506989 Α7 Β7 五、發明說明（f ) 發明夕抟術鏔醻 (請先閱讀背面之注意事項再填寫本頁) 本發明像關於一種芳香族羧酸之製造方法及裝置，可 將含有烷基取代基或部份氧化酸烷基取代基之烷基芳香 族化合物，利用含氧氣體進行液相氧化。 習知抟術 芳香族羧酸類為重要之基礎化學品，尤其是芳香族二 羧酸，可用做纖維，樹脂等之原料。例如對苯二甲酸做為 聚酯原料，近年來需要量增加。 芳香族羧酸之製法一般是採取在氧化反應槽中，以重 金鼷化合物和溴化物為觸媒，於含乙酸等低級脂肪族羧 酸之反應溶劑中，令甲基取代之芳香族化合物與含氣氣 體接觸，進行液相氣化之方法〇此種製法中，偽於氣化 反應器内，導入對二甲苯等烷基取代芳香族化合物原料 ，乙酸溶劑和觸媒之混合物，以及空氣等含氣氣體，進 行氧化反應，生成對苯二甲酸等芳香族羧酸。 經濟部智慧財產局員工消費合作社印製 從氣化反應器排出之氧化排氣，會附帶溶劑或觸媒等 ，為回收再用，設有連接氣化反應槽上部之蒸餾塔，利 用排氣熱進行蒸餾，回收溶劑回流到氧化反應槽（特公 昭5 4 _ 1 4 0 9 8和恃開平6 - 2 7 9 3 5 3號）。此法是將蒸餾塔流 出的排氣，在冷凝器中以冷卻水冷卻，使排氣中的蒸氣 冷凝，令冷凝水用流到蒸餾塔，用於蒸餾。 在此種氧化反應器上部設有蒸餾塔之裝置中，含大量 水的餾份保持蒸餾塔。此等餾份在蒸餾塔下方的乙酸等 反應溶劑濃度高，可就此回流到氧化反應器，往上則反 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐） 506989 A7 B7 五、發明說明（ 全應 若反 份化 餾氣 的入 塔流 餾劑 蒸溶 C在的 增持度 遞保濃 量 ，低 份時因 的止則 水停 ， 而急器 ，緊應 減在反 遞置化 度裝氧 濃，到 劑此流 溶因回 應都 且 ο 啓 P. 0 以置 難裝 置型 裝大 使為 .成 度必 溫體 和全 度 ， 濃成 的構 液塔 應 一 反以 低塔旨 降餾要 ，蒸明 器因發 和 法溫 方低 造 、 製度 之濃 酸低 羧含 族止 香防反 芳可化 種 ，氣 一 時到 供況流 提情回 於等塔 在LK餾 ，停蒸 的急從 目緊份 之置餾 明裝之 發，劑 本置溶 裝度 易 容 置 裝 使 器 應 置 裝 及 法 方 造 製 〇 之 化酸 型羧 小族 塔香 餾芳 蒸下 使如 可於 時關 同偽 ， 明 動發 啓本 再 造 製 之 酸 羧 族 香 芳 t 0 (請先閱讀背面之注意事項再填寫本頁) ，以 中 ， :器下 含應在 包反存 ，化媒 為氧觸 徽在化 特物氧 其合 ， ， 化 内 法族劑 方香溶 芳應 基反 烷之 令酸 ,羧 驟族 步肪 化脂 氧含 於 羧 族 香 芳 成 生 下 壓 高 溫 高 在 化 氧 相 液 行 進 體 氣 氧 ， 含酸 一 化 第氣 入至 導流 氣回 排份 化餾 氣的 的劑 器溶 應 應 反反 化含 氧令 將 ， ，餾 驟蒸 步行 餾進 蒸内 一 塔 第餾 蒸 經濟部智慧財產局員工消費合作社印製 餾第 蒸至 二流 第回 入份 導餾 氣之 排劑 的溶 塔應 餾反 蒸度 一 溫 第低 將含 ， 令 驟 ， 步餾 餾蒸 ，蒸行 器二進 應第内 反 塔 者第 液在 流驟 回步 之凝 塔冷 餾間 蒸中 一 有 第具 至中 出其 取 ， 塔法 餾方 蒸載 二所 第項 ，從 1 塔可第 餾中逑 蒸其上 一 如 2 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 506989 厂——_______________, Λ7 !-^-L—____________ 五、發明說明（）） 一蒸餾塔和第二蒸餾塔間設置中間冷卻器，將第一蒸 餾塔排氣中的蒸氣加以冷凝者。 3 .如上述第1項之方法，其中在第一蒸餾塔和第二蒸餾 塔間設有副再沸器，將第一蒸餾塔的排氣加熱，導入 第二蒸餾塔者。 4. 如上述第1至3項中任一項之方法，其中可從第一蒸 餾塔下方取出餾份者。 5. —種芳香族羧酸之製造裝置，包括 氧化反應器，將烷基芳香族化合物在含脂肪族羧酸 之反應溶劑中，於氧化觸媒存在下，以含氧氣體進行 液相氣化，在高溫高壓下生成芳香族羧酸； 第一蒸餾塔，導入氧化反應器的氧化排氣，進行蒸 餾，將含反應溶劑之餾份回流至氣化反應器； 第二蒸餾塔，導入第一蒸餾塔的排氣，進行蒸餾將 含低溫度反應溶劑之餾份回流至第一蒸餾塔； 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閒讀背面之注意事項再填寫本頁) 訂---------線< 蒸之 蒸， 第 C 二中 二熱 從 者第氣 第加 可 液和排 和氣 中 流塔塔 塔排 其 回餾餾 餾之 ， 之蒸蒸 蒸塔 置 塔一一 一餾 裝 ^ 第第 第蒸 之 -¾在將 在一 載 第中可 中第 記 至其， 其將 項 出 ，器 ，可 一 取置卻 置，。任 可裝冷 裝器者中 塔載間。載沸内項 鋪所中者所再塔 7 蒸項有凝項副餾至 二 5 設冷 5 有蒸 5 第第間以第設二第 中述之加述間第述 其上塔氣上塔入上 如餾蒸如餾導如 _·· 經濟部智慧財產局員工消費合作社印製 506989 A7 B7 五、發明說明（1 下明 塔說 餾蜇 蒸簡 一 式 圖 對 為 圖 圖 統 条 之 例 施 實 置 〇 裝 者造 份製 餾酸 出甲 取二 方 ，苯 有 具 用 可 料 原 化 氣 之 酸 羧 族 香 芳 造 製 中 法 方 调一 發 本 物 合 化 族 香 芳 之 基 代 取 基 烷 的 V-·, 化料 氧原 份化 部氣 或稱 基單 代時 取有 基下 烷以 環 單 可 為 物 合 化 族 香 芳 等 此 基 甲 如 例 有 基 代 取 基 焼C4述- X 上 C 〇 等 環基 多丙 為異 可和 亦基 基 烷 丙 正 N 基 乙 基 0 如 例 有 基 烷 之 化 氧 份 部 而 族 香 芳 代 取 基 烷 即 物 合 化 C 族 等香 基芳 烷之 羥基 、代 基取 羧基 、烷 基有 _ 具 間苯 、 甲 苯二 基對 丙 、 異苯 二 甲 對二 、間 苯 、 基苯 丙基 異甲 二基 間丙 如異 例對 有 、 ,苯 例基 體甲 具基 之丙 烴異 類 WTS 4 C 苯 -基 C1N3 有二 具 ， 等類 類苯 苯基 基甲 甲二 四 ， 及類 以苯 ，基 類烷 苯多 基或 甲二 三之 、個 - 2 基 烷 異二 (請先閱讀背面之注意事項再填寫本頁) 有 1 C 具 有等 具類 等苯 類聯 苯基 基甲 丙二 或二 之 個 4- 2 基 烷 類 苯 基 烷 基 烷 等 類 苯 聯 基 烷 多 之 値 4 經濟部智慧財產局員工消費合作社印製 具物 ， 合 又化 逑 部 有 烷 化 氧 中 烷 等苯 基甲,2 烷間酸 羥、甲 或醛苯 基苯K 羧基甲 基之甲 部 經 基 甲 ,s0 物 、 合基 化醛 族]¾ 香前 芳為 之成 基 ， 代化 取氣 基份 上 基 甲 4 種 4 、二 、酸或 醛甲獨 苯苯單 基醯可 甲甲此 3-3-凡 有 、〇 例酸等 體甲類 具苯苯 0 甲 _ 物對甲 合 、6 化酸· 觸 為 物 合 化 溴 和 物 合 化 屬 金 重 用 使 中 C法 用方 使明 合發 混本 上在 以 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 506989 Α7 Β7 五、發明說明（S ) (請先閱讀背面之注意事項再填寫本頁) 媒，其化合物例如下。即重金屬化合物中之重金屬有例 如鈷、錳、鎳、鉻、結、銅、鉻、給、鈽等。可單獨或 組合使用，尤以鈷和錳組合使用為佳。 此等重金屬化合物有例如乙酸鹽、硝酸鹽、乙醯基丙 剛酸鹽、環烷酸鹽，甘油硬脂酸鹽，溴化物等，以乙酸 鹽為佳。 溴化合物有例如分子溴、溴化氫、溴化銷、溴化鉀、 溴化鈷、溴化錳等無機溴化物，甲基溴，二溴甲烷，溴 仿，τ基溴，溴化甲基甲苯，二溴乙烷，三溴乙烷，四 溴乙烷等有機溴化合物等。此等溴化合物可單獨或二種 以上混合使用。 本發明中，上述重金屬化合物和溴化合物組合構成之 觸媒，對每1莫耳重金屬原子具有溴原子〇β〇5〜10莫耳， 以0.1〜2莫耳範圍為佳。此等觸媒，以反應溶劑中的重 金屬濃度通常10〜10000ΡΡ祖範圍使用，以1〇〇〜5000ppffi 為佳。 經濟部智慧財產局員工消費合作社印製 本發明方法之氧化步驟，是在氧化反應器中，於前逑 觸媒存在下，在含低級脂肪族羧酸之反應溶劑中，將氧 化原料之芳香族化合物，利用含分子氯之氣體，進行液 相氧化，而得芳香族羧酸製品。 上述含分子氧之氣體，有例如氧或空氣等，惟實用上 以使用空氣為佳。含分子氧的氣體，需以超過將氧化原 料的芳番族化合物氯化成芳香族羧酸之必要量供應。使 用空氣為含分子氣之氣體時，相對於每公斤芳香族化合 -7- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 506989 l [^v^l — L-----補充i 五、發明說明（〇 物，以2〜2 0 N m 3 ，最好是2 · 5〜1 5 N m 3比例供應至反應 条為佳。 (請先閱讀背面之注意事項再填寫本頁) 用做反應溶劑的低級脂肪族羧酸具體例，有乙酸、丙 酸、丁酸等。低级脂肪族羧酸可單獨用做反應溶劑，可 與水混合成混合物狀態用做反應溶劑。反應溶劑之具體 例有乙酸、丙酸、丁酸，及其混合物，或此等低级脂肪 族羧酸與水之混合物 其中乙酸和水之混合物，尤以對 乙酸1 0 G重量份，混合水1〜2 0重量份之混合物為佳，而 以5〜1 5重量份更好。 氧化反應的溫度通常為1 〇 〇〜2 5 G °C範圍，以1 5 Q〜2 2 0 °C為佳。反應壓力以可保持反應条為液相之壓力以上即 可。 由如此反應可得與芳香族化合物氧化原料相對應之芳 香族羧酸。芳香族羧酸之具體例有對苯二甲酸、異苯二 甲酸、2,6-苯二甲酸，4,4’-聯苯二羧酸等芳香族二羧 酸；苯偏三酸，苯均三酸等芳香族三羧酸；苯均四酸等 芳香族多羧酸等。 經濟部智慧財產局員工消費合作社印 本發明方法適用於製造芳香族二羧酸，或者不溶於或 難溶於反應溶劑之芳香族羧酸，尤其適用於製造對苯二 甲酸。 生成之對苯二甲酸等芳香族羧酸結晶析出，成為漿液 ，從氣化反應槽取出此漿液，經固液分離，回收結晶， 卽可得粗製對苯二甲酸等粗製生成物。 如此所得粗製生成物的結晶中，令帶有氣化反應中間 -8- 本紙張尺度適用中國國家標準（CNS)A4規格（21〇χ 297公釐） 經濟部智慧財產局員工消費合作社印製 506989 A7 B7 五、發明說明（Ί) 體或雜質，經粗製生成物瑢解、氣化處理、還原處理等 精製步驟，使對苯二甲酸等結晶析出時，可得含結晶之 漿液。由此等漿液回收結晶，即得精製對苯二甲酸等精 製物〇 本發明製造裝置包含氣化反應器，將烷基芳香族化合 物在含脂肪族羧酸之反應溶劑中，於氣化觸媒存在下， 以含氧氣體進行液相氧化，在高溫高懕下生成芳香族羧 酸；第一蒸餾塔，導入氧化反應器的氣化排氣，進行蒸 餾，將含反應溶劑之餾份回流至氧化反應器；第二蒸餾 塔，導入第一蒸餾塔的排氣，進行蒸餾，將含低濃度反 瞧溶劑之餾份園流至第一蒸餾塔；其中第二蒸餾塔可取 出至第一蒸餾塔之回流液。 第一蒸餾步驟偽將氧化排氣導入連接至氣化反應器上 方之第一蒸餾塔（高壓蒸餾塔），利用氧化反應器的發熱 進行蒸餾，令含反應溶劑的餾份從塔底回流氧化反應器 ，並將含蒸氣和非冷凝性氣體之排氣從塔頂棑出。第一 蒸餾塔可用特公昭5 4 - 1 4 0 9 8號所示與氣化反應器分開， 或如特開平6 - 2 7 9 3 5 3號所示設在氡化反應器上方。蒸餾 塔可用多層塔，惟以充镇塔為佳，，此持芳香族羧酸的 結晶或觸媒等徹細固體捕集機構，例如固體捕集盤，以 設在充镇層下側為佳。 第二蒸餾步驟僳將第一蒸餾塔之排氣導入第二蒸餾塔 進行蒸餾之步驟。第二蒸餾塔傷與第一蒸餾塔獨立配置 ，將第一蒸餾塔塔頂排氣導入塔底進行蒸餾，令餾出含 -9 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁)506989 Α7 Β7 V. Description of the invention (f) Invention invention (please read the precautions on the back before filling this page) The present invention is like a method and a device for producing an aromatic carboxylic acid. Alkyl aromatic compounds based on radically or partially oxidizing acid alkyl substituents are subjected to liquid-phase oxidation using an oxygen-containing gas. Aesthetics: Aromatic carboxylic acids are important basic chemicals, especially aromatic dicarboxylic acids, which can be used as raw materials for fibers and resins. For example, terephthalic acid is used as a polyester raw material, and demand has increased in recent years. The production method of aromatic carboxylic acid is generally adopted in an oxidation reaction tank, using a heavy metal compound and a bromide as a catalyst, and in a reaction solvent containing a lower aliphatic carboxylic acid such as acetic acid. A method of gas-gas contacting and liquid-phase gasification. In this manufacturing method, pseudo-xylene and other alkyl-substituted aromatic compounds, a mixture of acetic acid solvent and catalyst, and air are introduced into the gasification reactor. The gas is oxidized to generate an aromatic carboxylic acid such as terephthalic acid. The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the oxidizing exhaust gas discharged from the gasification reactor, which will be accompanied by solvents or catalysts. For recycling, a distillation tower connected to the upper part of the gasification reaction tank is used to utilize the exhaust heat Distillation was performed, and the recovered solvent was refluxed to the oxidation reaction tank (Texaco 5 4 _ 1 4 0 9 8 and Xi Kaiping 6-2 7 9 3 5 3). In this method, the exhaust gas flowing out of the distillation column is cooled with cooling water in a condenser to condense the vapor in the exhaust gas, and the condensed water is flowed to the distillation column for distillation. In the device provided with a distillation column in the upper part of such an oxidation reactor, the fraction containing a large amount of water maintains the distillation column. These fractions have a high concentration of reaction solvents such as acetic acid below the distillation tower, and can be refluxed to the oxidation reactor in this way. Above the paper size, the Chinese National Standard (CNS) A4 (210 x 297 mm) is applicable. 506989 A7 B7 V. Description of the invention (All should be reversed if the distillate gas enters the tower stream and the distillate is evaporated. The concentration of C will increase and the concentration will be maintained. When it is low, the water will stop, and the emergency device should be reduced to The anti-displacement degree is filled with oxygen concentration, and the solution is due to the dissolution. P P. 0 The ambassador of the installation device is the temperature. The degree must be warm and full. The concentrated structured liquid tower should be reversed. The main purpose of the distillation is to reduce the distillation. The steamer is made low by the method and method, and the system is rich in acid and low carboxylic acid. LK distillation, the urgent need to stop the distillation from the immediate installation of the distillate, install the solvent, easy to install the device, the device should be installed and made by the French acid acid carboxyl family tower aroma distillation Under the steaming condition, if the acid can be closed at the same time, the acid carboxylic acid produced by the re-formation Family Fragrant t 0 (please read the precautions on the back before filling this page), in which: the bottom of the container contains the anti-storage in the package, the chemical medium is the oxygen contact emblem, the chemical features are oxygenated, and the internal French family The formula is soluble in aromatic acid, and the carboxylic acid of the alkane group is contained in the carboxyl group. Fatty oxygen is contained in the carboxyl group. Under high pressure and high temperature, the gaseous oxygen travels in the oxygenated liquid phase. Dissolve the gas into the solvent of the distillate. The oxygen-containing order should be reversed, and the distillate should be distilled on foot and then distilled into the first column of the distillate. The dissolving column of the second-flow first-distillation gas-removing agent should be distilled at the lowest temperature, and the steam distillation step should be included. The first step in the cold distillation of the condensing tower of the condensing tower is from the first to the middle. The tower method distills the steam and loads the second item. From the first tower, the distilling steam is steamed. National Standard (CNS) A4 Specification (210 X 297 mm) 506989 Factory ——_______________, Λ7!-^-L —____________ V. Description of the invention ()) An intercooler is installed between the first distillation column and the second distillation column to condense the vapor in the exhaust gas from the first distillation column. 3. The method according to item 1 above, wherein a secondary reboiler is provided between the first distillation column and the second distillation column, and the exhaust gas from the first distillation column is heated and introduced into the second distillation column. 4. The method according to any one of items 1 to 3 above, wherein the distillate can be taken out from below the first distillation column. 5. —A kind of aromatic carboxylic acid manufacturing device, including an oxidation reactor, the alkyl aromatic compound in a reaction solvent containing an aliphatic carboxylic acid, in the presence of an oxidation catalyst, liquid phase gasification with an oxygen-containing gas An aromatic carboxylic acid is generated at a high temperature and pressure; the first distillation column is introduced into the oxidation exhaust of the oxidation reactor, and distillation is performed to return the fraction containing the reaction solvent to the gasification reactor; the second distillation column is introduced into the first The exhaust of the distillation column is subjected to distillation to return the fraction containing the low-temperature reaction solvent to the first distillation column; This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the first Please fill in this page again.) Order --------- Line of steaming, steaming of the second, second, and second heat followers, the first, the second, the liquid, and the exhaust gas. Distilling it, the steaming steaming tower is set up one by one. ^ The first steaming -¾ will be recorded in the first load in the first load, it will be out of the project, the device, can be placed one at a time. . Anyone who can install a cold loader in the tower load room. Reloading tower in the boiler house of the internal charge 7 steaming item has condensing side distillate to 2 5 set cold 5 has steaming 5th second to the second and the second one is added to the upper part of the gas described above Distilling and distilling, distilling, distilling, and so on _ ·· Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs's Consumer Cooperatives 506989 A7 B7 V. Description of the invention Really install the contents of the product to distill the acid and take the two sides. The benzene has the acid carboxyl group aromatics which can be used to make raw gas. The French method transfers the base of the compound aromatic group to the alkane. V- ·, when the oxygen of the raw material is converted into the radical gas or the radical is monobasic, an alkyl radical is used, and the cyclomono may be a chemical compound, such as a fragrant aromatic compound. C o and other cyclic polypropenes are isocoryl and alkanepropane n-N-ethylethyl. For example, if the alkane has an oxygen moiety and the family aryl is replaced by an alkane, the C group and other aryl aryls are synthesized. Hydroxy, substituted group is carboxyl, alkyl has _ with m-benzene, toluene diyl C, isophenylene terephthalate, m-phenylene, phenylphenylisopropylidene, m-propylene, etc. There are two different types of propane isopropane, WTS 4 C, benzene-based C1N3, etc. Types of phenylphenyl methyl dimethyl benzene, and benzene, alkane phenyl polymethyl or methyl benzene, dimethyl alkane bis (please read the precautions on the back before filling this page) There are 1 C Benzene biphenyl methylpropane or diphenyl 4- or 2-phenyl alkane, phenyl alkyl alkane, or other phenyl phenyl alkane, etc. 4 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs There are phenyl methyl groups such as alkylene in alkylating oxygen, 2 alkyl hydroxy, methyl or aldehyde phenylbenzene, K carboxymethyl, methyl group, methyl group, s0 compound, and aldehyde group. ] ¾ Xiangqianfang is the base, and it is substituted with four kinds of dimethyl groups on the gas base. 4, 2, di, acid, or aldehyde methyl monophenylbenzene monomethyl methacrylic acid, such as 3-3-everything, 0 acid, etc. Body A with phenylbenzene Reuse the Chinese C method, make the Minghe hair mixed, and apply the Chinese National Standard (CNS) A4 specification (210 X 297 mm) at this paper size. 506989 Α7 Β7 V. Description of the invention (S) (Please read the back first Please fill in this page again), the compounds are as follows. That is, the heavy metals in the heavy metal compounds include, for example, cobalt, manganese, nickel, chromium, junction, copper, chromium, hydrogen, and thallium. It can be used alone or in combination, especially cobalt and manganese. These heavy metal compounds include, for example, acetate, nitrate, ethanoylpropanoate, naphthenate, glyceryl stearate, bromide and the like, and acetate is preferred. Bromine compounds include inorganic bromides such as molecular bromine, hydrogen bromide, bromide, potassium bromide, cobalt bromide, manganese bromide, methyl bromide, dibromomethane, bromoform, tau bromide, methyl bromide , Dibromoethane, tribromoethane, tetrabromoethane and other organic bromine compounds. These bromine compounds can be used singly or in combination of two or more kinds. In the present invention, the catalyst composed of the combination of the above heavy metal compound and bromine compound has a bromine atom of 0 β 05 to 10 mol per 1 mol of heavy metal atom, and a range of 0.1 to 2 mol is preferable. These catalysts are usually used in the range of 10 to 10,000 PP ancestors in the concentration of heavy metals in the reaction solvent, preferably 100 to 5000 ppffi. The oxidation step of the method of the present invention is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs in an oxidation reactor in the presence of a catalyst in the presence of a catalyst in the reaction solvent containing the lower aliphatic carboxylic acid. The compound is subjected to liquid-phase oxidation using a gas containing molecular chlorine to obtain an aromatic carboxylic acid product. The molecular oxygen-containing gas is, for example, oxygen or air, but it is preferable to use air in practice. The molecular oxygen-containing gas needs to be supplied in an amount exceeding the amount necessary to chlorinate the aromatic compound of the oxidation raw material to an aromatic carboxylic acid. When using air as a molecular gas-containing gas, relative to the aromatic compound per kg -7- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 506989 l [^ v ^ l — L-- --- Supplement i V. Description of the invention (〇 物 ， 2 ～ 2 0 N m 3, preferably 2 · 5 ～ 1 5 N m 3 ratio to the reaction bar is better. (Please read the precautions on the back first) Fill in this page again) Specific examples of lower aliphatic carboxylic acids used as reaction solvents include acetic acid, propionic acid, butyric acid, etc. The lower aliphatic carboxylic acids can be used alone as the reaction solvent, and can be mixed with water to form a mixture for the reaction. Solvents. Specific examples of the reaction solvent are acetic acid, propionic acid, butyric acid, and mixtures thereof, or mixtures of these lower aliphatic carboxylic acids and water, among which a mixture of acetic acid and water, especially 10 G parts by weight of acetic acid, mixed A mixture of 1 to 20 parts by weight of water is preferred, and 5 to 15 parts by weight is more preferred. The temperature of the oxidation reaction is usually in the range of 100 to 25 G ° C, and 15 to 20 ° C The reaction pressure should be at least the pressure that can keep the reaction strip in the liquid phase. An aromatic carboxylic acid corresponding to an aromatic raw material for oxidation. Specific examples of the aromatic carboxylic acid include terephthalic acid, isophthalic acid, 2,6-phthalic acid, 4,4'-biphenyldicarboxylic acid, and the like. Aromatic dicarboxylic acids; Aromatic tricarboxylic acids such as trimellitic acid, trimesic acid, etc .; Aromatic polycarboxylic acids such as pyromellitic acid, etc. The method of the present invention is applicable to the production of aromatics. Dicarboxylic acids, or aromatic carboxylic acids that are insoluble or hardly soluble in the reaction solvent, are particularly suitable for the production of terephthalic acid. The resulting aromatic carboxylic acids such as terephthalic acid crystallize out and become a slurry from the gasification reaction tank. Take out this slurry, separate it by solid-liquid, and recover the crystals. The crude products such as crude terephthalic acid can be obtained. The crystals of the crude products obtained in this way have a gasification reaction in the middle -8- This paper is applicable to China Standard (CNS) A4 specification (21 × χ297 mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed 506989 A7 B7 V. Description of the invention (Ί) The body or impurities are decomposed, gasified, and reduced by the crude product Processing In the step, when crystals such as terephthalic acid are precipitated, a slurry containing crystals can be obtained. From this slurry, the crystals can be recovered to obtain refined products such as terephthalic acid. The manufacturing device of the present invention includes a gasification reactor, Aromatic compounds in a reaction solvent containing an aliphatic carboxylic acid, in the presence of a gasification catalyst, are subjected to liquid-phase oxidation with an oxygen-containing gas to generate an aromatic carboxylic acid at a high temperature and high temperature; a first distillation column is introduced into the oxidation reaction The gasification exhaust of the reactor is subjected to distillation, and the fraction containing the reaction solvent is refluxed to the oxidation reactor; the second distillation column is introduced into the exhaust of the first distillation tower, and the distillation is performed, and the fraction containing the low-concentration reverse solvent is distilled. The stream flows to the first distillation column; the second distillation column can take out the reflux liquid of the first distillation column. In the first distillation step, the oxidation exhaust gas is pseudo-introduced into a first distillation column (high-pressure distillation column) connected above the gasification reactor, and the heat generated by the oxidation reactor is used for distillation, so that the fraction containing the reaction solvent is refluxed from the bottom of the oxidation reaction. And exhaust gas containing vapor and non-condensable gas from the top of the tower. The first distillation column can be separated from the gasification reactor as shown in JP 5 4-1 4 0 9 8 or can be installed above the tritiated reactor as shown in JP 6-2 7 9 3 5 3. The distillation column can be a multi-layer column, but a filling town tower is preferred. This solid solid trapping mechanism, such as a crystal or catalyst of an aromatic carboxylic acid, such as a solid trap tray, is preferably located on the lower side of the charging town. . The second distillation step: a step of introducing the exhaust gas from the first distillation column into the second distillation column for distillation. The second distillation column is separately configured from the first distillation column. The exhaust gas from the top of the first distillation column is introduced into the bottom of the column for distillation, so that the distillate contains -9-This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) (Please read the notes on the back before filling this page)
Li--------訂---------缚 506989 經濟部智慧財產局員工消費合作社印製 A7 _B7__ 五、發明說明（ί ) 有低濃度反應溶劑的餾份回流至第一蒸餾塔。第二蒸餾 塔構成和第一蒸餾塔大致相同，惟不需要固體捕集層等 固體捕集機構。由第二蒸餾塔回流至第一蒸餾塔的回流 液，可利用設置支路等方法取出条外，緊急停止等情況 時可時取出条外，防止回流至第一蒸餾塔，藉此防止回 流至氧化反應器降低反應液之濃度和溫度 第一蒸餾塔和第二蒸餾塔基本上是把習用蒸餾塔一分 為二。從反應熱回收高溫熱能時，在兩塔間設有中間冷 卻器，將第一蒸餾塔的排氣加以冷卻，使排氣所含蒸氣 冷凝，進行熱回收，此時第二蒸餾塔的塔徑可以縮小〇 另外，若帶入氣化反應器的水鼍多，僅就反應熱而言 ，回流比低，以致増加第一和第二蒸餾塔合計塔高，則 在第一蒸餾塔和第二蒸餾塔之間設置外側再沸器，將第 一蒸餾塔之排氣加熱，即可降低第二蒸餾塔的塔高。 以此第一和第二蒸餾塔進行蒸餾時，隨氧化排氣排出 含反應溶劑之餾份，即回流至氧化反應器。此餾份除反 應溶劑處β未反應烷基芳香族化合物，生成之芳香族羧 酸，觸媒等，以濃縮狀態，做為塔底液回流到氧化反應 器。其中，芳香族羧酸結晶或觸媒等固體，在蒸餾塔下 方補集。原料芳香族羧酸或副産物，以及反應溶劑等， 從第一蒸餾塔下方至第二蒸餾塔上方，依序餾出沸點由 高往低之生成物。 第二蒸_塔的排氣中含有大量蒸氣，雖設有冷凝器， 將其冷凝水等水回流至第二蒸餾塔以進行蒸餾，惟第二 -10- 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐） (請先閱讀背面之注意事項再填寫本頁) 1T---------線- 經濟部智慧財產局員工消費合作社印製 506989 Α7 Β7 五、發明說明（1 ) 蒸餾塔餾出的反應溶劑等濃度低。通常蓮轉中，此等第 二蒸餾塔的低濃度餾份偽回流至第一蒸餾塔，在第一蒸 餾塔吸取餾出之餾份，成為高濃度餾份，回流至氧化反 應器，再利用於氧化反應。 其中，裝置在緊急停止之際，低濃度、低溫度之餾份 會再回流至氧化反應器，降低氣化反應器之反應液濃度 ，以致裝置的再啓動困難，故本發明在裝置緊急停止等 情況時，第二蒸餾塔的餾份不回流至第一蒸餾塔，而是 取出条外。因此可以防止因低濃度，低溫度餾份回流到 氧化反應器使反應液的濃度或溫度降低，故再啓動容易。 在第一蒸餾塔下方設備盤等液體取出機槽時，亦可從 第一蒸餾塔下方取出餾份，以防第一蒸餾塔的餾份回流 至氧化反應器。第一蒸餾塔取出的餾份，可用做氧化反 應器取出的漿液經固液分離所得結晶之洗淨水β 第一蒸餾塔的排氣與中間冷卻器加以冷卻塔，在回收 排氣中之熱時，可同時將排氣中所含蒸氣之一部份冷凝 ,以減少排氣容積，因而縮小第二蒸餾塔的塔徑。中間 冷卻器可用鍋型冷凝器以發生蒸汽，由此蒸汽宜藉蒸汽 渦輪機回收能鼍。中間冷凝器改用外側再沸器時，可提 高回流比，降低第二蒸餾塔高度β 蒸餾塔的排氣和蒸氣於冷凝器利用冷卻水冷卻，將排 氣中的蒸氣冷凝9可生成冷凝水回流至蒸餾塔，同時將 冷卻水蒸發，發生新的蒸汽為佳。可用複數冷凝器，令 排氣依次通過呈階段性冷凝，分別獲得從高能量的蒸汽 一 11 一 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 0 訂：--------線-- 506989 A7 _B7 五、發明說明（P) 到低能量的蒸汽，將此蒸汽導入蒸汽渦輪機内，可以良 好效率回收能量。 由於使鍋型冷凝器，不必設有蒸汽發生容器，即可發 生蒸汽。故控制冷凝器的溫度，使冷凝步驟的排氣溫度 為5 0〜1 5 0 °C，以9 0〜1 2 0 °C為佳，即可令乙酸甲酯及其 他雜質大部份保持在棑氣中，因而冷凝水即可就此回流 至蒸餾塔，亦可用於洗淨結晶，加以有效利用，同時將 反_生成的水做為剩餘水排除条外時，可使排水處理容 易。 冷凝器的排氣可視需要在回收乙酸甲酯處，可在燃燒 器燃燒，將燃燒氣體導入氣體渦輪機，以回收能量。利 用氣體渦輪機和蒸汽渦輸機所回收能量，將含氣氣體加 可轉 還之 ，機 外輪 應渦 反體 化氣 氧、 行機 進輪 率渦 效汽 有蒸 了就 除，，W 器而 應體 反具 化 C 氣力 入電 導收 壓回 33 轉 此 用 共 軸 轉 -ST 之 機 〇 電量 發能 和收 機回 達於 壓用 接利 連效 接有 直可 .即 軸 ， 動軸 蒸停 二急 第緊 將置 可裝 ，遇 驟 ， 步 外 餾条 蒸出 二取 第份 如餾 一 之 第塔 有餾 設蒸 ,· 一 明第 發至 本流 照回 按塔 餾 ---------------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 流化 回型 份小 餾塔 的簾 劑蒸 溶使 度並 溫 ， 低動 /τ 7ΤΠΤΠ 、 啓 度再 濃易 低容 含置 It裝 防使 可 ， ，器 時應 況反 情化 等氣 fh至 製 之 酸 甲 二 應 對 43 明 説 画 附 照 參 態 形 施 實 之 明 施發 實本 之就 晛Η 發 在 ο 画 統 条 之 例 施 實 置 裝 及 法 製 酸 甲 二 苯 對 為 C 圓 下 1 如第 置 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員工消費合作社印製 506989 A7 B7 五、發明說明（Η) 第1 I覇中，ί為氧化反應器，上部直接連接充镇層式第 一蒸餾塔2，在其出口側經由具有鍋型中間冷卻器4之管 路L Γ連接第二蒸餾塔3。第二蒸餾塔3的塔底徑由具有泵 的管線L 2 ,連接第一蒸餾塔2上方。 對苯二甲酸製法，僳由管線L 3供應對二甲苯做為烷基 芳香族化合物原料，乙酸為反應溶劑，重金屬化合物和 溴化合物為觸媒，至氧化反應器1，由管線L 4供應空氣， 做為含氣氣體，在高溫高壓下進行液相氧化，以生成對 苯二甲酸。生成之對苯二甲酸即結晶析出，形成漿液。 氣化反應器1的氧化排氣出高溫高壓狀態進入第一蒸 餾塔2，通過充填層2 a間進行蒸餾。氧化排氣所含固體， 於下方之固體捕集盤21)除去並回流。第一蒸餾塔2下方 餾出高沸點餾份之對苯二甲酸或副産品，低沸點餾份的 乙酸一部份在比較上方餾出。此等餾份連同固體做為塔 底液回流至氧化反應器〇 第一蒸餾塔2的排氣由管線L 1進入中間冷卻器4的管 侧，利用殼側的冷卻水，使氣體中所含蒸氣一部份冷凝 ,以減少氣體的容景，同時將殼側的冷卻水一部份蒸發 ，發生蒸汽〇部份蒸氣在中間冷郤器4冷凝，排氣則進 入具有充镇層3 a之第二蒸餾塔3，殘餘乙酸在此實質餾出 。含乙酸的餾份由管線L 2利用泵5回流至第一蒸餾塔2。 裝置緊急停止時，即停止泵5,由管線L5排出回流液。 如此將蒸餾塔分成複數段，可從分段的蒸餾塔排出回 流液，緊急停止時可防止低濃度、低溫度的餾份回流至 -13 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 506989 匕:· A7 B7 五、發明說明（、>) 氣化反應器1。在第一蒸餾塔2和第二蒸蹓塔3間設有中 間冷卻器4 ,以回收部份熱，同時將部份蒸汽冷凝，減少 氣體容最，即可縮小第二蒸餾塔3之塔徑。中間冷卻器 4可以改設外側再沸器加熱，在此情況下可降低第二蒸 餾塔3的塔高。 第二蒸餾塔3的排氣依序通過冷冷器6 a，6 b ,利用殼側 的冷卻水使蒸汽冷凝，進入氣水分離器下進行氣水分離 ，冷凝水一部份由管線L 6回流至第二蒸餾塔3。在中間 冷卻器4和冷凝器6 a , 6 b利用熱交換，使殼側的冷卻水 蒸發，發生新的蒸汽。此蒸汽在中間冷卻器4側為高溫 高壓之高能景，在冷凝器6b惻依次成為低能量，分別由 管線1.7&，[71)，17^進入蒸汽渦輪機8，回收能量做為渦輪 機轉動力，由管線L8進入復水器9復水，由管線L9分流於 管線1, 9 a , L 9 b , L 9 c，做為冷卻水在中間冷卻器4和冷凝器 6 a，6 b循環。 在氣水分離器7分離的排氣，控制成在冷凝器6b出口 側的溫度為5 0〜1 5 (TC，以9 0〜1 2 0°C為佳，以保持乙酸 甲酯及其他雜質呈氣體狀態，由管線L 10導入加熱器11 内加熱。加熱過的排氣導入燃燒器1 2，通過觸媒層進行 燃燒。燃燒氣體導入氣體渦輪機13内膨脹，回收能量做 為渦輪機轉動力。氣體渦輪機1 3的排氣導入排氣處理裝 置1 4，將溴化合物等吸收除去，將排氣從管線L 1 1排出。 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐） ---------------------訂---------線· (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 506989 經濟部智慧財產局員工消費合作社印製 A7 B7_ 五、發明說明（、？） 蒸汽渦輪機8和氣體渦輪機1 3連結於同一轉動軸1 5， 構成能量回收裝置，對此轉動軸1 5施加負荷，使與壓縮 機1 6和發電機1 7連結。因此，利用蒸汽渦輪機8和氣體 渦輸機13画收之轉動能驅動氣體壓縮機16，將管線L12供 應之空氣壓縮，由管線L4供應含氣氣體至氣化反應器1, 進行氯化反應，並轉動發電機1 7，回收能量做為電力。 裝置啓動時，供電給發電機17，驅動氣體壓縮機6,蒸 汽渦輪機8和氣體渦輸機1 3 ,開始氣化反應，從進行氧 化反應附帶排出的氣化排氣，依次利用蒸汽渦輪機8和 氣體渦輪機1 3回收能量^移至正常蓮轉時，由於氣化反 應為發熱反應，由發熱繼續回收能量，除氣體壓縮機16 之外，還可利用泵5等動力，以及加熱等，進行蓮轉。 在氯化反應器】中利用氣化反應生成對苯二甲酸酸， 經結晶析出，形成漿液，由管線L15排出此漿液，以固 液分離器2 1進行固液分離。分離之母液為防止雜質積留 ,可部扮由管線L16排出，大部份由管線L17經管線L3循 環至氧化反應器1〇分離之結晶由管線L18移至固液分離 器2 2，此時利用由第一蒸餾塔2下方在管線L 1 9排出的 乙酸水洗淨，加以固液分離。管線L 2 0是在裝置緊急停 止時，排出蒸餾塔2的稀乙酸水，為防止氧化反應器1 内反應液稀釋而設，通常像關閉。 在固液分離器2 2分離之母液，由管線L 2 1循環至氣化 反應器1 ,結晶由管線L 2 2導入乾燥機2 3内加以乾燥，得 粗製對應二甲酸（C T A )。固液分離器2 1，2 2使用一個裝置 -15- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ---------------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 506989 Α7 Β7 十tS 年月日補充丨 五、發明說明（α 位 意 任 後 r 其 或 間 中 在 可 亦 , 0 淨壓 洗低 水至 酸降 乙壓 用高 途從 中壓 在把 可， , 置 機線 燥管 乾用 利 酸 甲二 苯 對 製 粗 的 過 燥 乾 線 管 由 和 水 疑 冷 之 應 供 ， 成 4* 2 形 機 ， 合水 混之 任環 進循 升之 因等 中媒 5 I 2 觸 置耙 裝镇 溫充 加入 在導 ，酸 酸甲 甲二 二苯 苯對 對製 製粗 粗之 之解 化溶 液 。 漿解 〇 溶 液而 漿溫 2 醛後 器苯理 應基處 反羧原 原4-還 還含Li -------- Order --------- Bound 506989 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _B7__ V. Description of the Invention (ί) Distillate with low concentration of reaction solvent refluxed to First distillation column. The structure of the second distillation column is substantially the same as that of the first distillation column, but a solid capture mechanism such as a solid capture layer is not required. The reflux liquid from the second distillation column to the first distillation column can be taken out of the strip by using a branch method, etc. In case of emergency stop, the strip can be taken out to prevent reflux to the first distillation column, thereby preventing reflux. The oxidation reactor reduces the concentration and temperature of the reaction solution. The first distillation column and the second distillation column basically divide the conventional distillation column into two. When recovering high-temperature thermal energy from the reaction heat, an intercooler is provided between the two towers to cool the exhaust gas from the first distillation tower to condense the steam contained in the exhaust gas for heat recovery. The diameter of the column can be reduced. In addition, if there is too much water in the gasification reactor, the reflux ratio is low only in terms of the heat of reaction, so that the total height of the first and second distillation columns is increased. An outer reboiler is arranged between the second distillation towers to heat the exhaust gas from the first distillation tower, thereby reducing the tower height of the second distillation tower. When the first and second distillation columns are used for distillation, the fraction containing the reaction solvent is discharged with the oxidation exhaust gas, that is, it is refluxed to the oxidation reactor. This fraction removes the β unreacted alkyl aromatic compound at the reaction solvent, the aromatic carboxylic acid produced, and the catalyst, etc., and returns to the oxidation reactor as a bottom liquid in a concentrated state. Among them, solids such as aromatic carboxylic acid crystals and catalysts are collected under the distillation column. The aromatic carboxylic acid or by-products of the raw materials, and the reaction solvent, etc., sequentially distill the products with high boiling points from below the first distillation column to above the second distillation column. The exhaust of the second steaming tower contains a large amount of steam. Although a condenser is provided, water such as condensed water is returned to the second distillation tower for distillation. However, the second paper size of this paper applies Chinese national standards (CNS ) A4 size (210 x 297 mm) (Please read the notes on the back before filling out this page) 1T --------- Line-Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 506989 Α7 Β7 V. Description of the invention (1) The concentration of the reaction solvent and the like distilled from the distillation column is low. Generally, in the lotus root transfer, the low-concentration fractions of these second distillation columns are pseudo-returned to the first distillation column, and the distillate fractions are absorbed in the first distillation column to become high-concentration fractions, which are refluxed to the oxidation reactor and reused. In the oxidation reaction. Among them, during the emergency stop of the device, the low-concentration and low-temperature fractions will be returned to the oxidation reactor to reduce the concentration of the reaction liquid in the gasification reactor, so that the restart of the device is difficult. In this case, the fraction of the second distillation column is not refluxed to the first distillation column, but is taken out of the bar. Therefore, it is possible to prevent the concentration or temperature of the reaction solution from being lowered due to the low-concentration, low-temperature distillate flowing back to the oxidation reactor, so that restarting is easy. When liquids such as equipment trays under the first distillation column are taken out of the machine tank, the fractions can also be taken out from below the first distillation column to prevent the fractions of the first distillation column from flowing back to the oxidation reactor. The fraction taken from the first distillation tower can be used as the crystallized washing water obtained by the solid-liquid separation of the slurry taken out of the oxidation reactor. Β The exhaust of the first distillation tower and the intercooler are added to the cooling tower to recover the heat in the exhaust. At the same time, a part of the steam contained in the exhaust gas can be condensed at the same time to reduce the volume of the exhaust gas, thereby reducing the diameter of the second distillation column. The intercooler can use a pan-type condenser to generate steam, so the steam should be recovered by a steam turbine. When the intermediate condenser is replaced with an external reboiler, the reflux ratio can be increased and the height of the second distillation column can be reduced. Β The exhaust gas and steam from the distillation column are cooled by cooling water in the condenser, and the vapor in the exhaust gas is condensed. It is refluxed to the distillation column, and at the same time, the cooling water is evaporated, and new steam is preferably generated. Multiple condensers can be used so that the exhaust gas can be condensed in stages in order to obtain high-energy steam. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). Please fill in this page again) 0 Order: -------- line-506989 A7 _B7 V. Description of the invention (P) To low-energy steam, which is introduced into the steam turbine, can recover energy with good efficiency . Since a pot-type condenser is used, it is not necessary to provide a steam generating container to generate steam. Therefore, the temperature of the condenser is controlled so that the exhaust temperature in the condensation step is 50 to 150 ° C, preferably 90 to 120 ° C, so that most of the methyl acetate and other impurities can be maintained at In the radon gas, the condensed water can be returned to the distillation column at this point, and it can also be used for washing and crystallization and effective utilization. At the same time, the waste water can be easily treated when the generated water is excluded from the strip. The exhaust gas from the condenser can be recovered at the methyl acetate as required, and can be burned in the burner to direct the combustion gas to the gas turbine to recover energy. Utilizing the energy recovered by gas turbines and steam vortex conveyors, the gas-containing gas can be returned, and the outer wheel of the engine should be vortexed to decompose gas oxygen, and the traveler's feed rate should be removed when steam is removed. The response of the body should be C. The pneumatic inlet conducts pressure and returns to 33. The coaxial-to-ST machine is used for this purpose. The power generation and the return of the machine are directly connected with the pressure. The shaft and moving shaft are steamed. After the second stop, it will be installed immediately. In the case of sudden steps, the second distillation column will take out the second portion. If the first column of the first distillation has a distillation setting, the first column will be sent to the current stream and the column will be distilled. ----------------- Order --------- line (please read the notes on the back before filling out this page) The curtain agent of the fluidized small fraction distillation column is steam-dissolved so that the temperature is low, low motion / τ 7ΤΠΤΠ, the opening degree is thicker, and the low-capacity container is equipped with it to prevent it from being used. fh Zhi's acid acid response should be 43. The description of the painting is based on the actual state of the application. Practical installation and legal acid methylbenzene are under C circle. 1 If the paper size is set, the Chinese National Standard (CNS) A4 specification (210 X 297 mm) is applied. Printed by the Employees ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 506989 A7 B7 V. Description of the invention (i) In the first I-bar, ί is an oxidation reactor, and the upper part is directly connected to the first ballast-type distillation column 2 and at the exit side thereof, via a line L with a pot-type intercooler 4 Γ Connected to the second distillation column 3. The bottom diameter of the second distillation column 3 is connected above the first distillation column 2 by a line L 2 having a pump. In the terephthalic acid production process, plutonium is supplied from line L 3 as the raw material of the alkyl aromatic compound, acetic acid is the reaction solvent, heavy metal compounds and bromine compounds are the catalysts, and to oxidation reactor 1, air is supplied from line L 4 As a gas containing gas, liquid-phase oxidation is performed at high temperature and pressure to generate terephthalic acid. The resulting terephthalic acid is crystallized out to form a slurry. The oxidizing exhaust gas from the gasification reactor 1 enters the first distillation column 2 at a high temperature and high pressure state, and is distilled through the filling layer 2a. The solids contained in the oxidized exhaust gas are removed from the solid trap 21) below and refluxed. Below the first distillation column 2, terephthalic acid or a by-product of a high-boiling fraction was distilled off, and a portion of the acetic acid of a low-boiling fraction was distilled off above the comparison. These fractions together with the solids are returned to the oxidation reactor as the bottom liquid. The exhaust gas from the first distillation column 2 enters the tube side of the intercooler 4 from the line L1, and the cooling water on the shell side is used to make the gas contained in the gas Part of the steam is condensed to reduce the appearance of the gas. At the same time, the cooling water on the shell side is partially evaporated, and steam is generated. Part of the steam is condensed in the intercooler 4, and the exhaust gas enters the In the second distillation column 3, residual acetic acid is substantially distilled off. The acetic acid-containing fraction was refluxed from the line L 2 by the pump 5 to the first distillation column 2. When the device is stopped in an emergency, the pump 5 is stopped and the reflux liquid is discharged from the line L5. Dividing the distillation column into multiple sections in this way can discharge the reflux liquid from the segmented distillation column, which can prevent the low-concentration and low-temperature fractions from flowing back to -13 during an emergency stop-This paper size applies the Chinese National Standard (CNS) A4 specification ( 210 X 297 mm) -------------------- Order --------- line (Please read the precautions on the back before filling this page) 506989 Dagger: · A7 B7 V. Description of the invention (>) Gasification reactor 1. An intercooler 4 is provided between the first distillation tower 2 and the second distillation tower 3 to recover part of the heat while condensing part of the steam to reduce the gas capacity, and the diameter of the second distillation tower 3 can be reduced. . The intercooler 4 can be replaced with an external reboiler for heating. In this case, the tower height of the second distillation column 3 can be reduced. The exhaust gas of the second distillation column 3 passes through the coolers 6 a and 6 b in sequence. The cooling water on the shell side is used to condense the steam and enter the gas-water separator for gas-water separation. Part of the condensed water is passed through the line L 6 Reflux to the second distillation column 3. The intercooler 4 and the condensers 6 a and 6 b use heat exchange to evaporate the cooling water on the shell side and generate new steam. This steam is a high-temperature and high-energy scene on the side of the intercooler 4 and becomes low-energy in sequence in the condenser 6b 恻, which enters the steam turbine 8 from lines 1.7 &, [71], 17 ^, and recovers the energy as the turbine's turning force From the line L8, it enters the dehydrator 9 to rehydrate, and from the line L9, it is divided into lines 1, 9a, L9b, and L9c, which are circulated as the cooling water in the intercooler 4 and the condensers 6a, 6b. The exhaust gas separated in the gas-water separator 7 is controlled so that the temperature on the outlet side of the condenser 6b is 50 ~ 15 (TC, preferably 90 ~ 120 ° C) to maintain methyl acetate and other impurities. In the gas state, it is introduced into the heater 11 through the line L 10 and heated in the heater 11. The heated exhaust gas is introduced into the burner 12 and burned through the catalyst layer. The combustion gas is introduced into the gas turbine 13 to expand, and the recovered energy is used as the turbine's rotational force. The exhaust gas from the gas turbine 1 3 is introduced into an exhaust treatment device 14 to absorb and remove bromine compounds, etc., and exhaust the exhaust gas from the pipeline L 1 1. The size of this paper applies to China National Standard (CNS) A4 (210 x 297 mm) ) --------------------- Order --------- Line · (Please read the notes on the back before filling in this page) Ministry of Economy Wisdom Printed by the Consumer Cooperative of the Property Bureau 506989 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7_ 5. Description of the invention (,?) The steam turbine 8 and the gas turbine 13 are connected to the same rotating shaft 15 to form an energy recovery device. This rotating shaft 15 applies a load to connect the compressor 16 and the generator 17. Therefore, The gas turbine 16 is driven by the rotational energy drawn by the steam turbine 8 and the gas scroll 13 to compress the air supplied from the line L12, and the gas containing gas is supplied to the gasification reactor 1 from the line L4 to perform the chlorination reaction and rotate The generator 17 recovers energy as electricity. When the device starts, it supplies power to the generator 17, drives the gas compressor 6, the steam turbine 8, and the gas turbine 1 3, and starts the gasification reaction, which is discharged from the oxidation reaction incidentally. The gasification exhaust gas is sequentially recovered by the steam turbine 8 and the gas turbine 1 3 ^ When moving to the normal lotus rotation, because the gasification reaction is a fever reaction, the energy is continuously recovered by the heat, in addition to the gas compressor 16, it can also be used The pump 5 and other power, as well as heating, etc., perform lotus rotation. In the chlorination reactor], the gasification reaction is used to generate terephthalic acid, which is crystallized and precipitated to form a slurry. 2 1 for solid-liquid separation. In order to prevent the accumulation of impurities, the separated mother liquid can be partially discharged from line L16, and most of it is circulated from line L17 through line L3 to the oxidation reactor. Move to solid-liquid separator 22, at this time, wash with acetic acid discharged from line L 1 9 under the first distillation column 2 and separate the solid-liquid. Line L 2 0 is discharged from the distillation column when the device is stopped in an emergency The dilute acetic acid water 2 is set to prevent the reaction liquid in the oxidation reactor 1 from diluting, and it is usually closed. The mother liquid separated in the solid-liquid separator 2 2 is circulated from the line L 2 1 to the gasification reactor 1 and the crystallization is carried out from the line. L 2 2 is introduced into the dryer 2 3 and dried to obtain the crude corresponding dicarboxylic acid (CTA). The solid-liquid separator 2 1, 2 2 uses a single device. -15- This paper applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) --------------------- Order --------- line (Please read the precautions on the back before filling this page) 506989 Α7 Β7 ten tS date five supplementary Shu, description of the invention (after bit according to any α r which is intended to be in the room or also, low water washing 0 net pressure drop of acetic acid to high pressure in the intermediate pressure can purposes,, Set the machine to dry the pipe. Use the dimethybenzene to make the thick over-dried pipe. The pipe should be supplied with water if it is suspected to be cold. It will be a 4 * 2 machine, mixed with water. Ren Huan follows the reason of the rise and so on. The medium 5 I 2 touches the rake, installs the town, warms the charge, adds the acid, methyl acid diphenylbenzene, and the pair to make the crude solution. Dissolve 〇 Solution and Serum temperature 2 Aldehyde postponer phenyl allergen base Carboxygen 4- Also contains
所 對 〇 mu ， 理 理處 處原 氫還 加以 行加 進質 ，雜 氫之 供表 G 2 代 L為 線π 管BA 由-C 力 壓 低 降 以 外 槽 析 晶 入 導 液 應 反 將 置 裝 溫 加 至 ’供 度 8 溫L2 低線 降管 以由 發 ， 蒸汽 水蒸 之液 液母 母之 發 蒸 ο 酸 甲二 苯 對 製 精 出 之 源 熱 做 用 定酸 不甲 所二 酸苯 甲對 二製 苯精 對出 製析 粗 。 解充 溶補 為等 ，油 中熱 5 2 ， 置汽 裝蒸 溫壓 加高 C 以 份 ， 部 熱 一 之 苯 2 對器 製離 精分 和液 液固 母為 成可 離亦 分 ， ，式 28段 器一 離為 分26 液器 固離 用分 利液 ，固 液 。 漿基 之甲 置 裝 卻 冷 入 導 9 2 L 由 ο 5 淨液 洗母 行之 進離 間分 中28 在器 ，0 段分 數液 複固 等在 (請先閱讀背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 質 I 3 ¾L 等線 酸管 乙由 苯 ， 對離 出分 析液 以母 ，與 卻32 冷置 裝 分 用 利 質 雜 之 出 析 除 之 質 雜 出 析 將 〇 外 条 出 排 加萃 在苯 而甲 應二 供對 8 J 2 的 IL應 線供 管 1 } 3 由 L 與線 此管 於以 33併 置合 裝液 取母 萃的 入凝 導冷 液25 母置 的裝 後溫 後線 質管 雜由 的份 出部 析一 不外 去另： 除 5 2 L ο 取線部 管 往 送 水 的 化 液 漿 為 做 份 部 間 中 的 3 塔 餾 蒸二 第 到 送 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 506989 A7 B7_ 五、發明說明（八） (請先閱讀背面之注意事項再填寫本頁) 在固液分離器2 8分離之結晶，於乾燥機2 9乾燥，成為 精製對苯二由酸（PTA)，由管線L33取出。在萃取裝置33 精製之剩水，由管線L34排出。此時，由於反應溶劑或副 産品均已除去，故排水處理容易。以萃取裝置33進行萃 取之二甲對苯，傺由管線L 3 6通過管線L 3，導入氣化反應 按上逑方法，蒸_塔分成二段，緊急時可由中間把回 流液排出条外，故可防止緊急時反應液的濃度和溫度下 降，因此，在緊急事故解除後可立刻再啓動，再度蓮轉 。若由第一蒸餾塔2的下方排出餾份，其效果更高。 第二蒸餾塔3排氣中的蒸氣，於冷凝器6a，6b冷凝後， 以氣震渦輪機1 3回收能量，則可防止乙酸及其他腐蝕性 物質或結塔物質損壞氣體渦輪機，進行能量回收。冷凝 所用冷卻水蒸發成蒸汽，利用蒸汽渦輪8回收能量，與 從排氣空氣回收能的情形相較，回收效率降低較少。此 時僳經數階段冷凝，可回收能量不同的蒸汽，提高能量 _收效率。將冷凝器fia，6b的冷凝水回流至蒸餾塔3時， 可防出蒸餾塔3堵塞，以良好效率進行蒸餾。 經濟部智慧財產局員工消費合作社印製 上逑管線L 2 4，L 2 5之水，亦可改為導入固液分離器2 8。 又，固液分離器2 1 , 22或28可分別為一個或二個，使用 旋轉篩，離心分離機等具有洗淨機構時，使用一値裝置 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 506989 A7 _B7 五、發明說明（小） 符號之說明 1 ..…..氧化反應器 (請先閱讀背面之注意事項再填寫本頁) 2 ......第一蒸餾塔 3 ......第二蒸餾塔 2 a，3 a ..充瑱層 2b.——固體捕集盤 4——…中間冷卻器 5……泵 6 a , 6 b…冷凝器 7氣水分離器 8 ..——蒸汽渦輪機 9 ......復水器 11 .....加熱器 12 .....燃燒器 13 .....氣體渦輸機 14。…排氣處理裝置 15 .....轉動軸 16 .....壓縮機 經濟部智慧財產局員工消費合作社印製 17 .——發電機 2 1，2 2 , 2 8 ..固液分離器 2 3，2 9 . 乾燥機 2 4.....混合機 2 5 .……加溫裝置 2 6.——還原反應器 -18- 本紙張尺度適用中國國家標準(CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員工消費合作社印製 506989 A7 _B7 五、發明說明（η ) 2 7.....晶析槽 3 1.....冷卻裝置 3 2.....分離裝置 33.....萃取裝置 -19 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----.—ί —--------訂---------線 (請先閱讀背面之注意事項再填寫本頁)For 〇mu, the reason is that the original hydrogen is also added, and the hydrogen supply table G 2 Generation L is the line π Tube BA is lowered by the -C pressure drop. Add to the supply of 8 temperature L2 low-line downcomer for steaming, steaming, steaming, liquid liquid mother and mother steaming ο acid methyl diphenyl to the source of the refined heat to do the acid benzoic acid benzoic acid benzoic acid The crude product of the benzene di-refinement system was analyzed. Degassing, dissolving and replenishing are equal. Heat in the oil is 5 2. Set the autoclave to autoclave and increase C by parts. Partial heat of benzene 2 is used to separate the fines and liquid-liquid solids. As soon as the segmenter is separated, it is divided into liquid and solid. Plasma-based armor is installed but cooled into the guide 9 2 L from ο 5 clean liquid washing the mother line into the gap between the 28 and the 0, fractional liquid recovery and so on (Please read the precautions on the back before filling this page ) Order-Printed I 3 ¾L isoline acid tube B of benzene from the Intellectual Property Bureau of the Ministry of Economic Affairs of the Ministry of Economic Affairs, made of benzene, the mother of the analysis solution, and the quality of the 32 cold storage equipment. The extraneous analysis will extract the outer row and extract it in benzene, and the second line should be supplied to the 8 J 2 IL line. 1} 3 From L and the line, this tube takes the condensate of the parent extract at 33 juxtaposition. Refrigerant liquid 25: The main part of the linear tube after the warm-up period is installed, and the other parts are separated. Except for 5 2 L ο take the liquid slurry sent from the line tube to the water to make 3 The paper size from the second distillation to the second is the size of the paper applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) 506989 A7 B7_ V. Description of the invention (8) (Please read the precautions on the back before filling this page) The crystals separated by the solid-liquid separator 2 8 are dried in a dryer 2 9 and become refined. Removed from the terephthalic acid (PTA) via line L33. The remaining water purified in the extraction device 33 is discharged through a line L34. At this time, since both the reaction solvent and by-products have been removed, the drainage treatment is easy. Dimethyl p-benzene is extracted by the extraction device 33. The tritium is introduced into the gasification reaction from the line L 3 6 through the line L 3. According to the above method, the steaming tower is divided into two sections, and the emergency liquid can be discharged out of the strip in the middle. Therefore, it is possible to prevent the concentration and temperature of the reaction liquid from decreasing during an emergency. Therefore, after the emergency is resolved, it can be restarted immediately, and then turned back again. When the distillate is discharged from below the first distillation column 2, the effect is even higher. The steam in the exhaust gas of the second distillation column 3 is condensed in the condensers 6a and 6b, and the energy is recovered by the gas shock turbine 13, which can prevent acetic acid and other corrosive substances or towering substances from damaging the gas turbine for energy recovery. The cooling water used for the condensation evaporates into steam, and the steam turbine 8 is used to recover the energy. Compared with the case where energy is recovered from the exhaust air, the recovery efficiency is reduced less. At this time, after several stages of condensation, steam with different energy can be recovered to improve energy recovery efficiency. When the condensed water of the condensers fia, 6b is refluxed to the distillation column 3, clogging of the distillation column 3 can be prevented, and distillation can be performed with good efficiency. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The water in the upper pipelines L 2 4 and L 2 5 can also be changed to the solid-liquid separator 2 8. In addition, the solid-liquid separator 2 1, 22 or 28 can be one or two respectively. When using a rotating screen, centrifugal separator and other cleaning mechanisms, use a stack of devices. The paper size is applicable to China National Standard (CNS) A4 specifications. (210 X 297 mm) 506989 A7 _B7 V. Description of the invention (small) Symbol description 1..... Oxidation reactor (please read the precautions on the back before filling this page) 2 ... A distillation column 3 ...... a second distillation column 2 a, 3 a ... a charge layer 2b.-A solid trap 4-... an intercooler 5 ... a pump 6 a, 6 b ... condensation Unit 7 Gas-water separator 8 ..-Steam turbine 9... Rehydrator 11 ..... Heater 12 ..... Burner 13 ..... Gas turbine 14 . … Exhaust gas treatment device 15 ..... Rotary shaft 16 ..... Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the Compressor 17 .—— Generator 2 1, 2 2, 2 8 .. Solid-liquid separation Dryer 2 3, 2 9. Dryer 2 4 ..... Mixer 2 5 ....... Heating device 2 6 .—— Reduction reactor-18- This paper size applies to China National Standard (CNS) A4 specifications ( 210 X 297 mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 506989 A7 _B7 V. Description of the invention (η) 2 7 ..... Crystallization tank 3 1 ..... Cooling device 3 2 ... .. Separation device 33 ..... Extraction device-19-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -----.— ί —------- -Order --------- Line (Please read the precautions on the back before filling this page)