution; (d) the separated purified Dp Pa is re-dissolved in the selective crystallization solvent to form a second solution; (e) The solvent is rapidly evaporated from the TPA of the second solution by sufficiently reducing the temperature and pressure, but the solution is not cooled to less than 5 (rc, so that the second stage purified TPA is crystallized from the second solution; (f) the second stage purified TPA is separated from the second solution; (g) the separated second stage purified TPA is washed with water (h) at a temperature between 150 ° C and 300 ° C, immerse the second stage of purified TPA separated by washing with water; (i) Filtration and drying of purified TPA in the second stage of soaking water; (j) adding an antisolvent to the filtered solution in (c) to precipitate substantially all TPA; and (k) from (j) The solution separated the precipitated TPA and combined the precipitated TPA with the original crude TPA for processing in (a); (l) passing the solvent from the filtered TPA-free in (k) The solution was evaporated to make the IPA crystallize at a temperature from 5 ° C to 100 ° C; (m) the crude Ipa of the crystal was separated from the solution in (1); the paper size is applicable to Chinese national standards (Cns) A4 size (210X297 mm) (Please read the precautions on the back before filling out this page)-Order printed by employee consumer cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs

ABCD, the employee consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, re-dissolves the crude IPA in a selective crystallization solvent at a temperature from 50 ° C to 250 ° C to form a second solution; (〇) via Reduce the temperature and pressure sufficiently to cause the solvent to evaporate rapidly from the IPA of the second solution, but not to cool the solution to less than $ 0, and crystallize the purified IP A from the second solution in (η); and (P) The second stage purified IPA from the second solution is separated and dried. 2. The method of claim 1, wherein the dispersion contains at least 0 to 20 ° /. Isophthalic acid (IPA), and a small amount of benzaldehyde (4-cba), 3-carboxybenzaldehyde (3-CBA) and selected from unreacted starting materials, solvents, products of side reactions and / or other undesirable Impurities of materials. 3. The method according to item 1 of the scope of patent application, wherein the selective crystallization solvent for TPA purification is selected from the group consisting of N-methylpyrrolidone (NMP), n, n-dimethylacetamide, N, N-dimethylfluorenamine, N-fluorenylhexahydropyridine, N-fluorenyl-2-pyrrolidone (such as n-ethylpyrrolidone), N_thiol alkyl-2-pyrrolidine Ketones (such as N_thiol ethyl_ 2_pyrrolidinone), n_alkyl-2 -thioρ ratios ρ_ (such as n · methyl_ 2 -thioρ ratios), n- Carbobenzyl-2-pyridinone (such as n-transethyl-2-pyhalidone), morphine (such as morpholine, and N-formylmorpholine), carbitol ls), Ci to & alcohols, ethers, amines, amidines, and esters, and mixtures thereof. 4. The method according to item 3 of the scope of patent application, wherein the selective crystallization solvent for purification of τρα is N-methylρ ratio ρ each ketone or n, N-dimethylacetamide. 5. The method according to item 4 of the scope of patent application, wherein the selective crystallizing agent for TPA purification is the same as N-methylρ than TT. 6 · The method of applying for the first item of the patent scope, which is used to make τρ a from -2-This paper size applies the Chinese national standard (CNS> A4 specification (210X297 mm) (Please read the precautions on the back before filling in this Page) Order 4. 487700 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs-3, "The inverse solution of precipitation of TPA / IPA solution precipitation in the scope of application for patents" is selected from the group consisting of methanol, water, methyl ethyl ketone, A group consisting of acetone, CjC alcohol, K methylbenzene, glutamate, esters, ethers, C to C ", private, water, and mixtures of them. 如 · If the method of the 6th scope of the patent application, ΤΡΔ / TPΔ V. ^ ^ is economical, in which the anti-solvent used to make TPA from the temple is methanol or water. 8 · As for the method of patent application scope item 7 tpa / tda .. Only < Wanfa, which is used to make The anti-solvent precipitated by AΤΑ from TPA / IPA Luoxin is methanol. 9. The method according to item 1 of the patent application, wherein the solvent used for recrystallization of Π > A and the selective crystallization solvent are selected from the group consisting of methanol, water, Ethyl ketone, acetone, CjCl2 alcohol, carbitol, ester, ether , I to c] 2 carboxylic acid, water, and mixtures thereof. 10. The method according to item 9 of the patent application, wherein the selective crystallization solvent used for recrystallization of purified IPA is methanol or water 11. The method as claimed in the scope of patent application e, wherein the anti-solvent is used at a reverse agent / solution ratio of 0-1 to 10 to precipitate the TPA. 1 2. As the method for scope of the patent application, The anti-solvent / solution ratio is in the range of 0.5 to 3. 1 * A method for purifying crude terephthalic acid (TP A) from a liquid dispersion produced by oxidizing mixed xylene, including: (a) Crude TPA is dissolved in a selective crystallization solvent at a temperature of from 50 ° C to 25 ° C to form a solution; (b) the purified acid is reduced from the solution by reducing the temperature and / or pressure; and (c) the solution is removed from the solution. The crystallized purified Tpa was separated; this paper size applies Chinese National Standard (CNS) A4 specification (21〇 > < 297 mm) (Please read the precautions on the back before filling this page} Order-487700 A8 B8 C8 D8 6. Scope of patent application (d) Redissolve the separated purified TPA in Selectively crystallize the solvent to form a second solution; (e) by sufficiently reducing the temperature and pressure to rapidly evaporate the solvent from the TPA of the second solution, but not cooling the solution to less than 50 ° C, and Crystallizing the second stage purified TPA from the second solution; (f) separating the second stage purified TPA from the second solution; (g) washing the separated second stage purified TPA with water; (h) At a temperature between 150 C and 300 ° C, soak the washed and purified second stage purified TPA with water; (i) filter and dry the soaked second stage purified TPA; (j ) Concentrate the solution by evaporation and cooling to concentrate the filtered solution in (c) to crystallize TPA and a small amount of IPA; (k) to separate the TPA of Shendian and a small amount from the solution in (j) IPA, and recycle the solid mixture for treatment in (a); (l) concentrate the filtered solution in (k) by secondary evaporation and cooling of the concentrated solution, so that TPA and a small amount of IPA is further crystallized; (m) the crystallized TPA and a small amount of IPA are separated from the solution in (1), and the solid mixture is Recycling for processing in (a); and printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) (η) send the filtered solution in (m) to Waste treatment equipment, or for further processing. 14 · The method according to item 13 of the scope of patent application, wherein the dispersion contains at least 0 to 20% of isog too acid (IP A), and a small amount of 4 -benzylbenzene (4 · CBA), 3-carboxybenzaldehyde (3-cba) and impurities selected from unreacted starting materials, solvents, products of side reactions and / or other undesirable materials. This paper size applies to China National Standard (CNS) A4 (210X297 mm). Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. A8 B8 C8 ^ ------__ D8_ 、 Applicable patent scope ---- such as the scope of patent application The method of 3, wherein the selective crystallization solvent for the purification of butyl pA is selected from the group consisting of N_methylp-biloxone (NMp), N_monomethylacetamide, and N, N-dimethylformamidine Amine, formyl hexahydropyridinium, N-alkylpyrrolidone (such as n_6 • ylpyrrolidone), N-thiol alkyl-2 · pyrrolidone (thiol ethyl_2_pyrrolidine Ketone), N_k-based 2-sulfo-p-pyridone (such as N_methyl-2_thiop-pyridone), n_lipidyl-2 -pyrrolidone (such as N_hydroxyethyl 2-pyrrolidinone), morpholine (such as morpholine, and N-formamylmorpholine), carbitol, 01 to < 312 alcohol, ether, amine, amidine, and ester, and mixtures thereof Group of people. 16. The method according to item 15 of the scope of patent application, wherein the selective crystallization solvent used for the purification of TpA is N.methylp. Bihalidone or n, N-dimethylacetamide. 17. The method according to item 16 of the scope of patent application, wherein the selective crystallization solvent used for TPA purification is N-methylpyrrolidone. 1 8 · —A method for purifying crude p-peracetic acid (TPA) from a liquid dispersion produced by self-oxidizing mixed xylene, including: (a) dissolving crude TPA at a temperature from 50 ° C to 25 (TC) in a selection (B) the purified acid is crystallized from the solution by reducing the temperature and / or pressure; and the purified TPA from which the crystals are separated from the solution; (c) if necessary, repeat this Dissolution and crystallization of TP a to obtain purified TPA of desired purity; (d) adding an anti-solvent to the solution from which the crystallized purified TpA was separated, so that substantially all of the TPA remaining in the solution was precipitated 。 This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page), 1T A8 B8 C8 D8 The Ministry of Economic Affairs Central Standardization Bureau employee consumer cooperative prints and applies for patents (E) The precipitated Tp a is isolated in the range (e); (f) the precipitant is evaporated from the solution obtained by adding an antisolvent and removing the precipitated Tρα to crystallize IPA, and thus purified and recovered and purified. 9 · If the scope of patent application The method according to item 18, further comprising dissolving and crystallizing the purified ΙρΑ to obtain IPA with a desired purity. 2 0 · The method according to item 18 in the patent application range, wherein the dispersion contains at least 0 to 20 ° / G of isog too acid (ΙΡΑ), and a small amount of 4-carboxybenzaldehyde (4-CB A), 3-carboxybenzaldehyde (3-CB A) and selected from unreacted starting materials, solvents, side reactions Products and / or impurities of other undesired materials. 2 1 · The method according to item 8 of the patent application, wherein the selective crystallization solvent for purification of τρΑ is selected from N-methylpyrrolidone (NMP ), N, N-dimethylacetamide, N, N-dimethylformamide, N-formamylhexahydropyridine, N-alkyl-2-pyrrolidone (such as n-ethylpyrrole Pyridinone), N-thiol feyl-2-pirketone (such as N-thiol ethyl-2 * ^ bilonidone), N-fluorenyl-2 -thiopyridinone (such as N -Methyl-2 -thiopyrrolidone), N-fe-yl 2-p-biloxone (such as N-ethyl-2 -p-pylidene), morphine (such as morphine, and N-fluorenylmorphine), carbitol, c! To C12 alcohol, A group consisting of amines, amines, amines, and esters, and mixtures thereof. 2 2. The method according to item 18 of the scope of patent application, wherein the antisolvent used to precipitate τρ A from the TPA / IPA solution is selected from the group consisting of Group consisting of methanol, water, methyl ethyl radical, acetone, C 1 to C 12 alcohol, carbitol, ester, ether, ci to Cj 2 carboxylic acid, water, and mixtures thereof. -6- This paper Λ Degree applies to Chinese National Standard (CNS) A4M (210X297 mm) (Please read the precautions on the back before filling this page)