201119993 六、發明說明： 【發明所屬之技術領域】 本發明係關於化學反應器及及庙士、t ^ 久夂應方法，且更具體地，係關於用 於製造芳錢酸的氧化反心，觀應时最大化反應速率與反 應純度’以及關於使用該氧化反應器製造芳香魏的方法，該方 法可以局效率與南產率產生芳香竣酸。 【先前技術】 芳香叛酸可為有用於作為各種基礎化學化合物者。例如，對寒 二甲酸⑽，亦即其為可使用作為如纖維、膜、塑膠瓶、容器用 樹脂等之《原料的代表性芳錢酸，而^τα的需求盘日俱 增。製造芳香減的-般方法，已知於液相氧化的方法1相氧 化可依下述方式實施，將如姑、鎂等重金屬化合物，及必要時可 使用作為雜_漠化合物，以衫香絲化合物，於反應器内 於例如乙酸等含有低階脂肪她酸的溶劑之中，於加壓狀態下盘 含氣氣體接觸。 〃 於上述製造芳香羧酸的方法中，該原料之芳香烷基化合物及該 乙酸及催化劑的混合物係置於包括有攪拌器形成於其内之反應器 中，且後續藉由將含氧氣體導入至該反應器而進行氧化反應，因 而獲得具有相對低溶解度的芳香羧酸。其次，該具有相對低溶解 度的芳香羧酸係連續地產生，以獲得粗製的芳香羧酸。接著 ， 粗製的芳香羧酸後續地係經分離且進行精製步驟因而產生高純产 芳香羧酸。 又 由芳香羧酸使用氧之液相氧化反應所使用之反應方法與反應 燒基之間的差異之製造芳香羧酸的方法而言’有許多建議的改良 3 201119993 技術。其中，對於作為代表性芳香羧酸之ΤΑ而言，已知有用於製 造ΤΑ的方法，包括氧化反應及跟隨其後之分離/精製步驟，以及 循環步驟。 然而，上述方法可仍具有需要克服之技術問題如下述者： 首先’在氧化反應時期有顯著量的殘餘未反應性烷基芳香化合 物產生，且有顯著量的所產生的奉反應性烷基芳香化合物包含於 排放氣體中，因而可能需要回收未反應性烷基芳香化合物的成本。 再者’使用作為聚酯原料之該芳香羧酸對其品質產生不良影 響，因而於製造該芳香缓酸時期所產生顯著量之例如4·缓基苯甲 醛(4-CBA)等雜質，可能仍存在。 第三為氧化反應時期因氧化分解可能發生使用作為溶劑之脂 肪族羧酸的顯著損耗，且因而可能發生經濟問題。 【發明内容】 本發明之一態樣係提供用於製造芳香羧酸的氧化反應器，其可 降低反應損耗且改良反應效率。 本發明之一態樣係提供使用該氧化反應器製造高純度與高效 率芳香羧酸的方法。 根據本發明之態樣，提供用於製造芳香羧酸的氧化反應器’該 氧化反應器包括：反應室；沿著該反應室之幾何蚕直軸設置的攪拌 軸；以及至少兩個攪拌器，其各包括攪拌翼，各攪拌翼具有曲面 部分或彎曲部分形成於攪拌翼的末端以使流體流入反應室而防止 流體殘留於反應室中’以及各攪拌翼係延著垂直於垂直軸旋轉的 方向，幅射狀地延伸。 201119993 於此情況中，該氧化反應器可包括彼此有空間相隔的第一攪拌 器與第二攪拌器，且各設置於反應室之攪拌轴，該第一攪拌器係 設置於該反應室的上方部以及該第二攪拌器細設置於該反應室的 下方部，以及該第一攪拌器與第二攪拌器之間的空間距離可為第 一攪拌器或第二攪拌器長度（直徑）的1.5倍。再者，該攪拌器的長 度（直徑）可為反應室内直徑的0.4至0.5倍。同時，第二攪拌器與 該反應室底表面之間的距離可為該第二攪拌器長（直徑）的0.5至1 倍。於此情況中，該攪拌器於反應室中的定位關係對於反應效率 或反應純度具有重大影響。 此外，該攪拌翼可包括至少兩個區面部份或彎曲部分。再者， 該攪拌翼可包括具有第一彎曲部分的第一攪拌翼，該第一彎曲部 分的彎曲角度為45至75度，以及具有第二彎曲部分的第二攪拌 翼，該第二彎曲部分額外地從第一攪拌翼具有彎曲角度為120至 160 度。 再者，該至少兩個攪拌器之各者可包括支持構件，以使該攪 拌翼彼此連接，且以使該攪拌翼與該攪拌軸彼此連接。於此情況 中，該支持構件可為圓形板，該圓形板包括垂直於該攪拌轴的上 表面以及具有相對於該上表面為傾斜表面的下表面。同時，該支 持構件的末端可替代一般曲線形狀而形成為鋸齒狀。 此外，該氧化反應器復可包括氣體輸送管用以將氣體自外侧注 入反應室；反應物輸送管用以將包括反應原料、溶劑與催化劑之 液體反應物進料至該反應室；回流輸送管用以將回流進料至該反 應室；產物排出管用以將反應後之產物排出至外側；以及氣體排 出管用以將所產生之反應後氣體在排出至外侧。 5 201119993 於此情況中’該氣體輪送管、該反應物輸送管以及該回流輸送 管可由設置該第二擾拌器之虛擬水平表面向著垂直轴方向，分別 定位於該第二攪拌器的一半長度内《再者，該氣體輪送管、該反 應物輸送管以及該回流輸送管可分別沿著該攪拌器旋轉的方向， 將該氣體、該反應物以及該回流進料至該反應室。 再者’該產物排出管可經設置以使該產物排出管的末端由垂直 軸而言係定位於第一攪拌器的上方。亦即’該產物排出管可形成 於該反應室的上方部份。 再者，該氧化反應器復可包括擋流器係經設置於該反應室的側 壁以阻擋液體流，因而調控該流體的流動。 再者，當由該氧化反應器之上方觀之，該氧化反應器可包括至 少兩個氣體輸送管係經設置為彼此緊鄰。 再者，至少一個氣體輸送管、至少一個反應物輸送管以及至少 一個回流輸送管，當由該氧化反應器之上方觀之，可以相等間距 規律地設置。 根據本發明之一態樣，係提供一種使用氧化反應器製造芳香羧 酸的方法，由垂直於垂直軸之中間部分的虚擬平面而言，該氧化 反應器劃分為上方部分與下方部分，且包括第—攪拌器與第二攪 拌器分別輻射狀地設置於該上方部分與該下方部份’以垂直於該 垂直軸，其中包括含氧反應氣體、烧基芳香化合物、溶劑、催化 劑與回流之液體反應物，係進料至該氧化反應器之下方部份，以 及反應後之產物與反應後之氣體係排出於該氧化反應器之上方部 份。於此情況中，回流溫度可低於該氧化反應器的内部溫度。 201119993 本發明之其他態樣、特徵及/或優勢將由後述說明部份所闡述， 以及部分由此說明書而可明瞭’或可藉由本發明實施本發明而得 知。 【發明的效果】 如上述例示具體例所述’本發明提供一種使用氧化反應器製造 芳香羧酸的方法，其巧"顯示優異的反應特性，且因而可降低未反 應原料的損耗以及所產生雜質的量’可減抑因氧化反應時期所使 用之溶劑的氧化分解造成的損耗’以及可顯著地改良整體反應效 率與所得產物之芳香叛酸的品質’結果為顯著降低生產成本。 亦即，根據例示具體例，裝設於該氧化反應器之攪拌軸之下方 部份之第二攪拌器周圍的未反應烷基芳香化合物的濃度與脂肪族 缓酸的反應速率可最大化。此外，氧化反應器中之未反應燒基芳 香化合物的濃度以及因乙酸的氧化反應造成之乙酸的損耗，可隨 著氧化反應器之液體表面的方向而顯著地降低。 因此’該反應器之氣相區域中的未反應烷基芳香化合物的濃度 可顯著地降低’以及排出至經安裝用於處理排放氣體之熱交換 器、蒸顧管柱等之未反應原料的排出量，可顯著地降低，因而可 省略補充回收步驟。再者，介於含氧氣體與該原料之烷基芳香化 合物之間的反應’係於與乙酸的反應之前進行，此可導致作為溶 劑之乙酸的損耗減低。 再者，根據例示具體例，產物經由其而排出至外側之產物排出 管係經設置於該氧化反應器的上方部份’因而可防止油氧化反應 所產生之芳香羧酸產物，混入與粘附於該氧化反應器的壁或底 7 201119993 部，而循環至該氧化反應器之下方部份。其結果，該產物可安定 地排出而不增加攪拌動力，因而在經濟效益與品質上或的顯著效 果。 【實施方式】 後文中，本發明將藉由實施例更具體予以說明。然而應了解 該等實施例僅用於說明目的，且不意圖限制本發明之範嘴。 第1圖為根據本發明之例示具體例之用於製造芳香羧酸之氧化 反應器100的截面示意圖。 參考第1圖’該用於製造芳香羧酸之氧化反應器100(後文稱為 「氧化反應器」）包括反應室H0、攪拌轴105、第一攪拌器12〇、 第二攪拌器130、氣體輸送管14〇、反應物輸送管15〇、回流輸送管 160、產物排出管17〇、氣體排出管180以及擋流器19〇。 根據本例示具體例之該反應室11〇可形成為圓柱型，然而本發 明並不限定於該者，且因此可形成為各種形狀。攪拌軸1〇5可形成 為沿著該反應室110之幾何垂直軸。該垂直轴可為對應於該圓柱反 應室110之懸轉軸的區域。該攪拌轴105可使用動力傳遞而傳遞旋 轉動力之該第一與第二攪拌器12〇與13〇。 該第與第二授拌器120與130可沿著垂直於該攪拌轴150的方 向’彼此間隔地輻射狀設置。該第一攪拌器120可設置於該反應室 110的上方部份’以及該第二攪拌器130可設置於該反應室11〇的下 方部份。再者，即使於該反應室110中可提供至少三個攪拌器，而 根據本例示具體例’係提供兩個攪拌器120與130。然而，將系統 的授摔動力與效率加以考量的情況下，其較佳為該氧化反應器1〇〇 8 201119993 具有兩個120與130。該第一與第二攪拌器12〇與13〇可具有沿著垂 直於攪拌轴105的單一方向或多個方向延伸之輻射狀結構。該第— 與第二攪拌器120與130可藉由相對於該攪拌軸1〇5旋轉而對於反 應物實施攪拌操作。 ' 該第-與第二授拌器12〇與13〇可為一種韓射狀葉輪，具有因輕 射狀架構而於該器末端創造出水平旋轉流的結構，且同時於 該反應室1对不創造氣體停留區域，以及可制任_拌器只要 可使流體平緩地流經該葉輪末端者即可。亦即，該第—與第二俊 辦企120與13G可具有於該反應室m中不創造氣體停留區域的結 =’且該攪拌器包括擾拌翼122與132，該攪拌翼具有形成於該= 、末端之曲面。卩伤或彎曲部分以使流體平緩地流經該授掉器 端。 小" 笛根據本例示具體例，該第一與第二授拌器12〇與m可分別具有 與二f m與第二攪拌翼m。再者，該第一與第二攪拌器120 軸105:紐由第一支持構件120與第二支持構件134分別與該攪拌 134^該個別之攪拌器120與130可藉由該支持構件124與 有带向著垂直於該齡轴105的方向，創造虛擬旋轉表面，且具 132。此^〜支持構件124與134的末端之至少兩個攪拌翼122與 板，該倾；，該支持構件124與134可形成為具有傾斜表面的圓形 直於該搜拌成於$圓形板之上表面或下表面’ ^相對於垂 成為弧形 05之虛擬表面為傾斜的。此外，該圓形板可具有形 只要該支<傾斜表面。該支持構件124與134可形成為任何形狀， 而，其較佳^件124與134係由該攪拌軸105幅射狀延伸即可。然 可為該支持構件124與134形成為具有較低傾斜表面之 201119993 圓开v板此乃因來自垂直循環流體之向上循環可受到增強。於傾 斜表面的隋:兄中’傾斜表面的角度可為相對於水平表面約15至20 度再者胃支持構件124與134的末端可形成為緩和曲線形狀， 然而亦可形成為銀齒狀。 第2(a)圖與的2(b)圖分別為根據本發明之例是具體例之攪拌器 之翼200之展開圖與截面圖。 參照第2(a)圖’該攪拌器之翼2〇〇如展開圖所示可具有梯形。顯 而易見地’該翼2〇〇可形成為具有至少一曲面部分或至少一彎曲部 分之各種形狀，而造成各種展開圖式。 該翼200可於第一彎曲部分212彎曲，其係對梯形的中心線為垂 直角度因而形成為楔形。再者，該翼2〇〇復可於第二彎曲部分222 彎曲，其係三角形ABC之BC段。於此情況中，該翼200可以第一彎 曲部分212的相反方向於第二彎曲部分222彎曲。接著，該翼2〇〇可 包括由第一彎曲部分212所形成之第一攪拌器21〇，以及由第二彎 曲部分222所形成之第二攪拌器220。此外，該翼200可具有由第一 彎曲部分212彎曲之楔形開口部分。該楔形開口部分可定向於該攪 拌器120與130的旋轉方向。 再次參照第2(a)圖，根據本例示具體例，該翼2〇〇的bc段可彎 曲為具有長度相對應於該梯形相對應段長度之65%至75%，以及該 翼200的AC段可彎曲為具有長度相對應於該梯形相對應段長度之 20%至30%。於此情況中’ AB段與AC段的b點與c點可根據反應室 110中之流體的特性而予以調整。 參照第2(b)圖，該第一彎曲部分212可具有角度（〇〇45至75度， 201119993 以及該第二彎曲部分222可於對該第一彎曲部分212為相反方向上 具有角度卵20至i60度4同的是，該角度⑷與(p)可根據該反應 室中之流體的特性而調整為具有各種角度。 如上所述，該攪拌器120與130可防止經導入該反應室ιι〇之含 有氧分子形式的氣體殘留於該反應室11G中，因此氣泡容易變細^ 且容易均勻地分散以增加氣體與液體之接觸面積，因而 與液體之間的質量運送特性。 : 上述之攪拌器uomso可包括至少兩個授掉翼122與134，以及 例如2至8個携拌翼122與134。特別地，該授掉器12〇與13〇較佳可 包括4至6個攪拌翼122與134。 參照第_，該擾拌器120與130之安裝位置對於反應室n〇中之 混合物的獅有重大影響，因而與賴拌器⑽與㈣的結構一起 可為達成本發明之態樣的重要因素。 根據本例示具體例’該第—攪拌⑽與該第二游議之間 該授拌器120與13°的長度(或直徑)_比例 直徑（T)的0.4至0.5倍，亦即D/T =〇 4至〇 幻門 m與該反應絲面之 ，該第二攪拌器 ⑶與⑽的長度⑼的-半，料拌器 當F/D <1.0時，上方搜掉 其中授拌未充分實施之未充分搜拌域可能重蠻’因而 搜拌巴域可ΤΑ 授摔區域。再者，當咖·5時，不足 搜料域U生於該第—顺該第二難器⑽之間的 201119993 中間部分。 此外，當D/T<0.4時，原料與含氧氣體之間的接觸可能不足， 因而質量運送係數可能減低。或者，當D/T>0.5時，不充足攪拌區 域可能產生於該攪拌器130的下方。類似地，當c/d<〇.5時，該; 足攪拌區域可能產生於該攪拌器130的下方。於不足攪拌區域的氧 化反應步驟可能難以進行，因而氧化反應的中間體產生會増加。 根據本例示具體例，該攪拌器12〇與13〇的旋轉速度可為1〇至 lOOrpm ,且較佳為70至90rpm。再者，該攪拌器之攪拌力可為 2.08W/M3至4.42kW/M3。 本發明之態樣可達成於氧化反應器1〇〇中運送之液體物質的運 送位置與運送方法、氣體的運送位置與運送方法、流體的運送位 置與運送方法、以及產物的排出位置與排出方法可彼此與該攪拌 器120與130的結構與安裝位置相關聯，以實施其所擁有的功能。 特別地’前述運送位置與運送方法以及排出位置與排出方法可根 據反應室110中之流體的移動而設計，且其可使反應效率與產物純 度最大化。 再次參照第1圖’該含氧氣體可經由氣體輸送管14〇運宋秩反應 室110。該含氧氣體可運送至該第二攪拌器13〇附近，或該反應室 110之底表面附近。此外，呈液體狀態之原料、催化劑與溶劑，可 使用反應物輸送管150運送至該反應室11〇。再者，該回流可經由 回流輸送管160運送至該反應室11〇。該回流可指稱一液體其中之 氧化反應後所獲得氣體元素於進行凝縮步驟後係經循環，且導入 該反應室110。 12 201119993 根據本例不具體例’該氣體輸送管140、該反應物輸送管15〇以 及該回流輸达管160，可根據經設置該第二攪拌器13〇於其上之虛 擬水平表面而設置為相對地接近於該第二攪拌器13〇。亦即，該輸 送管140、150及160可分別設置於該第二攪拌器13〇的一半長度①) 内，由該虛擬表面向著該攪拌轴1〇5的方向。 此外，如上所述，於該第二攪拌器13〇的支持構件134為圓形板 且具有相對於該圓形板之上表面為較低傾斜表面的情況中，該氣 體輸送管140可向下設置於該第二攪拌器I%的下方。 第3圖為根據例示具體例之該氣體輸送管34〇、該反應物輪送管 350及該流體輸送官360係分別設置於該反應室11〇之平面示意圖。 參照第3圖，該氣體輸送管340、該反應物輸送管350及該流體 輸送管360可以彼此間固定的間隔與以規律地設置。全部6個氣體 輸送管340群2個分為1群可彼此緊鄰，全部3個反應物輸送管35〇可 規律地設置為與緊鄰的管具有120度的角度，以及2個回流輸送管 360可設置為彼此相向。介於該輸送管340、350及360之間的各間 隔可實際上為相同的。經由該輸送管340、350及360的設置，可增 加於液體狀態混合氣體、物質與該回流時期之彼此接觸面積，且 可獲得該混合物之均勻分散物。 〇 再者，經***該反應室110之該輸送管340、350及360之各者的 末端部份，可向著攪拌器120、130的旋轉方向彎曲，且較佳係向 著該旋轉方向的正切方向，因而使該氣體、該反應物與該回流可 於旋轉方向進料至該反應室11〇。此乃因為該氣體、該反應物與該 回流可根據該混合之流動方向進料至該反應室110。 13 201119993 再次參照第1圖’該回流可為溶劑經該氧化反應器110所產生之 反應熱予以蒸發、濕氣等所組成之混合物，可為藉由安裝於該氧 化反應器外側之熱交換器（未示於圖中）所凝縮之液體元素，且可為 其中不可凝氣體係經分離的氣體元素。該回流可經由回流輸送管 160進料至該反應室11〇而予以循環。於此情況中，該回流溫度可 較該反應室110之内部溫度更低，而更具體地，可較該反應室110 之内部溫度低約20°C至60°C ° 根據例示具體例，可製造該芳香羧酸，以使反應原料之烷基芳 香化合物，例如對二甲苯，與例如乙酸之溶劑，可與欲反應之含 氧氣體接觸。一般而言，該反應室I10之内部溫度可藉由因與該含 氧氣體接觸所造成之氧化反應熱的產生而變的更高，且因此氧化 反應速度可逐漸加速，因而例如乙酸之該溶劑之氧化分解速度可 加速。然而’根據本例示具體例’由於回流係經由回流輸送管160 以較低溫度進料至該反應室110,該回流可作用為降低因氧化反應 所加熱之環境溫度。因此，例如乙酸之該溶劑的氧化分解可受到 減抑。亦即’此減抑效果可藉由使該具有低溫之回流共存於該氧 化反應之反應物（包括氣體）的附近而獲得。 再者’本發明之該攪拌器120與130可分別地設置於該反應室 110之上方部份與下方部份。當該回流不進料至該反應室110時， 經運送至該攪拌器130副近之原料（烷基芳香化合物）的氧化梵映可 逐漸於藉由該第二攪拌器130所產生之水平旋轉流體中發生，且同 時可發生乙酸的氧化分解。然而，由於垓據有低溫之回流係混合 至該水平旋轉流體’引起液線溫度降低，該烷基芳香化合物之氧 化反應可發生於該乙酸之氧化分解之前。因此，因例如乙酸之該 201119993 溶劑的氧化反應所造成的損失可顯著地降低° 此外，由於運送至該反應是110之下方部分之水平旋轉流體的 大部份氧氣，係於該第二攪拌器130附近的水平旋轉流體中消耗’ 未反應烷基芳香化合物的濃度、所產生雜質的濃度以及乙酸的反 應速率，可於該第二授拌器130附近予以最大化。然而’未反應烧 基芳香化合物與所產生雜質的氧化反應，可藉由升高殘餘氣體與 該攪拌器所產生之合適向上循環流體與水平旋轉流體’而於該己 酸的氧化之前進行。於此情況中，該未反應烷基芳香化合物與所 產生雜質的氧化反應可前進如同該烷基芳香化合物與該雜質較接 近該反應室110的上方部分，因此該未反應烷基芳香化合物與所產 生雜質實際上不殘留於該氧化反應器之液體表面。 因此’藉由該向上循環流體所運送之該未反應烷基芳香化合物 的濃度、該所產生的雜質以及該乙酸之氧化速率可根據其在該反 應室110的高度而顯示其特定的分散，且更具體地，可隨著該烧基 芳香化合物、該雜質以及該乙酸越接近該氧化反應器100的上方部 份（液體表面）而降低。 根據本例示具體例，相對接近於該氧化反應器100的液體表面 的未反應烷基芳香化合物的濃度，排除不可凝氣體元素，可為約 0.01重量或更少，較佳約〇〇〇7重量。/❶或更少，且更較佳約0.005 重量％或更少。於此情況中，該氧化反應器之氣相部分之未反應烷 基芳香化合物的濃度，排除不可凝氣體元素，可為約〇.〇2重量％或 更少，較佳約0.015重量％或更少，且更較佳约001重量％或更少， 其為顯注的小量’不需要藉由氣體排出處理的分離與回收步驟。 15 £ 201119993 再次參照第1圖，該產物排出管170的末端係設置於該地一攪拌 器120的上方部份，以使該氧化反應後的產物可由該反應室110的 上方部分或液體表面，經由該產物排出管170而排出。因此，突出 於該反應室11〇外側之該產物排出管17〇的定位部分可不顯著地加 以限制。此外’氧化反應後所產生的氣體元素可經由連接至該反 應室110之上蓋的氣體排出管180，排出至該反應室110外側。 如上所述’根據本例示具體例之用於製造芳香羧酸之氧化反應 器100 ’可包括攪拌器120與130以產生水平旋轉流體與向上循環流 體之授拌器，且可適用於運送該含氧氣體、例如原料之呈液體狀 態之物質、以及該回流至該第二攪拌器130附近，因而可藉由該氧 化反應器100中之上升氣體與該攪拌器丨2〇與13〇所產生之合適的 向上循環流體與該水平旋轉流體而進行氧化反應。於此情況中， 該氧化反應隨者更接近該氧化反應器100的上方部分而可更顯著 地進行，以及該未反應原料不存在於該液體表面附近。 亦即，該氧化反應器1〇〇之反應溶液表面附近的烷基芳香化合 物的濃度，可為約0.01重量％或更少，且轉換為芳香羧酸之反應速 率可為約99.99重量。/。。更具體地，未反應烷基芳香化合物於該氧 化反應器的反應溶液表面附近的濃度，排除不可凝氣體元素可 為約0.01重量％，較佳為0.007重量％，且更較佳約〇 〇〇5重量％或更 少。 一般而言，於液體表面附近之烷基芳香化合物 餘的院基芳香化合物可藉由熱交換器、高㈣ 柱、與由該氧化反應器UH)之上方部分的排放氣體一起予以回收， 然而，本發明不需要此回收步驟。 201119993 此外’當產物的排出係於傳統的氧化反應器之底表面附近進行 時，該產物排出管可能因固體物質粘附於氧化反應器的壁上與沉 降而堵寨，然而，本例示具體例可避免此類問題。亦即，本例示 具體例之氧化反應器100可連續地且長時間的進行產物的排出功 能以改良操作效率。 使用根據本例示具體例之芳香羧酸’可降低作為溶劑之乙酸的 反應速率，且以該氧化反應中所產生之芳香羧酸為基準之音氧化 反應所造成之損失可為約2.7重量％或更少，且較佳可為約2.5重量 %或更少。 再次參照第1圖’該氧化反應器100可包括設置於該反應室11〇 之側壁的擋流器190,以調控流體流動。可以相等間隔設置2至8個 擋流器。擋流器190的寬度可為約該反應室110内直徑（τ)的5%至 20%。此外’該擋流器190可需要安裝於該反應室11〇中之反應溶液 表面為相等或更低的位置。當該檔流器190係安裝於較該反應溶液 表面更高的位置時，漿體元素可能斜升而粘附於該反應溶液表面 之上的擋流器190的壁上，因而可能有晶體生長。此晶體可能落入 該反應室110而中斷該樣化反應器100的穩定運轉。 後文中，將詳細說明製造芳香羧酸的方法。 氧化步驟 (1) 烷基芳香化合物（原料） 作為烷基芳香化合物，亦即使用於本例示具體例之原料，可使 用含有烧基之芳香化合物。組成芳香化合物之芳香環化合物可為 單一環（單環)化合物或多重環（多環)化合物。 17 201119993 作為烷基，可使用甲基、乙基、正丙基與異丙基。再者，該烷 基可具有官能基。例如，作為官能基可使用醛基'醯基、羧基與 羥基等。 作為京玩機取代之芳香化合物之例，可列舉烷基苯類、烷基萘 類與烷基聯苯類，其具有2至4個烷基，各烷基具有1至4個碳原子， 例如間-二異丙基苯、對-二異丙基苯、間-異丙基曱苯、對-異丙基 曱苯、間-二甲苯、對-二甲苯、三甲基等。 再者，作為含有烷基之芳香化合物，可使用除了烷基外含有取 代基之化合物。該含有烷基之芳香化合物之例，可列舉3-曱基苯 曱醛、4-曱基苯曱醛、間-甲基苯甲酸、對-曱基苯曱酸、3-甲醯基 苯曱酸、2-甲基-6-甲醯基萘等。上述化合物可單獨使用或組合2或 多種使用。 (2)用於製造對苯二甲酸的氧化步驟 將對二曱苯做為該氧化反應器之原料、溶劑、催化劑、含氧氣 體與產生於分離步驟之母液之某些元素的循環溶液，其等將於後 文中詳細說明，置入該氧化反應器100中，且接著予以反應。作為 溶劑，可使用脂肪族羧酸如乙酸、丙酸、甲酸、乳酸等，然而， 較佳使用包括乙酸作為主要元素之溶劑。當使用對苯二曱酸作為 原料時，該溶劑之使用量可為一般原料之1至10倍，較佳為2至8 倍，且更較佳為3至6倍。當該乙酸的用量顯著少時，所產生將体 的濃度顯著增加，且引起管線堵塞的問題；而當該乙酸的用量顯 著大時，可能需要較大的設備且造成經濟上的問題。 作為本例示具體例之溶劑，較佳可使用乙酸與水之混合物。於 18 201119993 此情況中’以乙酸為100重量份為基準’水可含有量為㈣重量 份’且以乙酸為UH)$量份為基準，較佳為5至15重量份。 作為含氧氣體之例，可列舉空氣、使用惰性氣體稀釋之氧氣以 及含空氣之大量氡氣等，㈣，實際上可使用空氣。以原料^耳 為基準，該含氧㈣可使用具有3莫耳至議莫耳的氧。 該氧化反應器⑽之線路中可具有氧含量約21體積％。= 氧化反應器刚所排故氣體中之氧濃度，可為W _ %，且較佳則.5_%㈣積％。 8體積 麵㈣限制，只要使賴催化劑可將炫基芳香化合物 於液體中經氧化而轉換為芳香缓酸即可。作為催化劑，可使= 金屬H且可使㈣化合物作為催化劑 化合物中之重⑽）、馨）、= :(组衣釓(Pb)、銓(Hf)、鈽(Ce)等。該等重金屬可單獨使用 5、’ 〇 $種使用。特別地，較佳使用⑸與仏的組合。作為重 屬物之例’可列舉乙酸鹽、墙酸鹽、乙酿乙酸鹽、蔡酸趟、 硬脂酸鹽、填化合物等，且特別地，可使用乙酸鹽與演化合；。 #作為邊化合物之例，可列舉無機演化合物，例如分子漠、演化 a /臭化臭化卸、漠化钻、演化猛等；以及有機漠化合物， 例如甲基漠'、*-、、ι φ ^ 、一 /吳〒坑、溴仿(bromoform)、苯甲基溴、溴甲基甲 + 、燒一 /臭乙燒、四溴乙烧等。該等溴化合物可單獨使 用或2種或多種組合使用。 田使用方香羧酸製造對笨二甲酸時，而氧化對二甲苯時使用溴 化σ物作為催化劑時’較佳可使用經由組合彡m漠化猛與漠 201119993 化氫組合所獲得之催化劑。 根據本例示具體例，作為經由組合重金屬化合物與溴化合物所 獲得之催化劑，以1莫耳重金屬為基準，可使用0.05莫耳至10莫耳 的溴原子，且較佳為0.1莫耳至5莫耳的溴原子。此催化劑作佣為溶 劑之重金屬催化劑，可使用量為約10質量ppm至10,000質量ppm， 且較佳為約100質量ppm至3，000質量ppm。 氧化反應溫度可為約140°C至250°C，且較佳為150°C至230°C。 當氧化反應的溫度顯著低時，氧化反應的速度會降低，而當氧化 反應的溫度顯著高時，作用為溶劑之乙酸的隱然所造成之損失會 增加。於氧化反應時期所產生之反應熱可為經由蒸發溶劑所產生 之蒸發熱，且可移除至該氧化反應器1〇〇之外側以調控該氧化反應 的溫度。所產生之蒸汽可由例如乙酸之溶劑、水等之可凝元素， 以及例如氮、氧等不可凝元素所組成。於此情況中，該蒸氣可經 由安裝於該氧化反應器100之外侧的熱交換器予以凝縮，且予以分 離為氣體與固體。其次，源自該氣體之排放氣體可運送至高溫吸 附管柱、蒸餾管柱、膨脹器等，因而可進行有效元素的回收與能 量的回收。經分離之液體可於該氧化反應器100中，循環作為回 流。此外，該蒸餾管柱可安裝於該氧化反應器100之上方部分以替 代熱交換器，因而可分離為水與溶劑。於此情況中，該溶劑可於 該氧化反應器100中循環，且含有該氣相元素之水可於熱交換器 中，分類為可凝縮元素與不可凝縮元素，且用於回收、能量回收 等目的之操作。 該氧化反應的壓力可需要至少能維持混合物至少於反應溫度 為液體狀態的壓力，且以需要至少大氣壓力。具體地，該反應壓 201119993 力可需要約〇.2MPa至6MPa的壓力’且較佳約〇.4MPa至3MPa的壓 力。為使所產生之芳香叛酸聚體易於運送，較佳可為相對高麼， 因此有助於減抑副反應。此外，由反應容器的抗壓性、安裝成本 等而言’較佳為相對低壓。 該氧化反應可連續地實施，以及該氧化反應的反應時間（平均 滯留時間）可為約30至300分鐘，且具體地約4〇至15〇分鐘。當反應 時間顯著短時，氧化反應可能實施不佳，引起芳香羧酸品質的劣 化；而當反應時間顯著長時，因乙酸之溶劑之引燃所造成的損失 可能增加，且氧化反應器之容量可能變大而引起經濟上的問題。 根據本例示具體例’必要時，可實施補助步驟。關於補助步驟， 對於經由氧化反應所獲得之產物之氧化步驟，可連續地至少於氧 的存在下進行，而不需要於比該氧化反應溫度為較低或較高的溫 度進料原料。 ^ 分離步驟 經由氧化步驟所獲得之產物，可予以結晶以增加晶體之 1 ’而後該結晶產物使用@ •液分離步驟予以清洗，或所 w 而 或 可使用該固-液分離步驟直接予以清洗。所獲得固體可為聚體 香致酸’且可進行精製步驟（其將於下文中詳細㈣）。之芳 離母液中之某些元素可經回收予叫纽化後，排除至’經分 經分離母液中之殘餘元素可經由維持溫度與壓力而予拉， 可經由氧化步驟之冷卻與循環而予以循環。 、寺， 精製步驟 可能需要精製所 經由該分離步驟所分離之該粗製之芳香羧酸， 21 201119993 含的雜質以改良純度。一般而言，該雜質可經由添加氫予以去氧 化而增加其等之溶解度，因而可因與有限度溶解芝芳香綾酸之溶 解度差異而予以分離。其次，該芳香羧酸可經清洗與乾燥以獲得 精緻之芳香羧酸。由於該經分離之母液含有去氧化之雜質與該芳 香羧酸之中間體，該經分離之母液可予以回收而使用於氧化反應。 上文中，揭示用於製造芳香羧酸，特別是高純度羧酸的方法， 且該方法可應用於製造中純度羧酸的方法，其可於高壓與高溫下 實施兩階段之氧化步驟而省略精製步驟。於該兩階段之氧化步驟 中，第一階段之氧化反應的產物可運送至第二階段之氧化反應 器，以及含氧氣體可運送至該氧化反應器，因而連續地實施該氧 化反應。然而該第一階段之氧化反應可與上述之氧化反應相同。 該第二階段之氧化反應的反應溫度可為約23〇。(：至29.(TC，且較佳 為約240°C至280°C。該第二階段之氧化反應的壓力可需要能維持 反應混合物為液體狀態的壓力。於此情況中，該第二階段之氧化 反應的壓力可為3MPa至lOMPa，以及滯留時間可為5至12〇分鐘， 且較佳為10至60分鐘。 由於漿體之部分芳香羧酸顆粒係經溶解且該顆粒之氧化中間 體係經由該兩階段之氧化反應而氧化兩種原因，該精製步驟可省 略。然而，相對於使用精製步驟所獲得之高純度羧酸之具有相對 低純度之中純度羧酸，可藉由該兩階段之氧化反應獲得。根據本 例示具體例之氧化反應器，可應用於氧化反應步驟以實施用於製 造中純度芳香羧酸。 後文中，本發明藉由實施例而更詳細說明。然而應了解，該等 實施例僅用於說明目的，且不用於侷限本發明之範嘴。 22 201119993 [實施例1] 1重罝份之對-甲苯、5重量份之乙酸以及〇 5重量份之水，進料 至氧化反應^，以及作料催化狀乙祕、乙酸鍾與漠化氮亦 進料至該氧化反應1於溫度約185。(：至195。(：與壓力約1_^至 1.7MPa的條件下f ；5&氧化反應9()分鐘氧化期間（平均滯留時間）。 具有钻、猛與漠的催化劑，以金屬@言，含量分別為3〇〇質量卯瓜、 300質量PPm與700質量ppme使用空氣作為含氧氣體。於此情況 中，具有氧含罝約21體積％的氣體與壓縮氣體係運送至該氧化反應 器，以使排入該氧化反應器之氣體之氧濃度具有3體積％至7體積 %。 使用第1圖之氧化反應器做為該氧化反應器。該第一與第二攪 拌器120與13G之各長度為2,55()毫米，由該氧化反應器底部至該第 一攪拌器130之垂直距離為ι，5〇〇毫米，以及由第二擾拌器13〇至該 第一攪拌器120的距離為3,200毫米。由該氧化反應器之上方部分排 出產物，其與第一攪拌器130相隔4,1〇〇毫米。例如壓縮氣體、回流、 原料、溶劑、催化劑等之反應物，係以該第二攪拌器13〇之旋轉方 向之正切方向，運送至與該第二攪拌器13〇接近相同的高度。輸送 管的設置係與第3圖之輸送管相同。該壓縮氣體經由氣體輸送管 140(總計6個管）運送，以及由對二甲苯、乙酸·水混合物與催化劑 所組成之乙酸溶液，係預先於混合室中混合，與分離步驟中所循 環之回收溶液，經由反應物輸送管150—起運送。該回流經由回流 輸送管（總計2個管）運送。此外’介於個別輸送管14〇、15〇與16〇， 與該第二授拌器130之旋轉圓周之間的距離為約1〇〇毫米。當運送 回流至該氧化反應器100時的溫度為15〇。〇至160。〇，而該氧化反應 £ 23 201119993 器100之内部溫度係較比較例1之内部溫度更低至少5度。此外，在 實施例1的氧化反應器的情況中，產物排出管170的阻塞現象歷時 半年亦不發生’理解到該氧化反應器100的穩定運轉。由該產物排 出管170所排出之產物係連續地運送至補助氧化反應器，且於溫度 180°C至190°C與壓力〇.9MPa至1.5MPa的條件下，實施例35分鐘的 反應時間（平均滯留時間）。該氣體（氧濃度21體積％)係進料至該氧 化反應器，以使該排出氣體之氧濃度為3體積％至7體積％，而後實 施低溫補助氧化反應。該補助氧化反應係使用安裝有傳統兩段碟 狀渦輪的反應器予以實施。 由補助氧化反應所獲得之產物係使用連接於反應器呈三階段 系列之晶體沉澱槽，以階段化的方式進行晶體沉澱，接著所得產 物係經由真空旋轉過濾器（RVF)予以固-液分離/清洗而獲得粗製之 對苯二曱酸。進行固_液分離步驟之反應母液的9〇%，係於氧化反 應器中循環。再者，例如催化劑、乙酸等之明顯物質係由殘於母 液回收’而運送至排出處理步驟後予以排出。 其次’該粗製之對苯二曱酸係運送至精製步驟，且於一般精製 條件下’實施上述之雜質的加氫反應。其次，該雜質經由上述晶 體沉澱/分離步驟而去氧化，以及該對苯二甲酸係經分離以獲得高 純度之對笨二甲酸《所得結果示於表1，其將與下文所述比較例1 的結果，一起於後文中說明。 [比較例η 使用氧化反應器，氧化反應係於與實施例1之氧化反應為相同 反應條件下貪施。起始反應溫度係與實施例1相同，然而，在氧化 S' 24 201119993 反應器之穩定運轉後得比較例1的内部溫度係比實施例之内部溫 南至少5度《該氧化反應器之内部結構示於第7圖。第7圖為比較例 1之用於製造芳香羧酸之氧化反應器7〇〇的截面示意圖。參照第7 圖，該氧化反應器700包括攪拌軸7〇5、反應室71〇、第一攪拌器 720、第二攪拌器730、氣體輸送管74〇、反應物輸送管75〇、回流 輸送官760'產物排出管770以及氣體排出管78〇。該氧化反應器7〇〇 的容量與實施例1相同，該第一與第二攪拌器72〇與73〇,分別包括 6個攪拌翼。此外，該第一與第二攪拌器72〇與73〇的定位，係與實 施例之第一與第二攪拌器12〇與13〇的定位相同。 該第一與第二攪拌器720與730的各別長度為2,300毫米，由該氧 化反應器700的底部至該第二攪拌器73()的垂直距離為Μ⑽毫米， 以及由該第二攪拌器73〇至該第一攪拌器72〇的距離為3,2〇〇毫米。 空氣的運送係於該第二麟器73晴近進行，由對二曱苯、乙 酸-水混合物與催化劑所組成之乙酸溶液，係與猶環於該分離步驟 之循環溶液混合，且運送至該第一龄器72崎近。產物由該氧化 反應器700的底部附近排出。 於該氧化反應後實施補助氧化反應，且與實施例相同條件實施 分離步驟與精製步驟，喊得高純度之對苯二曱酸。由實施例1與 比較例1所獲得之結果示於表J。 表1中L對二曱笨(ρχ)之殘餘濃度為該氧化反應器之液體表面 附近的ΡΧ濃度（重量％)，產率為由渺頓原料所獲得之高純度隊本 二甲酸(ΡΤΑ)的產物量（公斤），以及乙酸損失為經由氧化反應器之 氧化反應所耗損< 相對於每-頓ΡΤΑ產物之乙酸量（公斤）。再者， 25 201119993 於反應之氣相區域中之ρχ濃度為排除反應氣象區域之不可凝氣體 的元素之PX濃度（重量％) ’以及PTA透光率為以及該PTA產物之苛 性鹼水溶液之波長340微米與10毫米光徑（optical path)之透光率 (%) 〇 [表1] 項目 實施例1 比較例1 PX-殘餘濃度（重量％) 0.0100 0.6000 產率（1噸PTA/100噸PX) 150.59 148.74 乙酸損失（公斤/噸，PTA產物） 26.5 28.5 反應器之氣相區域中之ρχ-濃度（重量〇/〇) 0.020 0.670 PTA透光率（％) 91 89 如表1所示，比較實施例1與比較例丨的結果，可發現反應產 率跫到改良，乙酸損失降低，以及該反應器之穩定運轉的歷時增 加。再者，可發現該氧化反應器之氣相區域中之未反應原料對二 甲笨顯著降低，而且不需要使用對二甲苯回收裝置。再者，如ρτΑ 透光率所示，ΡΤΑ產物之苛性鹼水溶液之透光率受到改良以及雜 質量，ΡΤΑ之代表性雜質為4_羧基苯甲醛(CBA)顯著降低。 第4圖係以實施例丨與比較例i所獲得之結果為基準 未反應對二甲苯的渡度相對於高度之示意圖。第5圖係以實施例^ 與比較例1所獲得之結果為基準之 所產生雜質(4-叛基苯甲搭(CBA))的濃度相對於高度之示意圖。第6 圖係以實施例1與比較例丨所獲得之結果為基準之 乙酸的反應速率相對於高度之示意圖。為獲得第4圖至第6圖的結 果’使料算流體動力學(CFD)，相對於向著該氧化反應器之液^ 26 201119993 表面的方向的濃度分散實施流體模擬(fluid simulati〇n)。 參照第4圖至第6圖，可發現該氧化反應器中之未反應對二甲 笨、殘餘4-CBA與乙酸之各者的濃度係顯著降低。再者，各別濃度 分散未顯示顯著變化，以及該氧化反應器之液體表面附近的濃度 分散則顯著降低。 雖然已顯示與s兒明本發明之一些例示具體例，但本發明並不偈 限於所揭示之例示具體例。替代地，本技術領域中具有通常知識 者應了解，可於不悖離本發明之原則與精神的情況下進行該等例 示具體例之變化，本發明之範疇係由申請專利範圍與其均等物所 界定。 【圖式簡單說明】 本發明之此等及/或其他態樣、特徵與優勢可由後述之例示真體 例的說明與下述圖式的結合而更明確且可容易理解： 第1圖為本發明例示具體例之用於製造芳香羧酸之氧化反應器 之截面示意圖； 第2(a)圖及第2(b)圖分別為本發明例示具體例之攪拌器之翼 的展開圖與截面圖； 第3圖為本發明例示具體例之設置於反應室中之代表性輪送 管狀態之平面示意圖； 第4圖為實施例1與比較例丨所得結果之未反應對二甲笨的 濃度相對於高度之示意圖； 第5圖為實施例1與比較例1所得結果之所產生雜質（4_幾基 § 27 201119993 苯甲醛(CBA))的濃度相對於高度之示意圖； 第6圖為實施例1與比較例1所得結果之乙酸的反應速率相 對於高度之示意圖； 第7圖為比較例1之用於製造芳香羧酸的氧化反應器之截面 示意圖。 【元件符號表】 100 ' 700 氧化反應器 105 ' 705 攪拌軸 110 、 710 反應室 120 ' 720 第一攪拌器 122 、 132 攪拌翼 124、134 支持構件 130 ' 220 ' 730 第二攪拌器 140 ' 340、740 氣體輸送管 150 ' 350 ' 750 反應物輸送管 160 ' 360 ' 760 回流輸送管 170 、 770 產物排出管 180 、 780 氣體排出管 190 、 790 擋流器 200 翼 212 第一彎曲部分 222 第二彎曲部分 C、F 距離 D 攪拌器長度 T 内直徑 α ' β 角度 A、Β、C 點201119993 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a chemical reactor and a temple, a t ^ long-term method, and more particularly, to an oxidation counter-center for producing aromatic acid, The method of maximizing the reaction rate and the purity of the reaction as well as the method for producing aromatic Wei using the oxidation reactor can produce aromatic citric acid with local efficiency and south yield. [Prior Art] Aromatic acid can be used as a basic chemical compound. For example, for the cold dicarboxylic acid (10), that is, it is a representative aromatic acid which can be used as a raw material such as a fiber, a film, a plastic bottle or a resin for a container, and the demand for ^τα is increasing. A method for producing aroma reduction, a method known for phase oxidation in liquid phase oxidation can be carried out in the following manner, and a heavy metal compound such as guar or magnesium, and if necessary, can be used as a hybrid compound to The compound is contacted with a gas-containing gas in a pressurized state in a solvent containing a low-order fatty acid such as acetic acid in a reactor.上述 In the above process for producing an aromatic carboxylic acid, the aromatic alkyl compound of the raw material and the mixture of the acetic acid and the catalyst are placed in a reactor including a stirrer formed therein, and subsequently introduced by introducing an oxygen-containing gas The oxidation reaction is carried out to the reactor, thereby obtaining an aromatic carboxylic acid having a relatively low solubility. Next, the aromatic carboxylic acid having a relatively low solubility is continuously produced to obtain a crude aromatic carboxylic acid. Next, the crude aromatic carboxylic acid is subsequently separated and subjected to a refining step to thereby produce a highly pure aromatic carboxylic acid. Further, there are many proposed improvements in the method for producing an aromatic carboxylic acid from the reaction method of the aromatic carboxylic acid using the liquid phase oxidation reaction of oxygen and the reaction of the alkyl group. Among them, as a representative aromatic carboxylic acid, a method for producing ruthenium is known, including an oxidation reaction followed by a separation/refining step, and a recycling step. However, the above method may still have technical problems to be overcome such as the following: First, 'a significant amount of residual unreacted alkyl aromatic compound is produced during the oxidation reaction period, and a significant amount of the resulting reactive alkyl aromatic group is produced. The compound is contained in the exhaust gas and thus may require the cost of recovering the unreacted alkyl aromatic compound. Furthermore, the use of the aromatic carboxylic acid as a raw material for polyester adversely affects the quality thereof, and thus a significant amount of an impurity such as 4·sulphonylbenzaldehyde (4-CBA), which is produced during the production of the aromatic acid retardation period, may still presence. The third is that a significant loss of the aliphatic carboxylic acid used as a solvent may occur due to oxidative decomposition during the oxidation reaction period, and thus economic problems may occur. SUMMARY OF THE INVENTION One aspect of the present invention provides an oxidation reactor for producing an aromatic carboxylic acid which can reduce reaction loss and improve reaction efficiency. One aspect of the present invention provides a method of producing a high purity and high efficiency aromatic carboxylic acid using the oxidation reactor. According to an aspect of the present invention, there is provided an oxidation reactor for producing an aromatic carboxylic acid. The oxidation reactor comprises: a reaction chamber; a stirring shaft disposed along a straight axis of the geometric silkworm of the reaction chamber; and at least two agitators, Each of which includes agitating blades each having a curved portion or a curved portion formed at the end of the agitating blade to allow fluid to flow into the reaction chamber to prevent fluid from remaining in the reaction chamber' and the agitating wings extending in a direction perpendicular to the vertical axis , extending in a radial shape. 201119993 In this case, the oxidation reactor may include a first agitator and a second agitator spaced apart from each other, and each of the agitator shafts disposed in the reaction chamber, the first agitator system being disposed above the reaction chamber And the second agitator is finely disposed at a lower portion of the reaction chamber, and a spatial distance between the first agitator and the second agitator may be 1.5 of a length (diameter) of the first agitator or the second agitator Times. Further, the length (diameter) of the agitator may be 0.4 to 0.5 times the diameter of the reaction chamber. At the same time, the distance between the second agitator and the bottom surface of the reaction chamber may be 0.5 to 1 times the length (diameter) of the second agitator. In this case, the positioning relationship of the agitator in the reaction chamber has a significant influence on the reaction efficiency or the purity of the reaction. Furthermore, the agitating wing may comprise at least two zone portions or curved portions. Furthermore, the agitating wing may include a first agitating wing having a first curved portion, the first curved portion having a bending angle of 45 to 75 degrees, and a second agitating wing having a second curved portion, the second curved portion Additionally, the first agitating wing has a bending angle of 120 to 160 degrees. Further, each of the at least two agitators may include a support member to connect the agitating blades to each other, and to connect the agitating blades and the agitating shaft to each other. In this case, the support member may be a circular plate including an upper surface perpendicular to the agitating shaft and a lower surface having an inclined surface with respect to the upper surface. At the same time, the end of the supporting member can be formed in a zigzag shape instead of the general curved shape. In addition, the oxidation reactor may include a gas delivery tube for injecting gas from the outside into the reaction chamber; a reactant delivery tube for feeding a liquid reactant including a reaction raw material, a solvent and a catalyst to the reaction chamber; and a reflux delivery tube for The feed is refluxed to the reaction chamber; the product discharge tube is used to discharge the reacted product to the outside; and the gas discharge tube is used to discharge the generated reaction gas to the outside. 5 201119993 In this case, the gas transfer tube, the reactant delivery tube and the return delivery tube may be positioned in the vertical axis direction by the virtual horizontal surface on which the second scrambler is disposed, respectively, and positioned at half of the second agitator Within the length, further, the gas transfer tube, the reactant delivery tube, and the return delivery tube can feed the gas, the reactant, and the reflux to the reaction chamber in a direction in which the agitator rotates, respectively. Further, the product discharge tube can be positioned such that the end of the product discharge tube is positioned above the first agitator by a vertical axis. That is, the product discharge pipe can be formed in the upper portion of the reaction chamber. Further, the oxidation reactor may include a flow barrier disposed through a side wall of the reaction chamber to block the flow of the liquid, thereby regulating the flow of the fluid. Further, when viewed from above the oxidation reactor, the oxidation reactor can include at least two gas delivery conduits disposed in close proximity to one another. Further, at least one gas delivery tube, at least one reactant delivery tube, and at least one reflux delivery tube, when viewed from above the oxidation reactor, can be disposed at equal intervals. According to an aspect of the present invention, there is provided a method for producing an aromatic carboxylic acid using an oxidation reactor, wherein the oxidation reactor is divided into an upper portion and a lower portion by a virtual plane perpendicular to a middle portion of the vertical axis, and includes The first agitator and the second agitator are respectively disposed radially on the upper portion and the lower portion to be perpendicular to the vertical axis, and include an oxygen-containing reaction gas, a pyrolysis aromatic compound, a solvent, a catalyst, and a reflux liquid. The reactant is fed to the lower portion of the oxidation reactor, and the product after the reaction and the gas system after the reaction are discharged to the upper portion of the oxidation reactor. In this case, the reflux temperature may be lower than the internal temperature of the oxidation reactor. Other aspects, features, and/or advantages of the invention will be set forth in the description of the appended claims. [Effects of the Invention] As described in the above specific examples, the present invention provides a method for producing an aromatic carboxylic acid using an oxidation reactor, which exhibits excellent reaction characteristics and thus can reduce the loss of unreacted raw materials and the resulting The amount of impurities 'reduces the loss caused by the oxidative decomposition of the solvent used in the oxidation reaction period, and can significantly improve the overall reaction efficiency and the quality of the aromatic product of the resulting product', resulting in a significant reduction in production cost. That is, according to the exemplified specific example, the reaction rate of the unreacted alkyl aromatic compound around the second agitator disposed under the agitating shaft of the oxidation reactor and the rate of the aliphatic acid retardation can be maximized. Further, the concentration of the unreacted aromatized compound in the oxidation reactor and the loss of acetic acid due to the oxidation reaction of acetic acid may be remarkably lowered as the direction of the liquid surface of the oxidation reactor. Therefore, the concentration of the unreacted alkyl aromatic compound in the gas phase region of the reactor can be significantly reduced and discharged to the unreacted raw material of the heat exchanger, the steam column, and the like installed for treating the exhaust gas. The amount can be significantly reduced, so that the supplementary recovery step can be omitted. Further, the reaction between the oxygen-containing gas and the alkyl aromatic compound of the raw material is carried out before the reaction with acetic acid, which causes the loss of acetic acid as a solvent to be reduced. Further, according to the exemplified specific example, the product discharge pipe through which the product is discharged to the outside is disposed in the upper portion of the oxidation reactor, thereby preventing the aromatic carboxylic acid product produced by the oil oxidation reaction from being mixed and adhered. In the wall or bottom of the oxidation reactor 7 201119993, and circulated to the lower part of the oxidation reactor. As a result, the product can be discharged safely without increasing the stirring power, and thus has a significant effect on economic efficiency and quality. [Embodiment] Hereinafter, the present invention will be more specifically described by way of examples. However, it is to be understood that the examples are for illustrative purposes only and are not intended to limit the scope of the invention. Fig. 1 is a schematic cross-sectional view showing an oxidation reactor 100 for producing an aromatic carboxylic acid according to an exemplary embodiment of the present invention. Referring to Fig. 1 'the oxidation reactor 100 for producing an aromatic carboxylic acid (hereinafter referred to as "oxidation reactor") includes a reaction chamber H0, a stirring shaft 105, a first agitator 12, a second agitator 130, The gas delivery tube 14A, the reactant delivery tube 15A, the return delivery tube 160, the product discharge tube 17A, the gas discharge tube 180, and the flow blocker 19A. The reaction chamber 11A according to the specific example of the present example can be formed into a cylindrical shape, but the present invention is not limited thereto, and thus can be formed into various shapes. The agitator shaft 1〇5 can be formed along the geometric vertical axis of the reaction chamber 110. The vertical axis may be a region corresponding to the suspension axis of the cylindrical reaction chamber 110. The agitating shaft 105 can transmit the first and second agitators 12A and 13A of the rotational power using power transmission. The first and second agitators 120 and 130 may be radially spaced apart from each other in a direction perpendicular to the agitating shaft 150. The first agitator 120 may be disposed at an upper portion of the reaction chamber 110 and the second agitator 130 may be disposed at a lower portion of the reaction chamber 11''. Further, even if at least three agitators are provided in the reaction chamber 110, two agitators 120 and 130 are provided according to the specific example of the present example. However, in the case of considering the power and efficiency of the system, it is preferred that the oxidation reactor 1 〇〇 8 201119993 has two 120 and 130. The first and second agitators 12A and 13A may have a radial structure extending in a single direction or in a plurality of directions perpendicular to the agitating shaft 105. The first and second agitators 120 and 130 can perform a stirring operation on the reactants by rotating relative to the stirring shaft 1〇5. The first and second agitators 12A and 13A may be a Korean-like impeller having a structure for creating a horizontal swirling flow at the end of the device due to a light-radiating structure, and simultaneously in the reaction chamber 1 The gas staying area is not created, and the reactor can be made as long as the fluid can flow smoothly through the end of the impeller. That is, the first and second enterprises 120 and 13G may have a junction in the reaction chamber m that does not create a gas staying area = ' and the agitator includes the spoiler wings 122 and 132, the agitating wing having a The surface of the = and end. The portion is bruised or bent to allow fluid to flow smoothly through the end of the applicator. Small " Flute According to the specific example of the present example, the first and second agitators 12A and m may have a second fm and a second agitating wing m, respectively. Furthermore, the first and second agitator 120 shafts 105: the first support member 120 and the second support member 134 are respectively coupled to the agitating unit 134, and the individual agitators 120 and 130 are supported by the supporting member 124 The belt has a direction perpendicular to the axis 105 of the age to create a virtual rotating surface with 132. At least two agitating blades 122 and a plate of the ends of the supporting members 124 and 134, the supporting members 124 and 134 may be formed into a circular shape having an inclined surface to be mixed with the round plate. The upper or lower surface '^ is inclined with respect to the virtual surface that is curved into the arc 05. In addition, the circular plate may have a shape as long as the branch <inclined surface. The support members 124 and 134 may be formed in any shape, and the preferred members 124 and 134 may extend from the agitating shaft 105 in a radial shape. However, the support members 124 and 134 can be formed to have a lower inclined surface. This is because the upward circulation from the vertical circulating fluid can be enhanced. The angle of the inclined surface of the slanting surface may be about 15 to 20 degrees with respect to the horizontal surface. Further, the ends of the stomach supporting members 124 and 134 may be formed into a gentle curve shape, but may be formed in a silver tooth shape. Figs. 2(a) and 2(b) are respectively a developed view and a cross-sectional view of the agitator wing 200 according to a specific example of the present invention. Referring to Figure 2(a), the agitator wing 2 may have a trapezoidal shape as shown in the expanded view. It is apparent that the wing 2 can be formed into various shapes having at least one curved portion or at least one curved portion to cause various development patterns. The wing 200 is bendable at the first curved portion 212, which is perpendicular to the centerline of the trapezoid and thus formed into a wedge shape. Furthermore, the wing 2 can be bent at the second curved portion 222, which is the BC segment of the triangle ABC. In this case, the wing 200 may be bent in the opposite direction of the first curved portion 212 from the second curved portion 222. Next, the wing 2〇〇 may include a first agitator 21〇 formed by the first curved portion 212 and a second agitator 220 formed by the second curved portion 222. Further, the wing 200 may have a wedge-shaped opening portion that is curved by the first curved portion 212. The wedge-shaped opening portion can be oriented in the direction of rotation of the agitators 120 and 130. Referring again to FIG. 2(a), according to the specific example of the present example, the bc segment of the wing 2〇〇 can be bent to have a length corresponding to 65% to 75% of the length of the trapezoidal corresponding segment, and the AC of the wing 200 The segments may be curved to have a length corresponding to 20% to 30% of the length of the corresponding trapezoidal segment. In this case, the points b and c of the 'AB segment and the AC segment can be adjusted according to the characteristics of the fluid in the reaction chamber 110. Referring to FIG. 2(b), the first curved portion 212 may have an angle (〇〇45 to 75 degrees, 201119993 and the second curved portion 222 may have an angled egg 20 in the opposite direction to the first curved portion 212. To i60 degrees 4, the angles (4) and (p) can be adjusted to have various angles according to the characteristics of the fluid in the reaction chamber. As described above, the agitators 120 and 130 can be prevented from being introduced into the reaction chamber. The gas containing oxygen molecules remains in the reaction chamber 11G, so that the bubbles are easily thinned and easily dispersed uniformly to increase the contact area between the gas and the liquid, and thus the mass transfer characteristics with the liquid. The uomso may include at least two transfer wings 122 and 134, and for example 2 to 8 carrying wings 122 and 134. In particular, the applicators 12 and 13 may preferably include 4 to 6 agitating blades 122. And 134. Referring to the _, the installation position of the scramblers 120 and 130 has a significant influence on the lion of the mixture in the reaction chamber n〇, and thus together with the structure of the immersion mixers (10) and (4), can achieve the aspect of the present invention. Important factor. According to this example The first stirring (10) and the second traveling between the feeder 120 and the length (or diameter) of 13° _ proportional diameter (T) 0.4 to 0.5 times, that is, D / T = 〇 4 to illusion Door m and the reaction silk surface, the length of the second agitator (3) and (10) (9) - half, the feeder is F/D <1.0, the upper search for the under-supplied field that is not fully implemented may be heavy and sturdy. Furthermore, when the coffee is 5, the insufficient search domain U is born in the middle part of the 201119993 between the first and the second difficulty (10). Also, when D/T <0.4, the contact between the raw material and the oxygen-containing gas may be insufficient, and thus the mass transport coefficient may be lowered. Alternatively, when D/T > 0.5, an insufficient agitation zone may be generated below the agitator 130. Similarly, when c/d <〇5, this; the foot agitation zone may be generated below the agitator 130. The oxidation reaction step in the insufficient agitation zone may be difficult to carry out, and thus the intermediate production of the oxidation reaction may increase. According to the specific example of the present example, the agitator 12 〇 and 13 〇 may have a rotational speed of 1 Torr to 100 rpm, and preferably 70 to 90 rpm. Further, the stirrer may have a stirring force of 2.08 W/M3 to 4.42 kW/M3. The aspect of the present invention can achieve a transport position and transport method of the liquid substance transported in the oxidation reactor 1 , a transport position and transport method of the gas, a transport position and transport method of the fluid, and a discharge position and discharge method of the product The structure and mounting position of the agitators 120 and 130 can be associated with one another to perform the functions they possess. In particular, the aforementioned transport position and transport method and discharge position and discharge method can be designed according to the movement of the fluid in the reaction chamber 110, and it can maximize the reaction efficiency and product purity. Referring again to Fig. 1, the oxygen-containing gas can be transported through the gas delivery tube 14 to the Song rank reaction chamber 110. The oxygen-containing gas may be delivered to the vicinity of the second agitator 13 or near the bottom surface of the reaction chamber 110. Further, the raw material, the catalyst and the solvent in a liquid state can be transported to the reaction chamber 11 by using the reactant delivery tube 150. Again, the reflux can be delivered to the reaction chamber 11 via a return conduit 160. The reflux may refer to a liquid in which the gas element obtained after the oxidation reaction is circulated after being subjected to the condensation step, and introduced into the reaction chamber 110. 12 201119993 According to this example, the gas delivery pipe 140, the reactant delivery pipe 15〇, and the return delivery pipe 160 may be disposed according to a virtual horizontal surface on which the second agitator 13 is disposed. It is relatively close to the second agitator 13 〇. That is, the conveying pipes 140, 150, and 160 may be respectively disposed in half the length 1) of the second agitator 13〇, from the virtual surface toward the agitating shaft 1〇5. Further, as described above, in the case where the support member 134 of the second agitator 13 is a circular plate and has a lower inclined surface with respect to the upper surface of the circular plate, the gas delivery tube 140 may be downward. It is disposed below the second agitator I%. Fig. 3 is a plan view showing the gas delivery pipe 34A, the reactant delivery pipe 350, and the fluid delivery officer 360, respectively, disposed in the reaction chamber 11 according to an exemplary embodiment. Referring to Fig. 3, the gas delivery tube 340, the reactant delivery tube 350, and the fluid delivery tube 360 may be spaced apart from each other at regular intervals. All 6 gas delivery pipes 340 group 2 are divided into 1 group and can be adjacent to each other, all 3 reactant conveying pipes 35 〇 can be regularly set to have an angle of 120 degrees with the adjacent pipe, and 2 return conveying pipes 360 can be Set to face each other. The spacing between the tubes 340, 350 and 360 may be substantially the same. Through the arrangement of the transfer pipes 340, 350, and 360, the contact area of the mixed gas in the liquid state, the substance and the reflow period can be increased, and a uniform dispersion of the mixture can be obtained. Further, the end portions of the respective transport tubes 340, 350, and 360 inserted into the reaction chamber 110 may be bent toward the rotational direction of the agitators 120, 130, and preferably toward the tangential direction of the rotational direction. Thus, the gas, the reactant and the reflux can be fed to the reaction chamber 11 in the direction of rotation. This is because the gas, the reactant and the reflux can be fed to the reaction chamber 110 in accordance with the flow direction of the mixing. 13 201119993 Referring again to FIG. 1 'the reflux may be a mixture of evaporation, moisture, etc. of the heat of reaction generated by the oxidation reactor 110, which may be a heat exchanger installed outside the oxidation reactor (not shown) the liquid element to be condensed, and may be a gas element in which the non-condensable gas system is separated. This reflux can be circulated through the return conduit 160 to the reaction chamber 11〇. In this case, the reflow temperature may be lower than the internal temperature of the reaction chamber 110, and more specifically, may be lower than the internal temperature of the reaction chamber 110 by about 20 ° C to 60 ° C ° according to an exemplary embodiment. The aromatic carboxylic acid is produced such that an alkyl aromatic compound of a reaction raw material such as p-xylene and a solvent such as acetic acid are contacted with an oxygen-containing gas to be reacted. In general, the internal temperature of the reaction chamber I10 can be made higher by the generation of heat of oxidation reaction caused by contact with the oxygen-containing gas, and thus the oxidation reaction rate can be gradually accelerated, and thus the solvent such as acetic acid The rate of oxidative decomposition can be accelerated. However, according to the specific example of the present example, since the reflux is fed to the reaction chamber 110 at a lower temperature via the reflux delivery pipe 160, the reflux can act to lower the ambient temperature heated by the oxidation reaction. Therefore, the oxidative decomposition of the solvent such as acetic acid can be suppressed. That is, the effect of this suppression can be obtained by allowing the reflux having a low temperature to coexist in the vicinity of the reactant (including gas) of the oxidation reaction. Further, the agitators 120 and 130 of the present invention may be respectively disposed at an upper portion and a lower portion of the reaction chamber 110. When the reflux is not fed to the reaction chamber 110, the oxidization of the raw material (alkyl aromatic compound) transported to the agitator 130 may gradually be rotated by the horizontally generated by the second agitator 130. Occurs in the fluid and at the same time oxidative decomposition of acetic acid can occur. However, the oxidation reaction of the alkyl aromatic compound may occur before the oxidative decomposition of the acetic acid because the liquid crystal temperature is lowered by mixing the low temperature reflux to the horizontal rotating fluid. Therefore, the loss due to the oxidation reaction of the 201119993 solvent such as acetic acid can be significantly reduced. Further, since the majority of the oxygen of the horizontal rotating fluid transported to the lower portion of the reaction is 110, the second stirrer is attached. The concentration of the unreacted alkyl aromatic compound, the concentration of the generated impurities, and the reaction rate of acetic acid in the horizontal rotating fluid near 130 can be maximized in the vicinity of the second agitator 130. However, the oxidation reaction of the unreacted aroma aromatic compound with the generated impurities can be carried out prior to the oxidation of the caproic acid by raising the residual gas and the appropriate upward circulating fluid and horizontal rotating fluid produced by the agitator. In this case, the oxidation reaction of the unreacted alkyl aromatic compound with the generated impurity may proceed as if the alkyl aromatic compound and the impurity are closer to the upper portion of the reaction chamber 110, and thus the unreacted alkyl aromatic compound and the The generated impurities do not actually remain on the surface of the liquid of the oxidation reactor. Therefore, the concentration of the unreacted alkyl aromatic compound carried by the upward circulating fluid, the impurity produced, and the oxidation rate of the acetic acid can be expressed according to their height at the height of the reaction chamber 110, and More specifically, it may decrease as the alkyl aromatic compound, the impurity, and the acetic acid are closer to the upper portion (liquid surface) of the oxidation reactor 100. According to the specific example of the present example, the concentration of the unreacted alkyl aromatic compound relatively close to the liquid surface of the oxidation reactor 100, excluding the non-condensable gas element, may be about 0.01 wt. or less, preferably about 7 wt. . /❶ or less, and more preferably about 0.005 wt% or less. In this case, the concentration of the unreacted alkyl aromatic compound in the gas phase portion of the oxidation reactor, excluding the non-condensable gas element, may be about 0.2% by weight or less, preferably about 0.015% by weight or more. Less, and more preferably about 001% by weight or less, which is a small amount of significant 'no need for separation and recovery steps by gas discharge treatment. 15 £ 201119993 Referring again to FIG. 1 , the end of the product discharge pipe 170 is disposed at an upper portion of the agitator 120 such that the product after the oxidation reaction can be from the upper portion of the reaction chamber 110 or the liquid surface. The product is discharged through the product discharge pipe 170. Therefore, the positioning portion of the product discharge pipe 17〇 protruding outside the reaction chamber 11〇 can be not significantly limited. Further, the gas element generated after the oxidation reaction can be discharged to the outside of the reaction chamber 110 via the gas discharge pipe 180 connected to the upper cover of the reaction chamber 110. As described above, the oxidation reactor 100' for producing an aromatic carboxylic acid according to the specific example of the present example may include agitators 120 and 130 to generate a horizontally rotating fluid and an upwardly circulating fluid agitator, and may be adapted to carry the inclusion An oxygen gas, for example, a material in a liquid state of the raw material, and the reflux to the vicinity of the second agitator 130, and thus can be generated by the ascending gas in the oxidation reactor 100 and the agitator 〇2〇 and 13〇 A suitable upward circulating fluid is oxidized with the horizontal rotating fluid. In this case, the oxidation reaction proceeds more closely with the upper portion of the oxidation reactor 100, and the unreacted raw material is not present near the surface of the liquid. That is, the concentration of the alkyl aromatic compound in the vicinity of the surface of the reaction solution of the oxidation reactor may be about 0.01% by weight or less, and the reaction rate for conversion to the aromatic carboxylic acid may be about 99.99 by weight. /. . More specifically, the concentration of the unreacted alkyl aromatic compound in the vicinity of the surface of the reaction solution of the oxidation reactor may be about 0.01% by weight, preferably 0.007% by weight, and more preferably about 不可. 5 wt% or less. In general, the remaining aromatic compound of the alkyl aromatic compound in the vicinity of the surface of the liquid can be recovered by a heat exchanger, a high (four) column, together with the exhaust gas from the upper portion of the oxidation reactor UH), however, The present invention does not require this recycling step. 201119993 In addition, when the discharge of the product is carried out near the bottom surface of the conventional oxidation reactor, the product discharge pipe may be blocked by the solid matter adhering to the wall of the oxidation reactor and settled. However, this example shows a specific example. This type of problem can be avoided. That is, the oxidation reactor 100 of the specific example of the present embodiment can perform the discharge function of the product continuously and for a long time to improve the operation efficiency. The use of the aromatic carboxylic acid according to the specific example of the present example can reduce the reaction rate of acetic acid as a solvent, and the loss due to the oxidation reaction of the aromatic carboxylic acid produced in the oxidation reaction can be about 2.7% by weight or Less, and preferably may be about 2.5% by weight or less. Referring again to Figure 1, the oxidation reactor 100 can include a baffle 190 disposed on a side wall of the reaction chamber 11A to regulate fluid flow. Two to eight flow stops can be placed at equal intervals. The width of the baffle 190 can be about 5% to 20% of the diameter (τ) of the reaction chamber 110. Further, the baffle 190 may require the surface of the reaction solution installed in the reaction chamber 11 to be equal or lower. When the flow damper 190 is installed at a position higher than the surface of the reaction solution, the slurry element may be inclined to adhere to the wall of the baffle 190 above the surface of the reaction solution, and thus crystal growth may occur. . This crystal may fall into the reaction chamber 110 to interrupt the stable operation of the sample reactor 100. Hereinafter, a method of producing an aromatic carboxylic acid will be described in detail. Oxidation step (1) Alkyl aromatic compound (raw material) As the alkyl aromatic compound, even if it is used as a raw material of the specific examples shown in the present example, an aromatic compound containing a burning group can be used. The aromatic ring compound constituting the aromatic compound may be a single ring (monocyclic) compound or a multiple ring (polycyclic) compound. 17 201119993 As the alkyl group, a methyl group, an ethyl group, a n-propyl group and an isopropyl group can be used. Further, the alkyl group may have a functional group. For example, as the functional group, an aldehyde group 'fluorenyl group, a carboxyl group, a hydroxyl group or the like can be used. Examples of the aromatic compound substituted by the Beijing playing machine include alkylbenzenes, alkylnaphthalenes and alkylbiphenyls having 2 to 4 alkyl groups each having 1 to 4 carbon atoms, for example. m-Diisopropylbenzene, p-diisopropylbenzene, m-isopropyl benzene, p-isopropyl benzene, m-xylene, p-xylene, trimethyl, and the like. Further, as the aromatic compound containing an alkyl group, a compound containing a substituent other than the alkyl group can be used. Examples of the alkyl group-containing aromatic compound include 3-mercaptophenylfurfural, 4-mercaptophenylfurfural, m-methylbenzoic acid, p-nonylbenzoic acid, and 3-methylmercaptobenzoquinone. Acid, 2-methyl-6-methylnonylnaphthalene, and the like. The above compounds may be used singly or in combination of two or more. (2) an oxidation step for producing terephthalic acid, which comprises diphenylbenzene as a raw material of the oxidation reactor, a solvent, a catalyst, an oxygen-containing gas, and a circulating solution of certain elements of the mother liquor produced in the separation step, Etc. will be described in detail later, placed in the oxidation reactor 100, and then reacted. As the solvent, an aliphatic carboxylic acid such as acetic acid, propionic acid, formic acid, lactic acid or the like can be used, however, a solvent including acetic acid as a main element is preferably used. When terephthalic acid is used as a raw material, the solvent may be used in an amount of from 1 to 10 times, preferably from 2 to 8 times, and more preferably from 3 to 6 times, to the usual starting materials. When the amount of the acetic acid is remarkably small, the concentration of the body is remarkably increased, and the problem of blockage of the line is caused; and when the amount of the acetic acid is remarkably large, a large apparatus may be required and an economic problem is caused. As the solvent of the specific example of the present embodiment, a mixture of acetic acid and water is preferably used. In the case of 18 201119993, the amount of water may be (iv) parts by weight and based on the amount of acetic acid (UH), preferably 5 to 15 parts by weight, based on 100 parts by weight of acetic acid. Examples of the oxygen-containing gas include air, oxygen diluted with an inert gas, and a large amount of helium containing air. (4) Actually, air can be used. Based on the raw material, the oxygen (4) can be used with oxygen having 3 moles to the moles. The oxidation reactor (10) may have an oxygen content of about 21% by volume in the line. = The concentration of oxygen in the gas just discharged from the oxidation reactor may be W _ %, and preferably .5_% (four) pp %. The 8 volume surface (4) is limited as long as the catalyzed catalyst can be converted into a aromatic acid by oxidizing the scented aromatic compound in a liquid. As the catalyst, = metal H can be used and the compound (4) can be used as the weight of the catalyst compound (10)), succinic, = (group 釓 (Pb), 铨 (Hf), 钸 (Ce), etc. 5, '〇 种 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Salt, compound filling, etc., and in particular, acetate can be used in combination with evolution; # As an example of a side compound, an inorganic compound can be cited, such as molecular desert, evolution a / odorization, desertification, evolution Meng et al; and organic desert compounds, such as methyl desert ', *-,, ι φ ^, I / Wu 〒 pit, bromoform (bromoform), benzyl bromide, bromomethyl methyl +, burn one / smell B Burning, tetrabromoethane, etc. These bromine compounds may be used singly or in combination of two or more kinds. When the sulphuric acid is used to produce the p-dicarboxylic acid, and when the p-xylene is oxidized, the brominated σ is used as the catalyst. It is preferable to use a catalyst obtained by a combination of 彡m desertification and the combination of hydrogen and desert 201119993 hydrogen. According to the specific example of the present example, as a catalyst obtained by combining a heavy metal compound and a bromine compound, from 0.05 mol to 10 mol of bromine atoms, and preferably from 0.1 mol to 5 mol, based on 1 mol of the metal. The bromine atom of the ear. The catalyst is used as a solvent heavy metal catalyst, and can be used in an amount of about 10 ppm by mass to 10,000 ppm by mass, and preferably about 100 ppm by mass to 3,000 ppm by mass. The oxidation reaction temperature can be about 140. °C to 250 ° C, and preferably 150 ° C to 230 ° C. When the temperature of the oxidation reaction is significantly low, the rate of oxidation reaction is reduced, and when the temperature of the oxidation reaction is significantly high, the acetic acid acting as a solvent The loss caused by the faint increase will increase. The heat of reaction generated during the oxidation reaction period may be the heat of vaporization generated by evaporation of the solvent, and may be removed to the outside of the oxidation reactor 1 to regulate the temperature of the oxidation reaction. The generated steam may be composed of a condensable element such as a solvent of acetic acid, water, or the like, and a non-condensable element such as nitrogen, oxygen, etc. In this case, the vapor may be installed in the oxidation reactor 1 The heat exchanger on the outer side of 00 is condensed and separated into gas and solid. Secondly, the exhaust gas from the gas can be transported to a high-temperature adsorption column, a distillation column, an expander, etc., thereby recovering effective elements. With the recovery of energy, the separated liquid can be circulated as reflux in the oxidation reactor 100. Further, the distillation column can be installed in the upper portion of the oxidation reactor 100 instead of the heat exchanger, and thus can be separated into water. And a solvent. In this case, the solvent may be circulated in the oxidation reactor 100, and the water containing the gas phase element may be classified into a condensable element and a non-condensable element in the heat exchanger, and used for recovery, The operation of the purpose of energy recovery, etc. The pressure of the oxidation reaction may require at least a pressure that maintains the mixture at least at the reaction temperature in a liquid state, and requires at least atmospheric pressure. Specifically, the reaction pressure 201119993 may require a pressure of about 22 MPa to 6 MPa and preferably a pressure of about 44 MPa to 3 MPa. In order to facilitate the transport of the resulting aromatic tickotropic polymer, it is preferably relatively high, thereby contributing to the reduction of side reactions. Further, it is preferably a relatively low pressure from the pressure resistance of the reaction vessel, the installation cost, and the like. The oxidation reaction can be carried out continuously, and the reaction time (average residence time) of the oxidation reaction can be from about 30 to 300 minutes, and specifically from about 4 to 15 minutes. When the reaction time is significantly short, the oxidation reaction may be poorly performed, causing deterioration of the quality of the aromatic carboxylic acid; and when the reaction time is significantly long, the loss due to ignition of the solvent of acetic acid may increase, and the capacity of the oxidation reactor It may become bigger and cause economic problems. According to this example, a specific example can be implemented as needed. With respect to the subsidizing step, the oxidation step of the product obtained by the oxidation reaction can be continuously carried out at least in the presence of oxygen without requiring a raw material to be fed at a temperature lower or higher than the temperature of the oxidation reaction. ^ Separation step The product obtained through the oxidation step may be crystallized to increase the crystal 1 ' and then the crystal product may be washed using the @•liquid separation step, or may be directly cleaned using the solid-liquid separation step. The solid obtained may be a polymer auxoic acid' and a refining step (which will be detailed later (d)). Some of the elements in the mother liquor can be recovered and recycled, and the residual elements in the separated mother liquor can be pre-drawn by maintaining temperature and pressure, which can be cooled and circulated through the oxidation step. cycle. , Temple, Purification Step It may be necessary to refine the impurities contained in the crude aromatic carboxylic acid, 21 201119993, separated by the separation step to improve the purity. In general, the impurities can be deoxidized by the addition of hydrogen to increase the solubility of the impurities, and thus can be separated by the difference in solubility of the limitedly dissolved oxalic acid. Second, the aromatic carboxylic acid can be washed and dried to obtain a fine aromatic carboxylic acid. Since the separated mother liquor contains deoxidized impurities and an intermediate of the aromatic carboxylic acid, the separated mother liquor can be recovered for use in the oxidation reaction. In the above, a method for producing an aromatic carboxylic acid, particularly a high-purity carboxylic acid, which is applicable to a process for producing a medium-purity carboxylic acid, which can perform a two-stage oxidation step at high pressure and high temperature, omits refining step. In the two-stage oxidation step, the product of the oxidation reaction of the first stage can be carried to the oxidation reactor of the second stage, and the oxygen-containing gas can be carried to the oxidation reactor, thereby continuously performing the oxidation reaction. However, the oxidation reaction of the first stage can be the same as the oxidation reaction described above. The reaction temperature of the second stage oxidation reaction may be about 23 Torr. (: to 29. (TC, and preferably about 240 ° C to 280 ° C. The pressure of the oxidation reaction of the second stage may require a pressure capable of maintaining the reaction mixture in a liquid state. In this case, the second The pressure of the oxidation reaction in the stage may be from 3 MPa to 10 MPa, and the residence time may be from 5 to 12 Torr, and preferably from 10 to 60 minutes. Since a part of the aromatic carboxylic acid particles of the slurry are dissolved and the oxidation of the particles is intermediate The system is oxidized by the two-stage oxidation reaction for two reasons, and the purification step can be omitted. However, the purity carboxylic acid having a relatively low purity relative to the high purity carboxylic acid obtained using the purification step can be used by the two The oxidation reaction of the stage is obtained. The oxidation reactor according to the specific example of the present example can be applied to the oxidation reaction step to carry out the process for producing a medium purity aromatic carboxylic acid. Hereinafter, the present invention will be described in more detail by way of examples. These examples are for illustrative purposes only and are not intended to limit the scope of the invention. 22 201119993 [Example 1] 1 part by weight of p-toluene, 5 parts by weight of acetic acid, and 5 parts by weight of water , feeding to the oxidation reaction ^, as well as the catalytic chemistry, acetic acid clock and desertification nitrogen are also fed to the oxidation reaction 1 at a temperature of about 185. (: to 195. (: with a pressure of about 1_^ to 1.7MPa Under conditions f; 5 & oxidation reaction 9 () minute oxidation period (average residence time). Catalyst with drill, fierce and desert, with metal @言, content is 3〇〇 quality, melon, 300 mass PPm and 700 mass The ppme uses air as the oxygen-containing gas. In this case, a gas having a volume of about 21% by volume of oxygen and a compressed gas system is transported to the oxidation reactor so that the oxygen concentration of the gas discharged into the oxidation reactor has 3 volumes. % to 7 vol%. The oxidation reactor of Figure 1 is used as the oxidation reactor. The lengths of the first and second agitators 120 and 13G are 2,55 () mm, from the bottom of the oxidation reactor to The vertical distance of the first agitator 130 is ι, 5 mm, and the distance from the second scrambler 13 to the first agitator 120 is 3,200 mm. The product is discharged from the upper portion of the oxidation reactor, It is 4,1 mm apart from the first agitator 130. For example, pressure The reactants of the gas, the reflux, the raw material, the solvent, the catalyst, and the like are transported to the same height as the second agitator 13〇 in the tangential direction of the rotation direction of the second agitator 13〇. It is the same as the conveying pipe of Fig. 3. The compressed gas is conveyed via a gas delivery pipe 140 (a total of 6 pipes), and an acetic acid solution composed of a paraxylene, acetic acid/water mixture and a catalyst is mixed in advance in the mixing chamber. And the recovered solution circulated in the separation step is transported through the reactant delivery pipe 150. The reflux is transported via a return pipe (a total of 2 pipes). In addition, 'between individual pipes 14 〇, 15 〇 and 16 〇 The distance from the rotating circumference of the second agitator 130 is about 1 mm. The temperature at which the reflux to the oxidation reactor 100 was carried was 15 Torr. 〇 to 160. 〇, and the oxidation reaction £ 23 201119993 The internal temperature of the apparatus 100 is at least 5 degrees lower than the internal temperature of Comparative Example 1. Further, in the case of the oxidation reactor of Example 1, the clogging phenomenon of the product discharge pipe 170 did not occur for half a year, and the stable operation of the oxidation reactor 100 was understood. The product discharged from the product discharge pipe 170 is continuously conveyed to the auxiliary oxidation reactor, and the reaction time of the embodiment is 35 minutes under the conditions of a temperature of 180 ° C to 190 ° C and a pressure of 9 9 MPa to 1.5 MPa ( Average residence time). The gas (oxygen concentration 21% by volume) was fed to the oxidation reactor so that the oxygen concentration of the exhaust gas was 3 vol% to 7% by volume, and then the low temperature auxiliary oxidation reaction was carried out. The auxiliary oxidation reaction was carried out using a reactor equipped with a conventional two-stage dish turbine. The product obtained by the auxiliary oxidation reaction is subjected to crystal precipitation in a staged manner using a crystal precipitation tank connected to the reactor in a three-stage series, and then the obtained product is subjected to solid-liquid separation via a vacuum rotary filter (RVF). The crude terephthalic acid was obtained by washing. 9% by mole of the reaction mother liquid subjected to the solid-liquid separation step was circulated in the oxidation reactor. Further, for example, a significant substance such as a catalyst or acetic acid is transported to the discharge treatment step after being recovered in the mother liquor, and is discharged. Next, the crude terephthalic acid is transported to the purification step, and the hydrogenation reaction of the above impurities is carried out under general purification conditions. Next, the impurities are deoxidized via the above crystal precipitation/separation step, and the terephthalic acid is separated to obtain high purity p-dicarboxylic acid. The results obtained are shown in Table 1, which will be compared with Comparative Example 1 described below. The results are explained together in the following text. [Comparative Example η An oxidation reactor was used, and the oxidation reaction was carried out under the same reaction conditions as in the oxidation reaction of Example 1. The initial reaction temperature was the same as in Example 1, however, the internal temperature of Comparative Example 1 after the stable operation of the reactor of S' 24 201119993 was at least 5 degrees higher than the internal temperature of the example "The interior of the oxidation reactor" The structure is shown in Figure 7. Fig. 7 is a schematic cross-sectional view showing an oxidation reactor 7A for producing an aromatic carboxylic acid of Comparative Example 1. Referring to Fig. 7, the oxidation reactor 700 includes a stirring shaft 7〇5, a reaction chamber 71, a first agitator 720, a second agitator 730, a gas delivery tube 74, a reactant delivery tube 75, and a reflux delivery officer. The 760' product discharge pipe 770 and the gas discharge pipe 78〇. The oxidation reactor 7 has the same capacity as in the first embodiment, and the first and second agitators 72 and 73 are respectively provided with six agitating blades. Further, the positioning of the first and second agitators 72A and 73A is the same as the positioning of the first and second agitators 12A and 13A of the embodiment. The respective lengths of the first and second agitators 720 and 730 are 2,300 mm, the vertical distance from the bottom of the oxidation reactor 700 to the second agitator 73 () is Μ(10) mm, and the second agitator The distance from the 73 〇 to the first agitator 72 为 is 3, 2 mm. The transportation of air is performed in the second forest 73, and the acetic acid solution composed of the p-quinone benzene, the acetic acid-water mixture and the catalyst is mixed with the circulating solution of the separation step, and transported to the The first age device is 72. The product is discharged from the vicinity of the bottom of the oxidation reactor 700. After the oxidation reaction, a supplementary oxidation reaction was carried out, and a separation step and a purification step were carried out under the same conditions as in the examples, and high-purity terephthalic acid was called. The results obtained in Example 1 and Comparative Example 1 are shown in Table J. The residual concentration of L to diterpene (ρχ) in Table 1 is the concentration of ruthenium (% by weight) near the surface of the liquid in the oxidation reactor, and the yield is the high purity of the crude dicarboxylic acid (ΡΤΑ) obtained from the raw materials of the 渺顿. The amount of product (kg) and the loss of acetic acid are depleted by the oxidation reaction in the oxidation reactor. < Amount of acetic acid (kg) relative to each hydrazine product. Furthermore, 25 201119993 The concentration of ρ 于 in the gas phase region of the reaction is the PX concentration (% by weight) of the element excluding the non-condensable gas in the reaction meteorological region 'and the PTA transmittance and the wavelength of the caustic alkali solution of the PTA product. Light transmittance (%) of 340 μm and 10 mm optical path 〇 [Table 1] Item Example 1 Comparative Example 1 PX-residual concentration (% by weight) 0.0100 0.6000 Yield (1 ton PTA/100 ton PX 150.59 148.74 Acetic acid loss (kg/ton, PTA product) 26.5 28.5 ρχ-concentration (weight 〇/〇) in the gas phase region of the reactor 0.020 0.670 PTA transmittance (%) 91 89 As shown in Table 1, comparison As a result of Example 1 and Comparative Example, it was found that the reaction yield was improved, the acetic acid loss was lowered, and the stable operation of the reactor was increased over time. Further, it was found that the unreacted raw material in the gas phase region of the oxidation reactor was remarkably lowered to the dimethyl group, and it was not necessary to use a paraxylene recovery device. Further, as shown by the light transmittance of ρτΑ, the light transmittance of the caustic alkali aqueous solution of the ruthenium product is improved and the amount of impurities, and the representative impurity of ruthenium is markedly lowered by 4-carboxybenzaldehyde (CBA). Fig. 4 is a graph showing the degree of unreacted p-xylene with respect to height based on the results obtained in Example 丨 and Comparative Example i. Fig. 5 is a graph showing the concentration of the impurity (4-recarbophene (CBA)) relative to the height based on the results obtained in the examples ^ and the comparative example 1. Fig. 6 is a graph showing the reaction rate of acetic acid with respect to the height based on the results obtained in Example 1 and Comparative Example. In order to obtain the results of Figs. 4 to 6 'to calculate the fluid dynamics (CFD), a fluid simulation was performed with respect to the concentration dispersion in the direction toward the surface of the liquid of the oxidation reactor. Referring to Figures 4 through 6, it was found that the concentration of unreacted p-diphenyl, residual 4-CBA and acetic acid in the oxidation reactor was significantly reduced. Further, the dispersion of the respective concentrations did not show a significant change, and the dispersion of the concentration near the surface of the liquid of the oxidation reactor was remarkably lowered. Although some specific examples of the invention have been shown and described, the invention is not limited to the specific examples disclosed. In addition, it is to be understood by those of ordinary skill in the art that the present invention can be practiced without departing from the spirit and scope of the invention. Defined. BRIEF DESCRIPTION OF THE DRAWINGS These and/or other aspects, features and advantages of the present invention will be more clearly understood from the following description of the exemplary embodiments and combinations of the following drawings: FIG. A schematic cross-sectional view showing an oxidation reactor for producing an aromatic carboxylic acid according to a specific example; FIGS. 2(a) and 2(b) are respectively a development view and a cross-sectional view of a wing of a stirrer according to a specific example of the present invention; 3 is a schematic plan view showing a state of a representative transfer tube provided in a reaction chamber according to a specific example of the present invention; FIG. 4 is a graph showing the concentration of unreacted dimethyl benzene in the results obtained in Example 1 and Comparative Example. Fig. 5 is a schematic diagram showing the concentration of impurities (4_base § 27 201119993 benzaldehyde (CBA)) relative to the height of the results obtained in Example 1 and Comparative Example 1; Fig. 6 is a view of Example 1 A schematic diagram of the reaction rate of acetic acid with respect to the result obtained in Comparative Example 1 with respect to the height; and Fig. 7 is a schematic cross-sectional view of the oxidation reactor for producing an aromatic carboxylic acid of Comparative Example 1. [Component Symbol Table] 100 '700 oxidation reactor 105' 705 agitator shaft 110, 710 reaction chamber 120' 720 first agitator 122, 132 agitating blades 124, 134 support member 130 '220 ' 730 second agitator 140 ' 340 740 gas delivery tube 150 '350 ' 750 reactant delivery tube 160 '360 ' 760 return delivery tube 170 , 770 product discharge tube 180 , 780 gas discharge tube 190 , 790 flow stop 200 wing 212 first curved portion 222 second Bending part C, F Distance D Stirrer length T Internal diameter α ' β Angle A, Β, C point
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