TWI249521B - Process of purifying and producing high purity aromatic polycarboxylic acids and derivatives thereof - Google Patents

Abstract

The present invention provides a solvent extraction purification method for aromatic polycarboxylic acids or derivatives that meet or exceed polymer-grade specification. The method includes dissolving a crude aromatic polycarboxylic acid or derivative in a base compound; removing impurities and excessive base compound; and removing residual base compound while making purified product. The purification method removes not only the impurities from the crude acid or derivative, but also the residual base compound from finished product that otherwise will contaminate the product. The salt in the cake is converted to product by acid-substitution, thermal decomposition, or electrolysis. The method uses base-extraction solvents to extract base compound and impurities from the salt. The residual base compound in the recovered product is then removed by leaching, stripping, thermal agitating with electromagnetic waves, or evaporation with thermal decomposition. The purification method allows eliminating crystallizers for crystallization and equipment for drying and pneumatically carrying. Finally, the purification method is combined with the oxidation and solvent recovery in prior art to use only one set of process steps, instead of two, to produce aromatic polycarboxylic acids or derivatives.

Description

1249521 五、發明說明（3) 薄膜、和模製樹脂。對苯二酸係難以純化，主要是因為其 於多數溶劑中具有低溶解度、高沸點、以及產物及雜質的 物性及化性相似。 另一種純化的方法是以溶劑萃取來除去雜質。溶劑萃 取較吸引人係因其成本較低，此法可追溯至1953 (美國專 利2,664,440)，或可能更早。早期所建議的溶劑並不穩定、 會與產物產生反應、有毒性、或無法將CTA純化至所要 求的程度。其後，Iwane (美國專利5,344 969)和mr〇watad (美國專利5,565,609)中揭露使用較為穩定溶劑的方法。 下列將概述這些方法。 1) 溶解粗酸：芳香聚羧酸與許多鹼化合物會形成鹽， 此鹽能溶於許多溶解溶劑中，諸如昇溫的水或醇。 2) 除去雜質·某些雜質能輕易地經由溶液之前處理來 分離，如以活性碳來吸附著色劑。但性質與酸接近 的雜質則須冷卻到至少30 °C，以結晶方式自母液分 離出來。 3) 產物回收：Hirowatari藉由熱處理將由前處理溶液 加熱分解，或在烯化二醇存在下，將蒸氣與該濃縮溶液接 觸而加熱分解。Iwane則將鹽沈澱並洗滌之，然後藉由加 熱分解，或添加一種酸取代性溶劑以取代鹽中的產物酸， 而將其轉變為一純化的產物。lwane亦藉由將酸取代性溶 劑直接加至溶液中以回收產物。 lwane和Hirowatari皆使用只含氮為異原子的胺化合 物，例如脂族、脂環、芳香族、或雜環的胺。Iwane以醇 V—-------*1 訂---------. (請先閱讀臂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1249521 V. INSTRUCTIONS (3) Film, and molded resin. Terephthalic acid is difficult to purify, mainly because of its low solubility, high boiling point, and similar physical and chemical properties of products and impurities in most solvents. Another method of purification is solvent extraction to remove impurities. Solvent extraction is more attractive because of its lower cost, which can be traced back to 1953 (US Patent 2,664,440), or possibly earlier. The solvents suggested in the early days were not stable, would react with the product, were toxic, or could not purify the CTA to the desired extent. A method of using a relatively stable solvent is disclosed in Iwane (U.S. Patent No. 5,344,969) and mr.watad (U.S. Patent No. 5,565,609). These methods are outlined below. 1) Dissolving crude acid: The aromatic polycarboxylic acid forms a salt with many alkali compounds, which are soluble in many dissolved solvents such as warmed water or alcohol. 2) Removal of impurities · Certain impurities can be easily separated by pre-treatment of the solution, such as adsorption of colorants with activated carbon. However, impurities of a nature close to the acid must be cooled to at least 30 ° C and separated from the mother liquor by crystallization. 3) Product recovery: Hirowatari is thermally decomposed by a heat treatment solution by heat treatment, or is heated and decomposed by contacting the vapor with the concentrated solution in the presence of an alkylene glycol. Iwane precipitates and washes the salt and then converts it to a purified product by thermal decomposition or by adding an acid-substituted solvent to replace the product acid in the salt. Lwane also recovers the product by adding an acid-substituted solvent directly to the solution. Both lwane and Hirowatari use amines containing only nitrogen as a hetero atom, such as aliphatic, alicyclic, aromatic, or heterocyclic amines. Iwane is ordered by alcohol V--------*1---------. (Please read the notes on the arm surface and fill out this page.) Printed by the Intellectual Property Office of the Ministry of Economic Affairs

1249521 A7 __ B7 五、發明說明（6) 議的有機鹼化合物皆含有氮，其會引起在製造聚酯時的顏 色及一些其他問題，且並無前案揭露該問題以及如何自產 物中除去該鹼化合物。 結晶體永遠於結晶時藉由包含而含有殘留溶液。若使 用一些已知方法，其可能包含多於0.1〇/〇的殘留鹼液，其 程度很接近CTA中的雜質含量。為了能適用於製造聚酯 該殘留鹼化已移除至約為百萬之幾的程度，其已接近PTA 雜質程度。因此，先前已知之溶劑萃取的習知技術可從粗 酸裡移除雜質，但卻將鹼化合物污染物殘留於產物中，使 其無法適用於製造聚酯。 該已知的方法皆未嘗試從終產物中除去殘留鹼。Iwane 教示使用酸溶劑，Hirowatari教示使用水來洗滌源自過濾 器終產物餅之驗化合物，而Lee則教示使用NMP、對二 甲苯、丙酮、甲基乙基酮、或甲醇來洗滌過濾餅。於使用 100 : 1比率的水來洗滌及將該過濾餅瀝濾10小時的實驗 中，所產生之純化產物仍含有大量的鹼化合物。此顯示， 一旦鹼化合物被包含在產物結晶中，就很難再被除去。由 於已知文獻並未討論此項問題，或其為熟悉該項技藝者所 知，但仍存在以待解決。 習知技藝之溶劑萃取純化方法中，皆明示或暗示地教 示置換氫化單元，且使用CTA為進料，只有Lee是例外。 他誤認為不需要使用結晶器或其他方法，即可直接將高量 的CTA自過滤的反應器流出物中回收。但大部份cta仍 存在於反應器流出物之母液中，且其需要相當長的駐留時 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） <請先閱讀臂面之注咅？事項再填寫本頁) S0------—訂---------^111· 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 1249521 A7 B7 五、發明說明（7) 間以沈澱CTA。因此，目前的製程需使用3-5個大結晶 器來回收CTA。本發明係建議使用急驟蒸發與蒸發以減 少駐留時間。 因為該純化方法本身也需要其他方法步驟：結晶、過 濾、乾燥及氣體輸送，習知技藝也需要二套步驟程序來生 產PTA。因此使用已知之溶劑萃取方法以生產芳香聚叛 酸皆面臨下列的缺點·· 1) 引入驗化合物，而污染該終產物。 2) 需要二套結晶、離心/過濾、乾燥及氣體输送的設備。 3) 產物中仍含有明顯可债測之雜質。 4) 需要相當長的駐留時間來結晶，因此需要數個大結 晶器。 5) 需要乾燥及及氣體輸送來製造終產物。 因此，本項發明的幾項目標為： 1) 提供一溶劑萃取純化方法，以除去粗酸中的雜質， 而符合或超過芳香聚羧酸聚合等級的規格。 2) 除去終產物中的鹼化合，以使其可適用於製造聚酯 纖維、薄膜、模製樹脂，或其他方面的應用。 3) 提供一用於製造聚合等級的芳香聚羧酸的方法，其 僅需一套製程步驟，以實質上降低投資及生產成本。 4) 減少用於結晶之結晶器的數目，或甚至完全不用。 5) 生產能直接用於製造聚酯的芳香聚羧酸，而不需使 用乾燥及氣體輸送的步驟程序。 更進一步的目標及優點，將會由所揭露之溶劑萃取方 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） ----------—-------^丨訂*-------- (請先閱讀脅面之注意事項再填寫本頁) ' -10- 1249521 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（8 ) 法而變為更明顯，且該方法很意外及驚許地發現其可移除 雜質至一目前標準HPLC所無法測出的程度。 發明招j年 本發明係提供一種芳香聚叛酸或其衍生物之溶劑萃取 純化方法，其純度能滿足或超過聚合等級。本方法包括將 一粗芳香聚叛酸或其衍生物，諸如甲基醋，溶解於一驗化 合物中；除去雜質及多餘的鹼化合物；及於製造純化產物 時，除去殘留鹼化合物。此純化方法不僅從粗酸或其衍生 物中除去雜質，同時也自終產物中除去會污染產物的殘留 驗化合物。過據餅裡的鹽可由酸取代、熱解、或電解的方 法轉換回產物。此法使用一種鹼萃取溶劑來萃取鹽裡面的 鹼化合物及雜質。於回收產物中的殘留鹼化合物而後可由 瀝濾、汽提、電磁波熱攪動、或蒸發與熱解，來進一步除 去。本純化方法可以不使用用於結晶之結晶器，以及用於 乾燥、或氣體輸送的設備。最後，本純化方法將結合傳統 技藝的氧化及溶劑萃取的步驟以僅使用一套製程步驟，以 實質上降低投資及生產成本。 發明之詳述 本發明係提供一芳香聚羧酸或其衍生物的溶劑萃取純 化方法，其純度滿足或超過聚合等級。此法能適用於任何 的聚羧酸，例如 PTA、IPA、TMA、2,6-NDA、2,7-NDA等。 此方法亦適用該酸的衍生物，包括酯，如對苯二酸二甲醋 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ---------V-------!<— 訂---— II-- (請先閱讀臂面之注意事項再填寫本頁) -11 - 1249521 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（10) 保護之溶劑。此會造成自產物裡除去殘餘鹼化合物變為極 端地困難。 習知技術藉由使用惰性氣體以避免將鹼化合物氧化以 避免引起產物顏色的變質，但這只能隱藏鹼化合物存在所 造成的問題。用於測量雜質的標準HPLC分析方法無法測 量非芳香族的鹼化合物；純化產物之顏色測量法亦無法檢 測鹼化合物，除非故意將鹼化合物氧化以顯示其存在。一 種簡單的檢測殘餘鹼化合物的方法是於長時高溫加熱以使 終產物反應變為非白的顏色。該殘餘鹼化合物的程度可用 目前的技術或顏色測量法，與由氫化純化的PTA比較其 純白度而測得。 於純化的鹽中，不與羧酸官能基結合的鹼化合物是多 餘的鹼化合物。僅從鹽中除去多餘的鹼化合物並不能完全 夠避免該回收產物接觸鹼化合物，因為鹼化合物仍是鹽的 一個成份。因此，需要另外方法來除去包含於回收之產物 結晶内的殘留鹼化合物，而這個方法是極困難和不明顯 的。 本項發明發現鹼萃取溶劑能從鹽及回收產物中萃取驗 化合物及雜質。合適的鹼萃取溶劑為任何一種不含氮的化 合物，並對目標結晶的溶解度低或能將鹽轉換成產物酸； 對鹼化合物和雜質溶解度高；並能容易從產物中分離，或 不需要分離，的化合物。此種溶劑可含經基、魏、醚、酮、 酯等其他的官能基。 除非另外明述，此溶劑萃取方法係於某一預定壓力 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ---------丨丨丨丨丨- 訂- 1---線▲ (請先閱讀臂面之注意事項再填寫本頁) -13- 1249521 Δ7 ' Α7 __ - ^ Β7 五、發明說明（12) 中，每莫耳羧基官能基的0-100莫耳，較佳為UO莫耳。 (請先閱讀脅面之注意事項再填寫本頁) 習知技藝皆使用傳統加熱將能量經由溶劑分子傳到鹽 離子使其克服引力來溶解粗酸。本項發明除了使用傳統加 熱方法外，亦可能使用電磁波的熱攪動來溶解粗酸或酯。 離子在電磁波下的熱攪動與傳統加熱或微波加熱相異。電 磁波同時對溶劑分子和鹽離子提供熱攪動，然而，鹽離子 會收到更大的攪動能量，以使離子來加熱其他的分子，而 有異於傳統的加熱方法。所以，其具有明顯的特性，諸如， 溶解度、溶劑蒸發、和結晶現象。例如由於鹽離子收到較 多的能量來溶解，但也可能更快地被熱解回原來的酸或酯 分子’而有不同的溶解度；由於較高的蒸氣蒸發而有較好 的結晶效率；因高能離子可能將一部分的鹽熱解回產物酸 或酯，而有不同的沈澱機制。其主要的優點是有效節省溶 解能源與時間。較少的溶解時間則能減少溶劑降解或與雜 質反應。 線； 經濟部智慧財產局員工消費合作社印製1249521 A7 __ B7 V. INSTRUCTIONS (6) The organic base compounds all contain nitrogen, which causes color and some other problems in the manufacture of polyesters, and there is no previous disclosure of this problem and how to remove it from the product. Alkali compound. The crystals always contain a residual solution by inclusion when crystallizing. If some known methods are used, it may contain more than 0.1 〇/〇 of residual lye, to a very close extent to the level of impurities in the CTA. In order to be suitable for the manufacture of polyesters, the residual alkalization has been removed to the extent of a few million, which is close to the extent of PTA impurities. Thus, the prior art known solvent extraction techniques remove impurities from the crude acid but leave the alkali compound contaminants in the product making it unsuitable for use in the manufacture of polyesters. None of the known methods attempt to remove residual base from the final product. Iwane teaches the use of an acid solvent, Hirowatari teaches the use of water to wash the test compound derived from the filter end product cake, and Lee teaches the use of NMP, p-xylene, acetone, methyl ethyl ketone, or methanol to wash the filter cake. In the experiment of washing with 100:1 ratio of water and leaching the filter cake for 10 hours, the purified product produced still contained a large amount of alkali compound. This shows that once the base compound is contained in the product crystal, it is difficult to remove it. This problem has not been discussed in the known literature, or is known to those skilled in the art, but still exists to be resolved. In the solvent extraction and purification methods of the prior art, the replacement hydrogenation unit is explicitly or implicitly taught, and CTA is used as the feed, with the exception of Lee. He mistakenly believes that high amounts of CTA can be directly recovered from the filtered reactor effluent without the use of crystallizers or other means. However, most of the cta is still present in the mother liquor of the reactor effluent, and it requires a considerable residence time. This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) <Read the arm face first What is the note? Matters fill out this page) S0-------book---------^111· Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Ministry of Printing and Economy Ministry Intellectual Property Bureau Staff Consumer Cooperatives Print 1249521 A7 B7 5. Invention Description (7) Precipitating CTA. Therefore, the current process requires the use of 3-5 large crystallizers to recover the CTA. The present invention suggests the use of flash evaporation and evaporation to reduce residence time. Since the purification process itself requires other process steps: crystallization, filtration, drying, and gas delivery, the prior art requires two sets of step procedures to produce PTA. Therefore, the use of a known solvent extraction method to produce aromatic poly-reagents faces the following disadvantages: 1) The test compound is introduced to contaminate the final product. 2) Two sets of equipment for crystallization, centrifugation/filtration, drying and gas delivery are required. 3) The product still contains impurities that are clearly detectable. 4) A relatively long residence time is required to crystallize, so several large crystallizers are required. 5) Drying and gas delivery are required to make the final product. Accordingly, several of the objectives of the present invention are: 1) to provide a solvent extraction purification process to remove impurities from the crude acid to meet or exceed the specifications of the aromatic polycarboxylic acid polymerization grade. 2) The alkali compound in the final product is removed to make it suitable for the production of polyester fibers, films, molded resins, or other applications. 3) A method for producing a polymeric grade of aromatic polycarboxylic acid that requires only one set of process steps to substantially reduce capital and production costs. 4) Reduce the number of crystallizers used for crystallization, or even not at all. 5) Production of aromatic polycarboxylic acids that can be used directly in the manufacture of polyester without the use of drying and gas delivery steps. Further goals and advantages will be applied to the proposed Chinese Standard (CNS) A4 specification (210 X 297 public) by the solvent extraction method. ---------- ----- ---^丨定*-------- (Please read the notice of the threat surface and then fill out this page) ' -10- 1249521 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A7 B7 V. Invention Description (8) The process became more apparent, and the method was surprisingly and astoundingly found to remove impurities to a level that could not be measured by current standard HPLC. SUMMARY OF THE INVENTION The present invention provides a solvent extraction and purification process for aromatic polyphenolic acid or a derivative thereof, which purity satisfies or exceeds the polymerization grade. The method comprises dissolving a crude aromatic polyhedric acid or a derivative thereof, such as methyl vinegar, in a test compound; removing impurities and excess alkali compound; and removing the residual alkali compound when the purified product is produced. This purification method not only removes impurities from the crude acid or its derivatives, but also removes residual compounds which contaminate the product from the final product. The salt in the cake can be converted back to the product by acid substitution, pyrolysis, or electrolysis. This method uses an alkali extraction solvent to extract the alkali compounds and impurities in the salt. The residual alkali compound in the recovered product can be further removed by leaching, stripping, electromagnetic wave agitation, or evaporation and pyrolysis. The purification method may not use a crystallizer for crystallization, or a device for drying or gas transport. Finally, the purification process combines the traditional techniques of oxidation and solvent extraction to use only one set of process steps to substantially reduce capital and production costs. DETAILED DESCRIPTION OF THE INVENTION The present invention provides a solvent extraction purification process for an aromatic polycarboxylic acid or a derivative thereof, the purity of which satisfies or exceeds the polymerization grade. This method can be applied to any polycarboxylic acid such as PTA, IPA, TMA, 2,6-NDA, 2,7-NDA, and the like. This method is also applicable to derivatives of the acid, including esters, such as terephthalic acid dimethyl vinegar. The paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ---------V -------!<- Order---- II-- (Please read the notes on the arm surface and fill out this page) -11 - 1249521 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed A7 B7 V , invention description (10) solvent for protection. This causes extreme difficulty in removing residual alkali compounds from the product. Conventional techniques avoid the problem caused by the presence of an alkali compound by using an inert gas to avoid oxidation of the alkali compound to avoid deterioration of the color of the product. A standard HPLC analytical method for measuring impurities cannot measure non-aromatic alkali compounds; the color measurement of the purified product also fails to detect the base compound unless the base compound is intentionally oxidized to show its presence. A simple method of detecting residual alkali compounds is to heat for a long period of time to cause the final product to react to a non-white color. The extent of the residual base compound can be measured by current techniques or color measurements as compared to pure whiteness of hydrogenated purified PTA. Among the purified salts, the base compound which does not bind to the carboxylic acid functional group is a residual base compound. The removal of excess alkali compound only from the salt does not completely prevent the recovered product from contacting the base compound since the base compound is still a component of the salt. Therefore, an additional method is required to remove the residual alkali compound contained in the crystal of the recovered product, which is extremely difficult and inconspicuous. The present invention has found that an alkali extraction solvent can extract compounds and impurities from salts and recovered products. Suitable alkali extraction solvents are any nitrogen-free compounds with low solubility in the target crystals or conversion of the salt to the product acid; high solubility to alkali compounds and impurities; and easy separation from the product or separation ,compound of. Such a solvent may contain other functional groups such as a base, a Wei, an ether, a ketone, an ester, and the like. Unless otherwise stated, this solvent extraction method is based on a predetermined pressure on the paper scale applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ---------丨丨丨丨丨- 1---Line ▲ (Please read the notes on the arm surface and then fill out this page) -13- 1249521 Δ7 ' Α7 __ - ^ Β7 V. In the invention description (12), 0- per carboxy functional group of the molar 100 moles, preferably UO moles. (Please read the note on the face first and then fill out this page.) Traditional techniques use traditional heating to transfer energy through the solvent molecules to the salt ions to overcome the gravitational force to dissolve the crude acid. In addition to the conventional heating method, the present invention may also use thermal agitation of electromagnetic waves to dissolve the crude acid or ester. The thermal agitation of ions under electromagnetic waves is different from conventional heating or microwave heating. Electromagnetic waves simultaneously provide thermal agitation of solvent molecules and salt ions. However, salt ions receive greater agitation energy, allowing ions to heat other molecules, unlike conventional heating methods. Therefore, it has obvious characteristics such as solubility, solvent evaporation, and crystallization. For example, because salt ions receive more energy to dissolve, but may also be pyrolyzed back to the original acid or ester molecule more quickly, and have different solubility; better crystallization efficiency due to higher vapor evaporation; Because high energy ions may pyrolyze a portion of the salt back to the product acid or ester, there are different precipitation mechanisms. Its main advantage is the effective saving of dissolved energy and time. Less dissolution time reduces solvent degradation or reacts with impurities. Line; Ministry of Economic Affairs, Intellectual Property Bureau, employee consumption cooperative, printing

Iwane和Hirowatari使用不含氧的胺化合物，而Lee 則使用吡咯烷酮化合物，其為一含羰與胺官能基特性的脂 環胺化合物。其他佳的含氧鹼化合物為具有醚和胺官能基 的特性之對氧氮己環鹼化合物。含氧的與不含氧的有機鹼 化合物在鹼度、介電常數、偶極距，或與溶解劑的吸溼性 (hygroscopic)方面均有明顯不同的特性。本項發明將利用 這些特性與優點將鹼化合物和雜質從終產物中移除。 含氧的鹽叫做鹼鹽，而且不含氧的鹽叫做正常鹽。大 部份的正常鹽能溶解於許多溶劑中，如水和醇。含醚的鹽 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -15· A7 1249521 _B7___ 五、發明說明（l4 ) 羧酸、1，9_蒽二羧酸、2,3,6·蔥三羧酸（anthracene tricarboxylic ) 、 1，4,5,8-蔥四羧酸（anthracene tetracarboxylic )、和2,3,6,7-蔥四叛酸。芳香聚羧酸亦包 括以任何比例混合的芳香聚羧酸，例如，2,6-奈二羧酸和 2,7-奈二羧酸。 至於鹼化合物，於鹼化合物上的氮原子可具有三或五 個價。該驗化合物包括所有在任何不同位置的異原子和碳 原子的結合，以及具有一個或多數個氫原子之飽和或不飽 和的化合物，氫原子可以被烷基、芳香基、或醯基所取代， 或所有這些化合物所延伸出來的銨鹽。如果在常態下該鹼 化合物呈固態或氣態，則可使用其水性液體。鹼化合物亦 包括任何比例的混合物。無機鹼可為氫氧化鈉、氫氧化鉀 等。 對氧氮己環化合物包括對氧氮己環（morpholine )、 N-甲基對氧氮己環（N-methylmorpholine ) ，N-乙基對氧 氮己環（N-ethylmorpholine ) 、N-丙基對氧氮己環（N- propylmorpholine ) 、N-異丙基對氧氮己環（N- isopropylmorpholine ) ，N-甲基對氧氮己環氧化物（N- methylmorpholine oxide ) 、N-苯基對氧氮己環（N- phenylmorpholine ) 、4·對氧氮己環丙腈（4- morpholinepropionitrile ) 、1-對氧氮己環-1·環己稀（1- morpholine-1-cyclohexene)等。其他含趟官能基的驗化合 物亦包括於環中含氮與氧原子之3到8個原子的單雜環化 合物，其包括°惡β坐新（oxazocines)、11惡納皮（oxazepines)、 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------------------I 訂·'-------- (請先閱讀臂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 -17- A7 1249521 B7___ 五、發明說明（15) 噁嗉（oxazines)、噁唑（oxazoles)、異噁唑（isoxazoles)、噁 代阿斯提（oxadiazetes)、°惡利論（oxazirines)等。 醯胺化合物包括脂族的醯胺，例如二甲基甲醯胺 (dimethylformamide ) 、二甲基乙醯胺 (dimethylacetamide )、乙搭胺（ethanamide )、乙醢胺 (acetamide )等。脂環醢胺包括口比咯烷酮（pyrrolidone )、 N-甲基口比 11各烧酮（N-methyl-pyrrolidone ) 、N-乙基 11 比口各 炫 _ ( N-ethyl-pyrrolidone ) 、N-烧基-2-口比洛烧嗣（N- alkyl-2-pyrrolidone ) 、N-氫硫烧基-2·11比洛烧綱（1^-mercaptoalkyl-2- pyrrolidone)、N-氫硫乙基-2-咐^各烧_ (N-mercaptoethyl-2-pyrrolidone )、N-烧基-2-硫代 σ比洛 烧 _ ( N-alkyl-2-thiopyrrolidone )、Ν-甲基-2-硫代口比哈 烧酮（N-methyl-2-thiopyrrolidone )、Ν-經燒基-2·σ比哈烧 酮（N-hydroxyalkyl-2-pyrrolidone )、以及 Ν_ 經乙基-2-口比哈烧酮（N-hydroxyethyl-2-pyrrolidone )、内醯胺 (lactam ) 等。芳香醯胺包括苯基乙醯胺 (phenylacetamide )、次苯基對苯搭胺（phenylene terephthalamide )等。 脂族胺包括甲胺、二甲胺、三甲胺、乙胺、二乙胺、 三乙胺、正丙胺、二正丙胺、三正丙胺、異丙胺、二異丙 胺、三異丙胺、乙二胺、N-甲基乙二胺、N，N’·二乙基乙 二胺、N，N’-二甲基乙二胺、N，N，N’-三甲基乙二胺、 N，N，N’，N’-四甲基乙二胺、1，2·二胺基丙烧、1，3-二胺基丙 烷、單乙醇胺、二乙醇胺、三乙醇胺、二曱基乙醯胺、二 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） I---I------ S·!!訂·，丨丨！丨丨 (請先閱讀臂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 A7 B7 1249521 i、發明說明（16) 甲基甲醯胺等。脂環胺包括甲基環己胺、N-甲基環己胺、 N，N’-二甲基環己胺、乙基環己胺、N-乙基環己胺、N，N，-二乙基環己胺、異丙基環己胺、N-異丙基環己胺、N，N，-二異丙基環己胺、乙稀亞胺、丙烯亞胺等。芳香族胺包括 Ν，Ν·二曱基苯胺、N，N-二乙基苯胺、n，N-二丁替苯胺、N，N-二甲基甲苯胺、N，N-二乙基甲苯胺等。雜環胺包括吡啶、 0底啶、N-甲基旅啶、N-甲基0比咯烷等。 較佳的鹼化合物為對氧氮己環、N-甲基-吡咯烷酮、 三甲胺、三乙甲胺、或三乙醇胺。 醇類包括脂族一經醇，諸如甲醇、乙醇、正丙醇、異 丙醇、正丁醇、異丁醇、另丁醇、叔丁醇、正戊醇、異戊 醇、另戊醇、叔戊醇、新戊醇、己醇、庾醇、辛醇、壬醇、 和癸醇；脂環一羥醇如環戊醇和環己醇等；脂族直鏈二羥 醇如乙二醇、二甘醇、丙二醇、丁二醇、以及戊二醇；脂 環二羥醇如1，2-環戊二醇、l，3-環戊二醇、丨，2_環己二醇、 環己二醇、1，4-環己二醇；和脂族多羥醇如丙三醇和 季戊四醇等。較佳為具有3個碳原子或3個碳原子以下的 脂族一羥醇或4個碳原子或4個碳原子以下的脂族直鏈二 羥醇。醇可為以任何比例之上述各種醇的混合。較佳的醇 為甲醇、乙醇、或烯烴基二醇（alkyleneglyc〇1)。 醚包括二甲醚、二戊醚、二***、異丙醚、正丁醚、 正己醚、氣化二甲醚、苯甲醚、二苯甲醚、環氧乙烷、二 -四氫吡喃、三-四氫吡喃、氧雜茂（furan)、四氫呋喃 (如灿沖咖⑽）、甲基-四氫呋喃（methyl- 本紙張尺度適用中關家標準（CNS)A4規格（210 X 297公髮） !!!!..! Ac (請先閱讀臂面之注意事項再填寫本頁) 訂--------- 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 1249521 A7 — B7 五、發明說明（17 ) tetrahydrofuran )、四氫 口比喃（tetrahydropyran )、甲基-四氫口比喃（methyl-tetrahydropyran )等。_ 包括丙_、甲 基乙基酮、甲基正丙酮、甲基正丁酮、甲基戊酮、甲基丙 酮、2-甲基環戊晒、環戊酮、環己酮等其他。酯包括乙二 醇甲醚、二乙二醇甲醚、乙二醇***、二乙二醇***、乙 二醇丙醚、乙二醇丁醚、乙二醇苯甲醚、二甘醇、三甘醇、 烧基甲醋（alkyl formate)、烧基醋醋（alkyl acetate)、 燒基丙醋（alkyl propionate )、草酸 6旨（oxalates )、烧 基乳酸醋（alkyl lactate )、石炭酸醋（carbonates )、苯酸 酉旨（benzoates)等0 除去雜質和多餘嫌化合物 此步驟以前處理、沈澱、分離、和洗滌過濾餅來除去 雜質。習知技術已教示，以溶液前處理及冷卻結晶來移除 雜質。此外，本發明將提供新方法以除去清洗過之過濾餅 内的雜質及多餘鹼化合物。 溶液前處理的目的是除去容易自溶液分離的雜質，例 如以活性碳吸附著色劑或添加劑、過濾不能溶解的雜質、 流出或刮掉漂流的雜質等。分離此等雜質的方法已廣為人 知，本項發明將不局限於任一特定的方法。如果粗酸内無 此類的雜質，則不需要溶液前處理。 結晶的目的是除去難分離且物性及化性與產物均很接 近的雜質。於一定的溫度和溶液成分下，雜質鹽的溶解度 不是較產物鹽低就是高。因此藉著溶液溫度及[或]成分的 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ϋ mmarnw I 11 I 11 l ϋ ϋ ϋ ϋ i^i J ^ ϋ i·— ϋ —Bi i^i I (請先閱讀臂面之注意事項再填寫本頁) -20- 1249521 A7 ---—--— B7 —_ 五、發明說明（18) 變化，具有低溶解度的雜質將先沈搬而與其他物質分離。 沈澱f物鹽則能自母液中分離那些高溶解度的雜質。 I技術使用冷卻方式結晶以分離雜質，而鹽類係以 般的方法來分離，如過濾或離心。因為需要很長的駐留 夺間使母液中的晶體能能夠慢慢成長，所以需要數個很大 的結晶器。另外的方式是控制溶液成分並冷卻，以減少所 需的駐留時間。當粗酸完全溶解後且在結晶之前，藉由一 般的方法，如蒸發或蒸館，來移除某預定量的溶液，以使 得冷卻後之溶劑仍有夠量的母液以分離雜質。此法雖能減 、但仍需相當的結晶駐留時間。此兩種方式皆嘗試儘量保 持多量的雜質於母液中以自純化鹽中分離而出。 習知技術通常使用鹼化合物來洗滌過濾鹽，因為溶解 劑會立刻將鹽溶解掉。由於鹽的枯度很高，所以洗滌效率 很低。除此之外，此法將使鹽含有多餘鹼化合物，因而增 加終產物中鹼化合物的含量。其他習知技術則教示使用脂 族烴或芳香烴類做洗滌溶劑。此法只是以洗滌溶劑來取代 晶體内的溶液，並無任何萃取的能力，且可能以其他形式 的污染物存在於終產物中。 本項發明使用鹼萃取溶劑以自鹽中除去多餘鹼化合物 及雜質。該新的方法包括以鹼萃取溶劑洗滌或瀝濾、於鹼 萃取溶劑存在下結晶鹽類、於鹼萃取溶劑存在下沈澱鹽 類、自鹽直接萃取以結晶，再鹽化及鹼替代鹽以結晶。 大部份的鹼萃取溶劑不會將鹽轉換回酸。但有些則 會，假若該溶劑係用以洗滌該己過濾之羰鹼鹽，但若能將 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀臂面之注音？事項再填寫本頁) 訂'--------^^丨 經濟部智慧財產局員工消費合作社印製 -21- 經濟部智慧財產局員工消費合作社印製 1249521 Α7 ------Β7____ 五、發明說明（ 鹽轉化鹼萃取溶劑與鹼化合物混合成適當的比例，則能減 少鹽的轉化。例如，以甲醇與50% ΝΜΡ之混合物來洗滌 過濾鹽’則能大大地減少鹽的轉化。該洗滌餅較佳係以鹽 的形態保存。 明言之，鹼萃取溶劑可以是水、過氧化氫、醇、醚、 盼、酮、酯等。先前巳經定義醇、醚、酮、和酯。鹼萃取 溶劑可單獨使用，或為二種或二種以上的溶劑以任何比例 混合之混合物，且該溶劑可以液態或汽態形式使用。較佳 的鹼萃取溶劑為水、甲醇、乙醇、烯烴基二醇、丙酮、四 氫吱喃、或四氫吡喃。雖然此步驟中的目標結晶為純化的 鹽’該使用的溶解劑係被排除。但下一步驟的目標結晶是 產物酸或其衍生物，則其可包含該使用過的溶解劑。 大部份雜質鹽的顏色並不是白色，而多餘鹼化合物皆 有教的氣味’與其他溶劑比較，如驗化合物或碳氫化合物， 以驗萃取溶劑洗滌或瀝濾的過濾餅，可有效改善其顏色與 氣味均。依定義，瀝濾並不同於洗滌過濾餅（Perry，s的 化工手冊，第6版，19_48頁）。洗滌與瀝濾的方法已廣為 人知’本項發明並不局限於使用任一特定方法。 驗萃取溶劑亦可於粗酸完全溶解後加入至溶液中。於 結晶過程中，鹼萃取溶劑的存在可減少包含於結晶内的鹼 化合物，同時也能從鹽中萃取雜質及鹼。另外，溶液中驗 萃取溶劑的存在亦可能改變結晶的機制，諸如形狀、大小、 和速率。例如，加入甲醇、丙酮、或四氫呋喃會增加 >ίΜΡ-ΡΤΑ鹽之結晶形狀及大小。 (請先閱讀臂面之注意事項再填寫本頁) 訂 ---------Iwane and Hirowatari use an oxygen-free amine compound, while Lee uses a pyrrolidone compound, which is an alicyclic amine compound containing carbonyl and amine functional properties. Other preferred oxygen-containing base compounds are the paraxanthene base compounds having the characteristics of ether and amine functional groups. Oxygen-containing and oxygen-free organic base compounds have significantly different properties in terms of alkalinity, dielectric constant, dipole moment, or hygroscopicity of the solvent. The present invention will utilize these properties and advantages to remove base compounds and impurities from the final product. Oxygenated salts are called alkali salts, and salts that do not contain oxygen are called normal salts. Most of the normal salts are soluble in many solvents such as water and alcohol. Ether-containing salts The paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -15· A7 1249521 _B7___ V. Description of invention (l4) Carboxylic acid, 1,9-indanedicarboxylic acid, 2, 3,6. anthracene tricarboxylic acid, 1,4,5,8-anthracene tetracarboxylic acid, and 2,3,6,7- onion tetrazoic acid. The aromatic polycarboxylic acid also includes aromatic polycarboxylic acids which are mixed in any ratio, for example, 2,6-nadicarboxylic acid and 2,7-nadicarboxylic acid. As the base compound, the nitrogen atom on the base compound may have three or five valences. The test compound includes all combinations of heteroatoms and carbon atoms at any different positions, as well as saturated or unsaturated compounds having one or more hydrogen atoms, which may be replaced by an alkyl group, an aryl group, or a fluorenyl group. Or an ammonium salt from which all of these compounds extend. If the base compound is in a solid or gaseous state under normal conditions, an aqueous liquid thereof can be used. The base compound also includes mixtures in any ratio. The inorganic base may be sodium hydroxide, potassium hydroxide or the like. p-Oxacyclohexane compounds include morpholine, N-methylmorpholine, N-ethylmorpholine, N-propyl N-propylmorpholine, N-isopropylmorpholine, N-methylmorpholine oxide, N-phenyl pair N-phenylmorpholine, 4-morpholinepropionitrile, 1-morpholine-1-cyclohexene, and the like. Other test compounds containing a ruthenium functional group also include a monoheterocyclic compound having 3 to 8 atoms of nitrogen and oxygen atoms in the ring, including oxazocines, 11 oxazepines, and The paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) --------------------I book ·'-------- (Please read the notes on the arm face and then fill out this page.) Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumer Cooperatives Printed -17- A7 1249521 B7___ V. Description of invention (15) oxazines, oxazoles, and Isozoles, oxadiazetes, oxazirines, etc. The guanamine compound includes an aliphatic guanamine such as dimethylformamide, dimethylacetamide, ethanamide, acetamide or the like. The alicyclic guanamine includes pyrrolidone, N-methyl-pyrrolidone, N-ethyl-pyrrolidone, N-ethyl-pyrrolidone, N-alkyl-2-pyrrolidone, N-hydrothiol-2,11-mercaptoalkyl-2-pyrrolidone, N-hydrogen Sulfurethyl-2-indole _ (N-mercaptoethyl-2-pyrrolidone), N-alkyl-2-thiopyrrolidone _ (N-alkyl-2-thiopyrrolidone), Ν-methyl- 2-thio-2-thiopyrrolidone, N-hydroxyalkyl-2-pyrrolidone, and Ν_ethyl-2- N-hydroxyethyl-2-pyrrolidone, lactam, and the like. Aromatic amides include phenylacetamide, phenylene terephthalamide, and the like. Aliphatic amines include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, tri-n-propylamine, isopropylamine, diisopropylamine, triisopropylamine, ethylenediamine , N-methylethylenediamine, N,N'diethylethylenediamine, N,N'-dimethylethylenediamine, N,N,N'-trimethylethylenediamine, N,N , N', N'-tetramethylethylenediamine, 1,2,diaminopropane, 1,3-diaminopropane, monoethanolamine, diethanolamine, triethanolamine, dimercaptoacetamide, two This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) I---I------ S·!! Booking·, 丨丨!丨丨 (Please read the note on the arm surface and then fill out this page.) Printed by the Intellectual Property Office of the Ministry of Economic Affairs, A7 B7 1249521 i. Description of invention (16) Methylformamide. Alicyclic amines include methylcyclohexylamine, N-methylcyclohexylamine, N,N'-dimethylcyclohexylamine, ethylcyclohexylamine, N-ethylcyclohexylamine, N,N,-di Ethylcyclohexylamine, isopropylcyclohexylamine, N-isopropylcyclohexylamine, N,N,-diisopropylcyclohexylamine, ethyleneimine, acrylimine, and the like. Aromatic amines include anthracene, quinone diphenyl aniline, N,N-diethylaniline, n,N-dibutylaniline, N,N-dimethyltoluidine, N,N-diethyltoluidine Wait. Heterocyclic amines include pyridine, oxadine, N-methyl bromopyridine, N-methyl 0-pyrrolidine, and the like. Preferred base compounds are p-oxazolidine, N-methyl-pyrrolidone, trimethylamine, trimethylamine or triethanolamine. Alcohols include aliphatic alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, isobutanol, tert-butanol, n-pentanol, isoamyl alcohol, pentanol, uncle Pentanol, neopentyl alcohol, hexanol, decyl alcohol, octanol, decyl alcohol, and decyl alcohol; alicyclic monohydric alcohols such as cyclopentanol and cyclohexanol; aliphatic linear dihydric alcohols such as ethylene glycol, two Glycol, propylene glycol, butanediol, and pentanediol; alicyclic dihydric alcohols such as 1,2-cyclopentanediol, 1, 3-cyclopentanediol, hydrazine, 2-cyclohexanediol, cyclohexane Alcohol, 1,4-cyclohexanediol; and aliphatic polyhydric alcohols such as glycerol and pentaerythritol. It is preferably an aliphatic monohydric alcohol having 3 carbon atoms or less or 4 or less carbon atoms or an aliphatic linear dihydric alcohol having 4 or less carbon atoms. The alcohol may be a mixture of the above various alcohols in any ratio. Preferred alcohols are methanol, ethanol, or alkene diols (alkyleneglyc®). Ethers include dimethyl ether, diamyl ether, diethyl ether, diisopropyl ether, n-butyl ether, n-hexyl ether, gasified dimethyl ether, anisole, diphenyl ether, ethylene oxide, di-tetrahydropyran , tri-tetrahydropyran, furan, tetrahydrofuran (such as Canchong (10)), methyl-tetrahydrofuran (methyl- paper scale applicable to the Central Standards (CNS) A4 specification (210 X 297 mil )!!!!..! Ac (Please read the notes on the arm face and then fill out this page) Order--------- Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Printed Economy Ministry Intellectual Property Bureau Staff Consumption Co-operatives print 1249521 A7 - B7 V. Description of invention (17) tetrahydrofuran), tetrahydropyran, methyl-tetrahydropyran and the like. _ includes C-, methyl ethyl ketone, methyl n-propanone, methyl n-butanone, methyl amyl ketone, methyl ketone, 2-methylcyclopentan, cyclopentanone, cyclohexanone and the like. Ester includes ethylene glycol methyl ether, diethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol ether, ethylene glycol propyl ether, ethylene glycol butyl ether, ethylene glycol anisole, diethylene glycol, three Glycol, alkyl formate, alkyl acetate, alkyl propionate, oxalates, alkyl lactate, carbonaceous vinegar ), benzoates, etc. 0 Removal of Impurities and Excess Compounds This step previously treats, precipitates, separates, and washes the filter cake to remove impurities. Conventional techniques have taught to remove impurities by solution pretreatment and cooling crystallization. In addition, the present invention will provide new methods for removing impurities and excess base compounds from the cleaned filter cake. The purpose of the solution pretreatment is to remove impurities which are easily separated from the solution, for example, adsorption of colorants or additives with activated carbon, filtration of insoluble impurities, elution or scraping of drifting impurities, and the like. Methods for separating such impurities are well known and the invention is not limited to any particular method. If there is no such impurity in the crude acid, no pretreatment of the solution is required. The purpose of crystallization is to remove impurities which are difficult to separate and which are close in physical and chemical properties to the product. The solubility of the impurity salt is not lower or higher than the product salt at a certain temperature and solution composition. Therefore, the Chinese National Standard (CNS) A4 specification (210 X 297 mm) is applied to the paper scale of the solution temperature and [or] composition. ϋ mmarnw I 11 I 11 l ϋ ϋ ϋ ϋ i^i J ^ ϋ i·— ϋ —Bi i^i I (please read the notes on the arm surface before filling in this page) -20- 1249521 A7 ------- B7 —_ V. Description of invention (18) Variation, impurities with low solubility Will be sunk and separated from other substances. The precipitated f salt can separate those high solubility impurities from the mother liquor. The I technique uses cooling to crystallize to separate impurities, and the salts are separated by a general method such as filtration or centrifugation. Because of the long residence required to allow the crystals in the mother liquor to grow slowly, several large crystallizers are required. Another way is to control the composition of the solution and cool it to reduce the required residence time. When the crude acid is completely dissolved and before crystallization, a predetermined amount of the solution is removed by a general method such as evaporation or steaming, so that the cooled solvent still has a sufficient amount of the mother liquid to separate the impurities. Although this method can be reduced, it still requires a considerable crystallization residence time. Both methods attempt to maintain as much of the impurities as possible in the mother liquor to separate from the purified salt. Conventional techniques typically use an alkaline compound to wash the filtered salt as the solubilizing agent will dissolve the salt immediately. The washing efficiency is very low due to the high dryness of the salt. In addition, this method will allow the salt to contain excess base compound, thereby increasing the amount of base compound in the final product. Other conventional techniques teach the use of aliphatic or aromatic hydrocarbons as washing solvents. This method simply replaces the solution in the crystal with a wash solvent, without any extraction capability, and may be present in the final product in other forms of contaminants. The present invention uses an alkali extraction solvent to remove excess alkali compounds and impurities from the salt. The novel method comprises washing or leaching with an alkali extraction solvent, crystallizing a salt in the presence of an alkali extraction solvent, precipitating a salt in the presence of an alkali extraction solvent, directly extracting from a salt to crystallize, re-salting, and substituting a salt for crystallization. . Most of the alkali extraction solvent does not convert the salt back to acid. However, some may be used if the solvent is used to wash the filtered carbonyl alkali salt, but if the paper size can be applied to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the arm surface first) Phonetic? Matters again fill out this page) Order '--------^^丨 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Printed-21- Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Printed 1249521 Α7 ---- --Β7____ V. Inventive Note (The salt conversion alkali extraction solvent is mixed with the alkali compound to a proper ratio to reduce the conversion of the salt. For example, washing the filtered salt with a mixture of methanol and 50% hydrazine can greatly reduce the salt. The washing cake is preferably preserved in the form of a salt. In essence, the alkali extraction solvent may be water, hydrogen peroxide, alcohol, ether, ketone, ketone, ester, etc. Previously defined alcohols, ethers, ketones, And the ester extraction solvent may be used singly or as a mixture of two or more solvents in any ratio, and the solvent may be used in a liquid or vapor form. The preferred alkali extraction solvent is water, methanol, ethanol. Alkenyl diol, C Ketone, tetrahydrofuran, or tetrahydropyran. Although the target crystal in this step is a purified salt, the solvent used is excluded. However, the target crystal of the next step is the product acid or its derivative. It may contain the used dissolving agent. Most of the impurity salts are not white in color, and the excess alkali compound has a taught smell. Compared with other solvents, such as test compounds or hydrocarbons, it is washed with an extraction solvent or The leached filter cake is effective in improving its color and odor. By definition, leaching is different from washing filter cakes (Perry, s Chemical Handbook, 6th Edition, pp. 19-48). Washing and leaching methods are well known. 'The invention is not limited to the use of any particular method. The extraction solvent can also be added to the solution after the crude acid is completely dissolved. During the crystallization process, the presence of the alkali extraction solvent can reduce the alkali compound contained in the crystal. At the same time, impurities and alkalis can be extracted from the salt. In addition, the presence of an extraction solvent in the solution may also change the mechanism of crystallization, such as shape, size, and rate. For example, adding A , Acetone, tetrahydrofuran or increase > crystalline salt of ίΜΡ-ΡΤΑ shape and size (Please Note read page and then fill the arm plane) --------- set.

-22- 1249521 A7 B7 五、發明說明（2〇) 藉由將酸取代溶劑加入至溶液中，於鹼萃取溶劑存在 下，可沈澱該純化的產物。而鹼萃取溶劑的存在能從沈澱 物中萃取雜質及鹼化合物。本項發明發現，對羰鹼鹽而言， 水是鹼萃取溶劑但也可以是酸取代溶劑，因它能從飽和溶 液裡直接沈澱出產物，但其他鹼萃取溶劑，如甲醇，在某 些溶液組成範圍内可沈澱鹽。然而，4_CB A與NMp鹽於 水中的溶解度比於甲醇中約低1〇倍。與習知技術所發表 利用洗滌以轉換鹽的方法比較，於鹼萃取溶劑存在，沈殿 產物會有較好之鹽轉換及結晶大小的控制，其係藉由溫度 控制、攪動、組成、和駐留時間來控制。於習知技術中， 將酸取代溶劑加入溶液以沈澱產物，而無鹼萃取溶劑的存 在。但因大部分雜質將隨產物一起沈澱，所以產物純度降 低0 右將大部份的溶液藉由蒸發或急驟蒸發自溶液中移 除’則將得到固態鹽或淤漿。一旦雜質於正常操作條件下 無法蒸發，其將都留於鹽中。習知技術皆藉由結晶來避免 此種狀況，其係將雜質保留於用於分離的母液中。然而， 本項發明很意外及驚訝地發現鹼萃取溶劑能從鹽中萃取雜 質與多餘驗化合物。如此該結晶方法則可完全免除結晶駐 留時間的要求。其產物回收效率則取決於鹽在鹼萃取溶劑 中的溶解度，以及溶解劑留於於漿中的量。另外與習知技 術之結晶相異處為，此種直接從鹽萃取的結晶並不需冷卻 用於結晶之溶液。加入驗萃取溶劑前，可將於聚裡的母液 分離或不分離。萃取後的溶液係以一般分離的方法與鹽分 本紙張尺度_中國國家標準（CNS)A4規格（210 X 297公爱) II ' ί i # (請先閱讀臂面之注意事項再填寫本頁)-22- 1249521 A7 B7 V. INSTRUCTION DESCRIPTION (2〇) The purified product can be precipitated by adding an acid-substituted solvent to the solution in the presence of an alkali extraction solvent. The presence of an alkali extraction solvent extracts impurities and alkali compounds from the precipitate. The present invention finds that, for the carbonyl base salt, water is an alkali extraction solvent but may also be an acid-substituted solvent because it can directly precipitate a product from a saturated solution, but other alkali extraction solvents such as methanol, in some solutions The salt can be precipitated within the composition range. However, the solubility of 4_CB A and NMp salts in water is about 1 times lower than that in methanol. Compared with the method disclosed in the prior art by using washing to convert salts, in the presence of an alkali extraction solvent, the sediment product has better salt conversion and crystal size control by temperature control, agitation, composition, and residence time. To control. In the prior art, an acid-substituted solvent is added to the solution to precipitate the product without the presence of an alkali-extracting solvent. However, since most of the impurities will precipitate with the product, the purity of the product will decrease by 0. The majority of the solution will be removed from the solution by evaporation or flash evaporation, and a solid salt or slurry will be obtained. Once the impurities are unable to evaporate under normal operating conditions, they will remain in the salt. Conventional techniques have avoided this by crystallization, which retains impurities in the mother liquor for separation. However, the present invention surprisingly and surprisingly finds that an alkali extraction solvent can extract impurities and excess compounds from the salt. Thus, the crystallization method completely eliminates the requirement of crystallization residence time. The product recovery efficiency depends on the solubility of the salt in the alkali extraction solvent and the amount of the solvent remaining in the slurry. Further, in contrast to the crystals of the prior art, such crystals extracted directly from the salt do not require cooling of the solution for crystallization. The mother liquor may be separated or not separated prior to the addition of the extraction solvent. The extracted solution is separated by general separation method and salt. Paper size _ China National Standard (CNS) A4 specification (210 X 297 public) II ' ί i # (Please read the following on the arm surface)

^1 1 I ϋ n I 訂*-------- 經濟部智慧財產局員工消費合作社印製 1249521 A7 經濟部智慧財產局員工消費合作社印製 五、發明說明（21 ) AA. 離0 將沈澱物重新溶解於溶解劑或鹼化合物中，並再結晶 該/谷液一次或數次，將達到以目前標準HpLC方法所無法 測出雜質的程度，或可將含更高鞭赁的粗酸純化至合乎聚 合等級的規格。因此，再生鹽結晶包括自該粗酸溶解液中 結晶鹽；分離，洗滌，和再溶解鹽；從溶液中再結晶鹽； 以一般方法分離及洗滌鹽。鹽較佳係在再結晶前完全溶 解。假如該洗滌餅在電磁波下的結晶或以會以轉化鹽鹼萃 取溶劑來洗滌，則可能會含產物酸，該酸可從鹽分離，或 不分離，或以鹼化合物重新再溶解以用於再鹽化。上面所 提議的任一結晶方法皆可使用於結晶及沈澱。但較佳係使 用以鹽直接萃取來結晶及再結晶的方法。若於鹼萃取溶劑 存在下使用沈澱產物，則較適用於最後的結晶程序。再結 晶的次數並無特殊的限制，較佳是丨_2次。 使用於上述之方法中用於移除雜質的鹼萃取溶劑不見 得是同一種類。其用量可為每莫耳羧基官能基的〇.1-1〇〇 莫耳，較佳為1-10莫耳。醚鹼鹽較佳使用的鹼萃取溶劑 是甲醇或乙醇。羰鹼鹽則較佳使用烯烴基二醇、丙嗣、四 氫11夫喃、或四氫σ比喃。 鹽驗取代是以另一種鹼來取代具有鹼化合物之第一鹽 中的驗化合物以提高產物回收率的方法。如前所述，幾驗 鹽較難形成且製備成本較高，但較易回收且回收成本較 低。例如，製造ΝΜΡ-ΡΤΑ鹽較製造對氧氮己環_ΡΤΑ鹽 昂貴數倍，但它能被較便宜的水來回收。本項發明發現鹽 (請先閱讀臂面之注意事項再填寫本頁) / 訂ί^1 1 I ϋ n I Order*-------- Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1249521 A7 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 5, Invention Description (21 ) AA. Re-dissolving the precipitate in a dissolving agent or an alkali compound, and recrystallizing the / trough solution one or several times, to the extent that impurities cannot be detected by the current standard HpLC method, or may be coarser with higher whip The acid is purified to a specification that meets the polymerization grade. Thus, the regenerated salt crystals include crystallized salts from the crude acid solution; separation, washing, and redissolution of the salt; recrystallization of the salt from the solution; separation and washing of the salt in a conventional manner. The salt is preferably completely dissolved prior to recrystallization. If the wash cake is crystallized under electromagnetic waves or washed with a salt-alkaline extraction solvent, it may contain product acid which may or may not be separated from the salt or re-dissolved with the base compound for reuse. Salinization. Any of the crystallization methods proposed above can be used for crystallization and precipitation. However, it is preferred to use a method in which the salt is directly extracted for crystallization and recrystallization. If a precipitated product is used in the presence of an alkali extraction solvent, it is more suitable for the final crystallization procedure. The number of recrystallizations is not particularly limited, and is preferably 丨2 times. The alkali extraction solvent used for the removal of impurities used in the above method is not necessarily of the same kind. It may be used in an amount of from 0.1 to 1 mole per mole of carboxyl functional group, preferably from 1 to 10 moles. The alkali extraction solvent preferably used for the ether base salt is methanol or ethanol. As the carbonyl base salt, an olefin diol, propylene hydride, tetrahydro 11 pentane or tetrahydro σ pentane is preferably used. The salt test is a method of substituting a test compound in the first salt of the base compound with another base to increase the product recovery. As mentioned earlier, several salts are more difficult to form and are more expensive to produce, but are easier to recycle and have lower recycling costs. For example, the manufacture of strontium-strontium salts is several times more expensive than the manufacture of p-oxonium sulfonium salts, but it can be recovered by less expensive water. This invention found salt (please read the notes on the arm surface before filling out this page) / order ί

本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -24- 1249521 A7 B7 I、發明說明（22) 的驗化合物可被另一高彿點的驗化合物所取代，所以，_ 鹼鹽或普通的鹽可被轉換成羰鹼鹽。因此，吾人能以較經 濟的鹼化合物來製備，且將其轉換成另一種鹽，以得較經 濟的產物法。將要被轉換的鹽與取代鹼在溶解劑存在或不 存在的狀況下混合。然後使用一般分離溶液的方法，如蒸 發或蒸館，以傳統加熱或電磁波方式，將取代的鹼化合物 及/或溶解劑從溶液移除。該取代的鹽可於存在或不存在 鹼萃取溶劑的情況下，冷卻沈澱出來，或自鹽直接鹼萃取 製備而得。一溶解劑，例如水，可用以溶解未轉化的鹽， 然後回收，或於一系列的步驟中繼續轉換。於另一鹼化合 物存在的情況下，鹽鹼取代也包括改變鹽的結晶，如形狀 或大小。取代的鹼化合物用量可為每莫耳羧基官能基的 0.1-100莫耳，較佳為1-10莫耳。 用以能鹽轉換鹼萃取溶劑或以酸取代溶劑來洗滌過濾 餅。此可視為洗滌與下一步之酸取代的合併步驟，它也是 Lee所使用的方法。然而，洗滌法在鹽的轉化及產物的性 質上具有相當小的控制性。本項發明認為在過濾前且於結 晶期間將化的產物沈澱出來，或以鹽的形成分離該沈澱 物’該鹽將在下一步驟中將被轉化，因為二者對鹽的轉化、 自該回收產物中萃取雜質及鹼化合物、以及產物顆粒的大 小具有較佳的控制性。對某些鹼鹽來說，鹽顆粒的大小會 影響產物顆粒的大小，而鹽顆粒的大小能以喷霧乾燥、調 節成分、駐留時間、溫度、攪動、或其他來控制。 因此’除去雜質的方法包括溶液前處理、冷卻結晶、 本紙張尺度適用中國國豕ί示準（CNS)A4規格（210 X 297公餐） 身 (請先閱讀臂面之注意事項再填寫本頁) 訂--------- 經濟部智慧財產局員工消費合作社印製 -25- 1249521 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（23) 溶液成分控制及冷卻結晶、於驗萃取溶劑存在下結晶鹽、 於鹼萃取溶劑存在下沈澱產物、自鹽直接萃取結晶、再生 鹽結晶、鹼鹽取代、以鹼萃取溶劑洗滌、以鹼萃取溶劑瀝 濾、或以上方法的所有可能組合。除了自該粗酸或其衍生 物移除雜質之外，此步驟亦將多餘鹼化合物從過濾餅中除 去，以降低以下述步驟所製得之終產物的鹼化合物含量。 製造纯化產物亦同時除去殘留螓化合物 此步驟的目的是假若該鹽量足夠則於過濾餅中，自鹽 回收產物，並/或在製造終產物前，除去殘留鹼化合物。 自該化鹽類中回收產物的方法包括酸取代、熱解、或電解。 該產物較佳係於鹼萃取溶劑存在下回收。因溶液成分、溫 度、攪拌 '和駐留時間均會影響產物顆粒的形狀和大小， 且這些因素應配合鹼與雜質的萃取以達最佳狀況。 酸取代 為了將鹽轉化為產物，一酸取代溶劑係被加入以取代 及沈殿該產物酸。該鹽可與驗萃取溶劑混合。且較佳係在 加入酸取代溶劑前將醚鹼鹽或一般鹽完全溶解，且較佳的 溶劑為水、甲醇、乙醇、烯烴基二醇、或其等之混合物。 幾驗鹽不溶於多數溶劑，而水為較佳的酸取代溶劑。水較 佳係在驗萃取溶劑存在下加入，該驗萃取溶劑係如甲醇、 乙醇、丙酮、四氫吡喃、或四氫吡喃。酸取代可於電磁波 下操作。具有鹼萃取溶劑的酸取代能降低回收產物中的殘 留鹼化合物和雜質的包含。 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 X 297公釐） -26- „ ------- t --------- (請先閱讀臂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 1249521 A7 ^ B7 五、發明說明（24) 酸取代溶劑可以是脂族羧酸、無機酸、水等。脂族羧 酸可以是甲酸、醋酸、丙酸、丁酸、羥基醋酸、乳酸、蘋 果酸、酒石酸、中酒石酸、檸檬酸、一氯醋酸、一漠醋酸 酸、一硝基酸酸、三氟醋酸、和三氯醋餿;而無機酸可以 是硝酸、鹽酸、溴化氫、碘化氫、硫磺酸、磷酸、和過氯 酸。如前所討論，水或鹼萃取溶劑可以是羰鹼鹽的酸取代 溶劑。酸取代溶劑可以是上述的酸以任何比例的混合物， 或為具有溶解劑或鹼萃取溶劑之任何比例的酸的混合物， 該酸的比例大於1 %的重量。 用於醚驗鹽或正鹽之較佳的酸取代溶劑為脂族羧酸， 且最佳為醋酸。用於羰鹼鹽則較佳為水。酸取代溶劑的用 量是於芳香聚羧酸内每莫耳羧官能基之〇·5-1〇〇的莫耳 數。通常的用量是比官能基的莫耳數多一點。 熱解 熱可於50-350°C範圍間加到化鹽中以熱分解該鹼化 合物。鹽可與具有理想沸點之鹼萃取溶劑混合，該沸點可 以壓力調控之。較佳的鹼萃取化合物為水、蒸氣、或醇。 熱可以藉由熱轉移方式添加，諸如熱傳導方式，或直接與 熱介質接觸。 除了上述傳統的加熱方法外，鹽亦可在電磁波下加熱 分解。較好的方法是將鹽與鹼萃取溶劑，如水、蒸氣、或 醇等，以任何比例混合，其可溶解或酸取代該鹽，且可吸 收電磁波以協助分解。電磁波能熱攪動這些分子並將它們 從無法吸收電磁波的產物結晶分離，溶液因而被分解成已 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -27- ------------------丨訂*----- (請先閱讀臂面之注意事項再填寫本頁) A7 1249521 —___B7 五、發明說明（25 ) 轉換的產物與未轉換鹽的混合物。維持一適當的溶劑濃度 和溫度可允許該溶液持續地將被電磁波分解。該鹼萃取溶 劑亦可以一連串步驟中加至該混合物中以進一步分解。未 轉換的鹽亦可藉由溶於溶解劑而與回收產物分離，且該濾、 液係可再循環或再以一連串步驟，藉由電磁波來熱解滤 液。因此，此方法可以分批或連績方式使用。與傳統方法 比較，電磁波熱解使用較少的能量及處理時間。例如，與 需要2-12小時的傳統方法比較，此方法只需0.04-0.6小 時。另外，由内而外的加入熱能方式可減少將驗化合物包 含於回收晶體内的機會。 該分解後的驗化合物較佳係以一般常用的方法自回收 產物中分離，如蒸發、真空吸取、蒸餾、吸收劑吸收、或 以惰性氣體、蒸氣、或溶解劑運離等。 對羰鹼鹽而言，以水或以蒸汽為鹼萃取溶劑，藉電磁 波作用，以蒸汽直接接觸來熱解為佳，因為它能同時熱解 又酸取代該鹽。於此種情況下，產物顆粒大小將由較容易 控制的鹽顆粒大小來決定。此外，以嫦烴基二醇為溶劑來 熱解及蒸發殘留的鹽與溶劑將能避免使用過濾、乾燥及氣 體搬運等步驟程序，此將於後面討論。 電解 將電流通到由純化鹽溶解於鹼萃取溶劑中所形成之溶 液中，以使得陰極將吸引鹼離子而陽極將吸引酸離子。如 果所施用之電流夠大，產物酸會在陽極周圍沈澱。另外的 方法是將酸取代溶劑或熱加在另一電極附近以沈澱該產物 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -------------------**丨訂---------- (請先閱讀臂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 -28- A7 B7 1249521 五、發明說明（26) 酸，同時於較弱的電場下，將鹼離子分離以減少鹼化合物 的包含。電極以目前常用方法來分開以減少圍繞於其他電 極之離子的干擾。此電解法類似目前已熟知的金屬元素電 解製造法，但此項發明並不局限於任一特定方法。所使用 之電流量並無特別的限制，其取決於理想的產率及欲分離 該離子的電場。電極將使用一不會與離子反應並且不會溶 入溶液中而污染產物的材料，或能將鹼陽離子沈積於電極 上的材料。較佳的鹼萃取溶劑為甲醇、乙醇、烯烴基二醇、 或這些溶劑的混合物。 該回收的產物結晶可使用目前常用的方法分離，且該 過濾餅可使用鹼萃取溶劑、酸取代溶劑，或以任何混合比 例的溶劑混合物來洗滌。若使用下列步驟，則有些回收產 物可以不需分離而直接處理。 習知技術只以洗滌方式除去殘留鹼化合物或使鹽轉化 為產物，而其不足以將鹼化合物除至理想程度。該終產物 含有相當高殘餘鹼化合物的原因為，已洗滌之餅含有太多 的鹼化合物、該產物回收時未自結晶中萃取殘留鹼化合 物、該含有太高鹼化合物之純化溶液直接用於熱解、該鹼 化合物迴流至熱解溶液中、或以洗滌溶液為酸取代溶劑而 殘留未轉換鹽於產物中等。 另一方面，本項發明儘可能將鹽中的多餘鹼化合物移 除，並自回收產物中萃取該殘留化合物以減少該殘留的鹼 化合物。然而，因為鹼化合物是鹽的一個成分，所以無法 於回收產物時完全避免接觸鹼。因此，此效用只能減少但 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ---------*----------丨訂--------- (請先閱讀嘴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 -29- 經濟部智慧財產局員工消費合作社印製 1249521 A7 B7 五、發明說明（27) 無法完全自回收產物中除去殘留驗化合物。前面所述的除 鹼步驟可以部份不做，但會增加產物中殘留鹼化合物的 量。因為移除殘留鹼化合物是很難的方法。所以較佳是降 低回收產物中的鹼化合物。 本項發明提供下列用於自該回收產物中除去殘留鹼化 合物的新方法，以製造一能適於製造聚酯的產物。該新方 法包括瀝濾、汽提、以電磁波熱攪動、蒸發與熱解、或以 上程序的組合。 該回收產物能以與鹼萃取溶劑混合，於預定的量及時 間内瀝濾，且再過濾一次或多次。以瀝濾或汽提過濾餅内 殘留溶劑的方法已廣為人知，而本項發明並不局限於任一 特定方法。但瀝濾或汽提僅能除去那些被吸附或截留的一 部分鹼化合物，而無法除去那包含於晶體内的鹼化合物。 電磁波熱攪動將電磁波施於回收產物或其與鹼萃取溶 劑的混合物中。此法類似於電磁波熱解鹽的方法，其重點 則是在除去包含於回收產物裡的殘留鹼化合物。電磁波能 被殘留的鹼化合物及溶劑吸收以引起熱攪動而發熱，然後 使吸附在表面或包含於晶體内的鹼離子及溶劑從晶體内分 離出來。該分解的驗化合物和其他溶劑則以氣體、液體吸 附、或以晶體週圍的鹼萃取溶劑瀝濾分離。鹼萃取溶劑可 於一預定期間或次數下，連續或分批次地加入過濾餅以協 助殘留鹽的分解。此方法能除去殘留鹼化合物且能同時乾 燥該產物結晶。 ---------丨 h 丨 ---丨！ U 丨訂----— — — — — — (請先閱讀臂面之注意事項再填寫本頁}This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -24-1249521 A7 B7 I, invention description (22) The test compound can be replaced by another high-spot test compound, so _ Alkali salts or common salts can be converted to carbonyl base salts. Therefore, we can prepare it with a more economical base compound and convert it to another salt to obtain a more economical product method. The salt to be converted is mixed with the replacement base in the presence or absence of a solvent. The substituted base compound and/or lysing agent is then removed from the solution by conventional means of separating the solution, such as evaporation or steaming, in a conventional heating or electromagnetic wave manner. The substituted salt can be precipitated by cooling in the presence or absence of an alkali extraction solvent or by direct alkali extraction from a salt. A solvent, such as water, can be used to dissolve the unconverted salt and then recovered, or continue to switch over a series of steps. In the presence of another base compound, the salt base substitution also includes altering the crystals of the salt, such as shape or size. The amount of the substituted base compound may range from 0.1 to 100 moles per mole of carboxyl functional group, preferably from 1 to 10 moles. The filter cake can be washed by salt-exchange of an alkali extraction solvent or by replacing the solvent with an acid. This can be seen as a combined step of washing with the next acid substitution, which is also the method used by Lee. However, the washing process has a relatively small degree of control over the conversion of the salt and the nature of the product. The invention contemplates precipitating the product prior to filtration and during crystallization, or separating the precipitate by salt formation. The salt will be converted in the next step because of the conversion of the salt from the recovery. The extraction of impurities and base compounds in the product, as well as the size of the product particles, is preferred for control. For some base salts, the size of the salt particles affects the size of the product particles, and the size of the salt particles can be controlled by spray drying, conditioning, residence time, temperature, agitation, or the like. Therefore, 'the method of removing impurities includes pre-solution treatment, cooling crystallization, and the paper size is applicable to China National Standards (CNS) A4 specifications (210 X 297 public meals). (Please read the notes on the arm surface before filling in this page) Order --------- Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing -25- 1249521 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (23) solution composition control and cooling crystallization, a crystalline salt in the presence of an extraction solvent, a precipitated product in the presence of an alkali extraction solvent, a direct extraction crystallization from a salt, a regenerated salt crystallization, an alkali salt substitution, an alkali extraction solvent wash, an alkali extraction solvent leaching, or all of the above methods May be combined. In addition to removing impurities from the crude acid or its derivatives, this step also removes excess base compound from the filter cake to reduce the alkali compound content of the final product obtained by the following procedure. The manufacture of the purified product also removes residual ruthenium compound. The purpose of this step is to remove the residual base compound from the salt recovery product if the amount of salt is sufficient, from the salt recovery product, and/or before the final product is produced. Methods for recovering products from the salts include acid substitution, pyrolysis, or electrolysis. The product is preferably recovered in the presence of an alkali extraction solvent. The composition and temperature of the solution will affect the shape and size of the product particles, and these factors should be combined with the extraction of alkali and impurities for optimum conditions. Acid Substitution In order to convert the salt to a product, an acid-substituted solvent is added to replace and precipitate the product acid. The salt can be mixed with the extraction solvent. Preferably, the ether base salt or the general salt is completely dissolved before the addition of the acid-substituted solvent, and the preferred solvent is water, methanol, ethanol, an alkene-based diol, or a mixture thereof. Several salts are insoluble in most solvents, and water is the preferred acid to replace the solvent. Preferably, the water is added in the presence of an extraction solvent such as methanol, ethanol, acetone, tetrahydropyran, or tetrahydropyran. Acid substitution can be operated under electromagnetic waves. The acid substitution with an alkali extraction solvent can reduce the inclusion of residual alkali compounds and impurities in the recovered product. This paper size applies to the Chinese National Standard (CNS) A4 specification (21〇X 297 mm) -26- „ ------- t --------- (Please read the arm face first) Fill in this page again) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 1249521 A7 ^ B7 V. Description of invention (24) The acid-substituted solvent may be an aliphatic carboxylic acid, a mineral acid, water, etc. The aliphatic carboxylic acid may be formic acid. Acetic acid, propionic acid, butyric acid, hydroxyacetic acid, lactic acid, malic acid, tartaric acid, tartrate, citric acid, monochloroacetic acid, monomethyl acetic acid, mononitro acid, trifluoroacetic acid, and trichloroacetic acid; The inorganic acid may be nitric acid, hydrochloric acid, hydrogen bromide, hydrogen iodide, sulfuric acid, phosphoric acid, and perchloric acid. As discussed above, the water or alkali extraction solvent may be an acid-substituted solvent of a carbonyl base salt. It is a mixture of the above-mentioned acids in any ratio, or a mixture of acids having a ratio of a solvent or an alkali extraction solvent, the ratio of the acid being more than 1% by weight. The preferred acid for ether salt or normal salt The substitution solvent is an aliphatic carboxylic acid, and is preferably acetic acid. Preferably, the amount of the acid-substituted solvent is the number of moles per 莫 5-1 每 per mole of the carboxy-functional group in the aromatic polycarboxylic acid. The usual amount is a little more than the molar number of the functional group. The antipyretic can be added to the salt in the range of 50-350 ° C to thermally decompose the base compound. The salt can be mixed with an alkali extraction solvent having a desired boiling point, and the boiling point can be pressure-regulated. The preferred alkali extract compound is water, Vapor, or alcohol. Heat can be added by thermal transfer, such as heat transfer, or directly in contact with the heat medium. In addition to the above conventional heating method, the salt can also be thermally decomposed under electromagnetic waves. The preferred method is to combine the salt with An alkali extraction solvent, such as water, steam, or alcohol, is mixed in any ratio, which dissolves or acid-substitutes the salt, and absorbs electromagnetic waves to assist decomposition. The electromagnetic wave thermally agitates these molecules and crystallizes them from products that cannot absorb electromagnetic waves. Separation, the solution is thus decomposed into the paper size applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -27------------------- *----- (Please read the note on the arm first) Matters refill this page) A7 1249521 —___B7 V. INSTRUCTIONS (25) Mixture of converted product and unconverted salt. Maintaining a suitable solvent concentration and temperature allows the solution to be continuously decomposed by electromagnetic waves. It may also be added to the mixture in a series of steps for further decomposition. The unconverted salt may also be separated from the recovered product by dissolving in a dissolving agent, and the filtrate, liquid system may be recycled or further in a series of steps, by electromagnetic waves. The solution is pyrolyzed. Therefore, this method can be used in batch or continuous mode. Compared with the conventional method, electromagnetic wave pyrolysis uses less energy and processing time. For example, compared with the conventional method requiring 2-12 hours, this method Just 0.04-0.6 hours. In addition, the addition of thermal energy from the inside out can reduce the chances of inclusion of the test compound in the recovered crystal. The decomposed test compound is preferably separated from the recovered product by a usual method such as evaporation, vacuum suction, distillation, absorption by an absorbent, or transported by an inert gas, a vapor, or a solvent. For the carbonyl alkali salt, it is preferred to use a water or a vapor as a base to extract the solvent, and it is preferred to use a direct contact with steam for pyrolysis, because it can simultaneously pyrolyze and acid replace the salt. In this case, the product particle size will be determined by the salt particle size that is easier to control. In addition, pyrolysis and evaporation of residual salts and solvents with hydrazine-based diols as solvents will avoid the use of filtration, drying and gas handling steps, as discussed later. Electrolysis The current is passed to a solution formed by dissolving the purified salt in an alkali extraction solvent such that the cathode will attract alkali ions and the anode will attract acid ions. If the applied current is large enough, the product acid will precipitate around the anode. Another method is to add an acid-substituted solvent or heat to another electrode to precipitate the product. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ----------- -------- ** - - - - 请 请 请 请 请 请 请 请 请 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 B7 1249521 V. INSTRUCTIONS (26) Acids, while under a weak electric field, separate alkali ions to reduce the inclusion of alkali compounds. The electrodes are separated by conventional methods to reduce interference with ions surrounding other electrodes. This electrolysis method is similar to the metal element electrolysis manufacturing method which is well known at present, but the invention is not limited to any particular method. The amount of current used is not particularly limited depending on the desired yield and the electric field at which the ions are to be separated. The electrode will use a material that will not react with the ions and will not dissolve in the solution to contaminate the product, or a material that will deposit an alkali cation on the electrode. Preferred base extraction solvents are methanol, ethanol, alkene based glycols, or mixtures of these solvents. The recovered product crystals can be isolated by a conventional method, and the filter cake can be washed with an alkali extraction solvent, an acid-substituted solvent, or a solvent mixture of any mixing ratio. If the following steps are used, some of the recovered products can be disposed of directly without separation. Conventional techniques only remove residual base compounds or convert salts into products by washing, which is insufficient to remove the base compound to a desired degree. The final product contains a relatively high residual alkali compound because the washed cake contains too much alkali compound, the product is not extracted from the crystallized residual alkali compound, and the purified solution containing the too high base compound is directly used for heat. The solution is refluxed into the pyrolysis solution, or the washing solution is replaced by an acid to leave the unconverted salt in the product. On the other hand, the present invention removes as much as possible the excess alkali compound in the salt and extracts the residual compound from the recovered product to reduce the residual alkali compound. However, since the alkali compound is a component of the salt, it is impossible to completely avoid contact with the alkali when recovering the product. Therefore, this utility can only be reduced, but the paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ---------*----------丨-------- (Please read the precautions of the mouth and then fill out this page) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing -29- Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 1249521 A7 B7 V. DESCRIPTION OF THE INVENTION (27) Residual test compounds cannot be completely removed from the recovered product. The alkali removal step described above may be partially omitted, but will increase the amount of residual alkali compound in the product. Because removing residual alkali compounds is a difficult method. Therefore, it is preferred to reduce the alkali compound in the recovered product. The present invention provides the following novel process for removing residual base compounds from the recovered product to produce a product which is suitable for the manufacture of polyesters. The new method includes leaching, stripping, electromagnetic wave agitation, evaporation and pyrolysis, or a combination of the above. The recovered product can be mixed with an alkali extraction solvent, leached in a predetermined amount of time, and filtered one or more times. The method of leaching or stripping the residual solvent in the cake is well known, and the present invention is not limited to any particular method. However, leaching or stripping only removes a portion of the base compound that is adsorbed or trapped, and does not remove the alkali compound contained in the crystal. Electromagnetic wave thermal agitation applies electromagnetic waves to the recovered product or its mixture with an alkali extraction solvent. This method is similar to the method of electromagnetic wave pyrolysis of salt, and the focus is on the removal of residual alkali compounds contained in the recovered product. The electromagnetic wave energy is absorbed by the residual alkali compound and the solvent to cause heat agitation to generate heat, and then the alkali ions and the solvent adsorbed on the surface or contained in the crystal are separated from the crystal. The decomposed test compound and other solvents are separated by gas, liquid adsorption, or leaching with an alkali extraction solvent around the crystal. The alkali extraction solvent may be added to the filter cake continuously or in batches for a predetermined period or number of times to assist in the decomposition of the residual salt. This method removes residual alkali compounds and simultaneously crystallizes the product. ---------丨 h 丨 ---丨! U ------------ (Please read the notes on the arm first and then fill out this page}

A7 1249521 ---------- 五、發明說明（28 ) 蒸發與熱解可蒸發殘留溶劑，如水或醋酸，並於50-350 °c，較佳是90-210 °C，熱解解殘留鹼化合物。該回收產 物係與一單聚物（monomer)，諸如烯烴基二醇混合、與一 由產物酸與該單聚物反應而得之募聚物（oligimer )混合， 該寡聚物具有一 1-100基本單元之鍵的大小、或與驗萃取 溶劑（如昇溫的水）混合。烯烴基二醇或寡聚物的高沸點係 可用以熱解殘留鹽並自溶液中蒸發殘餘溶劑。除此之外， 烯烴基二醇為聚合聚酯的構造份子，該溶液或過濾餅能直 接用以生產聚酯。此不需要乾燥及氣體輸送的步驟程序。 如果聚酯設備不與純化設備合併，則此方法可在任一處執 行。較佳係使用熱轉移或電磁波熱擾動來加熱以避免引入 其他成分。所蒸發的殘留溶劑則以真空吸取或其他適當方 法移除。該烯烴基二醇的佳量為聚合時所需的量，以使得 該處理後的溶液能直接用以製造聚酯。此步驟亦可應用於 現有的方法以避免藉該預乾燥之終產物與烴基二醇混合之 乾燥及氣體輸送的步驟程序。此法所處理的溶液異於上述 產物回收的熱解溶液，因其含相當量的驗化合物和其他溶 劑，所以不適用以製造聚酯。 用於產物回收、洗濯、瀝滤、汽提、電磁波熱撥動、 或蒸發與熱解的驗萃取溶劑不一定是同一種類。驗萃取溶 劑的用量並無特別的限制，通常是每莫耳之羧官能基的 0.5-1000莫耳數。 若不使用烯烴基二醇來蒸發與熱解來移除殘留的驗化 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -------------------^丨訂 --------- (請先閱讀臂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 31- 1249521 A7A7 1249521 ---------- V. Description of the invention (28) Evaporation and pyrolysis can evaporate residual solvents, such as water or acetic acid, at 50-350 ° C, preferably 90-210 ° C, heat The residual base compound is decomposed. The recovered product is mixed with a monomer such as an olefin-based diol, and mixed with an oligimer obtained by reacting a product acid with the monomer, the oligomer having a 1- The size of the key of the 100 base unit, or mixed with an extraction solvent such as warmed water. The high boiling point of the olefinic diol or oligomer can be used to pyrolyze the residual salt and evaporate residual solvent from the solution. In addition to this, the olefin-based diol is a constituent of the polymeric polyester which can be used directly to produce the polyester. This step procedure does not require drying and gas delivery. If the polyester equipment is not combined with the purification equipment, this method can be performed at any point. It is preferred to use heat transfer or electromagnetic wave thermal disturbance to heat to avoid introduction of other components. The evaporated residual solvent is removed by vacuum suction or other suitable method. The preferred amount of the olefin-based diol is the amount required for the polymerization so that the treated solution can be directly used to produce a polyester. This step can also be applied to existing processes to avoid the step of drying and gas transport by mixing the pre-dried final product with the hydrocarbyl glycol. The solution treated by this method is different from the pyrolysis solution recovered from the above product, and since it contains a considerable amount of the test compound and other solvents, it is not suitable for the production of polyester. The solvent used for product recovery, washing, leaching, stripping, electromagnetic hot-swapping, or evaporation and pyrolysis is not necessarily the same type. The amount of the extraction solvent to be used is not particularly limited and is usually 0.5 to 1000 moles per gram of the carboxyl functional group. If the olefin-based diol is not used for evaporation and pyrolysis to remove the residual test paper, the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ------------ -------^丨定--------- (Please read the notes on the arm face and then fill out this page) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 31- 1249521 A7

經濟部智慧財產局員工消費合作社印製 五、發明說明（29) 合物（假若其是需要的話），該純化的產物係可使用目前方 法中之以流動之惰性氣體來乾燥以除去殘留溶液。而另外 的方法是使用前述的電磁波來乾燥。 溶劑萃取的純化方法可於空氣、蒸氣、惰性氣體（如 氮、氬、氦）、或還原氣體（如氫或分子量較低的烴氣體） 下操作。這個方法可用於分批、半分批、或連績的方法裡。 迴流能改善產物回收和溶劑使用效率。例如，滤液可 以迴流至前一步驟或用以洗滌或瀝濾，以減少溶劑需求並 改善產物回收。迴流的濾液可以處理或不處理。該濾、液可 以任何適當的方法處理，如蒸餾、過濾、離心、沈殿、蒸 發、冷卻、加多溶劑、或以上的任何組合。迴流以改良效 率的方法已廣為人知’本項發明並不局限於任一特定方 法。 由以上提供的純化方法所得的產物純度很意外並驚對 地發現以目前標準HPLC測量方法竟無法測出雜質。與 先前技術的產物純度比較，約純一百倍。將產物高溫烘烤 之顏色亦能達到目前的標準，其係暗示該鹼化合物應已除 至一可以接受的程度。低雜質的PTA提供許多優點：聚 合時的大分子量、更強更細的纖維、低保特瓶的氧滲透、 增加紡紗轉速以生產纖維、及許多尚未發現的優點。 生^豪高纯度芳香聚羧酸或其衍生物之輕佬方法的搞速 上述之純化方法與習知技術之氧化和溶劑及催化劑回 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------- 訂'-------- (請先閱讀臂面之注意事項再填寫本頁) •32- 經濟部智慧財產局員工消費合作社印製 1249521 A7 B7 發明說明< :31 ) 4) 該純化方法可以不需要結晶器來結晶。 5) 該純化方法藉使用婦烴基二醇來蒸發與熱解， 以避免乾燥及氣體輸送的步驟程序。 6) 該純化方法使用物理分離方法而不是化學反應 方法來除去雜質，因此純化的投資及生產成本 均較低。 7) 該純化方法能生產出比目前方法純度更高的產 物。此提供很多如前所述之潛在優點。 本項發明發揮這些相互增效的優點和不明顯的特徵， 以提供一套前所未建議的結合，其實質上僅需較低投資及 生產成本。該結合包括氧化、溶解粗酸、從純化鹽中除去 雜質及驗化合物、於自鹽回收產物時亦同時除去殘留鹼化 合物、以及回收溶劑及催化劑。此製程的步驟程序描述如 下： 氧化反應 這個步驟透過將具有氧分子之對應的烷基氧化而生產 芳香聚羧酸。此芳香聚羧酸的氧化已於過去50年被廣泛 地研究，本項發明可使用任何先前的方法，而不局限於任 一特定方法。 中世紀公司所發展的方法係為一廣泛適用的氧化方 法’其以醋酸為溶劑來協助淤漿的混合和循環；以重金屬， 如始和錳，為催化劑；以含溴的化合物為促進劑。反應條 件通常是在175-230 °C和1500-3000 kPa的範圍内。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -34- ϋ H ϋ .1 ϋ ϋ ϋ · 1 n i-i i-i L. ϋ 一 φν i ϋ I ϋ I — (請先閱讀脅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 1249521 A7 __B7 _ 五、發明說明（32 ) 該饋送包括迴流物，其含催化劑、反應器溶劑、或自 溶解一鹽之步驟而來之中間產物，該鹽係於溶解劑中由粗 酸與驗化合物所形成、自純化鹽中除去雜質及驗化合物、 及溶劑及催化劑回收等步驟程序。 落解粗酸或衍生物 將粗芳香聚羧酸或其衍生物溶解於鹼化合物中已被描 述。先前也曾提到，該純化方法能以源自主要製程之反應 器流出物或CTA為一粗酸。因此，在這二種極端間有許 多選擇以製備粗酸。例如，若以源自急驟蒸發之反應器流 出物之游漿為粗酸，則反應器溶劑及催化劑將隨雜質一齊 出現於濾液中’其而後在溶劑及催化劑的回收步驟中被回 收。其他選擇是將習知技術所教示的方法，將反應器的溶 劑及催化劑自粗酸中分離出，而習知技術所教示之方法諸 如急驟蒸發、蒸發、加熱/冷卻、結晶、過濾、離心澄清 器、蒸餾、分類塔、水力旋風器、旋風分離器、沈降、以 水取代母液、薄膜滲透、或目前製造CTA的任一中間步 驟。該分離的母液可迴流至反應器或送到溶劑及催化劑回 收的步驟程序。本項發明並不局限於任一特定方法來分離 反應器流出物。但較佳的分離方法是蒸發該急驟蒸發反應 器流出物内的大部分母液，並迴流一小部分自酸分離之含 催化劑的母液。蒸發可或不於電磁波下使用。這個方法能 在不使用結晶方式下，從反應器流出物中回收大部分的粗 酸0 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀臂面之注意事項再填寫本頁} 訂··-------- 1249521 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（33 ) 粗酸的另外可能來源是來自處理或未處理過的迴流遽 液，或從溶劑及催化劑回收的步驟程序而來。 除去雜質和多餘的鹼化合物 月’J面已經描述如何除去雜質。如前所述，控制成分以 冷卻結晶能減少所需結晶器的數目，自鹽直接萃取的結晶 方法則能夠完全避免使用結晶器。 處理或未處理過的濾液可迴流至其他步驟程序，或送 至丨谷劑及催化劑回收的步驟程序。部份雜質必須從這個步 驟程序分開以避免繼續累積，而這可以任何合適的方法進 行。其中一例為自一包含大量雜質之所選擇之濾液蒸發溶 劑，其底部殘留物則迴流至反應器，或以產物回收的方法， 在迴流之前，將雜質鹽轉回成雜質。 於製造純化產物時亦同時除去殘留驗化合物 前面已描述過這個步驟。若使用烯烴基二醇以蒸發及 熱解來除去殘㈣化合物，則目前的乾燥或氣體輸送步驟 程序可不需要。 與從前製程PTA方法所得之粒子大小比較，以酸取 代方法所回收的產物顆粒一般較小，但較均勻。若以烯烴 基二醇來除去殘留鹼化合物，則處理後的混合物能直接用 於製造PET。然而，如有必要的話，重新溶解及再結晶則 能重新調1 PTA的鬆密度。此可藉由目前已存在之製造 設備的多種方法來達成。該再結晶後的ρτΑ鬆密度不僅 -------- -------- (請先閱讀臂面之注意事項再填寫本頁)Printed by the Intellectual Property Office of the Ministry of Economic Affairs, Employees' Cooperatives. V. Inventive Note (29) Compound (if it is needed), the purified product can be dried using a flowing inert gas in the current method to remove the residual solution. Another method is to use the aforementioned electromagnetic waves to dry. The solvent extraction purification method can be operated under air, steam, an inert gas (e.g., nitrogen, argon, helium), or a reducing gas (e.g., hydrogen or a lower molecular weight hydrocarbon gas). This method can be used in batch, semi-batch, or consecutive methods. Reflow improves product recovery and solvent use efficiency. For example, the filtrate can be refluxed to the previous step or used for washing or leaching to reduce solvent requirements and improve product recovery. The refluxed filtrate can be treated or not. The filtrate and liquid may be treated by any suitable means such as distillation, filtration, centrifugation, immersion, evaporation, cooling, addition of a solvent, or any combination of the above. The method of refluxing to improve efficiency is well known. The present invention is not limited to any particular method. The purity of the product obtained by the purification method provided above was unexpected and it was surprisingly found that impurities could not be detected by the current standard HPLC measurement method. Compared to the purity of the prior art product, it is about one hundred times pure. The color of the product baked at a high temperature can also meet current standards, which implies that the base compound should have been removed to an acceptable level. Low impurity PTA offers a number of advantages: large molecular weight during polymerization, stronger and finer fibers, oxygen permeation of low-wet bottles, increased spinning speed to produce fibers, and many undiscovered advantages. The method of purifying the high-purity aromatic polycarboxylic acid or its derivative is the above-mentioned purification method and the conventional technology of oxidation and solvent and the catalyst paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X). 297 mm) --------- Order '-------- (please read the note on the arm first and then fill out this page) • 32- Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative 1249521 A7 B7 Description of Invention < :31 ) 4) The purification method can be performed without a crystallizer. 5) The purification method uses a glyco-diol to evaporate and pyrolyze to avoid drying and gas transport steps. 6) The purification method uses physical separation methods instead of chemical reaction methods to remove impurities, so the investment and production costs of purification are low. 7) This purification method produces a product that is more pure than current methods. This provides a number of potential advantages as previously described. The present invention exploits these synergistic and non-obvious features to provide a previously unrecognized combination that requires substantially less investment and production costs. The combination includes oxidation, dissolution of the crude acid, removal of impurities and purification of the compound from the purified salt, simultaneous removal of the residual base compound upon recovery of the product from the salt, and recovery of the solvent and catalyst. The procedure of this process is described as follows: Oxidation reaction This step produces an aromatic polycarboxylic acid by oxidizing the corresponding alkyl group having an oxygen molecule. The oxidation of this aromatic polycarboxylic acid has been extensively studied over the past 50 years, and any prior methods can be used in the present invention without being limited to any particular method. The method developed by the Medieval Company is a widely applicable oxidation method which uses acetic acid as a solvent to assist in the mixing and circulation of the slurry; heavy metals such as virgin and manganese as catalysts; and bromine-containing compounds as promoters. The reaction conditions are usually in the range of 175 to 230 ° C and 1500 to 3000 kPa. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -34- ϋ H ϋ .1 ϋ ϋ ϋ · 1 n ii ii L. ϋ φν i ϋ I ϋ I — (Read first Precautions for the threat surface Please fill out this page) Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed 1249521 A7 __B7 _ V. Invention Description (32) The feed includes a reflux containing catalyst, reactor solvent, or self-dissolving salt The intermediate product is a step of a step of forming a solvent from a crude acid and a test compound, removing impurities and a compound from the purified salt, and recovering the solvent and the catalyst. The crude acid or derivative is dissolved. The dissolution of the crude aromatic polycarboxylic acid or its derivative in the alkali compound has been described. It has also previously been mentioned that the purification process can be a crude acid from the reactor effluent or CTA derived from the main process. Therefore, there are many options between these two extremes to prepare crude acid. For example, if the slurry from the reactor effluent from the flash evaporation is a crude acid, the reactor solvent and catalyst will appear in the filtrate along with the impurities' which are then recovered in the solvent and catalyst recovery steps. Other options are the methods taught by the prior art to separate the solvent and catalyst of the reactor from the crude acid, as taught by conventional techniques such as flash evaporation, evaporation, heating/cooling, crystallization, filtration, centrifugation clarification. , distillation, sorting column, hydrocyclone, cyclone, settling, replacing mother liquor with water, membrane permeation, or any intermediate step in the current manufacture of CTA. The separated mother liquor can be returned to the reactor or sent to the solvent and catalyst recovery steps. The invention is not limited to any particular method for separating reactor effluent. However, a preferred method of separation is to evaporate most of the mother liquor in the flash evaporative reactor effluent and reflux a small portion of the catalyst-containing mother liquor separated from the acid. Evaporation may or may not be used under electromagnetic waves. This method can recover most of the crude acid from the reactor effluent without using crystallization. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the attention of the arm surface first) Matters fill out this page} Order··-------- 1249521 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Printing V. Invention Notes (33) Another possible source of crude acid is from treated or untreated The reflux sputum, or the procedure from the solvent and catalyst recovery procedures. Removal of impurities and excess alkali compounds has been described how to remove impurities. As mentioned earlier, controlling the components to cool the crystallization can reduce the required crystallizer The number of crystallization methods that are directly extracted from salt can completely avoid the use of crystallizers. The treated or untreated filtrate can be returned to other procedures or sent to the threshing agent and catalyst recovery steps. This step is programmed to avoid further accumulation, and this can be done by any suitable method. One of the examples is to evaporate the solvent from a selected filtrate containing a large amount of impurities. The bottom residue is refluxed to the reactor, or the product is recovered, and the impurity salt is returned to the impurity before the reflux. The residue is also removed during the manufacture of the purified product. This step has been described previously. The olefin-based diol is removed by evaporation and pyrolysis to remove the residual (IV) compound, so the current drying or gas transport step procedure may not be required. The product particles recovered by the acid substitution method are generally smaller compared to the particle size obtained from the prior process PTA process. However, it is more uniform. If the residual alkali compound is removed by the olefin-based diol, the treated mixture can be directly used for the manufacture of PET. However, if necessary, the redissolution and recrystallization can re-adjust the bulk density of PTA. This can be achieved by a variety of methods of existing manufacturing equipment. The re-crystallized ρτΑ bulk density is not only -------- -------- (please read the attention of the arm surface first) Please fill out this page again)

本紙張尺度_巾關家標準（CNS)A4規格（210 X 297公髮 -36- 1249521 A7 B7 五、發明說明（34) 會與目前市售的PTA —樣，而且純度更高而包含更少的 雜質。 (請先閱讀臂面之注意事項再填寫本頁) 溶劑及催化劑回收 除了使用目前已知方法來回收反應器溶劑、水、催化 劑外，這個步驟程序也回收鹼化合物、鹼萃取溶劑、酸取 代溶劑（如果它被用以回收產物且不同於反應器溶劑）、 和溶解劑（如果其可被使用且不同於水）。另外，從一些 純化步驟程序的直接迴流濾液可能也含有殘餘雜質和產 物0 並非所有成分皆必須回收至其等之純化形式。某些成 分能以混合物回收。例如，於溶解粗酸的步驟中，可使用 鹼化合物和溶解劑的混合物。再者，如果該混合物包含一 些酸取代溶劑，其對純化效率也並無明顯的影響。 經濟部智慧財產局員工消費合作社印製 於所有溶劑中，某些溶劑可能形成共沸混合物。如果 以酸取代法來回收產物，則驗化合物和酸取代溶劑可能會 形成電解質。然而，用於分離這些成分的方法已廣為人知， 如蒸餾、過濾、離心、沈殿、蒸發、熱解、冷卻、薄膜滲 透、以更強的鹼來取代、以較更強的酸來取代、加入另一 物質以破壞共沸混合物等。本項發明亦可能使用電磁波於 蒸發、蒸餾、和熱解等。 結論 -37- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1249521 A7This paper size _ towel home standard (CNS) A4 specifications (210 X 297 mil-36- 1249521 A7 B7 five, invention description (34) will be the same as the currently marketed PTA, and the purity is higher and contains less Impurities. (Please read the notes on the arm surface and fill out this page.) Solvent and Catalyst Recovery In addition to using the currently known methods to recover the reactor solvent, water, and catalyst, this step also recovers the alkali compound, the alkali extraction solvent, The acid replaces the solvent (if it is used to recover the product and is different from the reactor solvent), and the solvent (if it can be used and is different from water). In addition, the direct reflux filtrate from some purification step procedures may also contain residual impurities. And not all of the components of product 0 must be recovered to their purified form. Some of the components can be recovered as a mixture. For example, in the step of dissolving the crude acid, a mixture of an alkali compound and a solvent can be used. Contains some acid-substituted solvents, which have no significant effect on purification efficiency. Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, printed in all solvents Some solvents may form an azeotrope. If the product is recovered by acid substitution, the test compound and the acid-substituted solvent may form an electrolyte. However, methods for separating these components are well known, such as distillation, filtration, centrifugation, Sedimentation, evaporation, pyrolysis, cooling, membrane permeation, substitution with a stronger base, substitution with a stronger acid, addition of another substance to destroy the azeotrope, etc. The invention may also use electromagnetic waves for evaporation, Distillation, pyrolysis, etc. Conclusion -37- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1249521 A7

五、發明說明（36) 代，如甲基等。 (請先閱讀臂面之注意事項再填寫本頁) 因此，本項發明的範圍應以附錄中的申請權利範圍及 其法律相等物來決定，而不是由所敘述的具體實施例來決 定。以下將舉例說明本項發明。 參考範例 表1所示為使用於實驗中之PTA製程所生產的對苯 二酸（CTA)雜質含量： 表1 4-CBA 苯甲酸 對甲苯酸 PTA(ppmw) 2436 1097 515 其中ppmw表示重量的百萬分之一。 比較性實施例1 表2所示為將與表1具有相同組成之ctA以習知技 藝所述之傳統的氫化反應純化方法，以獲得一具有如表2 所示之雜質含量的PTA產物： 表2 4-CBA 苯甲酸 對甲苯酸 PTA(ppmw) 15 無法測得 141 經濟部智慧財產局員工消費合作社印製 同樣地，表3所示為由其他來源所得之PTA產物之 雜質含量： 表3 4-CBA 苯甲酸 對甲苯酸 PTA(ppmw) 25 52 150 該純化產物之雜質含量係顯示典型商用之聚合等級之 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1249521 經濟部智慧財產局員工消費合作社印製 A7 Β7 五、發明說明（37) 對苯二酸。 比較性實施例2 (除去雜質但未除去鹼化合物） 將150克表1所述之〇：丁人樣品與198克的對氧氮己 環及180克的水混合。將該溶液加熱至1〇〇 〇c使CTA完 全溶解，隨之冷卻至室溫使之沈澱。過濾淤漿使與母液分 離，而後以對氧氮己環洗滌過濾餅以獲得一 196克的濕 餅。然後將該回收之固體與84克的水和22克的對氧氮己 環混合。將該溶液溫度升至110°c以蒸發57c c的冷凝物， 然後將該溶液冷卻至室溫使之沈澱。而後，以對氧氮己環 洗滌過濾、餅以獲得145克的純鹽。然後，將該鹽與235克 的醋酸和14克的水混合使PTA沈澱。然後以約6〇〇克的 水洗滌過滤餅。然後濕餅在烤箱中以約275 °C乾燥4小 時，以獲得40克之乾的已純化PTA。表4為HpLC分析 雜質的結果。雖然所測的B-值表示餅的顏色為6.5，較標 準值1.6高約4倍。這顯示ρτΑ裡含有過量的對氧氮己 環0 表4 4-CBA 苯甲酸 對甲笨酸 PTA(ppmw) 無法測得 無法測得 無法測得 比較性實施例3 (藉由直接添加醋酸以沈澱產物） 將3克表1所述之CTA樣品在室溫下完全溶於含有 5·〇1〇克之三乙胺及9.047克的甲醇溶液中。然後加入7.57 克的醋酸以沈殿結晶，然後過濾及乾燥以得2· 179克的對 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -------------------^丨訂--------- (請先閱讀臂面之注意事項再填寫本頁) -40- 1249521 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（38) 苯二酸。以HPLC分析顯示該含有如表 5所示之雜質的酸V. Description of invention (36) Generation, such as methyl. (Please read the following information on the arm face and then fill out this page.) Therefore, the scope of the invention should be determined by the scope of the appendices and the legal equivalents thereof in the appendices, rather than the specific embodiments described. The invention will be exemplified below. Reference Example Table 1 shows the terephthalic acid (CTA) impurity content produced by the PTA process used in the experiment: Table 1 4-CBA Benzoic acid p-toluic acid PTA (ppmw) 2436 1097 515 where ppmw represents the weight of 100 One in ten thousand. Comparative Example 1 Table 2 shows a conventional hydrogenation reaction purification method of ctA having the same composition as that of Table 1 by a conventional technique to obtain a PTA product having an impurity content as shown in Table 2: 2 4-CBA benzoic acid p-toluic acid PTA (ppmw) 15 Unmeasured 141 Ministry of Economic Affairs Intellectual Property Bureau employees consumption cooperatives printed the same, Table 3 shows the impurity content of PTA products obtained from other sources: Table 3 4 -CBA benzoic acid p-toluic acid PTA (ppmw) 25 52 150 The impurity content of this purified product shows the typical commercial polymerization grade of this paper scale applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1249521 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A7 Β7 5, invention description (37) terephthalic acid. Comparative Example 2 (Immediate removal of impurities but no removal of alkali compound) 150 g of the sputum sample described in Table 1 was mixed with 198 g of p-oxazide and 180 g of water. The solution was heated to 1 Torr to completely dissolve the CTA, followed by cooling to room temperature to precipitate. The slurry was filtered to separate from the mother liquor, and then the filter cake was washed with a nitrous oxide ring to obtain a 196 g wet cake. The recovered solid was then mixed with 84 grams of water and 22 grams of p-oxazide. The temperature of the solution was raised to 110 ° C to evaporate 57 c c of condensate, and then the solution was cooled to room temperature to precipitate. Thereafter, the cake was filtered with a pad of nitrous oxide to obtain 145 g of a pure salt. Then, the salt was mixed with 235 g of acetic acid and 14 g of water to precipitate PTA. The filter cake was then washed with about 6 grams of water. The wet cake was then dried in an oven at about 275 °C for 4 hours to obtain 40 grams of dried purified PTA. Table 4 shows the results of HpLC analysis of impurities. Although the measured B-value indicates that the color of the cake is 6.5, it is about 4 times higher than the standard value of 1.6. This shows that ρτΑ contains an excess of p-oxocyclopentane. Table 4 4-CBA Benzoic acid vs. benzoic acid PTA (ppmw) Undetectable Unmeasurable Comparative Example 3 (precipitated by direct addition of acetic acid) Product) 3 g of the CTA sample described in Table 1 was completely dissolved in a methanol solution containing 5·〇1 g of triethylamine and 9.047 g of methanol at room temperature. Then add 7.57 grams of acetic acid to crystallize the sap, then filter and dry to obtain 2. 179 grams of the Chinese National Standard (CNS) A4 specification (210 X 297 mm) for this paper scale ---------- ---------^丨定--------- (Please read the note on the arm face and then fill out this page) -40- 1249521 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative System 5, invention description (38) phthalic acid. The acid containing the impurity shown in Table 5 was shown by HPLC analysis.

實施例1 (自瀝據之沈殿物的直接萃取結晶法） 將4〇克表1所述之CTA樣品與52克的對氧氣己環 及48克的水混合。將溶液加熱至u〇〇c以溶解cta並 且蒸發約29 e.e.的冷凝物，隨之冷卻至室溫使之沈殿。 以曱醇洗蘇及Μ過渡餅後得55克的濕餅。該濕餅與3〇 克的甲醇混合’然後加85克的醋酸至溶液中以沈澱對 苯二酸。然後以約35克的甲醇洗滌該濕餅，再以35克的 甲醇瀝濾3次，以得一 31.5克的濕餅。濕餅在烤箱中以 約250 乾燥4小時後得24克的乾餅。該餅的Β值為 2.73，其仍高於標準值’且HPLC分析顯示該含有表6之 雜質的PTA。 表6 4-CBA 苯甲酸 對甲笨酸 PTA(ppmw) 20.8 無法測得 無法測得 實施例2(藉由蒸發與熱解之再鹽化的結晶法） 將925克如表1所述之CTA樣品與11〇3克的對氧氮 己環及1205克的水混合。將溶液加熱至11〇並蒸發約 404 c.c·的冷凝物，且在急速結晶之前停止。隨之將溶液 冷卻至至溫停置4小時以沈殿結晶。加入250克乙醇以稀 釋淤漿，並以750克乙醇洗滌及瀝濾過濾餅後得1455克 本紙張尺&適用中國國家標準（CNS)A4規格（21G X 297公餐)" ' - -------Γ -------- (請先閱讀臂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 1249521 A7 --------______ 五、發明說明（39) 的鹽。取1005克的鹽溶於465克的水。將溶液加熱至1〇9 C，且在蒸發約280c.c的冷凝物後急速結晶。以65〇克 乙醇瀝濾該鹽，且以250克乙醇洗滌過濾餅，以得7〇2克 的純鹽。將3 5克的鹽溶於4〇克的水及40克的乙醇中， 且將60克的醋酸加入溶液中以沈澱該產物結晶。然後以 約200克的水洗滌及瀝濾過濾餅3次後得27·5克的濕餅。 而後與130克的EG混合。該溶液係在常壓下加熱至15〇_ 160 C ’直到沒有任何褐色液體被冷凝且自該溶液分離。 熱液馬上被過濾，以300克水洗滌及瀝濾後得15·4克的 濕餅。將放在一吸附劑上的濕餅於微波爐内以中度功率加 熱20分鐘，隨之在烤箱中以約250 °C乾燥4小時後得11.6 克的乾餅。該餅的B-值為1.58,其符合該標準值，且HPLC 分析顯示該含有表7之雜質的PTA。 表7 4-CBA 苯甲酸 對甲苯酸 PTA(ppmw) 無法測得 無法測得 無法測得 實施例3 (模擬反應器流出物之條件以及瀝濾） 將150克如表1所述之CTA樣品於室溫下溶於一與 急驟蒸發之反應器流出物組成物相似之組成物的溶液中。 該溶液含有202克對氧氮己環、191克水、29克48。/〇氫 漠酸、0.23克録乙脂酸四水化合物、〇·3克鎖醋酸四水化 合物、和60克的醋酸。該溶液溫度加熱至11() 〇c以溶解 CTA並蒸發79 c.c的冷凝液。該溶液隨即被冷卻至室溫 以沈澱，並以甲醇洗滌及瀝濾過濾餅後得278克的濕餅。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ---Γ — ··-------^ 丨訂：-------- (請先閱讀臂面之注意事項再填寫本頁) -42- 1249521 A7 B7 五、發明說明（4〇) (請先閱讀臂面之注意事項再填寫本頁) 該濕餅則與133克的水混合，並將該溶液溫度加熱至110 °C以蒸發88 c.c的冷凝液，且該溶液隨即被冷卻至室溫 以沈澱。該過濾餅以甲醇洗滌及瀝濾後得160克的濕餅。 該濕餅然後與16 0克的甲醇混合’而後加入18 〇克的醋酸 以沈澱對苯二酸。以500克的水洗滌和瀝濾該濕餅，並 以3 5克甲醇瀝滤3次以得12 3克的濕餅®將放在一吸附 劑上的濕餅於微波爐内以中度功率加熱20分鐘，隨之在 烤箱中以約250 °C乾燥4小時後得73克的乾餅。該餅的 B-值為2.22，所有金屬含量均低於指定標準，且HPLC 分析顯示該含有表8之雜質的PTA。 表8 4-CBA 苯甲酸 對甲苯酸 PTA(ppmw) 無法測得 無法測得 無法測得 實施例4 (以電磁波熱解） 經濟部智慧財產局員工消費合作社印製 將10.05克之實施例2的純鹽樣品溶於6克的水中。 將溶液在600瓦微波爐中加熱3分鐘，且該殘留的混合 物含有9.29克的固體。6.27克的水與該固體混合，並於 微波爐中加熱3分鐘以得8.82克的固體。而後，6.66克 的水再與固體混合並加熱3分鐘以得8.49克固體。該固 體再與10.85克的水混合，並於微波爐中加熱4分鐘以 得8.14克的固體。該固體繼續與9.59克的水混並於微波 爐中加熱3分鐘以得7.82克的固體。以上每個步驟中， 重量的減少係來自鹽的分解。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -43-Example 1 (Direct extraction crystallization from Sediment) 4 g of the CTA sample described in Table 1 was mixed with 52 g of oxygen-enhanced ring and 48 g of water. The solution was heated to u〇〇c to dissolve cta and evaporate about 29 e.e. of condensate, which was then cooled to room temperature to allow it to settle. 55 grams of wet cake was obtained after washing the saponin and the transition cake with decyl alcohol. The wet cake was mixed with 3 g of methanol' and then 85 g of acetic acid was added to the solution to precipitate terephthalic acid. The wet cake was then washed with about 35 grams of methanol and leached three times with 35 grams of methanol to give a 31.5 grams of wet cake. The wet cake was dried in an oven at about 250 for 4 hours to give 24 grams of dry cake. The cake had a enthalpy value of 2.73, which was still above the standard value' and HPLC analysis showed the PTA containing the impurities of Table 6. Table 6 4-CBA benzoic acid to benzoic acid PTA (ppmw) 20.8 Undetectable Example 2 (crystallization by re-salting by evaporation and pyrolysis) 925 g of CTA as described in Table 1 The sample was mixed with 11 〇 3 g of p-oxyxene and 1205 g of water. The solution was heated to 11 Torr and about 404 c.c. of condensate was evaporated and stopped before rapid crystallization. The solution was then cooled to a temperature of 4 hours to crystallize the chamber. Add 250 g of ethanol to dilute the slurry, and wash and leaching the cake with 750 g of ethanol to obtain 1455 g of paper tape & Chinese National Standard (CNS) A4 specification (21G X 297 public) " ' - - ------Γ -------- (Please read the notes on the arm face and then fill out this page) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1249521 A7 --------______ 5. Salt of invention (39). 1005 grams of salt was dissolved in 465 grams of water. The solution was heated to 1 〇 9 C and rapidly crystallized after evaporation of about 280 c.c of condensate. The salt was leached with 65 g of ethanol, and the filter cake was washed with 250 g of ethanol to obtain 7 2 g of a pure salt. 35 g of the salt was dissolved in 4 g of water and 40 g of ethanol, and 60 g of acetic acid was added to the solution to precipitate the crystal of the product. Then, the cake was washed and leached with about 200 g of water for 3 times to obtain 27.5 g of a wet cake. It is then mixed with 130 grams of EG. The solution was heated to 15 〇 160 C ' at normal pressure until no brown liquid was condensed and separated from the solution. The hot liquid was immediately filtered, washed with 300 g of water and leached to obtain 15.4 g of a wet cake. The wet cake placed on a sorbent was heated at a moderate power for 20 minutes in a microwave oven, followed by drying at about 250 ° C for 4 hours in an oven to obtain 11.6 grams of dry cake. The cake had a B-value of 1.58, which met the standard value, and HPLC analysis showed the PTA containing the impurities of Table 7. Table 7 4-CBA benzoic acid p-toluic acid PTA (ppmw) Undetectable Undetectable Example 3 (Simulation of reactor effluent conditions and leaching) 150 grams of CTA sample as described in Table 1 was It is dissolved in a solution of a composition similar to the flash evaporating reactor effluent composition at room temperature. The solution contained 202 grams of p-oxonium, 191 grams of water, and 29 grams of 48. /〇 Hydrogen acid, 0.23 g of ethyl sulphate tetrahydrate, 〇·3 g of acetic acid tetrahydrate, and 60 g of acetic acid. The solution was heated to 11 () 〇c to dissolve the CTA and evaporate the condensate of 79 c.c. The solution was then cooled to room temperature to precipitate, and the cake was filtered with methanol and leached to give 278 g of wet cake. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) ---Γ — ··-------^ ::-------- (Please read the arm first Note: Please fill out this page again) -42- 1249521 A7 B7 V. Inventive Note (4〇) (Please read the note on the arm surface and then fill out this page) The wet cake is mixed with 133 grams of water and will The solution was heated to 110 ° C to evaporate 88 cc of condensate, and the solution was then cooled to room temperature to precipitate. The filter cake was washed with methanol and leached to give a 160 g wet cake. The wet cake was then mixed with 160 grams of methanol' and then 18 grams of acetic acid was added to precipitate terephthalic acid. The wet cake was washed and leached with 500 grams of water and leached 3 times with 35 grams of methanol to give 12 3 grams of wet cake®. The wet cake placed on a sorbent was heated in a microwave oven at moderate power. After 20 minutes, it was dried in an oven at about 250 ° C for 4 hours to obtain 73 grams of dry cake. The cake had a B-value of 2.22, all metal contents were below the specified standards, and HPLC analysis showed the PTA containing the impurities of Table 8. Table 8 4-CBA benzoic acid p-toluic acid PTA (ppmw) can not be measured undetectable Example 4 (with electromagnetic wave pyrolysis) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 10.05 grams of Example 2 pure The salt sample was dissolved in 6 grams of water. The solution was heated in a 600 watt microwave oven for 3 minutes and the residual mixture contained 9.29 grams of solids. 6.27 grams of water was mixed with the solid and heated in a microwave oven for 3 minutes to give 8.82 grams of solids. Thereafter, 6.66 g of water was mixed with the solid and heated for 3 minutes to obtain 8.49 g of a solid. The solid was mixed with 10.85 grams of water and heated in a microwave for 4 minutes to give 8.14 grams of solids. The solid was then mixed with 9.59 grams of water and heated in a microwave oven for 3 minutes to give 7.82 grams of solid. In each of the above steps, the reduction in weight is due to the decomposition of the salt. This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -43-

Claims (1)

1249521 公告本j丨 申5青專利範圍 修正 經濟部智慧財產局員工消費合作社印製 第88120223號專利申請案申請專利範圍修正年麥月，J7# 1 · 種用於製造經純化之有機酸或其衍生Ur的方法^ 括： 將一粗有機酸或其衍生物溶於一鹼化合物中； 除去雜質； 回收該經純化之有機酸或其衍生物；以及 除去吸附，截留，或包含於該經純化之有機酸或其 衍生物中的該殘留鹼化合物； 其中該粗有機酸或該衍生物係選自於下述物質所組 成的群組：對苯二酸（PTA)、間苯二酸（IPA)、鄰苯二酸 (OPA)、偏苯三酸（TMA)、苯三甲酸（hemimellitic acid )、 苯均二酸（trimesic acid )、苯均四酸（pyromellitic acid )、 苯六竣（mellitic acid )、萘二魏酸（naphthalene dicarboxylic)、萘三叛酸（naphthalene tricarboxylic)、 萘四叛酸（naphthalene tetracarboxylic )、蔥二叛酸 (anthracene dicarboxylic )、蔥三叛酸（anthracene tricarboxylic )、蔥四敌酸（anthracene tetracarboxylic )、 對苯二酸二甲酯（DMT)、 二甲萘.二羧酯 (dimethyl-naphthalene dicarboxylate，NDC )、經水解 的聚酯及其混合物，且 其中該鹼化合物包括對氧氮己環化合物、醯胺化合 物、無機驗、胺化合物及氨。 2.如申請專利範圍第1項之方法，其中該粗有機酸或其衍 生物係於電磁波下以熱攪動溶解之。 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 丨_裝 寫本頁) ·- 46 1249521 A8 B8 C8 D8 經濟部智慧財產局員工消費合作社印製 六、申請專利範圍 3.如申請專利範圍第Μ之方法，其中該粗有機酸或其衍 生物係溶解於該鹼化合物及一溶解劑中。 4·如申明專利範圍第i項之方法，其中吸附，截留，或包 含於該經純化之有機酸或其衍生物中的該殘留鹼化合 物係藉由利用電磁波之熱授自或藉由熱解之蒸發作用 來除去。 5· —種用於製造經純化之有機酸、寡聚物或其衍生物的方 法，其包括·· 溶解由一粗有機酸或其衍生物及一鹼化合物所形成 的鹽； 選用一或多種方法以自該粗有機酸或其等之衍生物 的鹽中，除去雜質和多餘的該鹼化合物，該方法係選自 於下述方法組成之組群··前處理、藉冷卻而結晶、藉控 制冷卻之成分而結晶、於鹼萃取溶劑存在下結晶鹽、於 驗萃取溶劑存在下沈澱產物、自鹽直接萃取結晶、再鹽 化結晶、鹽基取代、以鹼萃取溶劑洗滌以及以鹼萃取溶 劑瀝遽； 從該鹽中回收該經純化之有機酸或其衍生物；以及 除去吸附，截留，或包含於該經純化之有機酸或其 衍生物中的該殘留鹼化合物； 其中該粗有機酸或該衍生物係選自於下述物質所組 成的群組：對苯二酸（PTA)、間苯二酸（IPA)、鄰苯二酸 (OPA)、偏苯三酸（tmA)、苯三甲酸（hemimellitic acid )、 本均二酸（trimesic acid )、苯均四酸（pyromellitic acid )、 ί裝-------·—訂：-------- (請先閲讀背面之注意事填寫本頁)1249521 Announcement This document is for the manufacture of purified organic acids or their application for the revision of the patent application scope of the Patent Application No. 88120223. The method for deriving Ur includes: dissolving a crude organic acid or a derivative thereof in a base compound; removing impurities; recovering the purified organic acid or a derivative thereof; and removing adsorption, entrapment, or inclusion in the purified The residual alkali compound in the organic acid or a derivative thereof; wherein the crude organic acid or the derivative is selected from the group consisting of terephthalic acid (PTA) and isophthalic acid (IPA) ), phthalic acid (OPA), trimellitic acid (TMA), hemimic acid, trimesic acid, pyromellitic acid, melpyric acid ), naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, anthracene dicarboxylic acid, onion trioxonic acid (anthracene tr Icarboxylic ), anthracene tetracarboxylic acid, dimethyl terephthalate (DMT), dimethyl-naphthalene dicarboxylate (NDC), hydrolyzed polyester, and mixtures thereof, and The base compound includes a p-oxoprene compound, a guanamine compound, an inorganic test, an amine compound, and ammonia. 2. The method of claim 1, wherein the crude organic acid or derivative thereof is dissolved by electromagnetic agitation under electromagnetic waves. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) (please read the note on the back _ _ write this page) ·- 46 1249521 A8 B8 C8 D8 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative The invention is directed to the method of claim 3, wherein the crude organic acid or a derivative thereof is dissolved in the alkali compound and a solvent. 4. The method of claim i, wherein the residual base compound adsorbed, trapped, or contained in the purified organic acid or derivative thereof is imparted or pyrolyzed by the use of heat of electromagnetic waves The evaporation is removed. 5. A method for producing a purified organic acid, oligomer or derivative thereof, which comprises: dissolving a salt formed from a crude organic acid or a derivative thereof and a base compound; The method removes impurities and excess alkali compounds from the salt of the crude organic acid or a derivative thereof, and the method is selected from the group consisting of the following methods: pretreatment, crystallization by cooling, and borrowing Control cooling component and crystallize, crystallize salt in the presence of alkali extraction solvent, precipitate product in the presence of extraction solvent, directly extract and crystallize from salt, re-salt crystallize, base substitution, wash with alkali extraction solvent, and extract solvent with alkali Leaching; recovering the purified organic acid or a derivative thereof from the salt; and removing the residual alkali compound adsorbed, trapped, or contained in the purified organic acid or a derivative thereof; wherein the crude organic acid Or the derivative is selected from the group consisting of terephthalic acid (PTA), isophthalic acid (IPA), phthalic acid (OPA), trimellitic acid (tmA), benzene. Trimethic acid ), trimesic acid, pyromellitic acid, 装装-------·-:-------- (please read the notes on the back) This page) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐〉 47 1249521 A8 B3 C8 D8 經濟部智慧財產局員工消費合作社印製 六、申請專利範圍 苯六羧（mellitic acid )、萘二羧酸（naphthalene dicarboxylic)、萘三竣酸（naphthalene tricarboxylic )、 萘四緩酸（naphthalene tetracarboxylic )、蔥二竣酸 (anthracene dicarboxylic )、蔥三叛酸（anthracene tricarboxylic)、蔥四竣酸（anthracene tetracarboxylic)、 對苯二酸二甲酯（DMT)、 二甲萘二羧酯 (dimethyl-naphthalene dicarboxylate，NDC )、經水解 的聚酯及其混合物，且 其中該鹼化合物包括對氧氮己環化合物、醯胺化合 物、無機鹼、胺化合物及氨。 6·如申請專利範圍第5項之方法，其中該粗有機酸係為一 對本—酸或 '一間苯二酸。 7. 如申请專利範圍第5項之方法，其中該粗有機酸係為一 2,6-萘二羧酸（2,6_NDA)、一 2,7_萘二羧酸或一萘二羧酸 之混合物。 8. 如申明專利圍第5項之方法，其中該鹽係於電磁波下 以熱攪動溶解。 9·如申請專利範圍第5項 貝<方去，其中該鹼化合物係為一 含氧的驗化合物。 10·如申請專利範圍第5項之大 只<万去，其中該鹽係溶於該鹼 化合物和一溶解劑中。 11.如申請專利範圍第5 ^ ^ 万法’其中該鹼化合物係為 對氧氮己環，且該鹽係溶於水中。 I2·如申請專利範圍第5項 N (C 準 標 家 !國 國 中 用 適 度 尺 張 紙 本 其中該鹼化合物係為 夂° 規 4 AThis paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 47 1249521 A8 B3 C8 D8 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed six, the patent application range of melamine (mellitic acid), naphthalene Naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, anthracene dicarboxylic acid, anthracene tricarboxylic acid, anthracene tetracarboxylic acid ), dimethyl terephthalate (DMT), dimethyl-naphthalene dicarboxylate (NDC), hydrolyzed polyester, and mixtures thereof, and wherein the base compound includes a p-oxoprene compound, A guanamine compound, an inorganic base, an amine compound, and an ammonia. The method of claim 5, wherein the crude organic acid is a pair of the present acid or 'isophthalic acid. The method of item 5, wherein the crude organic acid is a mixture of a 2,6-naphthalene dicarboxylic acid (2,6-NDA), a 2,7-naphthalenedicarboxylic acid or a naphthalenedicarboxylic acid. The method of claim 5, wherein the salt is dissolved by thermal agitation under electromagnetic waves. 9. The method of claim 5, wherein the alkali compound is an oxygen-containing test compound. · As in the patent application, the fifth item is only < 10,000, wherein the salt is dissolved in the alkali compound and a solubilizing agent. 11. If the patent application is in the 5th ^ million method, wherein the alkali compound is Oxygen azide ring, and the salt is dissolved in water. I2·If the scope of application of the patent item 5 item N (C standard standard! In the country of China with a moderate ruler sheet paper, the alkali compound is 夂 ° gauge 4 A ---- (請先閱讀背面之注意事填寫本頁) 訂---------养 48 1249521 經濟部智慧財產局員工消費合作社印製 、申晴專利範圍 三甲胺、三乙胺、或三乙醇胺，且該鹽係溶於水或 13.如申請專利範圍第5項之 化合物。 具中錢係為-酿胺 14·如申請專利範圍第13項之方法，其中該酿胺化合物係 為N-甲基吡咯烷酮（nmp )。 15.如申請專利第5項之方法，其中祕化合物係為 一醯胺化合物，且該鹽係溶於一溶解劑中。 以如申請專利範圍第5項之方法，其中該驗萃取溶劑 括水、甲醇、乙醇、烯烴基二醇 四氫ϋ比喃。 I7·如申請專利範圍第5項之方法 溶劑存在下，加入一酸取代溶劑 化之有機酸或其衍生物。 •如申請專利範圍第5項之方 熱解，以從該鹽回收該經純化之有機酸或其衍生物 Η.如申請專利範圍第5項之方法，其中吸附，截留％ 包含於該經純化之有機酸或其衍生物中的該殘留鹼化 合物是藉由電磁波之熱攪動或藉由熱解之蒸發作用 除去。 2〇· —種用於製造經純化之有機酸、募聚物或其衍生物 方法，其包括： 溶解由一粗有機酸或其衍生物及一鹼化合物所形成 的鹽； 利用一或多個方法以自該鹽中除去該雜質，該方法 包 丙酮、四氫呋喃、或 其中藉由在一驗萃取 以從該鹽回收該經純 其中藉使用電磁波之 或 化 來 的 (請先閱讀背面之注意事 裝---------訂_·-------- 填寫本頁)---- (Please read the note on the back to fill out this page) Order --------- raise 48 1249521 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed, Shen Qing patent range trimethylamine, triethylamine Or triethanolamine, and the salt is soluble in water or 13. The compound of item 5 of the patent application. The method of claim 13 is the method of claim 13, wherein the amine compound is N-methylpyrrolidone (nmp). 15. The method of claim 5, wherein the secret compound is a monoamine compound and the salt is dissolved in a solvent. The method of claim 5, wherein the extraction solvent comprises water, methanol, ethanol, and an alkene diol tetrahydropyrene. I7·Method of Patent Application No. 5 In the presence of a solvent, an acid is added to replace the solvated organic acid or a derivative thereof. • Pyrolysis of the fifth aspect of the patent application to recover the purified organic acid or its derivative from the salt. The method of claim 5, wherein the adsorption, retention % is included in the purification. The residual alkali compound in the organic acid or its derivative is removed by thermal agitation of electromagnetic waves or by evaporation of pyrolysis. 2. A method for producing a purified organic acid, a polymer or a derivative thereof, comprising: dissolving a salt formed from a crude organic acid or a derivative thereof and a base compound; using one or more The method removes the impurity from the salt, and the method comprises acetone, tetrahydrofuran, or wherein the extraction is performed by an extraction to recover the purity from the salt, and the electromagnetic wave is used. Pack---------order _·-------- fill out this page) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公犮） 49 1249521 A8 B8 C8 D8 經濟部智慧財產局員工消費合作社印制取 、申請專利範圍 . 係選自於下述方法組成之族群：自鹽直接萃取結晶、使 用一鹼萃取溶劑之再鹽化結晶，以及鹽基取代； 其中該粗有機酸或該衍生物係選自於下述物質所組 成的群組：對苯二酸（PTA)、間苯二酸（IPA)、鄰苯二酸 (OPA)、偏苯三酸（TMA)、苯三曱酸（hemimellitic acid )、 苯均三酸（trimesic acid )、苯均四酸（pyromellitic acid )、 苯六叛(mellitic acid )、萘二竣酸（naphthalene dicarboxylic )、萘三叛酸（naphthalene tricarboxylic )、 萘四羧酸（naphthalene tetracarboxylic )、蔥二羧酸 (anthracene dicarboxylic )、蔥三叛酸（anthracene tricarboxylic )、蔥四叛酸（anthracene tetracarboxylic )、 對苯二酸二甲酯（DMT)、 二甲萘二羧酯 (dimethyl-naphthalene dicarboxylate，NDC )、經水解 的聚酯及其混合物，且 其中該驗化合物包括對氧氮己環化合物、.醢胺化合 物、無機鹼、胺化合物及氨。 21·如申請專利範圍第20項之方法，其中該粗有機酸或其 衍生物係為一粗芳香多叛酸。 22·如申請專利範圍第20項之方法，其中該鹽係於電磁波 下藉熱攪動溶解之。 23·如申請專利範圍第20項之方法，其中該鹽係溶於一溶 解劑中。 24·如申請專利範圍第20項之方法，其中該鹼化合物係為 一含氧的驗化合物。 (請先閱讀背面之注意事This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 metric tons) 49 1249521 A8 B8 C8 D8 Ministry of Economic Affairs Intellectual Property Office Employees' Consumption Cooperatives Printed and applied for patents. It is selected from the following methods. Group: direct extraction crystallization from salt, resalting crystallization using a base extraction solvent, and base substitution; wherein the crude organic acid or the derivative is selected from the group consisting of terephthalic acid (PTA), isophthalic acid (IPA), phthalic acid (OPA), trimellitic acid (TMA), hemimic acid, trimesic acid, pyromellitic acid (pyromellitic acid), mellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, anthracene dicarboxylic acid, onion Anthracene tricarboxylic acid, anthracene tetracarboxylic acid, dimethyl terephthalate (DMT), dimethyl-naphthalene dicarboxylate (NDC), water Polyesters and mixtures thereof, and wherein the test compound comprises cyclohexyl ring nitrogen oxygen compound. Mince amine compound, an inorganic base, ammonia and amine compounds. 21. The method of claim 20, wherein the crude organic acid or derivative thereof is a crude aromatic polyreaction acid. 22. The method of claim 20, wherein the salt is dissolved by heat agitation under electromagnetic waves. 23. The method of claim 20, wherein the salt is dissolved in a solvent. 24. The method of claim 20, wherein the base compound is an oxygen-containing test compound. (Please read the notes on the back first) · 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公涅） 50 1249521 A8 B8 C8 D8 經濟部智慧財產局員工消費合作社印製 t、申請專利範圍 25. 如申請專利範圍第20項之方法，其更進一步包括藉由 酸取代、熱解、或電解方式，從該鹽中回收該經純化之 有機酸或其衍生物。 26. 如申請專利範圍第20項之方法，其更進一步包括除去 該經純化之有機酸或其衍生物中之殘留驗化合物。 27. —種用於製備一經純化之溶液以製造聚酯之方法，該 經純化之溶液係由一芳香多羧酸、寡聚物或其衍生物， 與一單體或募聚物所組成，該方法包含： 將一含殘餘溶劑的芳香多羧酸或其衍生物與一單體 或寡聚物混合；以及 藉由增加溫度至50°C-350°C之間，以除去該殘餘溶劑； 其中該芳香多羧酸或其衍生物包括對苯二酸 (terephthalic acid)、間苯二酸（isophthalic acid)、鄰苯二 酸（orthophthalic acid)、偏苯三酸（trimellitic acid)、苯三 曱酸（hemimellitic acid)、苯均三酸（trimesic acid)、苯均 四酸（pyromellitic acid)、苯六叛酸（mellitic acid)、萘二 叛酸（naphthalene dicarboxylic acid)、萘三敌酸 (naphthalene tricarboxylic acid)、萘四叛酸（naphthalene tetracarboxylic acid)、蔥二叛酸（anthracene dicarboxylic acid)、蔥三竣酸（anthracene tricarboxylic acid)、蔥四竣 酸（anthracene tetracarboxylic acid)、對苯二酸二甲酯 (DMT)、二甲萘二緩酉旨（dimetl^yl-naphthalene dicarboxylate，NDC)及水解的聚酯。 (請先閱讀背面之注意事寫本頁) 裝 . 線. 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐〉 1249521 A8 B8 C8 D8 經濟部智慧財產局員工消費合作社印製 t、申請專利範圍 28. 如申請專利範圍第27項之方法，其中該單體係為一烯 烴基二醇。 29. 如申請專利範圍第27項之方法，其中該殘餘溶劑含一 鹼化合物。 30. —種用於製造純芳香多羧酸、募.聚物或其衍生物的方 法，其包括： 藉由將一具有氧分子之芳香化合物或其衍生物上的 烷基於催化劑和溶劑存在下氧化，以製造一粗芳香多羧 酸或其衍生物； 以急驟蒸發與蒸發來將該溶劑從該粗芳香多羧酸或 其衍生物中分離； 溶解一由該粗芳香多竣酸或其衍生物和一驗化合物 所形成的鹽； 除去該粗芳香多羧酸或其衍生物鹽中的雜質； 從該鹽中回收該純芳香多羧酸或其衍生物；以及 除去該芳香多叛酸或其衍生物中的該殘留驗化合 物； 其中該芳香多叛酸或其衍生物包括對苯二酸 (terephthalic acid)、間苯二酸（isophthalic acid)、鄰苯二 酸（orthophthalic acid)、偏苯三酸（trimellitic acid)、苯三 甲酸（hemimellitic acid)、苯均三酸（trimesic acid)、苯均 四酸（pyromellitic acid)、苯六竣酸（mellitic acid)、萘二 敌酸（naphthalene dicarboxylic acid)、萘三幾：酸 (naphthalene tricarboxylic acid)、萘四叛酸（naphthalene (請先閱讀背面之注意事 丨裝 寫本頁) 訂： 本紙張尺度適用中國國家標準（CNS)A4規格（2〗0 χ 297公釐） 52 1249521 A8 B8 C8 D8 經濟部智慧財產局員工消費合作社印製 •申請專利範圍 tetracarboxylic acid)、蔥二叛酸（anthracene dicarboxylic acid)、蒽三叛酸（anthracene tricarboxylic acid)、蔥四叛 酸（anthracene tetracarboxylic acid)、對苯二酸二甲酉旨 (DMT)、二曱萘二竣酉旨（dimethyl-naphthalene dicarboxylate，NDC)及水解的聚酯，且 其中該鹼化合物包括對氧氮己環化合物、醯胺化合 物、無機驗、胺化合物及氨。 31 ·如申請專利範圍第3 0項之方法，其中該鹽係溶於該驗 化合物及一溶解劑中。 32·如申請專利範圍第30項之方法，其中該催化劑是以過 濾或洗滌從該粗芳香多羧酸中分離。 33. —種用於製備一經純化之有機酸、寡聚物或其衍生物 的方法，其包括： 於電磁波下，藉由熱攪動以溶解一含有雜質之粗有 機酸或其衍生物於一鹼化合物中；以及 除去該雜質； 其中該粗有機酸或該衍生物係選自於下述物質所組 成的群組：對苯二酸（PTA)、間苯二酸（IPA)、鄰苯二酸 (0PA)、偏苯三酸（TMA)、苯三甲酸（hemimellitic acid )、 笨均三酸（trimesic acid )、苯均四酸（pyromellitic acid )、 苯六魏（mellitic acid )、萘二竣酸（naphthalene dicarboxylic)、萘三羧酸（naphthalene tricarboxylic)、 秦四叛酸（naphthalene tetracarboxylic )、蒽二叛酸 (anthracene dicarboxylic )、蔥三羧酸（anthracene 後適用中國國家標準（CNS)A4規格（210 χ 297公釐） 53 (請先閱讀背面之注意事 · I I I I I I I ^ ,^ΙΙΙΙΙΙΙ — ，填寫本頁)· This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 cc) 50 1249521 A8 B8 C8 D8 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing t, patent application scope 25. If the scope of patent application is 20 The method further comprising recovering the purified organic acid or a derivative thereof from the salt by acid substitution, pyrolysis, or electrolysis. 26. The method of claim 20, further comprising removing the residual compound from the purified organic acid or derivative thereof. 27. A method for preparing a purified solution for producing a polyester, the purified solution consisting of an aromatic polycarboxylic acid, an oligomer or a derivative thereof, and a monomer or a polymer. The method comprises: mixing an aromatic polycarboxylic acid or a derivative thereof containing a residual solvent with a monomer or oligomer; and removing the residual solvent by increasing the temperature to between 50 ° C and 350 ° C; Wherein the aromatic polycarboxylic acid or a derivative thereof comprises terephthalic acid, isophthalic acid, orthophthalic acid, trimellitic acid, benzotriazole Hemimellitic acid, trimesic acid, pyromellitic acid, mellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid Acid), naphthalene tetracarboxylic acid, anthracene dicarboxylic acid, anthracene tricarboxylic acid, anthracene tetracarboxylic acid, terephthalic acid Methyl ester (DMT), dimethyl naphthalate unitary purpose buffer (dimetl ^ yl-naphthalene dicarboxylate, NDC) and the hydrolysis of the polyester. (Please read the note on the back to write this page) Packing. Line. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1249521 A8 B8 C8 D8 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing The method of claim 27, wherein the single system is a monoolefin diol. The method of claim 27, wherein the residual solvent comprises a base compound. 30. A method for producing a pure aromatic polycarboxylic acid, a polymer or a derivative thereof, comprising: by using an alkyl group having an oxygen molecule or a derivative thereof in the presence of a catalyst and a solvent Oxidizing to produce a crude aromatic polycarboxylic acid or a derivative thereof; separating the solvent from the crude aromatic polycarboxylic acid or a derivative thereof by flash evaporation and evaporation; dissolving one from the crude aromatic polydecanoic acid or its derivative And a salt formed by the test compound; removing impurities in the crude aromatic polycarboxylic acid or a derivative thereof; recovering the pure aromatic polycarboxylic acid or a derivative thereof from the salt; and removing the aromatic polydox acid or its The residual test compound in the organism; wherein the aromatic polytoxaic acid or a derivative thereof comprises terephthalic acid, isophthalic acid, orthophthalic acid, trimellitic acid (trimellitic acid), hemimic acid, trimesic acid, pyromellitic acid, mellitic acid, naphthalene dicarboxylic acid, Naphthalene tricarboxylic acid, naphthalene tricarboxylic acid (naphthalene (please read the back of the note beforehand): Order: This paper scale applies to China National Standard (CNS) A4 specifications (2〗 0 χ 297 mm) 52 1249521 A8 B8 C8 D8 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing • patent application range tetracarboxylic acid), onionracene dicarboxylic acid, anthracene tricarboxylic acid, onion four Anthracene tetracarboxylic acid, dimethyl phthalate (DMT), dimethyl-naphthalene dicarboxylate (N) DC) and a hydrolyzed polyester, and wherein the base compound comprises a p-oxazane compound, a guanamine compound, an inorganic test, an amine compound, and ammonia. 31. The method of claim 30, wherein the salt is dissolved in the test compound and a solubilizing agent. 32. The method of claim 30, wherein the catalyst is separated from the crude aromatic polycarboxylic acid by filtration or washing. 33. A method for preparing a purified organic acid, oligomer or derivative thereof, comprising: dissolving a crude organic acid containing an impurity or a derivative thereof in a base by thermal agitation under electromagnetic waves And removing the impurity; wherein the crude organic acid or the derivative is selected from the group consisting of terephthalic acid (PTA), isophthalic acid (IPA), and phthalic acid. (0PA), trimellitic acid (TMA), hemimic acid, trimesic acid, pyromellitic acid, mellitic acid, naphthalene dicarboxylic acid (naphthalene dicarboxylic), naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, anthracene dicarboxylic acid, onion tricarboxylic acid (anthracene applies Chinese National Standard (CNS) A4 specification (210 χ 297 mm) 53 (Please read the notes on the back first, IIIIIII ^ , ^ΙΙΙΙΙΙΙ — , fill out this page) 1249521 A8 B8 C8 D8 六、申請專利範圍 tricarboxylic)、蔥四叛酸（anthracene tetracarboxylic)、 對苯二酸二甲酯（DMT)、二甲萘二羧酯 (dimethyl-naphthalene dicarboxylate 5 NDC )、經水解 的聚酯及其混合物，且 其中該鹼化合物包括對氧氮己.環化合物、醯胺化合 物、無機鹼、胺化合物及氨。 34·如申請專利範圍第33項之方法，其中該粗有機酸或其 衍生物係溶於該鹼化合物和一溶解劑中。 35·如申請專利範圍第33項之方法，其進一步包括回收該 純有機酸或其衍生物。 36.如申請專利範圍第33項之方法，其中該殘留鹼化合物 係於回收該經純化之有機酸或其衍生物後去除。 (請先閱讀背面之注意事1 寫本頁) · 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 541249521 A8 B8 C8 D8 VI. Patent application tricarboxylic), anthracene tetracarboxylic acid, dimethyl terephthalate (DMT), dimethyl-naphthalene dicarboxylate 5 NDC, hydrolyzed Polyester and mixtures thereof, and wherein the base compound includes a p-oxazane ring compound, a guanamine compound, an inorganic base, an amine compound, and ammonia. 34. The method of claim 33, wherein the crude organic acid or a derivative thereof is dissolved in the base compound and a solubilizing agent. 35. The method of claim 33, further comprising recovering the pure organic acid or a derivative thereof. 36. The method of claim 33, wherein the residual base compound is removed after recovering the purified organic acid or derivative thereof. (Please read the note on the back 1 to write this page) · Printed by the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs This paper scale applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 54