經濟部智慧財產局S工消費合作社印製 512141 A7 _____B7 五、發明説明（1 ) — "~~" ' '^〜---^ 發明之詳細說明 發明背景 發明領域 本發明係有關-種自含有芳香族聚竣酸（例如對 )晶體之淤漿中回收晶體的方法和裝置，更特別的是，戈Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, S Industrial Consumer Cooperative, 512141 A7 _____B7 V. Description of Invention (1) — " ~~ " Method and apparatus for recovering crystals from slurry containing aromatic polyacid (e.g. para) crystals, more particularly,
關一種製造適合用於製造粗質對酞酸（以下簡稱爲c τI )之對酞酸的方法和裝置。 先前技藝A method and an apparatus for manufacturing a terephthalic acid suitable for manufacturing crude terephthalic acid (hereinafter abbreviated as c τI). Prior art
國際公開專利案w〇8 9/1 1 3 2 3揭示於CTA 或尚純度對献酸（以下簡稱爲p 丁 A )的製造過程中，使 用旋轉真空過濾器（以下簡稱爲r v F )於含對酞酸晶體 的淤漿之固/液分離步驟。 另方面，USP5，527，957揭示於CTA製 造過程中，使用水利用具有數個區之鏈帶過濾器來沖洗， 而所用的水在冷凝之後或直接回到氧化階段。 最近，對酞酸製造工廠的規模變得更大，而每年例如 900，〇〇〇噸製造量的工廠目前是在考慮中。此大規 模的工廠需要大量的沖洗用水，而任何上述文獻之一未曾 對沖洗的廢液進行有效的處理。例如，當使用9 5 %醋酸 溶液使爲洗液時，於採用與每年9 0 0，0 0 0噸之 P TA製造規模相等的C TA製造工廠中，爲達此目的所 需之醋酸溶液的量估計爲約5 0噸/小時，基本上’此與 沖洗的廢液的量相等。於傳統的醋酸回收區中如此大量的 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）International Publication Patent No. WO 8 9/1 1 3 2 3 is disclosed in the manufacturing process of CTA or noble acid (hereinafter referred to as p-butyl A), using a rotary vacuum filter (hereinafter referred to as rv F) A solid / liquid separation step of a slurry of terephthalic acid crystals. On the other hand, USP 5,527,957 discloses that during the CTA manufacturing process, water is used for rinsing with a chain filter having several zones, and the water used is returned to the oxidation stage after condensation or directly. Recently, the scale of a terephthalic acid manufacturing plant has become larger, and a plant with a production capacity of, for example, 900,000 tons per year is currently under consideration. This large-scale factory requires a large amount of flushing water, and any of the above documents has not effectively treated the flushing waste liquid. For example, when a 95% acetic acid solution is used as a lotion, the acetic acid solution required for this purpose is produced in a CTA manufacturing plant using a PTA manufacturing scale equal to 90,000 tons per year. The amount is estimated to be about 50 tons / hour, which is basically equal to the amount of flushing waste liquid. Such a large amount of paper in the traditional acetic acid recycling area is suitable for the Chinese National Standard (CNS) A4 specification (210X297 mm)
Γ 裝----；-IΊ訂--------線 Γ請先閱讀背面之注意事項再填寫本百C -4 - 經濟部智慧財產局員工消費合作社印製 512141 A7 B7 五、發明説明（2 ) 沖洗廢液之處理造成醋酸區的規模龐大，以致相當地不方 便。例如，假設醋酸回收區是由用以自母液除去水之蒸倉留 柱所組成，則如上所述之大規模工廠將需要數個大規模蒸 餾柱。 發明總論 本發明之目的是提供一種製造芳香族聚羧酸的方法和 裝置，其中有效地除去大量的沖洗廢液。 本發明之另一個目的是提供一種製造對酞酸的方法和 裝置，且其於使用醋酸溶液作爲沖洗液之對酞酸製造過程 中確保一種有效之沖洗廢液的處理。 本發明之另一個目的是提供一種製造C T A的方法和 裝置，且其於使用醋酸溶液作爲沖洗液之C T A製造過程 中確保一種有效之沖洗廢液的處理。 爲了達到上述的目的，根據本發明之觀點提供的是： 混合芳香族聚烷基（即聚烷基苯，例如間二甲苯和對二甲 苯）、醋酸、氧化觸媒、和反應促進劑之步驟以提供混合 的起始物，氧化該混合的起始物之氧化/結晶步驟以形成 芳香族聚羧酸的淤漿，在該淤漿置於旋轉過濾器上且旋轉 的同時以洗液沖洗淤漿以進行固/液分離而分別得到溼的 芳香族聚羧酸、由淤漿分離出的母液、和沖洗的廢液之固 /液分離和沖洗步驟，自由淤漿分離出的母液中回收羧酸 成份和使所回收的羧酸成份回到混合步驟之回收/回饋步 驟，及直接使沖洗的廢液回到混合步驟之直接回饋步驟。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐） ,φ IΧΦ衣 ： - 訂 J 線 (請先閲讀背面之注意事項再填寫本頁) -5- 512141 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（3) 根據此安排，即使沖洗廢液的數量龐大，其可再循環到混 合歩驟而無須再滯留於其他的系統中例如羧酸回收系統， 如此使得以防止其他系統的處理規模變大。由於回收/回 饋步驟與直接回饋步驟同時進行，因此氧化反應中所產生 的水可於回收/回饋步驟中除去，如此使得整個系統中處 理液體的水的量保持在指定値或更低。 圖示之簡單說明 圖1是一用以顯不本發明之製造對献酸的裝置之例子 的方塊圖。 主要元件對照 —"""11 n 批衣 ·1 J 訂"Γ" 11 n 線 (請先閲讀背面之注意事項再填寫本頁) 1 混合器 2 氧化反應器 3 空氣管 4 結晶區 5 液/固分離區 6 乾燥區 7 醋酸回收區 8 醋酸回收管 9 管線 10 洗液管 11 管線 11a 管線 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -6 - 經濟部智慧財產局員工消費合作社印製 512141 A7 ____B7__ 五、發明説明（4 ) 較佳體系之詳細說明 圖中’參考符號1表示一混合器，其中對二甲苯、觸 媒（例如鈷、錳、鎳、鉻等）、溴（作爲反應促進劑）、 和醋酸（作爲溶劑）一起混合以形成起始物，而後送進隨 後的氧化反應器2。氧化反應器2中，來自混合器1之混 合的起始物以由管線3送進的空氣氧化以製造對酞酸和雜 質（例如4 一羧基苯甲醛（下文中簡稱爲4 一 C B A )， 其爲對二甲苯之氧化反應的副產物）。結晶區4中，由氧 化反應器2送來的產物緩緩地冷卻以得含有對酞酸晶體的 淤漿，令此母液淤漿於液/固分離區5中利用R V F的方 法進行固/液分離而得對酞酸濾餅和母液（管線1 1 ，主 要是由醋酸所組成）。對酞酸濾餅是由約1 〇 %母液沉積 而得，及以醋酸沖洗以除去存在於母液的雜質例如觸媒和 副產物。固/液分離區5中沖洗後的醋酸廢液藉由管線 1 1和1 1 a送至混合器1 ，藉由管線1 1送至醋酸回收 區7。部份分離出的母液直接回到混合器1 ，然而，此時 母液含有因氧化反應而產生水，及其他的母液送至醋酸回 收區7，通常利用蒸餾管柱而除去水，繼之經由醋酸回收 管8再循環至混合器1 ，及經由洗液管1 〇再循環至固/ 液分離區5中的R V F。自R V F上除下沖洗後的濾餅， 及繼之於乾燥區6中乾燥以得C T A。 固/液分離區5中的R V F中，如國際公開專利案 W〇8 9 / 1 1 3 2 3所述，洗液的流徑和母液的流徑彼 本紙張尺度適用中國國家標準（CNS ) A4規格(210X 297公釐）^ ~ ； 批衣 ： ^ 訂J 111 (請先閲讀背面之注意事項再填寫本頁) 512141 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（5 ) 此完全分隔開，且分別獨自放流。因此，沖洗濾餅後，醋 酸沖洗液的廢液含有附著於濾餅上的溶液成份，及因此除 了醋酸之外，亦含有雜質例如4 一 C B A等，及水。爲了 有效沖洗，實質量之沖洗用的醋酸是必要的，例如 900， 000噸/年規模的工廠中，其可達50噸/小 時。另一方面，於上述規模的工廠中，於R V F中分離出 的母液的量估計約2 2 0噸/小時，其中有1 5 4噸/小 時的量直接送回到混合器1中，而其餘之6 6噸/小時的 量則送至醋酸回收區7中，並於除去水之後回到混合器1 中。此例中，5 0噸/小時的沖洗廢液以及1 5 4噸/小 時直接回饋者係在無任何除去雜質和水之處理步驟的情況 下直接回到混合器1中。是故，於2 7 0噸/小時之回饋 量中只除去6 6噸/小時中的水是足夠的，如此，使得以 於C T A系統中連續除去水。特別的是，於此例中，具有 較低量水之沖洗廢液可完全地直接回到混合物1 ，而具有 較高量水之分離的母液則分成二個物流，如此使需要量的 物質回到混合物1 ，而另一物流則進行除水。因此，與沖 洗廢液和分離出的母液未彼此分開但只分隔成二個物流（ 一是回到混合物1 ，另一個則進行除水）之系統相比較時 ，本發明之系統於回到混合物1之水的量可被降低，同時 混合物1中起始物中的水量亦可加以降低。 根據U S P 5，5 2 7，9 5 6，對以醋酸沖洗而言 ，沖洗速率係經擇爲0 . 2 1。沖洗速率係經擇爲〇 · 1 至0.5，宜爲0.2至0.4，更宜爲0_35至 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） I I I I I I —· I 士κ I I —— I I 丁.— (請先閱讀背面之注意事項再填寫本頁) -8- 512141 A7 __ __ ____ B7 五、發明説明（6 ) 〇 · 4。此例中，沖洗速率經發現爲〇 · 3 8。 根據本發明’當以大量醋酸溶液利用r V F沖洗 C T A辦獎時’所得之沖洗廢液可再循環至氧化反應之起 始'物的預備階段’此無須任何用以處理大量之含有重質物 質例如觸媒之醋酸廢液的特殊步驟或裝置，如此可降低設 備的成本。 (請先閱讀背面之注意事項存填寫本頁) 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（210x 297公釐） -9-Γ Install ----; -IΊ order -------- line Γ Please read the notes on the back before filling in this one. C -4-Printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs 512141 A7 B7 V. Description of the invention (2) The treatment of the washing waste liquid causes the scale of the acetic acid area to be so large that it is rather inconvenient. For example, assuming that the acetic acid recovery zone is made up of a distillation column retention column to remove water from the mother liquor, a large-scale plant as described above will require several large-scale distillation columns. SUMMARY OF THE INVENTION An object of the present invention is to provide a method and an apparatus for producing an aromatic polycarboxylic acid in which a large amount of washing waste liquid is effectively removed. Another object of the present invention is to provide a method and an apparatus for manufacturing terephthalic acid, and to ensure an effective processing of a waste washing liquid in a process of manufacturing terephthalic acid using an acetic acid solution as a washing liquid. Another object of the present invention is to provide a method and an apparatus for manufacturing CTA, and to ensure an effective treatment of the waste effluent during the CTA manufacturing process using an acetic acid solution as a rinsing solution. In order to achieve the above object, according to the viewpoint of the present invention, the following steps are provided: mixing an aromatic polyalkyl (ie, polyalkylbenzene, such as m-xylene and p-xylene), acetic acid, an oxidation catalyst, and a reaction promoter; To provide a mixed starting material, the oxidation / crystallization step of the mixed starting material is oxidized to form a slurry of aromatic polycarboxylic acid, and the slurry is rinsed with a washing solution while the slurry is placed on a rotary filter and rotated. The solid / liquid separation of the slurry to obtain wet aromatic polycarboxylic acid, the mother liquor separated from the slurry, and the solid / liquid separation and washing steps of the washed waste liquid, respectively, and the carboxylic acid is recovered from the mother liquor separated from the slurry. The acid component and the recovery / return step for returning the recovered carboxylic acid component to the mixing step, and the direct return step for directly returning the flushed waste liquid to the mixing step. This paper size is applicable to Chinese National Standard (CNS) A4 specification (210 × 297 mm), φ I × Φ clothing:-Order J line (please read the precautions on the back before filling this page) -5- 141141 Staff of Intellectual Property Bureau, Ministry of Economic Affairs Printed by Consumer Cooperative A7 B7 V. Description of Invention (3) According to this arrangement, even if the amount of washing waste liquid is huge, it can be recycled to the mixing step without remaining in other systems such as carboxylic acid recovery system, so that To prevent the processing scale of other systems from becoming larger. Since the recovery / return step is performed simultaneously with the direct feedback step, the water generated in the oxidation reaction can be removed in the recovery / return step, so that the amount of liquid-treated water in the entire system is maintained at a specified level or lower. Brief Description of the Drawings Fig. 1 is a block diagram showing an example of an apparatus for producing an acid donor according to the present invention. Comparison of main components— " " " 11 n batch clothing · 1 J order " Γ " 11 n wire (Please read the precautions on the back before filling this page) 1 Mixer 2 Oxidation reactor 3 Air tube 4 Crystallization Zone 5 Liquid / Solid Separation Zone 6 Drying Zone 7 Acetic Acid Recovery Zone 8 Acetic Acid Recovery Pipe 9 Pipeline 10 Washing Liquid Pipe 11 Pipeline 11a Pipeline This paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -6-Ministry of Economic Affairs Printed by the Intellectual Property Bureau employee consumer cooperative 512141 A7 ____B7__ V. Description of the invention (4) Detailed description of the better system In the figure, 'reference symbol 1 represents a mixer, in which paraxylene and catalysts (such as cobalt, manganese, nickel, Chromium, etc.), bromine (as a reaction accelerator), and acetic acid (as a solvent) are mixed together to form a starting material, and then sent to a subsequent oxidation reactor 2. In the oxidation reactor 2, the mixed starting materials from the mixer 1 are oxidized with air sent from the pipeline 3 to produce terephthalic acid and impurities (for example, 4-carboxycarboxybenzaldehyde (hereinafter referred to as 4-CBA)), which Is a by-product of the oxidation reaction of para-xylene). In the crystallization zone 4, the product sent from the oxidation reactor 2 is slowly cooled to obtain a slurry containing terephthalic acid crystals, and the mother liquor slurry is subjected to solid / liquid in the liquid / solid separation zone 5 using the RVF method. Separate to obtain a p-phthalic acid filter cake and mother liquor (line 1 1, mainly composed of acetic acid). The terephthalic acid filter cake is obtained by depositing about 10% of the mother liquor, and rinsed with acetic acid to remove impurities such as catalysts and by-products present in the mother liquor. The flushed acetic acid waste liquid in the solid / liquid separation zone 5 is sent to the mixer 1 through lines 11 and 1 1 a, and sent to the acetic acid recovery area 7 through line 11. Part of the separated mother liquor is directly returned to the mixer 1, however, at this time, the mother liquor contains water generated by the oxidation reaction, and other mother liquors are sent to the acetic acid recovery zone 7, usually by using a distillation column to remove water, and then passing through The recovery pipe 8 is recycled to the mixer 1 and to the RVF in the solid / liquid separation zone 5 via the washing liquid pipe 10. The rinsed filter cake was removed from the R V F and then dried in the drying zone 6 to obtain C T A. In the RVF in the solid / liquid separation zone 5, as described in International Publication Patent No. WO 8 9/1 1 2 3 3, the flow path of the washing liquid and the flow path of the mother liquid are based on Chinese paper standards (CNS). A4 specifications (210X 297 mm) ^ ~; Approval: ^ Order J 111 (please read the precautions on the back before filling this page) 512141 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description ) This is completely separated and released separately. Therefore, after washing the filter cake, the waste liquid of the acetic acid washing solution contains the solution components attached to the filter cake, and therefore, in addition to acetic acid, it also contains impurities such as 4-CBA, etc., and water. For effective rinsing, solid acetic acid for rinsing is necessary. For example, in a 900,000-ton / year plant, it can reach 50 tons / hour. On the other hand, in a plant of the above scale, the amount of mother liquor separated in the RVF is estimated to be about 220 tons / hour, of which 154 tons / hour is directly returned to the mixer 1, and the rest An amount of 66 tons / hour is sent to the acetic acid recovery zone 7 and returned to the mixer 1 after removing water. In this example, the 50 ton / hour washing waste liquid and the 154 ton / hour direct feedback were returned directly to the mixer 1 without any treatment steps to remove impurities and water. Therefore, it is sufficient to remove only water from 66 ton / hour in the feedback amount of 270 ton / hour, so that the water is continuously removed from the CTA system. In particular, in this example, the washing waste liquid with a lower amount of water can be returned directly to the mixture 1, while the separated mother liquid with a higher amount of water is divided into two streams, so that the required amount of material is returned. To mixture 1 while the other stream is dewatered. Therefore, when compared with a system in which the washing waste liquid and the separated mother liquor are not separated from each other but only separated into two streams (one is returned to the mixture 1 and the other is removed from the water), the system of the present invention returns the mixture The amount of water in 1 can be reduced, and the amount of water in the starting material in mixture 1 can be reduced. According to U S P 5,5 2 7,9 5 6, for acetic acid washing, the washing rate is selected to be 0.21. The washing rate is chosen to be from 0.1 to 0.5, preferably from 0.2 to 0.4, and more preferably from 0 to 35. This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) IIIIII — · I κκ II —— II D. — (Please read the precautions on the back before filling out this page) -8- 512141 A7 __ __ ____ B7 V. Description of the invention (6) 0.4. In this example, the rinse rate was found to be 0.38. According to the present invention, when a large amount of acetic acid solution is used to wash the CTA for prizes, the washing waste liquid obtained can be recycled to the starting stage of the oxidation reaction. This does not require any treatment of large quantities of heavy substances. For example, the special step or device of the acetic acid waste liquid of the catalyst can reduce the cost of the equipment. (Please read the precautions on the back and fill in this page first.) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The paper size applies to China National Standard (CNS) A4 (210x 297 mm). -9-