經濟部中央榡準局員工消費合作社印製 A7 __B7__ 五、發明説明（/ ) 本發明條有關一種用以生産一芳番族羧酸（bb方説， 對苯二甲酸）的方法，其方法乃藉箸將前述羧酸的一前身 (比方説，對二甲苯）進行液相氣化。 在一種廣為使用的生産對苯二甲酸的方法中，對二甲 苯在昇高的溫度和壓力的條件下，在一液相反應中，使用 空氣或其他氣氣來源，進行氣化；該氣化傜在一含有一 C2 〜C6單羧酸（比方說，醋酸）的反應溶劑中，配合使用一 含有一種或一種以上的重金靥成份，以及一種或一種以上 的含有溴的肋催化劑化合物的条統而進行的。在該反應溶 劑中有水的存在，而水的生成是該氣化反應的一個結果産 物。該氣化反應伴隨著放出一反應排放氣，其通常包含（ 主要是）氮、未經反應的氣、二氧化硝、一氣化硝和溴代 甲烷。 . 由於這個反應是放熱的反應，在實務上，通常是藉著 讓該單羧酸溶劑蒸發而除去反匾的熱，其結果生成一含有 單羧酸和水的一氣態的反應器頂上流。該頂上流可以不同 方式加工。舉個例說，有一個方式是渉及將該頂上流通到 一冷凝条統，在該条統中，大部份的單羧酸和水被冷凝， 該冷凝物有部份回到該反應器作為回流，有部份再進一步 加工，用以將單羧酸再循環到該氣化反應（參閲，舉個例 説，美國專利4 7 7 7 28 7 ) ^該頂上氣流的来經冷凝的成份經 從該冷凝糸統排出β 在另一種方式中，該頂上氣流可經直接地通到一蒸皤 塔，在該蒸餾塔中，幾乎所有的·單羧酸被分離並被當作一 底層産品而回收；而頂層産品包含蒸汽和其他成份（參閲 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） l· I ：------裝------訂---^---^ (請先閲讀背面之注意事項再填寫本頁) A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（y ) 比方説，英國專利1 3 7 3 2 3 0)。在上面這兩種方式中，所取 得的一 〃下氣"（排放流）可做進一步加工，以回收能源 用以生産該芳香族羧酸。日本專利JP-A-55-95 1 7掲示了一* 種用以處理該下氣以回收能源的方法。 本發明傺有關自該氣化反應器衍生而來的〃下氣〃的 處理。 根據本發明的一第一實施例，提供了一種用以生産一 芳香族羧酸的方法，該方法包含： 將一芳番族羧酸的前身，在一液相C2〜C6單羧酸溶劑（該 溶劑含水）中，配合使用一含有一種或一種以上的重金屬 及溴的催化糸統進行氣化； 在舁高的®力下，從該反應汲取一頂上氣流，其含有（最 主要的）水、單羧酸及氣態的副産品，包括澳代甲烷，並 且將該高壓氣流餓送到裝置中，以便將前述單羧酸自該頂 上氣流中除去，以生産一含有（最主要的）水及溴代甲烷 的高壓，去除了單羧酸的氣流； 將該髙壓，去除了單羧酸的氣流進行高溫燃燒，以便將溴 代甲烷轉化成溴及/或溴化氫；以及 將該含有溴及/或溴化氫的經過處理的氣流通到一能源回 收条統》 最好，壓力和溫度的條件經過控制，以防止溴及/或 溴化氫在通過能源回收的過程中冷凝《» 在進行燃燒（最好是催化燃燒）之後，該氣流可不經 滌氣即通到該能源回收条統》 因此，毋需在該經處理過的氣流經通到該能源回收条 本纸張尺度適用中國國家標準（CNS ) Λ4規格（21〇X297公釐） (請先閱讀背面之注意事項#填寫本頁) Ί— In I - —J-i - f - —Γ I I -1-—- 1 ί - I I i 訂 線 經濟部中央標準局負工消費合作杜印製 A7 __B7__五、發明説明（+) 統之前，藉著（比方說）對該氣流進行滌氣而去除相當地 具腐蝕性的溴化合物情況下，該經處理過的氣流的溫度可 被維持，且藉箸控制溫度和壓力條件而能克服腐蝕問題， 以確保該具強烈腐蝕性的溴化合物（含複數）在通過該能 源回收条统的過程中，能維持在氣相。這麽一來，在進行 高溫燃燒過程中，藉著該氣流溫度的增加，而毋需使用昂 貴的抗腐蝕材質來製作該能源回收条統。因此，舉個例來 説，該能源回收条統（比方説，一氣體渦輪機）可以使用 較傳統的材質，像是高鉻钢或奧斯田不锈辆來製作。 在導入到該能源回收糸統之前，該氣流至少有一部份 可用來對該燃燒步驟的上游氣流進行預熱》 最好，在通到該能源回收糸統之後，該經處理過的氣 體經過處理以去除幾乎金部的溴代物及/或溴化氫》 最好，能將單羧酸從該頂上氣流除去到一個程度，以 使得該經過處理的氣流的水含量超過其單羧酸含童。 通常，至少有重量比百分之九十，更好的是至少有重 量比百分之九十五的前逑單羧酸經從該頂上氣流除去。 用以將醋酸從該頂上流除去的裝置較合適的是一分離 塔，比方說，一曼層式和盛盤式蒸餾或精餾塔，其能夠有 效地進行分離，以使得該單羧酸溶劑的重量比至少有95¾ , 更好的是，大約98!ί,最好的是，至少大約99%,自該氧化 反應，從該頂上氣流中除去。 該分離塔最好是以與進行該氧化反應的同樣（或接近 的）壓力來操作β該分離塔可與該氣化皮應器分別裝置， 以適當的管線將反應器連接到分離塔，以便將該頂上流輸 本紙浪尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） ； ' 丨.—裝------訂^---_----線 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 A7 一 _„ 五、發明説明（〆） 送到分離塔。或者，分離塔可直接裝置到氣化反應器的上 方並與之結合成一體。 因此，在本發明一較佳的實施例中，該從氣化反應器 蒸汽衍生而來的高壓頂上氣流〔該氣化反應器蒸汽通常含 有（除了水和單羧酸以外）殘留的氣、副産品氣體（像是 溴代甲烷、醋酸甲酯，是該氣化反應的結果）、二氧化硪 、一氣化磺和氮氣〕經通到該分離塔以除去絶大部份的單 羧酸溶劑。其結果，該自分離塔所排放出來的"下氣〃（ 排放）氣流將處於高壓，且將含有（除了大量的蒸汽形態 的水以外）殘留的氧、副産品氣體（像是溴代甲烷、醋酸 甲酯，是該氣化反應的結果）、二氣化磺、一氣化磺和氮 氣。因此，這麼一來，從該分離塔所排放出來的該高壓〃 下氣〃排放氣流構成了 一重要昀能源來源，其可以藉由適 合的裝置（比方說，一膨脹器）經举取。 通常，從該氣化反應器汲取的頂上氣流的殘留氣體含 量構成該存在於該頂上氣流中的該不可凝集物的體積比的 大約3¾到8%之間β最好，該液相氧化過程是在正常條件下 操作，而使得該〃下氣〃排氣流中殘留的氣氣的量是足夠 的，以避免必須要在加壓條件下供入更多的氯氣到該"下 氣〃排氣流的處理加工，而同時又能確保，在該〃下氣〃 排氣流中幾完全不虞有缺氣氣的風險，且不致産生相當有 害的情況（這樣的情況，如果該頂上氣流含有過量的氧氣 時會産生的）β 本發明的燃燒步驟（最好是·催化的燃燒）其作用在該 高壓"下氣〃排放氣流在輸送到該能源回收裝置之前，去 本紙張尺度適用中國國家標準（CNS ) Λ4規格（2]0Χ297公釐） - —«II I II —II - -I J - I -- -I - - : - ——I ,_1Τ (請先閲讀背面之注意事項再填寫本頁) 經濟部中央樣準局負工消f合作社印裝 A7 B7 ~~ - . _______ -____ -. -. _ 五、發明説明（Γ) 除存在該高壓〃下氣"排放氣流中的可燃成份，並且能夠 在該排放氣流通到陔能源回收条統之前，升高該排放氣流 的溫度，因而增加能源的回收，並旦避免腐蝕性的溴化物 (比方説，溴化氫）在該条统中的露結β藉箸通過蒸汽或 一升火的加熱器，或藉著直接以燃料升火加熱及/或噴射 諸如醋酸甲酯、甲醇、甲烷、丙烷、丁烷等的輔助燃料， 而升到更高溫度。 在該燃燒步驟中，該排放氣流最好是與一合適的觸媒 接觴，以使得至少有一相當大部份的該等可燃燒成份可經 轉化成不致破鳆環保的形式。9外，該催化的氣化的結果 ,也使得溴代甲烷轉化成溴及/或溴化氩.這些可是非常 地具腐蝕性的，但是，依照本發明，在受控制的條件下通 到該能源回收条統，而不經過該排放氣流滌氣，而避免了 原先不可避免的溫度減降，如果在將該排放氣流在通到該 能源回收裝置之前，先行進行滌氣，則將不可避免的造成 溫度的減降，而在該經滌氣的排放氣流通到該能源回收条 統之前，勢必要進行預熱。此外，在本發明的方法中，是 有可能避免該經過燃燒的排放氣流預熱，而如果使用其他 方法，為了在將該排放氣流通到該能源回牧裝置之前，將 所有已凝集的水再行蒸發，是有必要進行預熱的。 在通過該能源回收裝置之後，且最好在除去幾乎全部 的溴之後（最好是以一種能將全部的或至少一絶大部份的 蒸汽成份保留在該排放氣流的方式進行），該排放氣流可 經凝集，以回收水，用以在供生.産對苯二甲酸的整«Μ加工 過程中進行再循環β該經回收的水可（舉個例説）用作： 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公鼙） _ 〆〆 : ^---->.·裝-- (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部中央標準局員工消費合作社印製 本纸悵尺度適用中國國家楯準（CNS ) Λ4規格（210X297公釐） A7 B7 五、發明説明（I ) 在將該單羧酸與該高壓頂上氣流分離的分離塔中一回 流；及/或 以（舉個例説）在吾等之前沾專利案EP-A-4 9859 1及 /或EP-A-502628中掲示的方式，製備供用在該芳香族羧 酸藉箸氫化作用而純化的，將該粗羧酸溶解時的溶劑。 因此，（舉個例說），在通過該能源回收条統之後， 該排放氣流可降超熱至一相當於（或接近）該氣流的露 點的溫度，並經滌氣以去除溴和溴化氳等成份（比方說， 使用一水性的苛性納>,而在這同時，將水成份保留在該 排放氣流中。該在其露點溫度的經滌氣的排放氣流可再經 凝集以除去其中所含水成份。儘管最好是在回收該氣流的 水蒸汽成份之前，將溴及溴化氫成份自該排放氣流中除去 ,我們並不排除在藉由凝結作用回收水之後，繼之以滌氣 來除去溴和溴化氫成份的可能性。 通常，在前述分離塔中，單羧酸的分離之後取得的該 排放氣流的颸力在5到25巴之間（比方説.在1 0到1 6巴之 間），而溫度則在1 6 (TC到2 0 (TC之間（比方說，溫度大約 是177°C， 而壓力是14巴）。在進行燃燒之前，該來自分 離塔的排放氣流最好是直接地或間接地加熱到一昇高的溫 度（比方説，使用高壓蒸汽、加熱油，在未經處理的以及 經處理的氣流之間進行熱交換，通過一燃燒油的加熱器， 或直接以燃料升火噴燒到該氣流裡），通常在250°C到4 50°G 之間（通常在大約300°C )。 視來自該催化的燃燒步驟可·得的釋出·的熱，或可將一 肋燃物導入到該燃燒區中《該助燃物最好是在導入該燃燒 1〆 ; , .裝 訂------k (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消费合作社印製 A7 —___!Z__ 五、發明説明（7 ) 區之前，先行與該氣流混合。將該助燃物與胲氣流進行有 效充份混合的裝置之一，在吾人之前的經過PCT公告的專 利申請案W0 94 /2 38 13中有掲示，該專利案的掲示内容已納 入本文中作為參考β 該肋燃物最好是（但不必然是）一包含了氣氣的物質 。可以使用各種助燃物，比方說，甲醇、醋酸甲酯、氫氣 、天然瓦斯、甲烷、丙烷、丁烷或這些成份的混合物。如 果用的是醋酸甲酯，它可方便地從對苯二甲酸生産步驟衍 生而來，因為它是以對二甲苯在醋酸溶劑中進行液相氣化 作用的一副産品形式而産生的。如果用的是甲烷，它可從 一用以處理在生産芳香族羧酸（比方說，對苯二甲酸）排 放物的一厭氧加工衍生而得β如果有需要，可將更多的空 氣導入到該燃燒區中以促進氣化。 該燃燒步驟的進行，是考慮到為了要確保，在接下來 的通過該能源回收条統的通道上的膨脹，從該排放氣流的 溴代甲烷成份衍生而來的溴和溴化氫仍雒持在氣相，致避 免在該能源回收条統中的露點腐蝕情況》通常，該燃燒步 驟是在配合一觸媒的情況下進行的，而自該氧化區排放的 該經過處理的〃下氣〃氣流的溫度大約在250°C到大約7 0 0 °C 之間，比方說，350°C到700°C,且視將該氣流在導入到該 催化燃燒區之前是否先經預熱，以及視是否用到一肋燃物 等情況而定。舉個例說.該催化燃燒可以一恃殊方式進行 ，致該經處理的氣體在離開該催化燃燒區時，其溫度在4 0 0 °C 之譜或更高些。如果不使用肋燃物，或如果該肋燃物是一 種很容易氣化的或是相當地容易氣化的助燃物時（比方說 ^紙張尺度適用中國國家梯準（CNS ) Λ4規格（210X297公釐） ~ (請先閲讀背面之注意事項再填寫本頁) -裳-Printed by A7 __B7__ of the Consumer Cooperatives of the Central Provincial Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (/) The present invention relates to a method for producing an aromatic carboxylic acid (bb side, terephthalic acid). The method is: A precursor (for example, para-xylene) of the aforementioned carboxylic acid is subjected to liquid-phase gasification by thorium. In a widely used method for producing terephthalic acid, p-xylene is subjected to elevated temperature and pressure conditions in a liquid phase reaction, using air or other gas sources for gasification; the gas In a reaction solvent containing a C2 to C6 monocarboxylic acid (for example, acetic acid), a compound containing one or more heavy metal compounds and one or more rib catalyst compounds containing bromine is used in combination. Systematic. The presence of water in the reaction solvent, and the formation of water is a consequence of the gasification reaction. The gasification reaction is accompanied by a reaction exhaust gas, which usually contains (mainly) nitrogen, unreacted gas, nitrous oxide, monogasified nitrate, and bromomethane. Since this reaction is an exothermic reaction, in practice, the heat of the anti-plaque is usually removed by evaporating the monocarboxylic acid solvent, and as a result, a gaseous reactor containing monocarboxylic acid and water flows upwards. The top stream can be processed in different ways. For example, there is a way to circulate the overhead to a condensation system. In this system, most of the monocarboxylic acid and water are condensed, and the condensate is partially returned to the reactor. As reflux, some are further processed to recycle the monocarboxylic acid to the gasification reaction (see, for example, U.S. Patent 4 7 7 7 28 7) ^ the condensed The components are discharged from the condensing system β. In another way, the overhead gas stream can be passed directly to a distillation column, in which almost all monocarboxylic acids are separated and used as a bottom layer. The product is recycled; and the top layer product contains steam and other ingredients (refer to the paper size applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) l · I -------- installation ------ Order --- ^ --- ^ (Please read the notes on the back before filling in this page) A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (y) For example, British patent 1 3 7 3 2 3 0). In both of the above methods, the obtained offgas " (emission stream) can be further processed to recover energy for the production of the aromatic carboxylic acid. Japanese patent JP-A-55-95 1 7 shows a method for treating the downgas to recover energy. The present invention relates to the treatment of sub-aerobic gas derived from the gasification reactor. According to a first embodiment of the present invention, a method for producing an aromatic carboxylic acid is provided. The method includes: using a precursor of an aromatic carboxylic acid in a liquid C2 ~ C6 monocarboxylic acid solvent ( The solvent contains water), and a catalytic system containing one or more heavy metals and bromine is used for gasification; under high pressure, a top gas is drawn from the reaction, which contains (mostly) water , Monocarboxylic acids and gaseous by-products, including Australian methane, and send the high-pressure gas stream to the device to remove the aforementioned monocarboxylic acid from the overhead gas stream to produce a (mostly) water and bromine Replacing the high pressure of methane to remove the gas stream of monocarboxylic acid; to pressurize the high pressure to remove the stream of monocarboxylic acid for high temperature combustion to convert bromomethane into bromine and / or hydrogen bromide; and The treated gas stream of hydrogen bromide is passed to an energy recovery system. Preferably, the pressure and temperature conditions are controlled to prevent the condensation of bromine and / or hydrogen bromide during the energy recovery process. combustion( After catalytic combustion), the air stream can pass to the energy recovery system without scrubbing. Therefore, there is no need to pass the treated air stream to the energy recovery system. ) Λ4 specification (21〇X297mm) (Please read the notes on the back #Fill this page first) Central Standards Bureau ’s work-consumption cooperation Du printed A7 __B7__ V. Before the invention (+) system, by (for example) scrubbing the gas stream to remove the relatively corrosive bromine compounds, the economic process The temperature of the treated gas stream can be maintained, and the problem of corrosion can be overcome by controlling the temperature and pressure conditions to ensure that the highly corrosive bromine compound (including plural) can pass through the energy recovery system. Maintained in the gas phase. In this way, during the high-temperature combustion process, by using the increase of the temperature of the air flow, it is not necessary to use expensive anti-corrosive materials to make the energy recovery system. So, for example, the energy recovery system (for example, a gas turbine) can be made from more traditional materials, such as high-chrome steel or Austen stainless cars. Before being introduced into the energy recovery system, at least a part of the gas stream can be used to preheat the upstream gas stream of the combustion step. Preferably, the treated gas is treated after passing to the energy recovery system. In order to remove the bromine and / or hydrogen bromide of almost gold, it is best to remove the monocarboxylic acid from the overhead gas stream to such an extent that the water content of the treated gas stream exceeds its monocarboxylic acid content. Generally, at least 90% by weight and more preferably at least 95% by weight of pro-fluorene monocarboxylic acid is removed from the overhead gas stream. A more suitable device for removing acetic acid from the overhead stream is a separation column, for example, a Mann-layer and tray-type distillation or rectification column, which can efficiently perform separation so that the monocarboxylic acid solvent The weight ratio is at least 95¾, more preferably, about 98! Ί, and most preferably, at least about 99%, is removed from the overhead gas stream by the oxidation reaction. The separation tower is preferably operated at the same (or near) pressure as the oxidation reaction is performed. The separation tower may be separately installed from the gasification reactor, and the reactor is connected to the separation tower with an appropriate pipeline so that Apply the size of the paper to the top of the paper to the Chinese National Standard (CNS) A4 specification (210 × 297 mm); '丨 .—installation ------ order ^ ---_---- line (please read the back first) Please pay attention to this page and fill in this page) A7 printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs I. The invention description (〆) is sent to the separation tower. Alternatively, the separation tower can be installed directly above the gasification reactor and connected with Therefore, in a preferred embodiment of the present invention, the high pressure overhead gas stream derived from the gasification reactor steam (the gasification reactor steam usually contains (except water and monocarboxylic acid) Residual gas, by-product gases (such as bromomethane, methyl acetate, as a result of the gasification reaction), thorium dioxide, monogas sulfon and nitrogen] are passed to the separation column to remove most of the monocarboxylic acid Acid solvent. As a result, this self-separation The downdraft (exhaust) gas stream discharged from the tower will be at a high pressure and will contain (except for a large amount of water in the form of steam) residual oxygen and by-product gases (such as methyl bromide and methyl acetate). The result of the gasification reaction), the second gaseous sulphur, the first gaseous sulphur and nitrogen. Therefore, in this way, the high pressure radon gas radon exhaust gas discharged from the separation tower constitutes an important radon energy source, which It is lifted by a suitable device (for example, an expander). Generally, the residual gas content of the overhead gas stream drawn from the gasification reactor constitutes the volume ratio of the non-condensable matter present in the overhead gas stream. About 3¾ to 8% β is best. The liquid-phase oxidation process is operated under normal conditions, so that the amount of residual gas in the exhaust gas stream is sufficient to avoid the need to Supply more chlorine gas to the processing of the " lower gas radon exhaust gas stream under pressure conditions, while at the same time ensuring that there is almost no risk of gas shortage in the lower gas radon exhaust gas stream, and Do not cause Harmful conditions (in this case, if the overhead gas stream contains excessive oxygen) β The combustion step of the present invention (preferably, catalytic combustion) acts on the high pressure " lower gas radon exhaust gas stream during transportation Before the energy recovery device, the paper size is in accordance with the Chinese National Standard (CNS) Λ4 specification (2) 0 × 297 mm)-«II I II —II--IJ-I--I--:-—— I, _1Τ (Please read the notes on the back before filling this page) The Central Bureau of the Ministry of Economic Affairs of the Ministry of Economic Affairs, F, Cooperatives, printed A7 B7 ~~-. _______ -____-.-. _ V. Description of the Invention (Γ) In addition to the presence of flammable components in the high-pressure radon " exhaust gas, and before the exhaust gas flows into the radon energy recovery system, the temperature of the exhaust gas can be increased, thereby increasing energy recovery and avoiding corrosiveness. The dew condensation β of the bromide (for example, hydrogen bromide) in the system is heated by steam or a litre heater, or by directly firing a fuel such as methyl acetate, Auxiliary fuels such as methanol, methane, propane, butane While rising to higher temperatures. In the combustion step, the exhaust gas stream is preferably contacted with a suitable catalyst so that at least a considerable portion of the combustible components can be converted into a non-destructive and environmentally friendly form. In addition, as a result of the catalytic gasification, bromine methane is converted to bromine and / or argon bromide. These can be very corrosive, but, in accordance with the present invention, they are passed to the under controlled conditions. The energy recovery system does not pass through the exhaust gas stream and avoids the originally unavoidable temperature drop. If the exhaust gas stream is cleaned before it is passed to the energy recovery device, it will be inevitable. This causes a decrease in temperature, and preheating is necessary before the exhaust gas stream passing through the scrubber passes to the energy recovery system. In addition, in the method of the present invention, it is possible to avoid the preheating of the burned exhaust gas stream, and if other methods are used, in order to re-condensate all the condensed water before passing the exhaust gas stream to the energy return grazing device, For evaporation, preheating is necessary. After passing through the energy recovery device, and preferably after removing almost all of the bromine (preferably in a manner that retains all or at least a substantial part of the steam components in the exhaust gas stream), the exhaust gas stream It can be agglomerated to recover water for recycling in the process of producing and producing terephthalic acid. The recovered water can (for example) be used as: This paper is applicable to China National Standard (CNS) Α4 Specification (210X297) 鼙 _ 〆〆: ^ ---- >. · Installation-(Please read the precautions on the back before filling this page) Order the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs The printed paper is sized according to the Chinese National Standard (CNS) Λ4 specification (210X297 mm) A7 B7 5. Description of the invention (I) The reflux is performed in a separation tower that separates the monocarboxylic acid from the high-pressure overhead gas stream; and / Or, for example, prepared in the manner shown in our prior patents EP-A-4 9859 1 and / or EP-A-502628 for purification of the aromatic carboxylic acid by hydrogenation The solvent used when the crude carboxylic acid is dissolved. Therefore, (for example), after passing through the energy recovery system, the exhaust gas stream can be superheated to a temperature equivalent to (or close to) the dew point of the gas stream and scrubbed to remove bromine and bromination成份 and other components (for example, use an aqueous caustic soda), and at the same time, retain the water component in the exhaust gas stream. The scrubbed exhaust gas stream at its dew point temperature can be agglomerated to remove it The water content. Although it is best to remove the bromine and hydrogen bromide components from the exhaust gas stream before the water vapor component of the gas stream is recovered, we do not rule out that after the water is recovered by condensation, it is followed by cleaning. Gas to remove bromine and hydrogen bromide components. Generally, in the aforementioned separation column, the exhaust gas obtained after the separation of the monocarboxylic acid has a force of between 5 and 25 bar (say, between 10 and 10). 16 bar) and the temperature is 16 (TC to 20 0 (for example, the temperature is about 177 ° C and the pressure is 14 bar). Before the combustion, the The exhaust gas stream is preferably heated directly or indirectly to a rise Temperature (for example, using high-pressure steam, heating oil, heat exchange between untreated and treated gas streams, passing through an oil-burning heater, or injecting fuel directly into the gas stream) , Usually between 250 ° C and 4 50 ° G (usually around 300 ° C). Depending on the heat that can be released from the catalytic combustion step, or a ribbed fuel can be introduced into the combustion In the area, "The combustion-supporting substance is best to be introduced into the combustion 1〆 ;, binding ----- k (Please read the precautions on the back before filling this page) Printed by A7 of the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs —___! Z__ V. Before the invention (7) zone, first mix with the airflow. One of the devices for effective and sufficient mixing of the combustion-supporting material and the radon airflow is the PCT published patent application WO 94 before my own. It is shown in / 2 38 13 that the content of the patent case has been incorporated herein by reference. The rib fuel is preferably (but not necessarily) a substance containing gas. Various combustion aids can be used, for example , Methanol, methyl acetate, hydrogen, natural tiles , Methane, propane, butane or a mixture of these ingredients. If methyl acetate is used, it can be easily derived from the terephthalic acid production step because it is a liquid phase in p-xylene in an acetic acid solvent. It is produced as a by-product of gasification. If methane is used, it can be derived from an anaerobic process used to treat the emissions of aromatic carboxylic acids (for example, terephthalic acid). If necessary, more air can be introduced into the combustion zone to promote gasification. The combustion step is carried out in order to ensure that the subsequent expansion on the passage through the energy recovery system, Bromine and hydrogen bromide derived from the bromomethane component of the exhaust gas stream are still held in the gas phase, so as to avoid dew point corrosion in the energy recovery system. Generally, the combustion step is in combination with a catalyst The temperature of the treated subducted radon gas discharged from the oxidation zone is about 250 ° C to about 700 ° C, for example, 350 ° C to 700 ° C, And depending on the airflow Whether the preheated prior to the catalytic combustion zone into, and depending on whether fuel used in the case of a rib and the like may be. For example, the catalytic combustion can be performed in a special way, so that the temperature of the treated gas when leaving the catalytic combustion zone is in the spectrum of 400 ° C or higher. If a ribbed fuel is not used, or if the ribbed fuel is a gasifier that is easily vaporized or is relatively easy to vaporize (for example, ^ paper size applies to China National Standards (CNS) Λ4 specification (210X297) %) ~ (Please read the notes on the back before filling in this page)--
*1T " 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（P) ，甲醇、醋酸甲酯、或氫氣），則出口的溫度可能大約在 2 5 0 eC到5 5 0°C之間，通常大約在3 5 0eC到5 5 0°C (比方說， 大約在48D°C)e如果使用的是一種不那麼容易氣化的肋燃 物（比方說，甲烷、丙烷、丁烷），則出口的溫度通常會 較高些，亦卽大約在40(TC到70(TC之間，通常在5 5 0°C到 7 Ο Ο 之間，比方説，在6 3 D °C之譜β 儘管最好是進行催化的燃燒，但是，我們也不排除在 不使用觭媒，而使用燃料供入方式來進行燃燒的可能性。 在這樣的場合，該氣流在燃燒之後的溫度通常會超過70 〇°C ，通常超過800°C,且最好是在該液相氣化時操作，以使得 自該氣化反應器汲出的該頂上氣流的氣氣含量增加，比方 說，相對於在該頂上氣流中不可凝集的成份，高出重量比 5¾，以避免了在該液相氣化加工的正常操作條件之下，另 行將加壓過氣氣供到該燃燒步驟的必要性。 通常，該燃燒步驟會採用持別選定的操作條件（比方 說，溫度、空間速度、觸媒組成）來進行的，以確保溴代 甲烷能夠幾完全地轉化成溴化氫和溴，造樣做的目的是在 儘量減少或避免轉化不成的溴化的芳香族化合物的産生， 逭類化合物具有高露點。此外，壓力和溫度亦須經過控制 ，以防止溴化氫及/或溴化合物在通經該能源回收糸統的 過程中凝結β 該能源回收条统可能産出機械能或電能，且可（比方 說）被用在該生産工廠中推動其他裝備，像是一空氣壓縮 機（其構成該糸統的一部份）用以將空氣、含豐富的氣氣 的空氣、含氣氣體或氣氣饋選到該反應器中，而該液相氣 本紙張尺度適用中國國家標準（CNS ) Λ4現格（210Χ297公f ) —Γ---------V:·裝------訂^------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 A7 __._B7_五、發明説明（7 ) 化即在該反應器中進行的β 依據本發明的另一實施例，提供了一種用以生産一芳 香族羧酸（像是對苯二甲酸）的方法β該方法包含將前述 芳香族羧酸的一前身（比方說，對二甲苯）在一包含一單 羧酸（比方說，醋酸）的一反應介質中進行氧化，以生成 一粗芳香族羧酸在前逑脂肪族羧酸中的混漿；將該粗酸自 前述混漿中回收；將該回收的粗酸溶解在水中；藉箸一包 含了將該溶液與氫氣接觸的反應純化該粗酸；以及將該經 純化的酸從前述溶液的該母液成份分離出來；前述方法另 包含下列步驟： 從該反應區，將一含有（待別是）單羧酸、水及溴代 甲烷的一高壓的頂上氣流汲出；在一分離塔中，將幾乎所 有的箪羧酸從前逑頂上氣流分ρ出來，在此同時，從前述 純化反應得來的水性母液亦同時供到該分離塔，致取得一 高壓〃下氣"氣流，其含有（特別是）自該氣化反應以及 該純化反應衍生而得的水，以及自該氣化反應而取得的溴 代甲烷；將前述高壓〃下氣〃氣流進行氣化（最好是在配 合一觸媒及/或一助燃劑情況下操作），致溴代甲烷經鞞 化成溴及/或溴化氫；將該處理過的含有溴及/或溴化氫 的氣體，以其蒸汽形式，在經過控制的溫度和壓力條件下 通經一能源回收条統，以使得溴及/或溴化氫的凝結作用 幾乎完全可以避免；以及在通經該能源回收糸統之後，將 幾乎金部的溴自該經處理的氣體中除去。 通常，在經過逭樣的處理方式除去溴之後，該經處理 過的氣體的溴含量的體積量比，低於4 ρρΒβ (请先閲讀背面之注意事項再填寫本頁) 、1Τ* 1T printed by A7 B7, Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the Invention (P), methanol, methyl acetate, or hydrogen), the temperature of the outlet may be about 2 50 eC to 5 5 0 ° C, usually between 3 5 0eC and 5 0 ° C (for example, about 48D ° C) e If you use a rib fuel that is not so easy to vaporize (for example, methane, propane, butane Alkane), the temperature of the outlet is usually higher, which is about 40 (TC to 70 (TC, usually between 5 50 ° C and 7 Ο Ο, for example, at 6 3 D ° C Spectrum β Although catalytic combustion is preferred, we do not rule out the possibility of using a fuel feed instead of a catalyst to perform combustion. In such cases, the temperature of the gas stream after combustion is usually Will exceed 70 ° C, usually over 800 ° C, and is preferably operated during the gasification of the liquid phase so that the gas content of the overhead gas stream drawn from the gasification reactor increases, for example, relative to The non-condensable components in the overhead gas stream are 5¾ higher than the weight ratio to avoid gasification in the liquid phase The necessity of separately supplying pressurized gas to this combustion step under the normal operating conditions of processing. Generally, this combustion step will adopt a different selected operating condition (for example, temperature, space velocity, catalyst composition) It is carried out to ensure that methyl bromide can be converted into hydrogen bromide and bromine almost completely. The purpose of sample preparation is to minimize or avoid the generation of brominated aromatic compounds that are not converted. 逭 compounds have high dew points. In addition, pressure and temperature must be controlled to prevent hydrogen bromide and / or bromine compounds from condensing during the passage of the energy recovery system. Β This energy recovery system may produce mechanical or electrical energy, and can (for example (Said) is used in the production plant to promote other equipment, such as an air compressor (which forms part of the system) to feed air, air rich in gas, gas containing gas or gas feed Selected into the reactor, and the paper size of the liquid phase gas is in accordance with the Chinese National Standard (CNS) Λ4 grid (210 × 297mm f) —Γ --------- V: · 装 ----- -Order ^ ------ line (please read the first Note: Please fill in this page again.) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. A7 __._ B7_ V. Description of the invention (7) The transformation is performed in the reactor. According to another embodiment of the present invention, A method for producing an aromatic carboxylic acid (such as terephthalic acid). The method includes combining a precursor (for example, para-xylene) of the foregoing aromatic carboxylic acid with a monocarboxylic acid (for example, , Acetic acid) in a reaction medium to produce a mixture of a crude aromatic carboxylic acid in a pro-aliphatic aliphatic carboxylic acid; the crude acid is recovered from the aforementioned slurry; the recovered crude acid is dissolved in Water; purifying the crude acid by a reaction comprising contacting the solution with hydrogen; and separating the purified acid from the mother liquor component of the solution; the method further includes the following steps: from the reaction zone, A high-pressure overhead gas stream containing (to be otherwise) monocarboxylic acid, water, and bromomethane is extracted; in a separation column, almost all of the fluorenic carboxylic acid is separated from the former overhead gas stream, and at the same time, from Aforementioned pure The aqueous mother liquor obtained from the reaction is also supplied to the separation tower at the same time, so as to obtain a high-pressure radon gas " gas stream, which contains (in particular) water derived from the gasification reaction and the purification reaction, and from the gas Brominated methane obtained by chemical reaction; gasification of the above-mentioned high pressure tritium gas stream (preferably operating in the presence of a catalyst and / or a combustion accelerator), resulting in bromide being tritiated into bromine and / Or hydrogen bromide; the treated bromine and / or hydrogen bromide-containing gas, in its vapor form, is passed through an energy recovery system under controlled temperature and pressure conditions so that bromine and / or bromine The condensation of hydrogen hydride is almost completely avoided; and after passing through the energy recovery system, almost the bromine of the gold portion is removed from the treated gas. In general, after removing bromine in a similar manner, the volume-to-volume ratio of the bromine content of the treated gas is less than 4 ρρΒβ (please read the precautions on the back before filling this page), 1T
i A 木紙張尺度適用中國國家標準（CNS ) Λ4規格（210X297公釐） 經濟部中央梯準局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS )八4規格（210X297公釐） A7 _B7 五、發明説明（（。） 該自經純化的芳香族酸分離的水性母液，（比方說， 藉箸使用像是在吾人之前的國際專利申請案W0 93/24440中 所掲示的過濾裝備），含有各種的雜質，反應中間産物， B外，亦含有以懸浮以及溶解形式的前述芳香族羧酸。藉 著將該水性母液再循環到該分離塔的方式，此等雜質，反 應中間産物以及溶解的芳香族羧酸成份可與該水性母液中 的水分離，並自該分離塔連同藉著該塔而回收的單羧酸回 到該氣化反應器形成底層産品。 通常，該水性母液的一主要部份經以這樣的方式（最 好以回流形式）再循環到該分離塔。 從該純化反應所回收的母液可經過處理（比方說，藉 由冷卻或蒸發）以自其中回收較不純的芳香族羧酸的結晶 ,而至少有一部份輪送到該分離塔的母液可包含在此等處 理方式之後所取得的次级母液。或者，由於該分離作業總 是在相當地高溫的條件下進行，自該純化反應回收的初鈒 母液，可在不經冷卻到任何重大的程度情況下，再循琛到 該分離塔，雖然它也可在經導入該分離塔之前先行過濾， 以去除任何愍浮的撤細物》 最好，該粗酸是藉箸將在前述混漿中的脂肪族羧酸用 水取代，與前述單羧酸分離，以生成一含有水的粗酸的溼 式沈積物，以用在該粗酸接下來的純化過程中（比方說， 藉替從前述溼的沈積物生成的一水性溶液進行氫化），而 用水來取代該單羧酸，是使用一結合了分離和水洗的過濾 器，（最好是）在昇高的壓力條件下操作而進行的。 該結合了分離和水洗的過濾器可包含一氣壓式的皮帶 (請先閲讀背而之注意事項再填寫本頁) 裝- 經濟部中央標準局員工消费合作社印製 A7 B7_五、發明説明（丨/ ) 過濂器、一氣懕式的迴轉式筒狀過濾器、一液壓式的多艙 式壓力鼓過濾器，或一帶有水洗裝置的離心機。在上述的 每一種場合中，該水洗作業可分階段進行，最好是以逆流 方式，以使得過濾餅塊可以用較純淨的水來水洗，因為水 是從一處結晶物自該母液分離出來的位置向下游前進。 通常，該過濾器是在一 0.1到15巴的壓力差的條件下 操作的（最好是在0.3到7巴之間），最好在該過濾器的較 低壓側的壓力不低於1巴，儘管我們並不排除該較低壓力 侧是處於一低於大氣壓的可能性β 本發明的另一實施例傑有關在繼高溫燃燒之後，將溴 及溴化氫自該氣流去除，尤其是有關將該氣流加以處理， 以去除溴成份，使得所有排放到大氣的排放物幾完金無此 等成份。像這樣的加工處理可以（舉傾例說）藉著使用水 對該氣流進行降超熱而進行的，並且將該氣流在一滌氣段 中使用一適合的水性滌氣介質進行接®以去除溴及溴化氯 。漠化氫的去除可藉箸（比方說）與溴化氬的水溶液進行 逆流接觸，或者，僅藉著與水進行接觸而加以去除，（比 方說）一噴水或灑水拴，而在此同時，對該經處理的氣流 進行降超熱。如果將該經處理的氣流與溴化氫水溶液進行 接觸的目的（比方說）是要回收溴化氫，以用作使用在該 氣化反應器中的觸媒条統的一部份，則是很恰當的。如果 不是為了這樣的目的，則可使用水。如果用到水的話，最 好能用足夠量的水來澆灌用以將經水處理過的氣流輸往下 游的管線，以防止腐蝕問題》至於溴的去除，可藉箸與一 諸如氫氣化納、磺酸納、磺酸氫納、溴化納、甲酸納、亞 ：---„----\:裝------訂j------線 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X297公釐） 經濟部中央標準局員工消費合作社印製 A7 ___ B7 五、發明説明（/> ) 硫酸鈉或含有這些成份的兩種或兩種以上的混合物（比方 說，氩氣化納與硫酸納）的一水溶液進行逆流接觸。 用以生産該芳香族羧酸的氣化反應，以及其後鑲的純 化作業，可以依照吾人之前的歐洲專利£卩-纟-49859 1和£卩-A-502628中的掲示方法來進行，該等專利的全部掲示内容 已經納入本文作為參考。 該芳香族羧酸可為對苯二甲酸，在這種場合，該經氣 化的用以生産對苯二甲酸的前身將是對二甲苯β或者，該 芳香族羧酸可為異苯二甲酸（前身為間二甲苯）或2,6-奈 -二羧酸（前身為2,6-二甲基荼）。 該氣化反應通常是在一大約120eC到大約240°C之間的 溫度，以及一至少是可將該反應混合物維持在液相條件的 壓力（通常為5巴到30巴）下_行的β 該催化条統的助催化成份含有溴，且通常是溴化氫、 分子的溴、溴化鈉及/或在本工藝中早已為人所知的合適 的有機的溴化合物。該腾媒条統的重金屬成份通常是姑及 /或錳的化合物，比方說，姑及/或磺酸錳。 依照本發明的另一實施例，提供了一種用以生産一芳 香族羧酸（像是對苯二酸）的方法，該方法包含將前述芳 香族竣酸的一前身（比方說，對二甲苯），在一含有一脂 肪族羧酸（比方說，醋酸）的反應介質中進行氣化，以生 産粗芳香族羧酸在前述脂肪酸中的混漿，以及用水來替代 在前逑混漿中的脂肪族羧酸，以生産一含有水的粗芳香族 羧酸的溼的堆積物，以便用在該粗羧酸的接下來的純化加 工（比方說，藉著從前逑溼的堆積物形成的一水性溶液進 (請先閱讀背面之注意事項再填寫本頁) •裝. -0 —4 本紙張尺度適用中國國家標準（CNS ) Α4規格（2丨〇Χ25»7公釐） 經濟部中央標準局貝工消费合作社印製 A7 _B7__ 五、發明説明（沒） 行氫化），而用水來替代該脂肪族羧酸，是藉箸使用一結 合了分離與水洗過濾裝置在昇髙的壓力的條件下操作而進 行的。其他步驟包括：將一高壓頂上氣流進行加工處理， 該氣流包含水、不凝結的氣體（像是氮氣和一氣/二氣化 碳），以及在該氣化反應過程中蒸發的有機物質（包括脂 肪族羧酸和溴代甲烷），以生産一含有水和有機物質的一 高壓氣態排放流，以使得該排放流的水含量超過有機物質 的含量，將該高壓氣態排放流進行高溫燃燒（最好是配合 使用一觸媒及/或一肋燃劑），並且伴隨箸溴代甲烷轉化 成溴及/或溴化氫，以及將溴及/或溴化氫自該經過處理 的氣態排放流除去β 最好，該高壓氣態排放流幾乎完全不含前述脂肪族羧 酸。因此，舉個例説，該頂上第流的處理最好是包括了在 一分離塔中將水與脂肪族羧酸分離的步驟，以使得回收的 脂肪族酸能被再循環到該反應器。最好，從該粗芳番族羧 酸的純化加工衍生的水性母液亦輸送到該蒸皤塔，（最好 是以回流方式），致該等出現在該水性母液中的雜質、反 應中間産物以及芳香族羧酸連同該氣態排放流的脂肪族羧 酸和水成份（包括從前述水性母液衍生的水）一起通到該 氧化反應。 大家應當知道，在文義容許情況下，本發明的前述第 一實施例之後的關聯說明中所定義的本發明的特點，也適 用在本文中所界定的其他實施例。 本紙張尺度適用中阈國家榡準（CNS ) Λ4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝· 經濟部中央標準局員工消費合作社印製 A 7 ___ _B7_ ._;_ 五、發明説明Gv：) 圖1係—流程圖的示意圖，其顯示出了本發明的一實施例， 其應用在邂理自用以生産對苯二酸的工廠衍生的棑放氣流； 以及 Η 2 顯示出用以降低該排放氣流的溴/溴化氫成份的一 滌氣裝置。 圖一部份 10 :管線 D :蒸餾塔（精餾器） R : 反應器 11 :管線 12 :熱交換器 13 : 再循環母液 Ρ :過濾、水洗、 純化、及回收等程序 14 : 混合器 16 :管線 U :燃燒單元 20 : 閥門 2 2 ·•溫度戚應器 24 :膨腥器 26 : 轉軸 28 :單元 30 :滌氣段 32 : 冷水交換器 34 :管線 圖二部份 50 :滌氣單元 52 :迫緊段 5 4 : 迫緊段 56:液體收集盤 58 :人 CJ 60 : 出口 62 :排出管線 64 :泵 66 : 入口管線 6 8 :出口管線 70 :泵 72 : 回流管線 7 4 :管線 76 :管線 78 : 清除管線 80 :管線 g :瓦斯（gas) w : 水（water) 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） (請先閲讀背面之注意事項再填寫本頁) 裝- 、1Τ (7 A7 _____ B7五、發明説明（(r) 實施例之詳細說明： 經濟部中央標準局員工消費合作社印製 參看圖1,通過管線10進入處理工廠的排放氣流傺從 一蒸餾塔或精餾器D衍生而來的，該蒸皤塔或精皤裝置僳 與一用以生産對苯二甲酸的反應器R有關聯，該生産方式俗 (比方説）藉箸在吾人之前的EP-A- 498591及/或EP-A-5 0 2 628中所掲示的方法，籍箸對二甲苯的液相氣化而進行 的〇在這兩個專利申錆案中所掲示的方法中，對二甲苯的 經過催化的液相氣化是在一含有醋酸的溶劑中進行的，以 生産對苯二酸，該觸媒条統含有重金屬（像是鈷及錳）， 以及溴化物助燃劑。該液相氣化的溫度是藉箸自該反應器 中抽取一蒸汽相的頂上流而控御的，該頂上流含有醋酸、 水、氣態的副産品（包括溴代甲烷和醋酸甲酯）以及氣體 (像是氮氣、一氣化硪、二氣化硪及氣氣）。在經過涉及 除去一大部份的醋酸的加工之後，取得了一氣態的排放流 (或稱〃下氣該排放氣流傜處於舁高的壓力。 在圃示的實施例中，該頂上流的加工處理通常包含將 該氣流通到一塔D,其作用乃為進行醋酸與水的分離《塔D 的操作使得重成份（像是醋酸）以一液相底層産品回收， 而輕的成份（像是水、氣態的副産品，像是溴代甲烷、醋 酸甲酯，以及氣體，像是氮氣、一氣化磺、二氣化硝和氣 氣）以一氣相頂層産品回收，其構成該高壓氣態的#下氣" 排放流，該排放流將被處理。在該生成的〃下氣"排放流 中的水是以蒸汽形態存在的。因此，舉個例說，儘管從該 本紙張尺度通用中國网家榡準（CNS ) A4規格（210X 297公釐） --;---.---,-裝-- (請先閲讀背面之注意事項再填寫本頁) 訂-. 線 經濟部中央標準局員工消費合作社印製 A7 B7五、發明説明（iU 氣化反應器汲取的頂上氣流可能含有醋酸和水的比例為70¾ 到953；的醋酸比30¾到5¾的水（依重量與重量的比），而從 塔D回收的高壓排放氣流通常含有醋酸和水的比例為0.53； 到1. 0J：的醋酸比99.53!到99. OX的水蒸汽（依重量與重置的 比）。該水蒸汽含量通常為全部的拂放流的重置比大約在 40¾到70Χ之間。 從塔D來的含有豐富的醋酸的底層産品經過管線11回 到氣化反應器R。這個底層産品將會含有醋酸和一些水， 另外，可能還含有其他有機物，像是以下述方式通到塔D的 對苯二甲酸的前身（含複數），（比方說），對甲苯酸。 該頂層産品，亦即含有水蒸汽作為主要成份的該高壓排放 流，通過管線10而除去》 在EP-A-498591和EP-A-50 26 28專利案中所掲示的方法 的一個待點是在該純化加工中生成的該水性的母液的處理 方式。該純化加工涉及對二甲苯的氣化而得的粗對苯二酸 的一水性溶液的氫化、純化的對苯二酸的結晶化，以及純 化的結晶與水性的母液的分離等過程。道搛所生成的水性 母液含有雜質和一些中間産物，像是對甲苯甲酸，而在之 前的加工方法中被視為一廢棄物。EP-A-498591和EP-A-502628 掲示了這初级母液至少有一部份可再循環到與該氣化反應 器有關聯的蒸皭塔，（最好以一回流餵流形式），而這樣 加工的方式使得高沸點的雜質（像是對甲苯甲酸）回牧在 該含豐富醋酸的底層産品中，而該底層産品乃取自該蒸豳 塔以便再循環到該氣化反應器。.自該純化加工回收的該母 液可經過處理或不經處理而再循環到該蒸蹓塔。這一類的 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） : ϋ· n I m n - - nl· 士1-- 1^1 n^i n m ' 0¾ ,-5¾ (請先閲讀背面之注意事項再填寫本頁) 經濟部中央榡準局貝工消费合作社印製 A7 B7五、發明説明（β) 處理（如果採用的話）可包含將該初级母液（藉箸冷卻或 蒸發）處理以沈澱更多的（但較不純的）對苯二酸，並且 將這樣生成的次级母液（以一回流饋流形式）餓送到該蒸 餾塔，以用來將水與醋酸分離0該較不純的對苯二酸沈澱 物亦經再循環到該氣化反應器，（比方說，藉著將它漿溶 到從該蒸餾塔衍生而來的醋酸中該純化母液以這樣的 使用方式亦可採用到本發明中，而該母液（經過處理或未 經處理）供送到該蒸餾塔D(最好以回流形式）。 本文中掲示的排放流的處理可（比方說）用在配合芳 香族的聚耧酸生産工廠，在該工廠中粗酸結晶與初鈒脂肪 族羧酸母液分離，而純化的酸结晶與初级水性母液分離， 並且使用一結合了固體分離和水洗的裝置以水洗滌，該分 離/水洗裝置可為吾人之前經辑公告的國際專利申請案 W0 9 3/2 4 4 4 0和W0 9 4/ 1 7 982中所述的装置，（該等專利案 的全部掲示内容已經納入本文中作為參考），使得因為水 洗的結果，該母液被水取代。因此，該结合了固體分離和 水洗的裝置或可（比方說）包含一皮帶式過據單元，其係 配合漿料側，在超大氣的條件下操作，或一經加壓的迴轉 式筒狀過濾單元，配合漿料側，在超大氣的條件下操作， 或一膝力鼓過濾單元（比方説，一 BHS-Fest壓力過濾鼓， 附有數個漿料接收室，在該等接收室中該母液藉箸在加壓 情況下供到該等接收室的水，自過濾餅塊排出）。 用以對粗對苯二酸進行過濾和水洗的加工，其後缠的 純化、回收和水洗，以及純化母.液的再循環在EP-A-4 9859 1 、EP-A-502 628、W0 9 3/2 4 4 4 0 和 W094/1 7982 中有詳細說明 --Γ---„----V ' 裝------訂 ^------線 (請先閲讀背面之注意事項再填寫本頁) 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 經濟部中央標準局員工消費合作杜印製 A7 B7五、發明説明（// ) 。因此，在本文中自無必要再予詳細說明，這些加工方法 經以字母”P”在圖1中表示，而該經再循環的母液（經處理 或未經處理）以數字”13”表示。 該排放氣流通常壓力在1 〇到1 6巴之間，.而谳度則在1 70°C 到190°C之間》該氣髏經使用高壓蒸汽作為熱源在熱交換 器12中預熱。通常，該氣流的溫度在經過這樣的熱交換之 後，大約在2 5 0°C到45ITC之間，最好在300°C到400°C之間 。然後，該氣流再進入一混合器14,而一助燃物亦同時通 過管線16經導入該混合器，該經混合的氣流和肋燃物再經 以1。到5 X 1 0# 1Γ丨之間的空間速度（最好在5 X 1 到 2xl(^h~)饋送到一催化的燃燒單元18。 一種方便的助燃劑乃是醋酸甲酯，其你在對苯二酸生 産過程中以副産品的形式産生<^另外，也可以使用其他不 同的助燃劑，或是配合其他助燃劑同時使用，尤其是那些 含有氧的化合物，比方說，甲醇。該肋燃劑經導入的量應 恰到好處，以使得該經自催化燃燒單元18排出的經過燃燒 的氣流溫度在4 0 0°C之譜或更高，通常在480°C之譜》—回 授裝置（包含在管線16中的閥門20,溫度烕測器22和適當 的控制裝備）經使用以將供到該混合器14的肋燃劑加以調 控，以使得能在單元18的排出口處維持所要的溫度。 在催化燃燒單元18中所用到的觸媒可包含任何適合的 氣化作用觸媒，以確保溴代甲烷幾乎能完全地轉化成溴和 溴化氫，而又同時確保，配合肋燃物（如果有霈要）、其 他的有機物（像是醋酸），幾乎.能夠完金地氣化，並且産 生出能夠使得在排出口維持所需溫度的熱通常，所使用 .-* - - I F II 1 I- IK · I (請先閲讀背面之注意事項再填寫本頁) 訂 -丨線 本紙張尺度適用中國國家椟準（CNS ) A4規格（210X297公釐） 經濟部中央榡準局貝工消費合作社印製 A7 B7五、發明説明（J) 到的觸媒包含一貴金屬觸媒，像是鉑及/或耙支架在一情 性材質架上《該支架或可為陶瓷或金羼，而形如一單塊或 小球。適合的市售觸媒可由下述觸媒製造商供應：Johnson Matth 莊生.麥賽公司（比方説，Halcocat AH/HTB-10或LHC觸媒） 、Allied Signal/Degussa 徳古薩公司（比方説，HDC-2 或 T2-HDC 觸媒）以及Engelhard英格哈待公司（比方説，VOCAT 30 0H 或 VOCAT 4 5 0H觸媒）。 繼催化燃燒之後，該經過處理的氣流通常溫度在4 Q0°C 到700°C之譜，而若該未經處理的氣流壓力在iD到16巴之 間時，該經過處理的氣流的歷力僅較該未經過處理的氣流 低一點兒，亦即大約在9. 5到15. 5巴。然後，該經過處理的 氣流再經通過膨脹器24,在該膨脹器中，該氣流的能源成.. 份轉換成機械動力，該機械動方通過轉軸26,可經適當地 用在對苯二酸生産過程中，比方說，作為動力输入，供一 空氣壓縮機用以將空氣在加壓情況下供到該生産線上的氣 化反應器，或是供産生電力供输送到厫匾内或輸送到其他 使用者〇在膨脹器24的排出口倒，該氣流的溫度通常在140°C 到2 0 0 °C之譜（比方說，大約170°C到200eC),而其壓力 接近大氣壓，tb方説，大約1.2巴。這裡所採用的溫度和 壓力條件應恰到好處，致在催化燃燒進行當中，從溴代甲 烷轉化成的溴和溴化氫能雒持在氣相，以避免任何露點腐 蝕的危險。這樣做法，比起在膨脹器24上游處使用滌氣裝 置（其結果導致使用膨脹器可萃取的能源減少），或是使 用昂貴的材料來製作膨脹器2 4，.可節省大量成本β 繼能源回收之後，該氣流經加工以除去溴化物成份， βΛ請先閱讀背面之注^K項再填寫本頁) ^i·— —^^1. — t n^i m^l I - i i I ·i A Wood paper scale is applicable to Chinese National Standard (CNS) Λ4 specification (210X297 mm) Printed by the Central Consumers ’Cooperative Bureau of the Ministry of Economic Affairs Employee Cooperatives This paper size is applicable to Chinese National Standard (CNS) eight-four specification (210X297 mm) A7 _B7 V. Description of the invention ((.) The aqueous mother liquor separated from the purified aromatic acid, (for example, by using filtering equipment like the one shown in my previous international patent application WO 93/24440), Contains various impurities, reaction intermediates, and B, as well as the aforementioned aromatic carboxylic acid in suspended and dissolved form. By recycling the aqueous mother liquor to the separation column, these impurities, reaction intermediates and dissolution The aromatic carboxylic acid component can be separated from the water in the aqueous mother liquor, and returned to the gasification reactor from the separation tower together with the monocarboxylic acid recovered through the tower to form a bottom product. Generally, a part of the aqueous mother liquor The main part is recycled to the separation column in this way (preferably in the form of reflux). The mother liquor recovered from the purification reaction can be processed (for example, by borrowing By cooling or evaporation) to recover less pure aromatic carboxylic acid crystals therefrom, and at least a portion of the mother liquor that is fed to the separation column may contain secondary mother liquor obtained after such treatments. Or, because The separation operation is always carried out at a relatively high temperature. The initial mother liquor recovered from the purification reaction can be recycled to the separation tower without cooling to any significant degree, although it can also be used at Before being introduced into the separation column, it is filtered to remove any floating fines. It is best that the crude acid is substituted with the aliphatic carboxylic acid in the aforementioned slurry by water to separate it from the aforementioned monocarboxylic acid. A wet deposit of crude acid containing water is generated for use in the subsequent purification of the crude acid (for example, by replacing an aqueous solution generated from the aforementioned wet deposit with hydrogenation) and replacing it with water The monocarboxylic acid is performed using a filter that combines separation and water washing, and (preferably) operates under elevated pressure conditions. The filter that combines separation and water washing may include a gas pressure type Belt (Please read the precautions before filling this page) Pack-Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7_V. Description of the invention (丨 /) Rotary device, one-shot rotary drum Filter, a hydraulic multi-chamber pressure drum filter, or a centrifuge with a water washing device. In each of the above cases, the water washing operation can be carried out in stages, preferably in a counter-current manner, to enable filtration The cake can be washed with relatively pure water, since the water advances downstream from a location where the crystals are separated from the mother liquor. Usually, the filter is operated at a pressure differential of 0.1 to 15 bar (Preferably between 0.3 and 7 bar), preferably the pressure on the lower pressure side of the filter is not less than 1 bar, although we do not rule out the possibility that the lower pressure side is at a subatmospheric pressure Property β Another embodiment of the present invention relates to the removal of bromine and hydrogen bromide from the gas stream after high temperature combustion, and in particular to the treatment of the gas stream to remove the bromine component, so that all emissions to the atmosphere How much money This and other ingredients. Processing such as this (by way of example) can be performed by superheating the airflow with water, and the airflow can be removed in a scrubbing section using a suitable aqueous scrubbing medium. Bromine and chlorine bromide. Removal of desertified hydrogen can be achieved by countercurrent contact with tritium (for example) with an aqueous solution of argon bromide, or only by contact with water (for example) with a spray of water or a spigot, and at the same time , Superheating the treated airflow. If the purpose (for example) of contacting the treated gas stream with an aqueous solution of hydrogen bromide is to recover hydrogen bromide for use as part of the catalyst system used in the gasification reactor, then Very appropriate. If this is not the case, water can be used. If water is used, it is best to use a sufficient amount of water to irrigate the pipelines used to transport the water-treated gas stream downstream to prevent corrosion problems. As for the removal of bromine, it can be combined with a solution such as hydrogenated sodium , Sodium sulfonate, Sodium hydrogen sulfonate, Sodium bromide, Sodium formate, Asia: ----------- \: Packing -------- Order j ------ line (please read the back first Please note this page before filling in this page) This paper size applies Chinese National Standard (CNS) Λ4 specification (210X297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 ___ B7 V. Description of Invention (/ >) Sodium sulfate or An aqueous solution containing two or more mixtures of these components (for example, sodium argon and sodium sulfate) is brought into countercurrent contact. The gasification reaction used to produce the aromatic carboxylic acid, and the subsequent purification The operation can be performed in accordance with the method shown in my previous European patents £ 卩-纟 -49859 1 and £ 卩 -A-502628, and the entire contents of these patents have been incorporated herein by reference. The aromatic carboxylic acid may be Terephthalic acid, in this case, the gasified The predecessor of terephthalic acid will be p-xylene β. Alternatively, the aromatic carboxylic acid may be isophthalic acid (formerly meta-xylene) or 2,6-naphthalene-dicarboxylic acid (formerly 2,6-dicarboxylic acid). Methylated). The gasification reaction is usually at a temperature between about 120eC and about 240 ° C, and a pressure at least capable of maintaining the reaction mixture in a liquid phase condition (typically 5 bar to 30 bar). The following β The promoter component of the catalytic system contains bromine and is usually hydrogen bromide, molecular bromine, sodium bromide, and / or suitable organic bromine compounds already known in the art. The heavy metal component of the tenter system is usually a compound that is / or manganese, for example, a compound // manganese sulfonate. According to another embodiment of the present invention, an aromatic carboxylic acid ( Such as terephthalic acid), which method comprises the steps of: a precursor (for example, p-xylene) of the aforementioned aromatic acid, in a reaction medium containing an aliphatic carboxylic acid (for example, acetic acid) Gasification to produce a blend of crude aromatic carboxylic acids in the aforementioned fatty acids, and Water to replace the aliphatic carboxylic acid in the front mash, to produce a wet deposit of crude aromatic carboxylic acid containing water for subsequent purification processing of the crude carboxylic acid (for example, by borrowing Enter an aqueous solution formed from the wet deposits before (please read the precautions on the back before filling out this page) • Loading. -0 —4 This paper size applies to China National Standard (CNS) Α4 size (2 丨 〇 × 25 »7mm) A7 printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs _B7__ 5. Description of the invention (not) Hydrogenation), and the use of water to replace the aliphatic carboxylic acid is a combination of separation and washing and filtration. The unit is operated under elevated pressure. Other steps include processing a high-pressure overhead gas stream that includes water, non-condensable gases (such as nitrogen and primary / secondary carbon dioxide), and Organic substances (including aliphatic carboxylic acids and bromomethane) evaporated during the gasification reaction to produce a high-pressure gaseous exhaust stream containing water and organic substances such that the water content of the exhaust stream exceeds Organic matter content, high-pressure gaseous exhaust stream is subjected to high temperature combustion (preferably with a catalyst and / or a rib fuel), and accompanied by the conversion of bromomethane to bromine and / or hydrogen bromide, and It is preferred that bromine and / or hydrogen bromide be removed from the treated gaseous exhaust stream. The high-pressure gaseous exhaust stream is almost completely free of the aforementioned aliphatic carboxylic acids. Therefore, for example, the overhead treatment preferably includes a step of separating water from the aliphatic carboxylic acid in a separation column so that the recovered aliphatic acid can be recycled to the reactor. Preferably, the aqueous mother liquor derived from the purification and processing of the crude aromatic carboxylic acid is also sent to the distillation tower (preferably in a reflux manner), so that impurities, reaction intermediates and the like appearing in the aqueous mother liquor And the aromatic carboxylic acid is passed to the oxidation reaction together with the aliphatic carboxylic acid and water components of the gaseous exhaust stream (including water derived from the aforementioned aqueous mother liquor). It should be known that, to the extent permitted by the context, the features of the present invention as defined in the associated description following the first embodiment of the present invention are also applicable to other embodiments defined herein. This paper size is applicable to the mid-threshold national standard (CNS) Λ4 specification (210X297 mm) (Please read the precautions on the back before filling out this page). Printing · Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A 7 ___ _B7_ ._ ; _ V. Description of the invention Gv :) Figure 1 is a schematic diagram of a flow chart showing an embodiment of the present invention, which is applied to the processing of a tritium-derived gas stream derived from a plant used to produce terephthalic acid; and Η 2 shows a scrubber unit to reduce the bromine / hydrogen bromide content of this exhaust gas stream. Part 10 of the figure: Line D: Distillation column (rectifier) R: Reactor 11: Line 12: Heat exchanger 13: Recycled mother liquor P: Filtering, water washing, purification, and recovery procedures 14: Mixer 16 : Pipeline U: Combustion unit 20: Valve 2 2 • Temperature responder 24: Expansion vessel 26: Rotary shaft 28: Unit 30: Gas scrubber section 32: Cold water exchanger 34: Pipeline part 50: Gas scrubber unit 52: Urgent section 5 4: Urgent section 56: liquid collection tray 58: person CJ 60: outlet 62: discharge line 64: pump 66: inlet line 6 8: outlet line 70: pump 72: return line 7 4: line 76: Line 78: Clear line 80: Line g: Gas (W): Water (Water) This paper size applies to China National Standard (CNS) Α4 specification (210X 297 mm) (Please read the precautions on the back before filling this page ) Equipment-1T (7 A7 _____ B7 V. Detailed description of the invention ((r) Detailed description of the embodiment: Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Refer to Figure 1, the exhaust gas stream entering the treatment plant through pipeline 10 Derived from the distillation column or rectifier D, the distillation A tower or a refinery plant is associated with a reactor R used to produce terephthalic acid. The production method is customary (for example) by EP-A-498591 and / or EP-A-5 before ours. The method shown in 0 2 628 is performed by liquid phase gasification of p-xylene. In the methods shown in these two patent applications, the catalytic liquid-phase gasification of p-xylene is It is carried out in a solvent containing acetic acid to produce terephthalic acid. The catalyst strip contains heavy metals (such as cobalt and manganese), and a bromide combustion accelerator. The temperature of the liquid phase gasification is obtained from the The top stream of a vapor phase is controlled and extracted in the reactor. The top stream contains acetic acid, water, gaseous by-products (including bromomethane and methyl acetate), and gases (such as nitrogen, tritiated tritium, and two gasifications). (Gas and gas). After a process involving the removal of a large portion of acetic acid, a gaseous exhaust stream is obtained (or called "downgas"), which is at a high pressure. In the illustrated embodiment, The top-up processing usually includes passing the air stream to a tower D, which The function is to separate acetic acid from water. The operation of column D allows heavy components (such as acetic acid) to be recovered as a liquid bottom product, while light components (such as water and gaseous by-products such as bromomethane and acetic acid). Methyl esters, as well as gases, such as nitrogen, primary gaseous sulphur, secondary gaseous nitrate, and gaseous gas) are recovered as a top-phase product of gas phase, which constitutes the high-pressure gaseous #down gas " exhaust stream, which will be processed. The water in this generated radon " exhaust stream exists in the form of steam. So, for example, even though the paper size is from the standard of China Netcom Standard (CNS) A4 (210X 297 mm)-; ---.---, --- Note: Please fill in this page again) Order-. Printed by the Consumers Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Invention Description (The overhead air stream drawn by the iU gasification reactor may contain acetic acid and water at a ratio of 70¾ to 953; Acetic acid ratio of 30¾ to 5¾ of water (based on weight to weight ratio), and the high pressure exhaust gas stream recovered from column D usually contains acetic acid and water in a ratio of 0.53; to 1. 0J: acetic acid ratio 99.53! To 99. OX Water vapor (depending on the weight to reset ratio). The water vapor content is usually about 40¾ to 70 × of the reset ratio of the total effluent stream. The bottom product rich in acetic acid from column D passes through line 11 Back to the gasification reactor R. This bottom product will contain acetic acid and some water, and may also contain other organics, such as the precursor (including plural) of terephthalic acid that is passed to tower D in the following way, (for example Said), p-toluic acid. The top product, which also contains This high-pressure exhaust stream with steam as the main component is removed through line 10. One of the highlights of the methods shown in the EP-A-498591 and EP-A-50 26 28 patents is that the Treatment method of aqueous mother liquor. The purification process involves hydrogenation of an aqueous solution of crude terephthalic acid obtained by vaporization of para-xylene, crystallization of purified terephthalic acid, and purified crystal and aqueous mother liquor. Separation and other processes. The aqueous mother liquor produced by Daojiao contains impurities and some intermediate products, such as p-toluic acid, and was considered a waste in the previous processing methods. EP-A-498591 and EP-A-502628 It is shown that at least a part of this primary mother liquor can be recycled to the distillation tower associated with the gasification reactor (preferably in the form of a reflux feed stream), and this processing method makes high boiling impurities (such as P-toluic acid) is grazed in the bottom product rich in acetic acid, and the bottom product is taken from the distillation tower for recycling to the gasification reactor. The mother liquor recovered from the purification process can be processed or Without passing It is recycled to the steaming tower. The paper size of this category applies the Chinese National Standard (CNS) A4 specification (210X297 mm): ϋ · n I mn--nl · Taxi 1-- 1 ^ 1 n ^ inm '0¾, -5¾ (Please read the notes on the back before filling out this page) Printed by the Central Bureau of Standards of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives, A7, B7 V. Description of the invention (β) Processing (if used) may include the elementary The mother liquor (by cooling or evaporation) is treated to precipitate more (but less pure) terephthalic acid, and the secondary mother liquor thus formed (in the form of a reflux feed) is starved to the distillation column for use with To separate water from acetic acid. The less pure terephthalic acid precipitate is also recycled to the gasification reactor, (for example, by slurrying it into acetic acid derived from the distillation column. The purified mother liquor can also be used in the present invention in this way, and the mother liquor (treated or untreated) is supplied to the distillation column D (preferably in reflux form). The treatment of the effluent stream shown in this article can be used, for example, in an aromatic polyacid production plant where the crude acid crystals are separated from the primary alkali aliphatic carboxylic acid mother liquor, and the purified acid crystals are separated from the primary aqueous The mother liquid is separated and washed with water using a device that combines solid separation and water washing. The separation / water washing device can be the international patent applications WO 9 3/2 4 4 4 0 and WO 9 4/1 The device described in 7 982 (the entire contents of these patents have been incorporated herein by reference) so that the mother liquor is replaced by water as a result of washing. Therefore, the device that combines solids separation and water washing may (for example) include a belt type data collecting unit, which is matched with the slurry side and operated under ultra-atmospheric conditions, or a pressurized rotary cylindrical filter Unit, with slurry side, operating under ultra-atmospheric conditions, or a knee drum filter unit (for example, a BHS-Fest pressure filter drum with several slurry receiving chambers, in which the mother liquor is (The water supplied to the receiving chamber under pressure is discharged from the filter cake). It is used for filtering and washing the crude terephthalic acid, and then purifying, recovering and washing with water, and purifying the mother liquor. The recycling of the liquid is in EP-A-4 9859 1, EP-A-502 628, W0 9 3/2 4 4 4 0 and W094 / 1 7982 are described in detail-Γ --- `` ---- V 'installation -------- order ^ ------ line (please read first Note on the back, please fill out this page again) This paper size is applicable to China National Standard (CNS) A4 specification (210X 297 mm). A7 B7 printed by the consumer cooperation of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (//). Therefore, it is not necessary to elaborate further in this article. These processing methods are indicated in Figure 1 with the letter "P" and the recycled mother liquor (treated or untreated) is indicated by the number "13". The pressure of the exhaust gas flow is usually between 10 and 16 bar, and the temperature is between 1 70 ° C and 190 ° C. The gas cross is preheated in the heat exchanger 12 using high pressure steam as a heat source. Generally, the temperature of the airflow after such heat exchange is between about 250 ° C and 45ITC, preferably between 300 ° C and 400 ° C. Then, the airflow enters a mixture. Device 14 and a combustion-supporting material is also introduced into the mixer through line 16 at the same time, the mixed gas stream and the ribbed fuel are then passed at a space velocity between 1 and 5 X 1 0 # 1Γ 丨 (preferably at 5 X 1 to 2xl (^ h ~) are fed to a catalyzed combustion unit 18. A convenient combustion accelerator is methyl acetate, which you produce as a by-product during the production of terephthalic acid < ^ In addition, also Other different combustion promoters can be used or combined with other combustion promoters, especially those compounds containing oxygen, such as methanol. The amount of rib fuel introduced should be just right so that the autocatalytic combustion unit 18 The temperature of the exhausted combustion gas stream is at or above 400 ° C, usually at 480 ° C.-Feedback device (valve 20 included in line 16, temperature detector 22 and appropriate controls) (Equipment) is used to regulate the rib fuel supplied to the mixer 14 so that the desired temperature can be maintained at the discharge port of the unit 18. The catalyst used in the catalytic combustion unit 18 may include any suitable Gasification catalyst to ensure bromoform It can be almost completely converted into bromine and hydrogen bromide, and at the same time, it can be combined with rib fuel (if necessary) and other organic substances (such as acetic acid) to almost completely gasify, and produce The heat that maintains the required temperature at the discharge port is usually used.-*--IF II 1 I- IK · I (Please read the precautions on the back before filling this page) Order-丨 The size of this paper is applicable to Chinese countries. Standard (CNS) A4 (210X297 mm) Printed by the Central Bureau of Standards of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, printed A7 B7 V. Description of the invention (J) The catalyst included contains a precious metal catalyst, such as platinum and / or harrow bracket In a sentimental material stand, "The stand may be ceramic or gold, and it looks like a monolith or a ball. Suitable commercially available catalysts can be supplied by the following catalyst manufacturers: Johnson Matth (for example, Halcocat AH / HTB-10 or LHC catalyst), Allied Signal / Degussa (for example , HDC-2 or T2-HDC catalysts) and Engelhard (for example, VOCAT 30 0H or VOCAT 4 5 0H catalysts). After catalytic combustion, the temperature of the treated gas stream is usually in the spectrum of 4 Q0 ° C to 700 ° C. If the pressure of the untreated gas stream is between iD and 16 bar, the history of the treated gas stream 5 至 15. 5 巴。 Only a little lower than the untreated airflow, that is, about 9.5 to 15. 5 bar. Then, the treated gas stream passes through the expander 24, in which the energy source of the gas stream is converted into mechanical power, and the mechanical moving part passes through the rotating shaft 26, and can be suitably used for terephthalic acid. In the acid production process, for example, as a power input, an air compressor is used to supply air to a gasification reactor on the production line under pressure, or to generate electricity for delivery to a plaque or conveyance. To other users, pour at the outlet of the expander 24. The temperature of the airflow is usually in the range of 140 ° C to 200 ° C (for example, about 170 ° C to 200eC), and the pressure is close to atmospheric pressure, tb Fang said about 1.2 bar. The temperature and pressure conditions used here should be just right, so that during the catalytic combustion, the bromine and hydrogen bromide converted from bromomethane can be held in the gas phase to avoid any danger of dew point corrosion. In this way, compared with using a scrubber device upstream of the expander 24 (which results in a decrease in the extractable energy of the expander), or using expensive materials to make the expander 24, a lot of costs can be saved After recycling, the gas stream is processed to remove the bromide component. Please read the note ^ K on the back before filling in this page) ^ i · — — ^^ 1.
、1T •丨線 本紙張尺度適用中國國家標準（CNS ) Λ4規格（2丨0'〆297公釐） 經濟部中央標準局員工消費合作社印製 A7 ___B7_ 五、發明説明（γ) 使得所有排放到大氣的排放物幾乎完全無此等成份。這樣 的加工可（比方說）藉著在單元28中使用水對該氣流進行 降超熱，並且在一滌氣段30中，讓該氣流與一適合的水性 滌氣介質接觸，以除去溴和溴化氫《溴化氫（比方說）可 葙箸與溴化氫溶液進行逆流接®而除去，而溴可藉著與一 諸如氳氣化納、硪酸納、硝酸氫納、溴化納、甲酸納、亞 硫酸納或含有逭些成份的兩種或兩種以上的混合物（比方 說，氫氣化鈉與亞硫酸納）的一水溶液進行逆流接觸而除 去。用來進行降超熱的水亦可同時用在該滌氣段。該經清 潔的排氣流（通常含有從重置比4U到70Χ的水蒸汽）再經 冷卻，（比方說，在一冷卻水交換器32中進行冷卻），以 回收其中一極大比例的（或最好是幾乎全部的）水，以用 在該處理廠的氣化及/或純化作業中再使用。在經凝集了 大部份的水之後，該排放氣流主要含有氪氣，且可被排放 到大氣及/或經用在該生産程序中的其他地方，比方説， 用作惰性化功能〇 儘管在圖1中並未示出，塔D可包括一滌氣段，而從（ tb方說）回收自該經清潔的排氣流的水所衍生來的水經管 線34供到該滌氣段，以便改進對苯二酸的更具揮發性的前 身（比方説，對甲苯甲酸）的回收，這前身如果不用這方 法回收，會随著在塔内以頂層産品形式的排放氣流，一同 排出該塔。這個滌氣段係位在將該回流氣流（純的母液） 導入塔D的點的上方，而供到遒個滌氣段的水可經預熱， 以便增加該頂層産品蒸汽的含量· <» 圖2示出了滌氣單元50的一種形式，其用以將該排放 本紙浪尺度適;f]中國國家標準（CNS ) Λ4規格（210X297公釐) : Μ -I ? HI nn —LI HI 1^1 ---I ____K • -吞 I (請先閱讀背面之注$項再填寫本頁) 經濟部中央標準局貝工消費合作社印裝 A7 !—_ϋ2_ 五、發明説明（叫） 氣體滌氣，以使得在該排放氣髖中溴化物的含董低於體積 比量4 ppm,更好的是，低於體稹比2 ΡΡΒ,而更好的是， 體積比的1 ΡΡ·β單元50包含一容器，其具有二經迫緊的 段5 2和54。所使用的迫緊可為任何適合的软式，比方說， 拉希格氏環、巴爾氏環等等》—液體收集盤56位在兩段52 、54之間。該排放氣流（連同用來澆灌管線的水），繼處 理以除去溴化氫之後，被饋送到在該容器5 0的底部的一入 口 58,進入該容器的該氣醱和液體即在該容器底部中衝擊 到一板（圈未示），以防止該氣體/液體混合物衡擊到在 入口 58對面容器壁的該部位上。通過該容器所産生的氣 體，横過經迫緊的兩段52、54,通過出口 60而離開，可被 排放到大氣。 所用到的滌氣液可以是任何適合的，能夠將溴化物從 該排放氣流除去的液體，包括上述的化學物。該滌氣液圍 繞著一環而循環，該環包括上段52、排出管線62、泵64及 入口管線66,以使得該液體流動的方向恰為流經該容器50 的氣流的方向的逆流。同樣地，在該容器50的下部形成的 該滌氣液的一第二再循環流藉著出口管線68、泵70和回流 管線72,相對於該氣流，亦恰為逆流β用過的滌氣液通過 管線74自該糸統清除，而添加的滌氣液通遇管線76輸入。 毎單位時間裡，通過該容器被泵卿的滌氣液的含量通常遠 遠超遇被清除的量，比方說，至少20:1的比例。比方說， 至少是30:1的比例（通常在40:1之譜）。一清除管線78交 聯泵64的出口和管線72,致在收集盤56中所收集到滌氣液 傜流到該較低的再循環液流環β在一修改的實施例中，清 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X297公釐） (請先閱讀背面之注$項再填寫本頁) 裝·、 1T • 丨 The paper size of this paper applies the Chinese National Standard (CNS) Λ4 specification (2 丨 0'〆297mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 ___B7_ V. Description of the invention (γ) makes all emissions to Atmospheric emissions are almost completely free of these components. Such processing can (for example) superheat the gas stream by using water in the unit 28, and in a scrubbing section 30, contact the gas stream with a suitable aqueous scrubbing medium to remove bromine and Hydrogen bromide Hydrogen bromide (for example) can be removed countercurrently with hydrogen bromide solution, and bromine can be removed by reacting with An aqueous solution of sodium formate, sodium sulfite, or a mixture of two or more of these components (for example, sodium hydride and sodium sulfite) is removed by countercurrent contact. The water used for superheat reduction can also be used in this scrubbing section. The cleaned exhaust stream (usually containing water vapor from a reset ratio of 4U to 70 ×) is then cooled (for example, cooled in a cooling water exchanger 32) to recover a large proportion (or Almost all) water is preferred for reuse in the gasification and / or purification operations of the treatment plant. After most of the water has been condensed, the exhaust gas stream mainly contains radon and can be discharged to the atmosphere and / or used elsewhere in the production process, for example, as an inertization function. Not shown in FIG. 1, the tower D may include a scrubbing section, and water derived from (tb-side) water recovered from the cleaned exhaust stream is supplied to the scrubbing section through a line 34, In order to improve the recovery of the more volatile precursor of terephthalic acid (for example, p-toluic acid), if this precursor is not recovered by this method, it will be discharged out of the tower along with the exhaust gas stream in the form of top product . This scrubbing section is located above the point where the reflux gas stream (pure mother liquor) is introduced into column D, and the water supplied to one scrubbing section can be preheated to increase the steam content of the top product. ≪ »Figure 2 shows a version of the scrubbing unit 50, which is used to adapt the emissions of the paper; f] Chinese National Standard (CNS) Λ4 specification (210X297 mm): Μ -I? HI nn —LI HI 1 ^ 1 --- I ____K • -Swallow I (please read the note on the back before filling in this page) Printed by A7, Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs! —_ ϋ2_ V. Description of the invention (called) Gas cleaning Gas, so that the bromide content in the ventilated hip is less than 4 ppm by volume, more preferably, less than 2 PPB, and even better, 1 PP · β unit by volume. 50 contains a container with two pressing sections 52 and 54. The urgency used can be any suitable soft type, for example, Raschig's ring, Barr's ring, etc.-the liquid collection tray 56 is located between the two sections 52, 54. The exhaust gas stream (together with the water used to water the pipeline), after treatment to remove hydrogen bromide, is fed to an inlet 58 at the bottom of the container 50, and the radon and liquid entering the container are in the container. A plate (circle not shown) was impacted in the bottom to prevent the gas / liquid mixture from striking against this part of the container wall opposite the inlet 58. The gas produced by the container passes through the two pressing sections 52, 54 and exits through the outlet 60, and can be discharged to the atmosphere. The scrubbing liquid used may be any suitable liquid capable of removing bromide from the exhaust gas stream, including the aforementioned chemicals. The scrubbing liquid circulates around a ring, which includes an upper section 52, a discharge line 62, a pump 64, and an inlet line 66, so that the direction of the liquid flow is exactly the reverse flow of the direction of the air flow passing through the container 50. Similarly, a second recirculation stream of the scrubbing liquid formed at the lower portion of the container 50 is also the counter-current β used scrubbing gas through the outlet line 68, the pump 70, and the return line 72. The liquid is removed from the system through the line 74, and the added scrubbing liquid is input through the line 76.毎 The amount of scrubbing liquid that is pumped through the container per unit time usually far exceeds the amount that is removed, for example, at least 20: 1. Let's say at least a 30: 1 ratio (usually in a 40: 1 spectrum). A purge line 78 exits the cross-link pump 64 and a line 72 so that the scrubbing liquid collected in the collecting tray 56 flows to the lower recirculating liquid flow ring β. In a modified embodiment, the paper is cleared The dimensions are applicable to the Chinese National Standard (CNS) Λ4 specification (210X297 mm) (Please read the note on the back before filling this page)
訂I 經濟部中央標準局貝工消費合作社印製 A7 ___B7 五、發明説明（y/) 除管線78可被省略，而滌氣液從該上部段52移送到下部段 54，以及移送到下部再循琛液流琢中，其可藉著讓在該收 集盤56中所收集的流液的溢流而進行的。少量的滌氣液（ 比方説 > 從泵70通遇管線80而導入到入口 58,以防止在入 口區域裡的任何腐蝕的危險β 在另一修改的資施例中，藉著在滌氣塔中在段52和段 54的下方再使用一迫緊段，溴化氫的滌氣步*可以和溴的 滌氣步糠結合，以使得該氣流最初先通經溴化氫滌氣段β 在該溴化氫滌氣段中，該滌氣液可為一溴化氫的水性溶液 ，相對於段52和段54,配合流琛的適當的清除和添加管線 ，在如上述的一再循琛流琛中流動。澳化氫的清除流可（ 比方説）输送到觸媒的添加流》 從上面這偁實施例，吾人可看出，該含溴化物的氣流 經過一兩段式的滌氣處理，使得在該氣流被從該容器排出 之前，溴化物幾乎完全地被除去β如稍早所述的，該滌氣 液可為任何一種適合用來有效地將溴化物除去的流液，而 最好是敵性金臑化合物。若（比方說）該滌氣液是氫氣化 納，逋流液會因為被吸收進入在該排放氣流中所含有的二 氣化碩的氫氧化物中的结果，而在該滌氣容器中被轉化成 磺酸納和酸式硪酸鹽β如果不使用氫氣化納，或除了使用 氫氯化納以外，該滌氣液可為（或可含有）前面提到的一 種或多種化學物，比方説，亞硫酸納或甲酸納或其他適合 的還原劑，或其他化合物，像是氳氣化鉀或尿素。 本紙張尺度逋用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 袈- 'ΙΤOrder A Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, printed A7 ___B7 V. Description of the invention (y /) Except for the pipeline 78, the scrubbing liquid can be transferred from the upper section 52 to the lower section 54 and the lower section 54 The Xunchen fluid flow can be performed by overflowing the fluid collected in the collecting tray 56. A small amount of scrubbing liquid (for example > is introduced from the pump 70 through the line 80 to the inlet 58 to prevent any danger of corrosion in the inlet area β. In another modified embodiment, In the tower, a pressing section is used below the section 52 and the section 54. The hydrogen bromide scrubbing step * can be combined with the bromine scrubber step so that the gas stream initially passes through the hydrogen bromide scrubbing section β at In the hydrogen bromide scrubbing section, the scrubbing liquid may be an aqueous solution of hydrogen bromide, relative to sections 52 and 54, with appropriate removal and addition pipelines of Liu Chen, in the above-mentioned repetitive circulation flow. It flows in the middle of Chen. The scavenging stream of Australian hydrogen can be (for example) transported to the added stream of the catalyst. From the above example, we can see that the bromide-containing gas stream is treated by one or two stages of scrubbing. So that the bromide is almost completely removed before the gas stream is discharged from the container, as described earlier, the scrubbing liquid may be any stream suitable for effectively removing bromide, and most It ’s a hostile gold compound. If (for example) the scrubbing liquid is hydrogenated, The flowing liquid will be absorbed into the dihydrated hydroxide contained in the exhaust gas stream, and will be converted into sodium sulfonate and acid sulfonate β in the scrubber container if not used. Sodium hydride, or in addition to using sodium hydrochloride, the scrubbing liquid may be (or may contain) one or more of the aforementioned chemicals, for example, sodium sulfite or sodium formate or other suitable reducing agents, Or other compounds, such as potassium carboxide or urea. This paper uses Chinese National Standard (CNS) A4 size (210X297 mm) (Please read the precautions on the back before filling this page) '-' ΙΤ