TWI410402B - Oxidation reactor for manufacturing aromatic carboxylic acid and method of manufacturing aromatic carboxylic acid using the same - Google Patents

Oxidation reactor for manufacturing aromatic carboxylic acid and method of manufacturing aromatic carboxylic acid using the same Download PDF

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TWI410402B
TWI410402B TW099135106A TW99135106A TWI410402B TW I410402 B TWI410402 B TW I410402B TW 099135106 A TW099135106 A TW 099135106A TW 99135106 A TW99135106 A TW 99135106A TW I410402 B TWI410402 B TW I410402B
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oxidation reactor
reaction
agitator
reaction chamber
gas
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TW201119993A (en
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Hyungjin Kim
Hansan Kim
Sungwo Chai
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Sam Nam Petrochemical Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/20—Mixing gases with liquids
    • B01F23/23—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids
    • B01F23/233—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids using driven stirrers with completely immersed stirring elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/20—Mixing gases with liquids
    • B01F23/23—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids
    • B01F23/233—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids using driven stirrers with completely immersed stirring elements
    • B01F23/2336—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids using driven stirrers with completely immersed stirring elements characterised by the location of the place of introduction of the gas relative to the stirrer
    • B01F23/23365—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids using driven stirrers with completely immersed stirring elements characterised by the location of the place of introduction of the gas relative to the stirrer the gas being introduced at the radial periphery of the stirrer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/05—Stirrers
    • B01F27/07—Stirrers characterised by their mounting on the shaft
    • B01F27/072—Stirrers characterised by their mounting on the shaft characterised by the disposition of the stirrers with respect to the rotating axis
    • B01F27/0726—Stirrers characterised by their mounting on the shaft characterised by the disposition of the stirrers with respect to the rotating axis having stirring elements connected to the stirrer shaft each by a single radial rod, other than open frameworks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/05—Stirrers
    • B01F27/11—Stirrers characterised by the configuration of the stirrers
    • B01F27/112—Stirrers characterised by the configuration of the stirrers with arms, paddles, vanes or blades
    • B01F27/1123—Stirrers characterised by the configuration of the stirrers with arms, paddles, vanes or blades sickle-shaped, i.e. curved in at least one direction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/05—Stirrers
    • B01F27/11—Stirrers characterised by the configuration of the stirrers
    • B01F27/19—Stirrers with two or more mixing elements mounted in sequence on the same axis
    • B01F27/191—Stirrers with two or more mixing elements mounted in sequence on the same axis with similar elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/80—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/80—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis
    • B01F27/90—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis with paddles or arms 
    • B01F27/902—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis with paddles or arms  cooperating with intermeshing elements fixed on the receptacle walls
    • B01F27/9021—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis with paddles or arms  cooperating with intermeshing elements fixed on the receptacle walls the elements being vertically arranged, e.g. fixed on the bottom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B01J19/006—Baffles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B01J19/0066—Stirrers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
    • C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00761—Details of the reactor
    • B01J2219/00763—Baffles
    • B01J2219/00765—Baffles attached to the reactor wall
    • B01J2219/00768—Baffles attached to the reactor wall vertical
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00761—Details of the reactor
    • B01J2219/00763—Baffles
    • B01J2219/00779—Baffles attached to the stirring means

Abstract

Disclosed are an oxidation reactor for manufacturing an aromatic carboxylic acid and a method of manufacturing the aromatic carboxylic acid using the oxidation reactor. The oxidation reactor includes a reaction chamber, a stirring shaft disposed along a geometric vertical axis of the reaction chamber, and at least two stirrers, each including stirring blades, each stirring blade having either a curved portion or a bent portion formed on an end of the stirring blade to enable fluid to flow in the reaction chamber while preventing the fluid from remaining in the reaction chamber, and each stirring blade being extended radially along a direction perpendicular to the vertical axis to be rotated.

Description

製造芳香羧酸的氧化反應器及使用其製造芳香羧酸的方法 Oxidation reactor for producing aromatic carboxylic acid and method for producing aromatic carboxylic acid using same

本發明係關於化學反應器及反應方法，且更具體地，係關於用於製造芳香羧酸的氧化反應器，該反應器可最大化反應速率與反應純度，以及關於使用該氧化反應器製造芳香羧酸的方法，該方法可以高效率與高產率產生芳香羧酸。 The present invention relates to a chemical reactor and a reaction method, and more particularly to an oxidation reactor for producing an aromatic carboxylic acid, which maximizes the reaction rate and reaction purity, and relates to the use of the oxidation reactor to produce aroma A method of producing a carboxylic acid with high efficiency and high yield.

芳香羧酸可為有用於作為各種基礎化學化合物者。例如，對苯二甲酸(TA)，亦即其為可使用作為如纖維、膜、塑膠瓶、容器用樹脂等之聚酯原料的代表性芳香羧酸，而且對TA的需求與日俱增。製造芳香羧酸的一般方法，已知於液相氧化的方法。液相氧化可依下述方式實施，將如鈷、鎂等重金屬化合物，及必要時可使用作為催化劑的溴化合物，以及芳香烷基化合物，於反應器內於例如乙酸等含有低階脂肪族羧酸的溶劑之中，於加壓狀態下與含氧氣體接觸。 The aromatic carboxylic acid can be used as a base chemical compound. For example, terephthalic acid (TA), that is, it is a representative aromatic carboxylic acid which can be used as a polyester raw material such as a fiber, a film, a plastic bottle, a resin for a container, etc., and the demand for TA is increasing. A general method for producing aromatic carboxylic acids is known as a method for liquid phase oxidation. The liquid phase oxidation can be carried out by using a heavy metal compound such as cobalt or magnesium, and if necessary, a bromine compound as a catalyst, and an aromatic alkyl compound, and containing a low-order aliphatic carboxylic acid in a reactor such as acetic acid or the like. Among the acid solvents, the oxygen-containing gas is contacted under pressure.

於上述製造芳香羧酸的方法中，該原料之芳香烷基化合物及該乙酸及催化劑的混合物係置於包括有攪拌器形成於其內之反應器中，且後續藉由將含氧氣體導入至該反應器而進行氧化反應，因而獲得具有相對低溶解度的芳香羧酸。其次，該具有相對低溶解度的芳香羧酸係連續地產生，以獲得粗製的芳香羧酸。接著，該粗製的芳香羧酸後續地係經分離且進行精製步驟因而產生高純度芳香羧酸。 In the above process for producing an aromatic carboxylic acid, the aromatic alkyl compound of the raw material and the mixture of the acetic acid and the catalyst are placed in a reactor including a stirrer formed therein, and subsequently introduced by introducing an oxygen-containing gas into the reactor The reactor is subjected to an oxidation reaction, thereby obtaining an aromatic carboxylic acid having a relatively low solubility. Secondly, the aromatic carboxylic acid having a relatively low solubility is continuously produced to obtain a crude aromatic carboxylic acid. Next, the crude aromatic carboxylic acid is subsequently separated and subjected to a refining step to thereby produce a high purity aromatic carboxylic acid.

由芳香羧酸使用氧之液相氧化反應所使用之反應方法與反應烷基之間的差異之製造芳香羧酸的方法而言，有許多建議的改良 技術。其中，對於作為代表性芳香羧酸之TA而言，已知有用於製造TA的方法，包括氧化反應及跟隨其後之分離/精製步驟，以及循環步驟。 There are many suggested improvements in the method for producing aromatic carboxylic acids from the difference between the reaction method used in the liquid phase oxidation reaction of the aromatic carboxylic acid and the reactive alkyl group. technology. Among them, for TA as a representative aromatic carboxylic acid, a method for producing TA is known, including an oxidation reaction followed by a separation/refining step, and a recycling step.

然而，上述方法可仍具有需要克服之技術問題如下述者：首先，在氧化反應時期有顯著量的殘餘未反應性烷基芳香化合物產生，且有顯著量的所產生的未反應性烷基芳香化合物包含於排放氣體中，因而可能需要回收未反應性烷基芳香化合物的成本。 However, the above method may still have technical problems to be overcome such as the following: First, a significant amount of residual unreacted alkyl aromatic compound is produced during the oxidation reaction period, and a significant amount of the resulting unreacted alkyl aromatic is produced. The compound is contained in the exhaust gas and thus may require the cost of recovering the unreacted alkyl aromatic compound.

再者，使用作為聚酯原料之該芳香羧酸對其品質產生不良影響，因而於製造該芳香羧酸時期所產生顯著量之例如4-羧基苯甲醛(4-CBA)等雜質，可能仍存在。 Further, the use of the aromatic carboxylic acid as a raw material for polyester adversely affects the quality thereof, and thus a significant amount of impurities such as 4-carboxybenzaldehyde (4-CBA) which is produced during the production of the aromatic carboxylic acid may still exist. .

第三為氧化反應時期因氧化分解可能發生使用作為溶劑之脂肪族羧酸的顯著損耗，且因而可能發生經濟問題。 The third is that a significant loss of the aliphatic carboxylic acid used as a solvent may occur due to oxidative decomposition during the oxidation reaction period, and thus economic problems may occur.

本發明之一態樣係提供用於製造芳香羧酸的氧化反應器，其可降低反應損耗且改良反應效率。 One aspect of the present invention provides an oxidation reactor for producing an aromatic carboxylic acid which reduces reaction loss and improves reaction efficiency.

本發明之一態樣係提供使用該氧化反應器製造高純度與高效率芳香羧酸的方法。 One aspect of the present invention provides a method of producing a high purity and high efficiency aromatic carboxylic acid using the oxidation reactor.

根據本發明之態樣，提供用於製造芳香羧酸的氧化反應器，該氧化反應器包括：反應室；沿著該反應室之幾何垂直軸設置的攪拌軸；以及至少兩個攪拌器，其各包括攪拌翼，各攪拌翼具有曲面部分或彎曲部分形成於攪拌翼的末端以使流體流入反應室而防止流體殘留於反應室中，以及各攪拌翼係延著垂直於垂直軸旋轉的方向，幅射狀地延伸。 According to an aspect of the present invention, there is provided an oxidation reactor for producing an aromatic carboxylic acid, the oxidation reactor comprising: a reaction chamber; an agitating shaft disposed along a geometric vertical axis of the reaction chamber; and at least two agitators Each of the agitating blades includes a curved portion or a curved portion formed at an end of the agitating blade to allow fluid to flow into the reaction chamber to prevent fluid from remaining in the reaction chamber, and each of the agitating wings extends in a direction perpendicular to the vertical axis. Extends in a radial shape.

於此情況中，該氧化反應器可包括彼此有空間相隔的第一攪拌器與第二攪拌器，且各設置於反應室之攪拌軸，該第一攪拌器係設置於該反應室的上方部以及該第二攪拌器細設置於該反應室的下方部，以及該第一攪拌器與第二攪拌器之間的空間距離可為第一攪拌器或第二攪拌器長度(直徑)的1.5倍。再者，該攪拌器的長度(直徑)可為反應室內直徑的0.4至0.5倍。同時，第二攪拌器與該反應室底表面之間的距離可為該第二攪拌器長(直徑)的0.5至1倍。於此情況中，該攪拌器於反應室中的定位關係對於反應效率或反應純度具有重大影響。 In this case, the oxidation reactor may include a first agitator and a second agitator spaced apart from each other, and each of the agitating shafts disposed in the reaction chamber, the first agitator being disposed at an upper portion of the reaction chamber And the second agitator is finely disposed at a lower portion of the reaction chamber, and a spatial distance between the first agitator and the second agitator may be 1.5 times the length (diameter) of the first agitator or the second agitator . Further, the length (diameter) of the agitator may be 0.4 to 0.5 times the diameter of the reaction chamber. Meanwhile, the distance between the second agitator and the bottom surface of the reaction chamber may be 0.5 to 1 times the length (diameter) of the second agitator. In this case, the positioning relationship of the agitator in the reaction chamber has a significant influence on the reaction efficiency or the reaction purity.

此外，該攪拌翼可包括至少兩個區面部份或彎曲部分。再者，該攪拌翼可包括具有第一彎曲部分的第一攪拌翼，該第一彎曲部分的彎曲角度為45至75度，以及具有第二彎曲部分的第二攪拌翼，該第二彎曲部分額外地從第一攪拌翼具有彎曲角度為120至160度。 Furthermore, the agitating wing may comprise at least two zone portions or curved portions. Furthermore, the agitating wing may include a first agitating wing having a first curved portion, the first curved portion having a bending angle of 45 to 75 degrees, and a second agitating wing having a second curved portion, the second curved portion Additionally, the first agitating wing has a bending angle of 120 to 160 degrees.

再者，該至少兩個攪拌器之各者可包括支持構件，以使該攪拌翼彼此連接，且以使該攪拌翼與該攪拌軸彼此連接。於此情況中，該支持構件可為圓形板，該圓形板包括垂直於該攪拌軸的上表面以及具有相對於該上表面為傾斜表面的下表面。同時，該支持構件的末端可替代一般曲線形狀而形成為鋸齒狀。 Further, each of the at least two agitators may include a support member to connect the agitating blades to each other, and to connect the agitating blades and the agitating shaft to each other. In this case, the support member may be a circular plate including an upper surface perpendicular to the agitating shaft and a lower surface having an inclined surface with respect to the upper surface. At the same time, the end of the support member can be formed in a zigzag shape instead of the general curved shape.

此外，該氧化反應器復可包括氣體輸送管用以將氣體自外側注入反應室；反應物輸送管用以將包括反應原料、溶劑與催化劑之液體反應物進料至該反應室；回流輸送管用以將回流進料至該反應室；產物排出管用以將反應後之產物排出至外側；以及氣體排出管用以將所產生之反應後氣體在排出至外側。 In addition, the oxidation reactor may include a gas delivery tube for injecting gas from the outside into the reaction chamber; a reactant delivery tube for feeding a liquid reactant including a reaction raw material, a solvent and a catalyst to the reaction chamber; and a reflux delivery tube for The feed is refluxed to the reaction chamber; the product discharge tube is used to discharge the reacted product to the outside; and the gas discharge tube is used to discharge the generated reaction gas to the outside.

於此情況中，該氣體輸送管、該反應物輸送管以及該回流輸送管可由設置該第二攪拌器之虛擬水平表面向著垂直軸方向，分別定位於該第二攪拌器的一半長度內。再者，該氣體輸送管、該反應物輸送管以及該回流輸送管可分別沿著該攪拌器旋轉的方向，將該氣體、該反應物以及該回流進料至該反應室。 In this case, the gas delivery tube, the reactant delivery tube, and the return delivery tube may be positioned within a half of the length of the second agitator by a virtual horizontal surface on which the second agitator is disposed toward the vertical axis. Further, the gas delivery tube, the reactant delivery tube, and the return delivery tube can feed the gas, the reactant, and the reflux to the reaction chamber in a direction in which the agitator rotates, respectively.

再者，該產物排出管可經設置以使該產物排出管的末端由垂直軸而言係定位於第一攪拌器的上方。亦即，該產物排出管可形成於該反應室的上方部份。 Further, the product discharge tube can be configured such that the end of the product discharge tube is positioned above the first agitator by a vertical axis. That is, the product discharge pipe can be formed in the upper portion of the reaction chamber.

再者，該氧化反應器復可包括擋流器係經設置於該反應室的側壁以阻擋液體流，因而調控該流體的流動。 Furthermore, the oxidation reactor may include a baffle disposed on a sidewall of the reaction chamber to block the flow of the liquid, thereby regulating the flow of the fluid.

再者，當由該氧化反應器之上方觀之，該氧化反應器可包括至少兩個氣體輸送管係經設置為彼此緊鄰。 Further, when viewed from above the oxidation reactor, the oxidation reactor can include at least two gas delivery conduits disposed in close proximity to one another.

再者，至少一個氣體輸送管、至少一個反應物輸送管以及至少一個回流輸送管，當由該氧化反應器之上方觀之，可以相等間距規律地設置。 Furthermore, at least one gas delivery tube, at least one reactant delivery tube, and at least one reflux delivery tube, when viewed from above the oxidation reactor, can be disposed at equal intervals.

根據本發明之一態樣，係提供一種使用氧化反應器製造芳香羧酸的方法，由垂直於垂直軸之中間部分的虛擬平面而言，該氧化反應器劃分為上方部分與下方部分，且包括第一攪拌器與第二攪拌器分別輻射狀地設置於該上方部分與該下方部份，以垂直於該垂直軸，其中包括含氧反應氣體、烷基芳香化合物、溶劑、催化劑與回流之液體反應物，係進料至該氧化反應器之下方部份，以及反應後之產物與反應後之氣體係排出於該氧化反應器之上方部份。於此情況中，回流溫度可低於該氧化反應器的內部溫度。 According to an aspect of the present invention, there is provided a method for producing an aromatic carboxylic acid using an oxidation reactor, wherein the oxidation reactor is divided into an upper portion and a lower portion by a virtual plane perpendicular to a middle portion of the vertical axis, and includes The first agitator and the second agitator are respectively radially disposed on the upper portion and the lower portion to be perpendicular to the vertical axis, and include an oxygen-containing reaction gas, an alkyl aromatic compound, a solvent, a catalyst, and a reflux liquid. The reactant is fed to the lower portion of the oxidation reactor, and the product after the reaction and the gas system after the reaction are discharged to the upper portion of the oxidation reactor. In this case, the reflux temperature may be lower than the internal temperature of the oxidation reactor.

本發明之其他態樣、特徵及/或優勢將由後述說明部份所闡述，以及部分由此說明書而可明瞭，或可藉由本發明實施本發明而得知。 The other aspects, features, and/or advantages of the invention will be set forth in the description of the appended claims.

如上述例示具體例所述，本發明提供一種使用氧化反應器製造芳香羧酸的方法，其可顯示優異的反應特性，且因而可降低未反應原料的損耗以及所產生雜質的量，可減抑因氧化反應時期所使用之溶劑的氧化分解造成的損耗，以及可顯著地改良整體反應效率與所得產物之芳香羧酸的品質，結果為顯著降低生產成本。 As described in the above specific examples, the present invention provides a method for producing an aromatic carboxylic acid using an oxidation reactor, which can exhibit excellent reaction characteristics, and thus can reduce the loss of unreacted raw materials and the amount of impurities generated, and can be suppressed The loss due to oxidative decomposition of the solvent used in the oxidation reaction period, and the overall reaction efficiency and the quality of the aromatic carboxylic acid of the obtained product are remarkably improved, with the result that the production cost is remarkably lowered.

亦即，根據例示具體例，裝設於該氧化反應器之攪拌軸之下方部份之第二攪拌器周圍的未反應烷基芳香化合物的濃度與脂肪族羧酸的反應速率可最大化。此外，氧化反應器中之未反應烷基芳香化合物的濃度以及因乙酸的氧化反應造成之乙酸的損耗，可隨著氧化反應器之液體表面的方向而顯著地降低。 That is, according to the exemplified specific example, the reaction rate of the unreacted alkyl aromatic compound around the second agitator disposed under the stirring shaft of the oxidation reactor and the aliphatic carboxylic acid can be maximized. Further, the concentration of the unreacted alkyl aromatic compound in the oxidation reactor and the loss of acetic acid due to the oxidation reaction of acetic acid may be remarkably lowered with the direction of the liquid surface of the oxidation reactor.

因此，該反應器之氣相區域中的未反應烷基芳香化合物的濃度可顯著地降低，以及排出至經安裝用於處理排放氣體之熱交換器、蒸餾管柱等之未反應原料的排出量，可顯著地降低，因而可省略補充回收步驟。再者，介於含氧氣體與該原料之烷基芳香化合物之間的反應，係於與乙酸的反應之前進行，此可導致作為溶劑之乙酸的損耗減低。 Therefore, the concentration of the unreacted alkyl aromatic compound in the gas phase region of the reactor can be remarkably lowered, and the discharge amount of the unreacted raw material discharged to the heat exchanger, distillation column or the like which is installed for treating the exhaust gas can be discharged. , can be significantly reduced, so the supplementary recovery step can be omitted. Further, the reaction between the oxygen-containing gas and the alkyl aromatic compound of the raw material is carried out before the reaction with acetic acid, which may result in a decrease in the loss of acetic acid as a solvent.

再者，根據例示具體例，產物經由其而排出至外側之產物排出管係經設置於該氧化反應器的上方部份，因而可防止油氧化反應所產生之芳香羧酸產物，混入與粘附於該氧化反應器的壁或底 部，而循環至該氧化反應器之下方部份。其結果，該產物可安定地排出而不增加攪拌動力，因而在經濟效益與品質上或的顯著效果。 Further, according to the exemplified specific example, the product discharge pipe through which the product is discharged to the outside is disposed in the upper portion of the oxidation reactor, thereby preventing the aromatic carboxylic acid product produced by the oil oxidation reaction from being mixed and adhered. On the wall or bottom of the oxidation reactor And circulate to the lower part of the oxidation reactor. As a result, the product can be discharged stably without increasing the stirring power, and thus has a significant effect on economic efficiency and quality.

後文中，本發明將藉由實施例更具體予以說明。然而，應了解該等實施例僅用於說明目的，且不意圖限制本發明之範疇。 Hereinafter, the present invention will be more specifically described by way of examples. However, it is to be understood that the examples are for illustrative purposes only and are not intended to limit the scope of the invention.

第1圖為根據本發明之例示具體例之用於製造芳香羧酸之氧化反應器100的截面示意圖。 Fig. 1 is a schematic cross-sectional view showing an oxidation reactor 100 for producing an aromatic carboxylic acid according to an exemplary embodiment of the present invention.

參考第1圖，該用於製造芳香羧酸之氧化反應器100(後文稱為「氧化反應器」)包括反應室110、攪拌軸105、第一攪拌器120、第二攪拌器130、氣體輸送管140、反應物輸送管150、回流輸送管160、產物排出管170、氣體排出管180以及擋流器190。 Referring to Fig. 1, the oxidation reactor 100 (hereinafter referred to as "oxidation reactor") for producing an aromatic carboxylic acid includes a reaction chamber 110, a stirring shaft 105, a first agitator 120, a second agitator 130, and a gas. The conveying pipe 140, the reactant conveying pipe 150, the return conveying pipe 160, the product discharge pipe 170, the gas discharge pipe 180, and the flow stopper 190.

根據本例示具體例之該反應室110可形成為圓柱型，然而本發明並不限定於該者，且因此可形成為各種形狀。攪拌軸105可形成為沿著該反應室110之幾何垂直軸。該垂直軸可為對應於該圓柱反應室110之懸轉軸的區域。該攪拌軸105可使用動力傳遞而傳遞旋轉動力之該第一與第二攪拌器120與130。 The reaction chamber 110 according to the specific example of the present example may be formed in a cylindrical shape, but the present invention is not limited thereto, and thus may be formed into various shapes. The agitator shaft 105 can be formed along the geometric vertical axis of the reaction chamber 110. The vertical axis may be a region corresponding to the suspension axis of the cylindrical reaction chamber 110. The agitating shaft 105 can transmit the first and second agitators 120 and 130 of rotational power using power transmission.

該第一與第二攪拌器120與130可沿著垂直於該攪拌軸150的方向，彼此間隔地輻射狀設置。該第一攪拌器120可設置於該反應室110的上方部份，以及該第二攪拌器130可設置於該反應室110的下方部份。再者，即使於該反應室110中可提供至少三個攪拌器，而根據本例示具體例，係提供兩個攪拌器120與130。然而，將系統的攪拌動力與效率加以考量的情況下，其較佳為該氧化反應器100 具有兩個120與130。該第一與第二攪拌器120與130可具有沿著垂直於攪拌軸105的單一方向或多個方向延伸之輻射狀結構。該第一與第二攪拌器120與130可藉由相對於該攪拌軸105旋轉而對於反應物實施攪拌操作。 The first and second agitators 120 and 130 may be radially disposed apart from each other in a direction perpendicular to the agitating shaft 150. The first agitator 120 can be disposed at an upper portion of the reaction chamber 110, and the second agitator 130 can be disposed at a lower portion of the reaction chamber 110. Further, even if at least three agitators are provided in the reaction chamber 110, according to the specific example of the present example, two agitators 120 and 130 are provided. However, in the case where the stirring power and efficiency of the system are taken into consideration, it is preferably the oxidation reactor 100. There are two 120 and 130. The first and second agitators 120 and 130 may have a radial structure extending in a single direction or in multiple directions perpendicular to the agitating shaft 105. The first and second agitators 120 and 130 can perform a stirring operation on the reactants by rotating relative to the agitating shaft 105.

該第一與第二攪拌器120與130可為一種輻射狀葉輪，具有因輻射狀架構而於該攪拌器末端創造出水平旋轉流的結構，且同時於該反應室110中不創造氣體停留區域，以及可使用任何攪拌器只要可使流體平緩地流經該葉輪末端者即可。亦即，該第一與第二佼辦企120與130可具有於該反應室110中不創造氣體停留區域的結構，且該攪拌器包括攪拌翼122與132，該攪拌翼具有形成於該攪拌翼末端之曲面部份或彎曲部分以使流體平緩地流經該攪拌器末端。 The first and second agitators 120 and 130 may be a radial impeller having a structure that creates a horizontal swirling flow at the end of the agitator due to the radial architecture, and at the same time does not create a gas retention zone in the reaction chamber 110. And any stirrer can be used as long as the fluid can flow smoothly through the end of the impeller. That is, the first and second offices 120 and 130 may have a structure in which no gas staying region is created in the reaction chamber 110, and the agitator includes agitating blades 122 and 132, and the agitating blades have a stirring formed thereon. A curved portion or curved portion of the end of the wing to allow fluid to flow smoothly through the end of the agitator.

根據本例示具體例，該第一與第二攪拌器120與130可分別具有第一攪拌翼122與第二攪拌翼132。再者，該第一與第二攪拌器120與130可經由第一支持構件120與第二支持構件134分別與該攪拌軸105連接。該個別之攪拌器120與130可藉由該支持構件124與134，向著垂直於該攪拌軸105的方向，創造虛擬旋轉表面，且具有形成於該支持構件124與134的末端之至少兩個攪拌翼122與132。此外，該支持構件124與134可形成為具有傾斜表面的圓形板，該傾斜表面形成於該圓形板之上表面或下表面，且相對於垂直於該攪拌軸105之虛擬表面為傾斜的。此外，該圓形板可具有形成為弧形之傾斜表面。該支持構件124與134可形成為任何形狀，只要該支持構件124與134係由該攪拌軸105幅射狀延伸即可。然而，其較佳可為該支持構件124與134形成為具有較低傾斜表面之 圓形板。此乃因來自垂直循環流體之向上循環可受到增強。於傾斜表面的情況中，傾斜表面的角度可為相對於水平表面約15至20度。再者，該支持構件124與134的末端可形成為緩和曲線形狀，然而亦可形成為鋸齒狀。 According to the specific example of the present example, the first and second agitators 120 and 130 may have a first agitating wing 122 and a second agitating wing 132, respectively. Furthermore, the first and second agitators 120 and 130 can be coupled to the agitating shaft 105 via the first support member 120 and the second support member 134, respectively. The individual agitators 120 and 130 can create a virtual rotating surface by the support members 124 and 134 in a direction perpendicular to the agitating shaft 105, and have at least two agitations formed at the ends of the supporting members 124 and 134. Wings 122 and 132. Further, the support members 124 and 134 may be formed as a circular plate having an inclined surface formed on an upper surface or a lower surface of the circular plate and inclined with respect to a virtual surface perpendicular to the agitating shaft 105 . Further, the circular plate may have an inclined surface formed in an arc shape. The support members 124 and 134 may be formed in any shape as long as the support members 124 and 134 are radially extended by the agitating shaft 105. However, it is preferable that the support members 124 and 134 are formed to have a lower inclined surface. Round plate. This is because the upward circulation from the vertical circulating fluid can be enhanced. In the case of an inclined surface, the angle of the inclined surface may be about 15 to 20 degrees with respect to the horizontal surface. Furthermore, the ends of the support members 124 and 134 may be formed in a gentle curved shape, but may be formed in a zigzag shape.

第2(a)圖與的2(b)圖分別為根據本發明之例是具體例之攪拌器之翼200之展開圖與截面圖。 2(a) and 2(b) are respectively a developed view and a cross-sectional view of the agitator wing 200 according to a specific example of the present invention.

參照第2(a)圖，該攪拌器之翼200如展開圖所示可具有梯形。顯而易見地，該翼200可形成為具有至少一曲面部分或至少一彎曲部分之各種形狀，而造成各種展開圖式。 Referring to Figure 2(a), the agitator wing 200 can have a trapezoidal shape as shown in the expanded view. Obviously, the wing 200 can be formed into various shapes having at least one curved portion or at least one curved portion, resulting in various deployment patterns.

該翼200可於第一彎曲部分212彎曲，其係對梯形的中心線為垂直角度因而形成為楔形。再者，該翼200復可於第二彎曲部分222彎曲，其係三角形ABC之BC段。於此情況中，該翼200可以第一彎曲部分212的相反方向於第二彎曲部分222彎曲。接著，該翼200可包括由第一彎曲部分212所形成之第一攪拌器210，以及由第二彎曲部分222所形成之第二攪拌器220。此外，該翼200可具有由第一彎曲部分212彎曲之楔形開口部分。該楔形開口部分可定向於該攪拌器120與130的旋轉方向。 The wing 200 is bendable at the first curved portion 212, which is perpendicular to the centerline of the trapezoid and thus formed into a wedge shape. Moreover, the wing 200 can be bent at the second curved portion 222, which is the BC segment of the triangle ABC. In this case, the wing 200 may be bent in the opposite direction of the first curved portion 212 from the second curved portion 222. Next, the wing 200 may include a first agitator 210 formed by the first curved portion 212 and a second agitator 220 formed by the second curved portion 222. Further, the wing 200 may have a wedge-shaped opening portion that is curved by the first curved portion 212. The wedge shaped opening portion can be oriented in the direction of rotation of the agitators 120 and 130.

再次參照第2(a)圖，根據本例示具體例，該翼200的BC段可彎曲為具有長度相對應於該梯形相對應段長度之65%至75%，以及該翼200的AC段可彎曲為具有長度相對應於該梯形相對應段長度之20%至30%。於此情況中，AB段與AC段的B點與C點可根據反應室110中之流體的特性而予以調整。 Referring again to FIG. 2(a), according to the specific example of the present example, the BC section of the wing 200 can be bent to have a length corresponding to 65% to 75% of the length of the trapezoidal corresponding section, and the AC section of the wing 200 can be Bending to have a length corresponding to 20% to 30% of the length of the corresponding portion of the trapezoid. In this case, points B and C of the AB segment and the AC segment can be adjusted according to the characteristics of the fluid in the reaction chamber 110.

參照第2(b)圖，該第一彎曲部分212可具有角度(α)45至75度， 以及該第二彎曲部分222可於對該第一彎曲部分212為相反方向上具有角度(β)120至160度。不同的是，該角度(α)與(β)可根據該反應室中之流體的特性而調整為具有各種角度。 Referring to FIG. 2(b), the first curved portion 212 may have an angle (α) of 45 to 75 degrees. And the second curved portion 222 may have an angle (β) of 120 to 160 degrees in the opposite direction to the first curved portion 212. The difference is that the angles (α) and (β) can be adjusted to have various angles depending on the characteristics of the fluid in the reaction chamber.

如上所述，該攪拌器120與130可防止經導入該反應室110之含有氧分子形式的氣體殘留於該反應室110中，因此氣泡容易變細小且容易均勻地分散以增加氣體與液體之接觸面積，因而改良氣體與液體之間的質量運送特性。 As described above, the agitators 120 and 130 prevent gas containing oxygen molecules introduced into the reaction chamber 110 from remaining in the reaction chamber 110, so that the bubbles are easily thinned and easily dispersed uniformly to increase the contact between the gas and the liquid. Area, thus improving the quality transport characteristics between the gas and the liquid.

上述之攪拌器120與130可包括至少兩個攪拌翼122與134，以及例如2至8個攪拌翼122與134。特別地，該攪拌器120與130較佳可包括4至6個攪拌翼122與134。 The agitators 120 and 130 described above may include at least two agitating blades 122 and 134, and for example, 2 to 8 agitating blades 122 and 134. In particular, the agitators 120 and 130 preferably may include from 4 to 6 agitating wings 122 and 134.

參照第1圖，該攪拌器120與130之安裝位置對於反應室110中之混合物的攪拌有重大影響，因而與該攪拌器120與130的結構一起可為達成本發明之態樣的重要因素。 Referring to Fig. 1, the mounting positions of the agitators 120 and 130 have a significant influence on the agitation of the mixture in the reaction chamber 110, and thus together with the structure of the agitators 120 and 130, may be an important factor in achieving the aspect of the present invention.

根據本例示具體例，該第一攪拌器120與該第二攪拌器130之間的距離(F)相對於該攪拌器120與130的長度(或直徑)(D)的比例(F/D)，可為1.0至1.5，且該攪拌氣的長度(D)可為該反應室110的內直徑(T)的0.4至0.5倍，亦即D/T=0.4至0.5。再者，該第二攪拌器130與該反應室110的底表面之間的距離(C)，可至少為該攪拌器120與130的長度(D)的一半，亦即，C/D=0.5至1.0。 According to the specific example of the present example, the ratio (F/D) of the distance (F) between the first agitator 120 and the second agitator 130 relative to the length (or diameter) (D) of the agitators 120 and 130 (F/D) It may be 1.0 to 1.5, and the length (D) of the stirring gas may be 0.4 to 0.5 times the inner diameter (T) of the reaction chamber 110, that is, D/T = 0.4 to 0.5. Furthermore, the distance (C) between the second agitator 130 and the bottom surface of the reaction chamber 110 may be at least half the length (D) of the agitators 120 and 130, that is, C/D=0.5. To 1.0.

當F/D<1.0時，上方攪拌區域與下方攪拌區域可能重疊，因而其中攪拌未充分實施之未充分攪拌區域可分別產生於該反應室110的上方攪拌區域與下方攪拌區域。再者，當F/D>1.5時，不足攪拌區域可能產生於該第一攪拌器120與該第二攪拌器130之間的 中間部分。 When F/D<1.0, the upper agitation zone and the lower agitation zone may overlap, and thus the insufficiently agitated zone in which the agitation is not sufficiently performed may be respectively generated in the upper agitation zone and the lower agitation zone of the reaction chamber 110. Furthermore, when F/D>1.5, an insufficient agitation region may be generated between the first agitator 120 and the second agitator 130. The middle part.

此外，當D/T<0.4時，原料與含氧氣體之間的接觸可能不足，因而質量運送係數可能減低。或者，當D/T>0.5時，不充足攪拌區域可能產生於該攪拌器130的下方。類似地，當C/D<0.5時，該不足攪拌區域可能產生於該攪拌器130的下方。於不足攪拌區域的氧化反應步驟可能難以進行，因而氧化反應的中間體產生會增加。 Further, when D/T < 0.4, the contact between the raw material and the oxygen-containing gas may be insufficient, and thus the mass transport coefficient may be lowered. Alternatively, when D/T > 0.5, an insufficient agitation zone may be generated below the agitator 130. Similarly, when C/D < 0.5, the insufficient agitation zone may be generated below the agitator 130. The oxidation reaction step in the insufficient agitation zone may be difficult to carry out, and thus the production of the intermediate of the oxidation reaction may increase.

根據本例示具體例，該攪拌器120與130的旋轉速度可為10至100rpm，且較佳為70至90rpm。再者，該攪拌器之攪拌力可為2.08W/M3至4.42kW/M3。 According to the specific example of the present example, the agitators 120 and 130 may have a rotational speed of 10 to 100 rpm, and preferably 70 to 90 rpm. Further, the agitating force of the agitator may be 2.08 W/M 3 to 4.42 kW/M 3 .

本發明之態樣可達成於氧化反應器100中運送之液體物質的運送位置與運送方法、氣體的運送位置與運送方法、流體的運送位置與運送方法、以及產物的排出位置與排出方法可彼此與該攪拌器120與130的結構與安裝位置相關聯，以實施其所擁有的功能。特別地，前述運送位置與運送方法以及排出位置與排出方法可根據反應室110中之流體的移動而設計，且其可使反應效率與產物純度最大化。 The aspect of the present invention can achieve the transport position and transport method of the liquid substance transported in the oxidation reactor 100, the transport position and transport method of the gas, the transport position and transport method of the fluid, and the discharge position and discharge method of the product can be mutually The structure and mounting position of the agitators 120 and 130 are associated to perform the functions they possess. In particular, the aforementioned transport position and transport method and discharge position and discharge method can be designed according to the movement of the fluid in the reaction chamber 110, and it can maximize reaction efficiency and product purity.

再次參照第1圖，該含氧氣體可經由氣體輸送管140運宋秩反應室110。該含氧氣體可運送至該第二攪拌器130附近，或該反應室110之底表面附近。此外，呈液體狀態之原料、催化劑與溶劑，可使用反應物輸送管150運送至該反應室110。再者，該回流可經由回流輸送管160運送至該反應室110。該回流可指稱一液體其中之氧化反應後所獲得氣體元素於進行凝縮步驟後係經循環，且導入該反應室110。 Referring again to FIG. 1, the oxygen-containing gas can be transported through the gas delivery tube 140. The oxygen-containing gas may be delivered to the vicinity of the second agitator 130 or near the bottom surface of the reaction chamber 110. Further, a raw material, a catalyst, and a solvent in a liquid state can be transported to the reaction chamber 110 using the reactant delivery tube 150. Again, the reflow can be delivered to the reaction chamber 110 via a return conduit 160. The reflux may refer to a liquid in which the gas element obtained after the oxidation reaction is circulated after being subjected to the condensation step, and introduced into the reaction chamber 110.

根據本例示具體例，該氣體輸送管140、該反應物輸送管150以及該回流輸送管160，可根據經設置該第二攪拌器130於其上之虛擬水平表面而設置為相對地接近於該第二攪拌器130。亦即，該輸送管140、150及160可分別設置於該第二攪拌器130的一半長度(D)內，由該虛擬表面向著該攪拌軸105的方向。 According to the specific example of the present example, the gas delivery tube 140, the reactant delivery tube 150, and the return delivery tube 160 may be disposed relatively close to each other according to a virtual horizontal surface on which the second agitator 130 is disposed. The second agitator 130. That is, the conveying pipes 140, 150, and 160 may be respectively disposed in a half length (D) of the second agitator 130, and the virtual surface faces the direction of the agitating shaft 105.

此外，如上所述，於該第二攪拌器130的支持構件134為圓形板且具有相對於該圓形板之上表面為較低傾斜表面的情況中，該氣體輸送管140可向下設置於該第二攪拌器130的下方。 Further, as described above, in the case where the support member 134 of the second agitator 130 is a circular plate and has a lower inclined surface with respect to the upper surface of the circular plate, the gas delivery pipe 140 may be disposed downward. Below the second agitator 130.

第3圖為根據例示具體例之該氣體輸送管340、該反應物輸送管350及該流體輸送管360係分別設置於該反應室110之平面示意圖。 Fig. 3 is a plan view showing the gas delivery tube 340, the reactant delivery tube 350, and the fluid delivery tube 360, respectively, disposed in the reaction chamber 110 according to an exemplary embodiment.

參照第3圖，該氣體輸送管340、該反應物輸送管350及該流體輸送管360可以彼此間固定的間隔與以規律地設置。全部6個氣體輸送管340群2個分為1群可彼此緊鄰，全部3個反應物輸送管350可規律地設置為與緊鄰的管具有120度的角度，以及2個回流輸送管360可設置為彼此相向。介於該輸送管340、350及360之間的各間隔可實際上為相同的。經由該輸送管340、350及360的設置，可增加於液體狀態混合氣體、物質與該回流時期之彼此接觸面積，且可獲得該混合物之均勻分散物。 Referring to Fig. 3, the gas delivery tube 340, the reactant delivery tube 350, and the fluid delivery tube 360 may be regularly spaced apart from each other to be regularly disposed. All 6 gas delivery pipes 340 group 2 are divided into 1 group and can be adjacent to each other, all 3 reactant conveying pipes 350 can be regularly set to have an angle of 120 degrees with the adjacent pipes, and 2 return conveying pipes 360 can be set For each other. The spacing between the tubes 340, 350 and 360 can be substantially the same. Through the arrangement of the conveying pipes 340, 350 and 360, the contact area of the mixed gas, the substance and the reflow period in the liquid state can be increased, and a uniform dispersion of the mixture can be obtained.

再者，經***該反應室110之該輸送管340、350及360之各者的末端部份，可向著攪拌器120、130的旋轉方向彎曲，且較佳係向著該旋轉方向的正切方向，因而使該氣體、該反應物與該回流可於旋轉方向進料至該反應室110。此乃因為該氣體、該反應物與該回流可根據該混合之流動方向進料至該反應室110。 Furthermore, the end portions of the respective transport tubes 340, 350, and 360 inserted into the reaction chamber 110 may be bent toward the rotational direction of the agitators 120, 130, and preferably toward the tangential direction of the rotational direction. The gas, the reactants and the reflux can thus be fed to the reaction chamber 110 in the direction of rotation. This is because the gas, the reactant and the reflux can be fed to the reaction chamber 110 in accordance with the flow direction of the mixing.

再次參照第1圖，該回流可為溶劑經該氧化反應器110所產生之反應熱予以蒸發、濕氣等所組成之混合物，可為藉由安裝於該氧化反應器外側之熱交換器(未示於圖中)所凝縮之液體元素，且可為其中不可凝氣體係經分離的氣體元素。該回流可經由回流輸送管160進料至該反應室110而予以循環。於此情況中，該回流溫度可較該反應室110之內部溫度更低，而更具體地，可較該反應室110之內部溫度低約20℃至60℃。 Referring again to FIG. 1, the reflux may be a mixture of solvent, evaporation, moisture, etc., generated by the oxidation reaction of the oxidation reactor 110, and may be a heat exchanger installed on the outside of the oxidation reactor (not The liquid element condensed as shown in the figure, and may be a gas element in which the non-condensable gas system is separated. This reflux can be circulated through the return conduit 160 to the reaction chamber 110. In this case, the reflux temperature may be lower than the internal temperature of the reaction chamber 110, and more specifically, may be lower than the internal temperature of the reaction chamber 110 by about 20 to 60 °C.

根據例示具體例，可製造該芳香羧酸，以使反應原料之烷基芳香化合物，例如對二甲苯，與例如乙酸之溶劑，可與欲反應之含氧氣體接觸。一般而言，該反應室110之內部溫度可藉由因與該含氧氣體接觸所造成之氧化反應熱的產生而變的更高，且因此氧化反應速度可逐漸加速，因而例如乙酸之該溶劑之氧化分解速度可加速。然而，根據本例示具體例，由於回流係經由回流輸送管160以較低溫度進料至該反應室110，該回流可作用為降低因氧化反應所加熱之環境溫度。因此，例如乙酸之該溶劑的氧化分解可受到減抑。亦即，此減抑效果可藉由使該具有低溫之回流共存於該氧化反應之反應物(包括氣體)的附近而獲得。 According to an exemplary embodiment, the aromatic carboxylic acid can be produced so that an alkyl aromatic compound of a reaction raw material such as p-xylene and a solvent such as acetic acid can be contacted with the oxygen-containing gas to be reacted. In general, the internal temperature of the reaction chamber 110 can be made higher by the generation of heat of oxidation reaction caused by contact with the oxygen-containing gas, and thus the oxidation reaction rate can be gradually accelerated, and thus the solvent such as acetic acid The rate of oxidative decomposition can be accelerated. However, according to the specific example of the present example, since the reflux is fed to the reaction chamber 110 at a lower temperature via the reflux delivery pipe 160, the reflux can act to reduce the ambient temperature heated by the oxidation reaction. Therefore, oxidative decomposition of the solvent such as acetic acid can be suppressed. That is, the depressing effect can be obtained by causing the reflux having a low temperature to coexist in the vicinity of the reactant (including gas) of the oxidation reaction.

再者，本發明之該攪拌器120與130可分別地設置於該反應室110之上方部份與下方部份。當該回流不進料至該反應室110時，經運送至該攪拌器130副近之原料(烷基芳香化合物)的氧化梵映可逐漸於藉由該第二攪拌器130所產生之水平旋轉流體中發生，且同時可發生乙酸的氧化分解。然而，由於垓據有低溫之回流係混合至該水平旋轉流體，引起液線溫度降低，該烷基芳香化合物之氧化反應可發生於該乙酸之氧化分解之前。因此，因例如乙酸之該 溶劑的氧化反應所造成的損失可顯著地降低。 Furthermore, the agitators 120 and 130 of the present invention may be respectively disposed at an upper portion and a lower portion of the reaction chamber 110. When the reflux is not fed to the reaction chamber 110, the oxidation of the raw material (alkyl aromatic compound) transported to the agitator 130 may gradually be rotated by the horizontally generated by the second agitator 130. Occurs in the fluid and at the same time oxidative decomposition of acetic acid can occur. However, since the reflux of the low temperature is mixed to the horizontal rotating fluid, causing the liquidus temperature to decrease, the oxidation reaction of the alkyl aromatic compound may occur before the oxidative decomposition of the acetic acid. Therefore, due to, for example, acetic acid The loss caused by the oxidation reaction of the solvent can be remarkably lowered.

此外，由於運送至該反應是110之下方部分之水平旋轉流體的大部份氧氣，係於該第二攪拌器130附近的水平旋轉流體中消耗，未反應烷基芳香化合物的濃度、所產生雜質的濃度以及乙酸的反應速率，可於該第二攪拌器130附近予以最大化。然而，未反應烷基芳香化合物與所產生雜質的氧化反應，可藉由升高殘餘氣體與該攪拌器所產生之合適向上循環流體與水平旋轉流體，而於該乙酸的氧化之前進行。於此情況中，該未反應烷基芳香化合物與所產生雜質的氧化反應可前進如同該烷基芳香化合物與該雜質較接近該反應室110的上方部分，因此該未反應烷基芳香化合物與所產生雜質實際上不殘留於該氧化反應器之液體表面。 In addition, since most of the oxygen of the horizontal rotating fluid transported to the lower portion of the reaction is 110, it is consumed in the horizontal rotating fluid near the second agitator 130, the concentration of the unreacted alkyl aromatic compound, and the generated impurities. The concentration and the reaction rate of acetic acid can be maximized in the vicinity of the second agitator 130. However, the oxidation reaction of the unreacted alkyl aromatic compound with the generated impurities can be carried out prior to oxidation of the acetic acid by raising the residual gas and the appropriate upward circulating fluid and horizontal rotating fluid produced by the agitator. In this case, the oxidation reaction of the unreacted alkyl aromatic compound with the generated impurity may proceed as if the alkyl aromatic compound and the impurity are closer to the upper portion of the reaction chamber 110, and thus the unreacted alkyl aromatic compound and the The generated impurities do not actually remain on the surface of the liquid of the oxidation reactor.

因此，藉由該向上循環流體所運送之該未反應烷基芳香化合物的濃度、該所產生的雜質以及該乙酸之氧化速率可根據其在該反應室110的高度而顯示其特定的分散，且更具體地，可隨著該烷基芳香化合物、該雜質以及該乙酸越接近該氧化反應器100的上方部份(液體表面)而降低。 Therefore, the concentration of the unreacted alkyl aromatic compound carried by the upward circulating fluid, the impurity produced, and the oxidation rate of the acetic acid can be expressed according to their height at the height of the reaction chamber 110, and More specifically, it may decrease as the alkyl aromatic compound, the impurity, and the acetic acid are closer to the upper portion (liquid surface) of the oxidation reactor 100.

根據本例示具體例，相對接近於該氧化反應器100的液體表面的未反應烷基芳香化合物的濃度，排除不可凝氣體元素，可為約0.01重量%或更少，較佳約0.007重量%或更少，且更較佳約0.005重量%或更少。於此情況中，該氧化反應器之氣相部分之未反應烷基芳香化合物的濃度，排除不可凝氣體元素，可為約0.02重量%或更少，較佳約0.015重量%或更少，且更較佳約0.01重量%或更少，其為顯注的小量，不需要藉由氣體排出處理的分離與回收步驟。 According to the specific example of the present example, the concentration of the unreacted alkyl aromatic compound relatively close to the liquid surface of the oxidation reactor 100, excluding the non-condensable gas element, may be about 0.01% by weight or less, preferably about 0.007% by weight or Less, and more preferably about 0.005% by weight or less. In this case, the concentration of the unreacted alkyl aromatic compound in the gas phase portion of the oxidation reactor, excluding the non-condensable gas element, may be about 0.02% by weight or less, preferably about 0.015% by weight or less, and More preferably, it is about 0.01% by weight or less, which is a small amount of significant interest, and does not require a separation and recovery step by gas discharge treatment.

再次參照第1圖，該產物排出管170的末端係設置於該地一攪拌器120的上方部份，以使該氧化反應後的產物可由該反應室110的上方部分或液體表面，經由該產物排出管170而排出。因此，突出於該反應室110外側之該產物排出管170的定位部分可不顯著地加以限制。此外，氧化反應後所產生的氣體元素可經由連接至該反應室110之上蓋的氣體排出管180，排出至該反應室110外側。 Referring again to FIG. 1, the end of the product discharge pipe 170 is disposed at an upper portion of the agitator 120 such that the product after the oxidation reaction can be passed from the upper portion or the liquid surface of the reaction chamber 110 via the product. The discharge pipe 170 is discharged. Therefore, the positioning portion of the product discharge pipe 170 that protrudes outside the reaction chamber 110 can be not significantly limited. Further, the gas element generated after the oxidation reaction may be discharged to the outside of the reaction chamber 110 via the gas discharge pipe 180 connected to the upper cover of the reaction chamber 110.

如上所述，根據本例示具體例之用於製造芳香羧酸之氧化反應器100，可包括攪拌器120與130以產生水平旋轉流體與向上循環流體之攪拌器，且可適用於運送該含氧氣體、例如原料之呈液體狀態之物質、以及該回流至該第二攪拌器130附近，因而可藉由該氧化反應器100中之上升氣體與該攪拌器120與130所產生之合適的向上循環流體與該水平旋轉流體而進行氧化反應。於此情況中，該氧化反應隨著更接近該氧化反應器100的上方部分而可更顯著地進行，以及該未反應原料不存在於該液體表面附近。 As described above, the oxidation reactor 100 for producing an aromatic carboxylic acid according to the specific example of the present example may include the agitators 120 and 130 to generate a horizontally rotating fluid and an agitator for circulating the fluid upward, and may be adapted to carry the oxygen. A gas, such as a material in a liquid state of the feedstock, and the reflux to the vicinity of the second agitator 130 are thereby suitably circulated by the ascending gas in the oxidation reactor 100 and the agitators 120 and 130. The fluid rotates with the horizontal to carry out an oxidation reaction. In this case, the oxidation reaction proceeds more significantly as it is closer to the upper portion of the oxidation reactor 100, and the unreacted raw material is not present near the surface of the liquid.

亦即，該氧化反應器100之反應溶液表面附近的烷基芳香化合物的濃度，可為約0.01重量%或更少，且轉換為芳香羧酸之反應速率可為約99.99重量%。更具體地，未反應烷基芳香化合物於該氧化反應器的反應溶液表面附近的濃度，排除不可凝氣體元素，可為約0.01重量%，較佳為0.007重量%，且更較佳約0.005重量%或更少。 That is, the concentration of the alkyl aromatic compound in the vicinity of the surface of the reaction solution of the oxidation reactor 100 may be about 0.01% by weight or less, and the reaction rate of conversion to the aromatic carboxylic acid may be about 99.99% by weight. More specifically, the concentration of the unreacted alkyl aromatic compound in the vicinity of the surface of the reaction solution of the oxidation reactor, excluding the non-condensable gas element, may be about 0.01% by weight, preferably 0.007% by weight, and more preferably about 0.005 by weight. % or less.

一般而言，於液體表面附近之烷基芳香化合物的殘餘量大，殘餘的烷基芳香化合物可藉由熱交換器、高壓吸附管柱或蒸餾管柱、與由該氧化反應器100之上方部分的排放氣體一起予以回收，然而，本發明不需要此回收步驟。 In general, the residual amount of the alkyl aromatic compound in the vicinity of the surface of the liquid is large, and the residual alkyl aromatic compound can be passed through a heat exchanger, a high pressure adsorption column or a distillation column, and a portion above the oxidation reactor 100. The exhaust gases are recovered together, however, the present invention does not require this recovery step.

此外，當產物的排出係於傳統的氧化反應器之底表面附近進行時，該產物排出管可能因固體物質粘附於氧化反應器的壁上與沉降而堵塞，然而，本例示具體例可避免此類問題。亦即，本例示具體例之氧化反應器100可連續地且長時間的進行產物的排出功能以改良操作效率。 Further, when the discharge of the product is carried out in the vicinity of the bottom surface of the conventional oxidation reactor, the product discharge pipe may be clogged by the solid matter adhering to the wall of the oxidation reactor and settled, however, the specific example of this example can be avoided. Such problems. That is, the oxidation reactor 100 of the specific example of the present embodiment can perform the discharge function of the product continuously and for a long time to improve the operation efficiency.

使用根據本例示具體例之芳香羧酸，可降低作為溶劑之乙酸的反應速率，且以該氧化反應中所產生之芳香羧酸為基準之音氧化反應所造成之損失可為約2.7重量%或更少，且較佳可為約2.5重量%或更少。 By using the aromatic carboxylic acid according to the specific example of the present example, the reaction rate of acetic acid as a solvent can be lowered, and the loss due to the oxidation reaction of the aromatic carboxylic acid produced in the oxidation reaction can be about 2.7% by weight or Less, and preferably may be about 2.5% by weight or less.

再次參照第1圖，該氧化反應器100可包括設置於該反應室110之側壁的擋流器190，以調控流體流動。可以相等間隔設置2至8個擋流器。擋流器190的寬度可為約該反應室110內直徑(T)的5%至20%。此外，該擋流器190可需要安裝於該反應室110中之反應溶液表面為相等或更低的位置。當該檔流器190係安裝於較該反應溶液表面更高的位置時，漿體元素可能斜升而粘附於該反應溶液表面之上的擋流器190的壁上，因而可能有晶體生長。此晶體可能落入該反應室110而中斷該樣化反應器100的穩定運轉。 Referring again to Figure 1, the oxidation reactor 100 can include a baffle 190 disposed on a sidewall of the reaction chamber 110 to regulate fluid flow. Two to eight flow stops can be placed at equal intervals. The width of the baffle 190 can be about 5% to 20% of the diameter (T) of the reaction chamber 110. Further, the baffle 190 may require a position of the reaction solution surface installed in the reaction chamber 110 to be equal or lower. When the flow damper 190 is installed at a position higher than the surface of the reaction solution, the slurry element may be inclined to adhere to the wall of the baffle 190 above the surface of the reaction solution, and thus crystal growth may occur. . This crystal may fall into the reaction chamber 110 to interrupt the stable operation of the sample reactor 100.

後文中，將詳細說明製造芳香羧酸的方法。 Hereinafter, a method of producing an aromatic carboxylic acid will be described in detail.

氧化步驟 Oxidation step

(1)烷基芳香化合物(原料) (1) Alkyl aromatic compounds (raw materials)

作為烷基芳香化合物，亦即使用於本例示具體例之原料，可使用含有烷基之芳香化合物。組成芳香化合物之芳香環化合物可為單一環(單環)化合物或多重環(多環)化合物。 As the alkyl aromatic compound, even if it is used as a raw material of the specific examples of the present examples, an aromatic compound containing an alkyl group can be used. The aromatic ring compound constituting the aromatic compound may be a single ring (monocyclic) compound or a multiple ring (polycyclic) compound.

作為烷基，可使用甲基、乙基、正丙基與異丙基。再者，該烷基可具有官能基。例如，作為官能基可使用醛基、醯基、羧基與羥基等。 As the alkyl group, a methyl group, an ethyl group, a n-propyl group and an isopropyl group can be used. Further, the alkyl group may have a functional group. For example, an aldehyde group, a thiol group, a carboxyl group, a hydroxyl group or the like can be used as the functional group.

作為京玩機取代之芳香化合物之例，可列舉烷基苯類、烷基萘類與烷基聯苯類，其具有2至4個烷基，各烷基具有1至4個碳原子，例如間-二異丙基苯、對-二異丙基苯、間-異丙基甲苯、對-異丙基甲苯、間-二甲苯、對-二甲苯、三甲基等。 Examples of the aromatic compound substituted by the Peking Machine include alkylbenzenes, alkylnaphthalenes and alkylbiphenyls having 2 to 4 alkyl groups each having 1 to 4 carbon atoms, for example. m-Diisopropylbenzene, p-diisopropylbenzene, m-isopropyltoluene, p-isopropyltoluene, m-xylene, p-xylene, trimethyl, and the like.

再者，作為含有烷基之芳香化合物，可使用除了烷基外含有取代基之化合物。該含有烷基之芳香化合物之例，可列舉3-甲基苯甲醛、4-甲基苯甲醛、間-甲基苯甲酸、對-甲基苯甲酸、3-甲醯基苯甲酸、2-甲基-6-甲醯基萘等。上述化合物可單獨使用或組合2或多種使用。 Further, as the aromatic compound containing an alkyl group, a compound containing a substituent other than the alkyl group can be used. Examples of the alkyl group-containing aromatic compound include 3-methylbenzaldehyde, 4-methylbenzaldehyde, m-methylbenzoic acid, p-methylbenzoic acid, 3-methylmercaptobenzoic acid, and 2- Methyl-6-methylnonylnaphthalene and the like. The above compounds may be used singly or in combination of two or more.

(2)用於製造對苯二甲酸的氧化步驟 (2) Oxidation step for producing terephthalic acid

將對二甲苯做為該氧化反應器之原料、溶劑、催化劑、含氧氣體與產生於分離步驟之母液之某些元素的循環溶液，其等將於後文中詳細說明，置入該氧化反應器100中，且接著予以反應。作為溶劑，可使用脂肪族羧酸如乙酸、丙酸、甲酸、乳酸等，然而，較佳使用包括乙酸作為主要元素之溶劑。當使用對苯二甲酸作為原料時，該溶劑之使用量可為一般原料之1至10倍，較佳為2至8倍，且更較佳為3至6倍。當該乙酸的用量顯著少時，所產生將体的濃度顯著增加，且引起管線堵塞的問題；而當該乙酸的用量顯著大時，可能需要較大的設備且造成經濟上的問題。 P-xylene is used as a raw material of the oxidation reactor, a solvent, a catalyst, a circulating solution of an oxygen-containing gas and certain elements of the mother liquid produced in the separation step, which will be described later in detail, and placed in the oxidation reactor. In 100, and then reacted. As the solvent, an aliphatic carboxylic acid such as acetic acid, propionic acid, formic acid, lactic acid or the like can be used, however, a solvent including acetic acid as a main element is preferably used. When terephthalic acid is used as a raw material, the solvent may be used in an amount of from 1 to 10 times, preferably from 2 to 8 times, and more preferably from 3 to 6 times, to the usual raw materials. When the amount of the acetic acid is remarkably small, the concentration of the body is remarkably increased, and the problem of blockage of the line is caused; and when the amount of the acetic acid is remarkably large, a large apparatus may be required and an economic problem is caused.

作為本例示具體例之溶劑，較佳可使用乙酸與水之混合物。於 此情況中，以乙酸為100重量份為基準，水可含有量為1至20重量份，且以乙酸為100重量份為基準，較佳為5至15重量份。 As the solvent of the specific example of the present embodiment, a mixture of acetic acid and water is preferably used. to In this case, the water may be contained in an amount of 1 to 20 parts by weight based on 100 parts by weight of the acetic acid, and preferably 5 to 15 parts by weight based on 100 parts by weight of the acetic acid.

作為含氧氣體之例，可列舉空氣、使用惰性氣體稀釋之氧氣以及含空氣之大量氧氣等，然而，實際上可使用空氣。以原料1莫耳為基準，該含氧氣體可使用具有3莫耳至100莫耳的氧。該空氣於該氧化反應器100之線路中可具有氧含量約21體積%。再者，由該氧化反應器100所排放氣體中之氧濃度，可為約1體積%至8體積%，且較佳約1.5體積%至3體積%。 Examples of the oxygen-containing gas include air, oxygen diluted with an inert gas, and a large amount of oxygen containing air. However, air can be actually used. The oxygen-containing gas may use oxygen having 3 to 100 moles based on the raw material 1 mole. The air may have an oxygen content of about 21% by volume in the line of the oxidation reactor 100. Further, the concentration of oxygen in the gas discharged from the oxidation reactor 100 may be from about 1% by volume to 8% by volume, and preferably from about 1.5% by volume to about 3% by volume.

催化劑並無特別限制，只要使用該催化劑可將烷基芳香化合物於液體中經氧化而轉換為芳香羧酸即可。作為催化劑，可使用重金屬化合物，且可使用溴化合物作為催化劑佐劑。含於該重金屬化合物中之重金屬之例可列舉鈷(Co)、錳(Mn)、鎳(Ni)、鉻(Cr)、鋯(Zr)、銅、鉛(Pb)、鉿(Hf)、鈰(Ce)等。該等重金屬可單獨使用或組合2或多種使用。特別地，較佳使用Co與Mn的組合。作為重金屬化合物之例，可列舉乙酸鹽、硝酸鹽、乙醯乙酸鹽、萘酸鹽、硬脂酸鹽、溴化合物等，且特別地，可使用乙酸鹽與溴化合物。 The catalyst is not particularly limited as long as the alkyl aromatic compound can be converted into an aromatic carboxylic acid by oxidation in a liquid using the catalyst. As the catalyst, a heavy metal compound can be used, and a bromine compound can be used as a catalyst adjuvant. Examples of the heavy metal contained in the heavy metal compound include cobalt (Co), manganese (Mn), nickel (Ni), chromium (Cr), zirconium (Zr), copper, lead (Pb), hafnium (Hf), and antimony. (Ce) and so on. These heavy metals may be used singly or in combination of two or more. In particular, a combination of Co and Mn is preferably used. Examples of the heavy metal compound include an acetate, a nitrate, an acetoacetate, a naphthate, a stearate, a bromine compound, and the like, and in particular, an acetate and a bromine compound can be used.

作為溴化合物之例，可列舉無機溴化合物，例如分子溴、溴化氫、溴化鈉、溴化鉀、溴化鈷、溴化錳等；以及有機溴化合物，例如甲基溴、二溴甲烷、溴仿(bromoform)、苯甲基溴、溴甲基甲苯、二溴乙烷、三溴乙烷、四溴乙烷等。該等溴化合物可單獨使用或2種或多種組合使用。 Examples of the bromine compound include inorganic bromine compounds such as molecular bromine, hydrogen bromide, sodium bromide, potassium bromide, cobalt bromide, manganese bromide, and the like; and organic bromine compounds such as methyl bromide and dibromomethane. Bromoform, benzyl bromide, bromomethyltoluene, dibromoethane, tribromoethane, tetrabromoethane, and the like. These bromine compounds may be used singly or in combination of two or more kinds.

當使用芳香羧酸製造對苯二甲酸時，而氧化對二甲苯時使用溴化合物作為催化劑時，較佳可使用經由組合溴化鈷、溴化錳與溴 化氫組合所獲得之催化劑。 When a terephthalic acid is produced using an aromatic carboxylic acid, and a bromine compound is used as a catalyst when oxidizing p-xylene, it is preferred to use a combination of cobalt bromide, manganese bromide and bromine. A catalyst obtained by combining hydrogen.

根據本例示具體例，作為經由組合重金屬化合物與溴化合物所獲得之催化劑，以1莫耳重金屬為基準，可使用0.05莫耳至10莫耳的溴原子，且較佳為0.1莫耳至5莫耳的溴原子。此催化劑作佣為溶劑之重金屬催化劑，可使用量為約10質量ppm至10,000質量ppm，且較佳為約100質量ppm至3,000質量ppm。 According to the specific example of the present example, as a catalyst obtained by combining a heavy metal compound and a bromine compound, from 0.05 mol to 10 mol of bromine atoms, and preferably from 0.1 mol to 5 mol, based on 1 mol of the metal. The bromine atom of the ear. The catalyst is a solvent heavy metal catalyst and can be used in an amount of from about 10 ppm by mass to 10,000 ppm by mass, and preferably from about 100 ppm by mass to 3,000 ppm by mass.

氧化反應溫度可為約140℃至250℃，且較佳為150℃至230℃。當氧化反應的溫度顯著低時，氧化反應的速度會降低，而當氧化反應的溫度顯著高時，作用為溶劑之乙酸的隱然所造成之損失會增加。於氧化反應時期所產生之反應熱可為經由蒸發溶劑所產生之蒸發熱，且可移除至該氧化反應器100之外側以調控該氧化反應的溫度。所產生之蒸汽可由例如乙酸之溶劑、水等之可凝元素，以及例如氮、氧等不可凝元素所組成。於此情況中，該蒸氣可經由安裝於該氧化反應器100之外側的熱交換器予以凝縮，且予以分離為氣體與固體。其次，源自該氣體之排放氣體可運送至高溫吸附管柱、蒸餾管柱、膨脹器等，因而可進行有效元素的回收與能量的回收。經分離之液體可於該氧化反應器100中，循環作為回流。此外，該蒸餾管柱可安裝於該氧化反應器100之上方部分以替代熱交換器，因而可分離為水與溶劑。於此情況中，該溶劑可於該氧化反應器100中循環，且含有該氣相元素之水可於熱交換器中，分類為可凝縮元素與不可凝縮元素，且用於回收、能量回收等目的之操作。 The oxidation reaction temperature may be from about 140 ° C to 250 ° C, and preferably from 150 ° C to 230 ° C. When the temperature of the oxidation reaction is remarkably low, the rate of the oxidation reaction is lowered, and when the temperature of the oxidation reaction is remarkably high, the loss caused by the invisibility of acetic acid acting as a solvent increases. The heat of reaction generated during the oxidation reaction period may be the heat of vaporization generated by evaporation of the solvent, and may be removed to the outside of the oxidation reactor 100 to regulate the temperature of the oxidation reaction. The generated steam may be composed of a condensable element such as a solvent of acetic acid, water, or the like, and a non-condensable element such as nitrogen or oxygen. In this case, the vapor may be condensed via a heat exchanger installed on the outer side of the oxidation reactor 100, and separated into a gas and a solid. Secondly, the exhaust gas derived from the gas can be transported to a high-temperature adsorption column, a distillation column, an expander, etc., thereby recovering effective elements and recovering energy. The separated liquid can be circulated in the oxidation reactor 100 as reflux. Further, the distillation column can be installed in an upper portion of the oxidation reactor 100 in place of the heat exchanger, and thus can be separated into water and a solvent. In this case, the solvent may be circulated in the oxidation reactor 100, and the water containing the gas phase element may be classified into a condensable element and a non-condensable element in the heat exchanger, and used for recovery, energy recovery, etc. Purpose of operation.

該氧化反應的壓力可需要至少能維持混合物至少於反應溫度為液體狀態的壓力，且以需要至少大氣壓力。具體地，該反應壓 力可需要約0.2MPa至6MPa的壓力，且較佳約0.4MPa至3MPa的壓力。為使所產生之芳香羧酸漿體易於運送，較佳可為相對高壓，因此有助於減抑副反應。此外，由反應容器的抗壓性、安裝成本等而言，較佳為相對低壓。 The pressure of the oxidation reaction may require at least a pressure that maintains the mixture at least at the reaction temperature in a liquid state, and requires at least atmospheric pressure. Specifically, the reaction pressure The force may require a pressure of from about 0.2 MPa to 6 MPa, and preferably from about 0.4 MPa to 3 MPa. In order to facilitate the transport of the resulting aromatic carboxylic acid slurry, it is preferably relatively high pressure, thereby contributing to the suppression of side reactions. Further, from the viewpoint of pressure resistance of the reaction container, installation cost, and the like, it is preferably relatively low pressure.

該氧化反應可連續地實施，以及該氧化反應的反應時間(平均滯留時間)可為約30至300分鐘，且具體地約40至150分鐘。當反應時間顯著短時，氧化反應可能實施不佳，引起芳香羧酸品質的劣化；而當反應時間顯著長時，因乙酸之溶劑之引燃所造成的損失可能增加，且氧化反應器之容量可能變大而引起經濟上的問題。 The oxidation reaction can be carried out continuously, and the reaction time (average residence time) of the oxidation reaction can be from about 30 to 300 minutes, and specifically from about 40 to 150 minutes. When the reaction time is significantly short, the oxidation reaction may be poorly performed, causing deterioration of the quality of the aromatic carboxylic acid; and when the reaction time is significantly long, the loss due to ignition of the solvent of acetic acid may increase, and the capacity of the oxidation reactor It may become bigger and cause economic problems.

根據本例示具體例，必要時，可實施補助步驟。關於補助步驟，對於經由氧化反應所獲得之產物之氧化步驟，可連續地至少於氧的存在下進行，而不需要於比該氧化反應溫度為較低或較高的溫度進料原料。 According to the specific example of this example, the subsidy step can be implemented as necessary. With regard to the subsidizing step, the oxidation step of the product obtained by the oxidation reaction can be continuously carried out at least in the presence of oxygen without requiring the feedstock to be fed at a temperature lower or higher than the temperature of the oxidation reaction.

分離步驟 Separation step

經由氧化步驟所獲得之產物，可予以結晶以增加晶體之沉澱量，而後該結晶產物使用固-液分離步驟予以清洗，或所製備漿體可使用該固-液分離步驟直接予以清洗。所獲得固體可為粗製之芳香羧酸，且可進行精製步驟(其將於下文中詳細說明)。此外，經分離母液中之某些元素可經回收予以去毒性化後，排除至外側，而經分離母液中之殘餘元素可經由維持溫度與壓力而予以保持，或可經由氧化步驟之冷卻與循環而予以循環。 The product obtained through the oxidation step may be crystallized to increase the amount of precipitation of the crystal, and then the crystal product may be washed using a solid-liquid separation step, or the prepared slurry may be directly washed using the solid-liquid separation step. The solid obtained may be a crude aromatic carboxylic acid and may be subjected to a refining step (which will be described in detail below). In addition, some of the elements in the separated mother liquor can be detoxified by recovery and removed to the outside, while the residual elements in the separated mother liquor can be maintained by maintaining temperature and pressure, or can be cooled and circulated via the oxidation step. And to cycle.

精製步驟 Refinement step

經由該分離步驟所分離之該粗製之芳香羧酸，可能需要精製所 含的雜質以改良純度。一般而言，該雜質可經由添加氫予以去氧化而增加其等之溶解度，因而可因與有限度溶解芝芳香羧酸之溶解度差異而予以分離。其次，該芳香羧酸可經清洗與乾燥以獲得精緻之芳香羧酸。由於該經分離之母液含有去氧化之雜質與該芳香羧酸之中間體，該經分離之母液可予以回收而使用於氧化反應。 The crude aromatic carboxylic acid separated by the separation step may require refining Impurities contained to improve purity. In general, the impurities can be deoxidized by the addition of hydrogen to increase the solubility of the impurities, and thus can be separated by the difference in solubility with the limited solubility of the aromatic carboxylic acid. Second, the aromatic carboxylic acid can be washed and dried to obtain a refined aromatic carboxylic acid. Since the separated mother liquor contains deoxidized impurities and an intermediate of the aromatic carboxylic acid, the separated mother liquor can be recovered for use in the oxidation reaction.

上文中，揭示用於製造芳香羧酸，特別是高純度羧酸的方法，且該方法可應用於製造中純度羧酸的方法，其可於高壓與高溫下實施兩階段之氧化步驟而省略精製步驟。於該兩階段之氧化步驟中，第一階段之氧化反應的產物可運送至第二階段之氧化反應器，以及含氧氣體可運送至該氧化反應器，因而連續地實施該氧化反應。然而該第一階段之氧化反應可與上述之氧化反應相同。該第二階段之氧化反應的反應溫度可為約230℃至290℃，且較佳為約240℃至280℃。該第二階段之氧化反應的壓力可需要能維持反應混合物為液體狀態的壓力。於此情況中，該第二階段之氧化反應的壓力可為3MPa至10MPa，以及滯留時間可為5至120分鐘，且較佳為10至60分鐘。 In the above, a method for producing an aromatic carboxylic acid, particularly a high-purity carboxylic acid, which is applicable to a method for producing a medium-purity carboxylic acid, which can perform a two-stage oxidation step at high pressure and high temperature, omits refining step. In the two-stage oxidation step, the product of the oxidation reaction of the first stage can be transported to the oxidation reactor of the second stage, and the oxygen-containing gas can be transported to the oxidation reactor, thereby continuously performing the oxidation reaction. However, the oxidation reaction of the first stage can be the same as the oxidation reaction described above. The reaction temperature of the second stage oxidation reaction may be from about 230 ° C to 290 ° C, and preferably from about 240 ° C to 280 ° C. The pressure of the second stage oxidation reaction may require a pressure that maintains the reaction mixture in a liquid state. In this case, the pressure of the oxidation reaction in the second stage may be from 3 MPa to 10 MPa, and the residence time may be from 5 to 120 minutes, and preferably from 10 to 60 minutes.

由於漿體之部分芳香羧酸顆粒係經溶解且該顆粒之氧化中間體係經由該兩階段之氧化反應而氧化兩種原因，該精製步驟可省略。然而，相對於使用精製步驟所獲得之高純度羧酸之具有相對低純度之中純度羧酸，可藉由該兩階段之氧化反應獲得。根據本例示具體例之氧化反應器，可應用於氧化反應步驟以實施用於製造中純度芳香羧酸。 Since the partial aromatic carboxylic acid particles of the slurry are dissolved and the oxidation intermediate system of the particles is oxidized by the two-stage oxidation reaction, the refining step can be omitted. However, a relatively low purity intermediate carboxylic acid relative to the high purity carboxylic acid obtained using the refining step can be obtained by the two-stage oxidation reaction. The oxidation reactor according to the specific example of the present example can be applied to an oxidation reaction step for carrying out the production of a medium purity aromatic carboxylic acid.

後文中，本發明藉由實施例而更詳細說明。然而應了解，該等實施例僅用於說明目的，且不用於侷限本發明之範疇。 Hereinafter, the present invention will be described in more detail by way of examples. However, it is to be understood that the examples are for illustrative purposes only and are not intended to limit the scope of the invention.

[實施例1] [Example 1]

1重量份之對二甲苯、5重量份之乙酸以及0.5重量份之水，進料至氧化反應器，以及作用為催化劑之乙酸鈷、乙酸錳與溴化氫亦進料至該氧化反應器。於溫度約185℃至195℃與壓力約1.0MPa至1.7MPa的條件下，實施氧化反應90分鐘氧化期間(平均滯留時間)。具有鈷、錳與溴的催化劑，以金屬而言，含量分別為300質量ppm、300質量ppm與700質量ppm。使用空氣作為含氧氣體。於此情況中，具有氧含量約21體積%的氣體與壓縮氣體係運送至該氧化反應器，以使排入該氧化反應器之氣體之氧濃度具有3體積%至7體積%。 1 part by weight of p-xylene, 5 parts by weight of acetic acid, and 0.5 part by weight of water are fed to the oxidation reactor, and cobalt acetate, manganese acetate and hydrogen bromide acting as catalysts are also fed to the oxidation reactor. The oxidation reaction was carried out for 90 minutes (average residence time) at a temperature of about 185 ° C to 195 ° C and a pressure of about 1.0 MPa to 1.7 MPa. The catalyst having cobalt, manganese and bromine in terms of metal is 300 ppm by mass, 300 ppm by mass and 700 ppm by mass, respectively. Air is used as the oxygen-containing gas. In this case, a gas having a oxygen content of about 21% by volume is transported to the oxidation reactor with a compressed gas system so that the oxygen concentration of the gas discharged into the oxidation reactor has from 3 to 7 vol%.

使用第1圖之氧化反應器做為該氧化反應器。該第一與第二攪拌器120與130之各長度為2,550毫米，由該氧化反應器底部至該第二攪拌器130之垂直距離為1,500毫米，以及由第二攪拌器130至該第一攪拌器120的距離為3,200毫米。由該氧化反應器之上方部分排出產物，其與第二攪拌器130相隔4,100毫米。例如壓縮氣體、回流、原料、溶劑、催化劑等之反應物，係以該第二攪拌器130之旋轉方向之正切方向，運送至與該第二攪拌器130接近相同的高度。輸送管的設置係與第3圖之輸送管相同。該壓縮氣體經由氣體輸送管140(總計6個管)運送，以及由對二甲苯、乙酸-水混合物與催化劑所組成之乙酸溶液，係預先於混合室中混合，與分離步驟中所循環之回收溶液，經由反應物輸送管150一起運送。該回流經由回流輸送管(總計2個管)運送。此外，介於個別輸送管140、150與160，與該第二攪拌器130之旋轉圓周之間的距離為約100毫米。當運送回流至該氧化反應器100時的溫度為150℃至160℃，而該氧化反應 器100之內部溫度係較比較例1之內部溫度更低至少5度。此外，在實施例1的氧化反應器的情況中，產物排出管170的阻塞現象歷時半年亦不發生，理解到該氧化反應器100的穩定運轉。由該產物排出管170所排出之產物係連續地運送至補助氧化反應器，且於溫度180℃至190℃與壓力0.9MPa至1.5MPa的條件下，實施例35分鐘的反應時間(平均滯留時間)。該氣體(氧濃度21體積%)係進料至該氧化反應器，以使該排出氣體之氧濃度為3體積%至7體積%，而後實施低溫補助氧化反應。該補助氧化反應係使用安裝有傳統兩段碟狀渦輪的反應器予以實施。 The oxidation reactor of Fig. 1 was used as the oxidation reactor. The lengths of the first and second agitators 120 and 130 are 2,550 mm, the vertical distance from the bottom of the oxidation reactor to the second agitator 130 is 1,500 mm, and the second agitator 130 to the first agitation The distance of the device 120 is 3,200 mm. The product exits from the upper portion of the oxidation reactor, which is 4,100 mm from the second agitator 130. For example, the reactants such as compressed gas, reflux, raw material, solvent, catalyst, etc. are transported to the same height as the second agitator 130 in the tangential direction of the rotation direction of the second agitator 130. The arrangement of the conveying pipe is the same as that of the conveying pipe of Fig. 3. The compressed gas is transported via a gas delivery tube 140 (a total of 6 tubes), and an acetic acid solution consisting of a p-xylene, an acetic acid-water mixture and a catalyst is mixed in advance in the mixing chamber and recycled in the separation step. The solution is shipped together via reactant delivery tube 150. This reflux is carried via a return line (2 tubes in total). Further, the distance between the individual conveying pipes 140, 150 and 160 and the rotating circumference of the second agitator 130 is about 100 mm. When the reflux is carried out to the oxidation reactor 100, the temperature is 150 ° C to 160 ° C, and the oxidation reaction The internal temperature of the device 100 is at least 5 degrees lower than the internal temperature of Comparative Example 1. Further, in the case of the oxidation reactor of Example 1, the clogging phenomenon of the product discharge pipe 170 did not occur for half a year, and stable operation of the oxidation reactor 100 was understood. The product discharged from the product discharge pipe 170 is continuously conveyed to the auxiliary oxidation reactor, and the reaction time (average residence time) of the embodiment is 35 minutes at a temperature of 180 ° C to 190 ° C and a pressure of 0.9 MPa to 1.5 MPa. ). The gas (oxygen concentration 21% by volume) was fed to the oxidation reactor so that the oxygen concentration of the exhaust gas was 3% by volume to 7% by volume, and then the low-temperature auxiliary oxidation reaction was carried out. The auxiliary oxidation reaction was carried out using a reactor equipped with a conventional two-stage dish turbine.

由補助氧化反應所獲得之產物係使用連接於反應器呈三階段系列之晶體沉澱槽，以階段化的方式進行晶體沉澱，接著所得產物係經由真空旋轉過濾器(RVF)予以固-液分離/清洗而獲得粗製之對苯二甲酸。進行固-液分離步驟之反應母液的90%，係於氧化反應器中循環。再者，例如催化劑、乙酸等之明顯物質係由殘於母液回收，而運送至排出處理步驟後予以排出。 The product obtained by the auxiliary oxidation reaction is subjected to crystal precipitation in a staged manner using a crystal precipitation tank connected to the reactor in a three-stage series, and then the obtained product is subjected to solid-liquid separation via a vacuum rotary filter (RVF). The crude terephthalic acid was obtained by washing. 90% of the reaction mother liquid subjected to the solid-liquid separation step is circulated in the oxidation reactor. Further, for example, a significant substance such as a catalyst or acetic acid is recovered from the mother liquor, and is discharged to the discharge treatment step.

其次，該粗製之對苯二甲酸係運送至精製步驟，且於一般精製條件下，實施上述之雜質的加氫反應。其次，該雜質經由上述晶體沉澱/分離步驟而去氧化，以及該對苯二甲酸係經分離以獲得高純度之對苯二甲酸。所得結果示於表1，其將與下文所述比較例1的結果，一起於後文中說明。 Next, the crude terephthalic acid is transported to the purification step, and the hydrogenation reaction of the above impurities is carried out under general purification conditions. Next, the impurities are deoxidized via the above crystal precipitation/separation step, and the terephthalic acid is separated to obtain high purity terephthalic acid. The results obtained are shown in Table 1, which will be described later together with the results of Comparative Example 1 described below.

[比較例1] [Comparative Example 1]

使用氧化反應器，氧化反應係於與實施例1之氧化反應為相同反應條件下實施。起始反應溫度係與實施例1相同，然而，在氧化 反應器之穩定運轉後得比較例1的內部溫度係比實施例之內部溫高至少5度。該氧化反應器之內部結構示於第7圖。第7圖為比較例1之用於製造芳香羧酸之氧化反應器700的截面示意圖。參照第7圖，該氧化反應器700包括攪拌軸705、反應室710、第一攪拌器720、第二攪拌器730、氣體輸送管740、反應物輸送管750、回流輸送管760、產物排出管770以及氣體排出管780。該氧化反應器700的容量與實施例1相同，該第一與第二攪拌器720與730，分別包括6個攪拌翼。此外，該第一與第二攪拌器720與730的定位，係與實施例之第一與第二攪拌器120與130的定位相同。 An oxidation reactor was used, and the oxidation reaction was carried out under the same reaction conditions as the oxidation reaction of Example 1. The initial reaction temperature is the same as in Example 1, however, in oxidation The internal temperature of Comparative Example 1 after the stable operation of the reactor was at least 5 degrees higher than the internal temperature of the example. The internal structure of the oxidation reactor is shown in Fig. 7. Fig. 7 is a schematic cross-sectional view showing an oxidation reactor 700 for producing an aromatic carboxylic acid of Comparative Example 1. Referring to Figure 7, the oxidation reactor 700 includes a stirring shaft 705, a reaction chamber 710, a first agitator 720, a second agitator 730, a gas delivery tube 740, a reactant delivery tube 750, a reflux delivery tube 760, and a product discharge tube. 770 and gas discharge pipe 780. The capacity of the oxidation reactor 700 is the same as that of the first embodiment, and the first and second agitators 720 and 730 respectively include six agitating blades. Further, the positioning of the first and second agitators 720 and 730 is the same as the positioning of the first and second agitators 120 and 130 of the embodiment.

該第一與第二攪拌器720與730的各別長度為2,300毫米，由該氧化反應器700的底部至該第二攪拌器730的垂直距離為1,500毫米，以及由該第二攪拌器730至該第一攪拌器720的距離為3,200毫米。 The respective lengths of the first and second agitators 720 and 730 are 2,300 mm, the vertical distance from the bottom of the oxidation reactor 700 to the second agitator 730 is 1,500 mm, and the second agitator 730 is The distance of the first agitator 720 is 3,200 mm.

空氣的運送係於該第二攪拌器730附近進行，由對二甲苯、乙酸-水混合物與催化劑所組成之乙酸溶液，係與循環於該分離步驟之循環溶液混合，且運送至該第一攪拌器720附近。產物由該氧化反應器700的底部附近排出。 The transportation of air is performed in the vicinity of the second agitator 730, and the acetic acid solution composed of the p-xylene, acetic acid-water mixture and the catalyst is mixed with the circulating solution circulated in the separation step, and transported to the first stirring. Near the 720. The product is discharged from the vicinity of the bottom of the oxidation reactor 700.

於該氧化反應後實施補助氧化反應，且與實施例相同條件實施分離步驟與精製步驟，而獲得高純度之對苯二甲酸。由實施例1與比較例1所獲得之結果示於表1。 After the oxidation reaction, a supplementary oxidation reaction was carried out, and a separation step and a purification step were carried out under the same conditions as in the examples to obtain a high-purity terephthalic acid. The results obtained in Example 1 and Comparative Example 1 are shown in Table 1.

表1中，對二甲苯(PX)之殘餘濃度為該氧化反應器之液體表面附近的PX濃度(重量%)，產率為由100噸原料所獲得之高純度隊本二甲酸(PTA)的產物量(公斤)，以及乙酸損失為經由氧化反應器之氧化反應所耗損之相對於每一頓PTA產物之乙酸量(公斤)。再者， 於反應之氣相區域中之PX濃度為排除反應氣象區域之不可凝氣體的元素之PX濃度(重量%)，以及PTA透光率為以及該PTA產物之苛性鹼水溶液之波長340微米與10毫米光徑(optical path)之透光率(%)。 In Table 1, the residual concentration of p-xylene (PX) is the PX concentration (% by weight) near the liquid surface of the oxidation reactor, and the yield is a high purity team of dicarboxylic acid (PTA) obtained from 100 tons of raw materials. The amount of product (kg), and acetic acid loss, is the amount of acetic acid (kg) relative to each PTA product consumed by the oxidation reaction through the oxidation reactor. Furthermore, The PX concentration in the gas phase region of the reaction is the PX concentration (% by weight) of the element excluding the non-condensable gas in the reaction meteorological region, and the PTA transmittance and the wavelength of the caustic alkali aqueous solution of the PTA product are 340 μm and 10 mm. Light transmittance (%) of the optical path.

如表1所示，比較實施例1與比較例1的結果，可發現反應產率受到改良，乙酸損失降低，以及該反應器之穩定運轉的歷時增加。再者，可發現該氧化反應器之氣相區域中之未反應原料對二甲苯顯著降低，而且不需要使用對二甲苯回收裝置。再者，如PTA透光率所示，PTA產物之苛性鹼水溶液之透光率受到改良，以及雜質量，PTA之代表性雜質為4-羧基苯甲醛(CBA)顯著降低。 As shown in Table 1, comparing the results of Example 1 with Comparative Example 1, it was found that the reaction yield was improved, the acetic acid loss was lowered, and the stable operation of the reactor was increased over time. Further, it was found that the unreacted raw material in the gas phase region of the oxidation reactor was significantly reduced in p-xylene, and it was not necessary to use a paraxylene recovery device. Further, as shown by the PTA transmittance, the light transmittance of the aqueous caustic alkali solution of the PTA product is improved, and the impurity amount, the representative impurity of PTA is markedly lowered by 4-carboxybenzaldehyde (CBA).

第4圖係以實施例1與比較例1所獲得之結果為基準之未反應對二甲苯的濃度相對於高度之示意圖。第5圖係以實施例1與比較例1所獲得之結果為基準之所產生雜質(4-羧基苯甲醛(CBA))的濃度相對於高度之示意圖。第6圖係以實施例1與比較例1所獲得之結果為基準之乙酸的反應速率相對於高度之示意圖。為獲得第4圖至第6圖的結果，使用計算流體動力學(CFD)，相對於向著該氧化反應器之液體 表面的方向的濃度分散實施流體模擬(fluid simulation)。 Fig. 4 is a graph showing the concentration of unreacted p-xylene relative to the height based on the results obtained in Example 1 and Comparative Example 1. Fig. 5 is a graph showing the concentration of the impurity (4-carboxybenzaldehyde (CBA)) relative to the height based on the results obtained in Example 1 and Comparative Example 1. Fig. 6 is a graph showing the reaction rate of acetic acid with respect to the height based on the results obtained in Example 1 and Comparative Example 1. To obtain the results of Figures 4 through 6, computational fluid dynamics (CFD) is used relative to the liquid toward the oxidation reactor. The concentration dispersion in the direction of the surface is subjected to fluid simulation.

參照第4圖至第6圖，可發現該氧化反應器中之未反應對二甲苯、殘餘4-CBA與乙酸之各者的濃度係顯著降低。再者，各別濃度分散未顯示顯著變化，以及該氧化反應器之液體表面附近的濃度分散則顯著降低。 Referring to Figures 4 through 6, it can be seen that the concentration of unreacted para-xylene, residual 4-CBA and acetic acid in the oxidation reactor is significantly reduced. Further, the respective concentration dispersions did not show a significant change, and the concentration dispersion in the vicinity of the liquid surface of the oxidation reactor was remarkably lowered.

雖然已顯示與說明本發明之一些例示具體例，但本發明並不侷限於所揭示之例示具體例。替代地，本技術領域中具有通常知識者應了解，可於不悖離本發明之原則與精神的情況下進行該等例示具體例之變化，本發明之範疇係由申請專利範圍與其均等物所界定。 While some specific examples of the invention have been shown and described, the invention is not limited to the specific embodiments disclosed. In addition, it is to be understood by those of ordinary skill in the art that the present invention can be practiced without departing from the spirit and scope of the invention. Defined.

100、700‧‧‧氧化反應器 100, 700‧‧‧ oxidation reactor

105、705‧‧‧攪拌軸 105, 705‧‧‧ stirring shaft

110、710‧‧‧反應室 110, 710‧‧‧Reaction room

120、720‧‧‧第一攪拌器 120, 720‧‧‧ first stirrer

122、132‧‧‧攪拌翼 122, 132‧‧‧ stirring wings

124、134‧‧‧支持構件 124, 134‧‧‧ Supporting components

130、220、730‧‧‧第二攪拌器 130, 220, 730‧‧‧ second stirrer

140、340、740‧‧‧氣體輸送管 140, 340, 740‧‧‧ gas delivery tubes

150、350、750‧‧‧反應物輸送管 150, 350, 750 ‧ ‧ reactant delivery tube

160、360、760‧‧‧回流輸送管 160, 360, 760‧‧‧ return duct

170、770‧‧‧產物排出管 170, 770‧‧‧ product discharge pipe

180、780‧‧‧氣體排出管 180, 780‧‧‧ gas discharge pipe

190、790‧‧‧擋流器 190, 790‧‧ ‧ flow stop

200‧‧‧翼 200‧‧ wings

212‧‧‧第一彎曲部分 212‧‧‧First bend

222‧‧‧第二彎曲部分 222‧‧‧ second bend

C、F‧‧‧距離 C, F‧‧‧ distance

D‧‧‧攪拌器長度 D‧‧‧Agitator length

T‧‧‧內直徑 T‧‧‧ inner diameter

α、β‧‧‧角度 α, β‧‧‧ angle

A、B、C‧‧‧點 A, B, C‧‧ points

本發明之此等及/或其他態樣、特徵與優勢可由後述之例示具體例的說明與下述圖式的結合而更明確且可容易理解：第1圖為本發明例示具體例之用於製造芳香羧酸之氧化反應器之截面示意圖；第2(a)圖及第2(b)圖分別為本發明例示具體例之攪拌器之翼的展開圖與截面圖；第3圖為本發明例示具體例之設置於反應室中之代表性輸送管狀態之平面示意圖；第4圖為實施例1與比較例1所得結果之未反應對二甲苯的濃度相對於高度之示意圖；第5圖為實施例1與比較例1所得結果之所產生雜質(4-羧基 苯甲醛(CBA))的濃度相對於高度之示意圖；第6圖為實施例1與比較例1所得結果之乙酸的反應速率相對於高度之示意圖；第7圖為比較例1之用於製造芳香羧酸的氧化反應器之截面示意圖。 The above and/or other aspects, features, and advantages of the present invention will be more clearly understood from the following description of the exemplary embodiments illustrated in the accompanying claims. A schematic cross-sectional view of an oxidation reactor for producing an aromatic carboxylic acid; FIGS. 2(a) and 2(b) are respectively a development view and a cross-sectional view of a wing of a stirrer according to a specific example of the present invention; A schematic plan view showing the state of a representative transfer tube provided in a reaction chamber in a specific example; FIG. 4 is a schematic view showing the concentration of unreacted p-xylene relative to the height obtained in Example 1 and Comparative Example 1; The impurities produced in the results obtained in Example 1 and Comparative Example 1 (4-carboxyl group) Schematic diagram of the concentration of benzaldehyde (CBA) relative to the height; FIG. 6 is a schematic diagram showing the reaction rate of acetic acid with respect to the results obtained in Example 1 and Comparative Example 1 with respect to height; and FIG. 7 is a diagram for producing aromatic in Comparative Example 1. A schematic cross-sectional view of an oxidation reactor for a carboxylic acid.

100‧‧‧氧化反應器 100‧‧‧Oxidation reactor

105‧‧‧攪拌軸 105‧‧‧Agitator shaft

110‧‧‧反應室 110‧‧‧Reaction room

120‧‧‧第一攪拌器 120‧‧‧First stirrer

122、132‧‧‧攪拌翼 122, 132‧‧‧ stirring wings

124、134‧‧‧支持構件 124, 134‧‧‧ Supporting components

130、220‧‧‧第二攪拌器 130, 220‧‧‧ second stirrer

140、340‧‧‧氣體輸送管 140, 340‧‧‧ gas delivery pipe

150‧‧‧反應物輸送管 150‧‧‧Reaction vessel

160‧‧‧回流輸送管 160‧‧‧Return pipe

170‧‧‧產物排出管 170‧‧‧Product discharge pipe

180‧‧‧氣體排出管 180‧‧‧ gas discharge pipe

190‧‧‧擋流器 190‧‧ ‧Binder

C、F‧‧‧距離 C, F‧‧‧ distance

D‧‧‧攪拌器長度 D‧‧‧Agitator length

T‧‧‧內直徑 T‧‧‧ inner diameter

Claims (24)

一種用於製造芳香羧酸的氧化反應器，該氧化反應器包含：一反應室；一攪拌軸，其沿著該反應室之一幾何垂直軸設置；以及至少兩個攪拌器，各包括複數攪拌翼，各該攪拌翼具有至少兩個曲面部分或至少兩個彎曲部分形成於各該攪拌翼的末端，以使流體在該反應室中流動，而防止流體殘留於該反應室中，以及各該攪拌翼係延著垂直於該垂直軸旋轉的方向，以幅射狀地延伸。 An oxidation reactor for producing an aromatic carboxylic acid, the oxidation reactor comprising: a reaction chamber; a stirring shaft disposed along a geometric vertical axis of the reaction chamber; and at least two agitators each comprising a plurality of stirring a wing, each of the agitating blades having at least two curved portions or at least two curved portions formed at an end of each of the agitating blades to allow fluid to flow in the reaction chamber to prevent fluid from remaining in the reaction chamber, and each of the wings The agitating wing extends in a radial direction in a direction perpendicular to the vertical axis. 如申請專利範圍第1項所述之氧化反應器，其中：該氧化反應器包括彼此隔開的一第一攪拌器與一第二攪拌器，且各設置於反應室之攪拌軸，該第一攪拌器係設置於該反應室的上方部以及該第二攪拌器係設置於該反應室的下方部，以及該第一攪拌器與第二攪拌器之間的空間距離為該第一攪拌器或該第二攪拌器的長度(直徑)的1至1.5倍。 The oxidation reactor of claim 1, wherein the oxidation reactor comprises a first agitator and a second agitator spaced apart from each other, and each of the agitating shafts disposed in the reaction chamber, the first An agitator is disposed at an upper portion of the reaction chamber and the second agitator is disposed at a lower portion of the reaction chamber, and a spatial distance between the first agitator and the second agitator is the first agitator or The second agitator has a length (diameter) of 1 to 1.5 times. 如申請專利範圍第1項所述之氧化反應器，其中各該攪拌器的長度(直徑)為該反應室之內直徑的0.4至0.5倍。 The oxidation reactor of claim 1, wherein each of the agitators has a length (diameter) of 0.4 to 0.5 times the inner diameter of the reaction chamber. 如申請專利範圍第2項所述之氧化反應器，其中該第二攪拌器與該反應室之一底表面之間的距離為該第二攪拌器的長度(直徑)的0.5至1倍。 The oxidation reactor of claim 2, wherein a distance between the second agitator and a bottom surface of the reaction chamber is 0.5 to 1 times the length (diameter) of the second agitator. 如申請專利範圍第1項所述之氧化反應器，其中各該攪拌翼包括具有一第一彎曲部分的一第一攪拌翼，該第一彎曲部分被彎折成一角度為45至75度，以及具有一第二彎曲部分的一第二攪拌翼，該第二彎曲部分額外地從該第一攪拌翼被彎折成一角度為120 至160度。 The oxidation reactor of claim 1, wherein each of the agitating blades comprises a first agitating wing having a first curved portion, the first curved portion being bent at an angle of 45 to 75 degrees, and a second agitating wing having a second curved portion, the second curved portion being additionally bent from the first agitating wing to an angle of 120 Up to 160 degrees. 如申請專利範圍第1項所述之氧化反應器，其中該至少兩個攪拌器各包括一支持構件，以使各該攪拌翼彼此連接，並且使各該攪拌翼與該攪拌軸彼此連接。 The oxidation reactor of claim 1, wherein the at least two agitators each comprise a support member such that each of the agitating blades is connected to each other, and each of the agitating blades and the agitating shaft are connected to each other. 如申請專利範圍第6項所述之氧化反應器，其中該支持構件為一圓形板，該圓形板包括一上表面以及一下表面，該上表面垂直於該攪拌軸，該下表面具有相對於該上表面為傾斜的一傾斜面。 The oxidation reactor of claim 6, wherein the support member is a circular plate, the circular plate comprising an upper surface and a lower surface, the upper surface being perpendicular to the agitating shaft, the lower surface having a relative The upper surface is an inclined surface that is inclined. 如申請專利範圍第7項所述之氧化反應器，其中該支持構件的一末端係形成鋸齒狀。 The oxidation reactor of claim 7, wherein one end of the support member is formed in a zigzag shape. 如申請專利範圍第2項所述之氧化反應器，更包含：一氣體輸送管，用以將氣體由一外側注入到該反應室；一反應物輸送管，用以將包括一反應原料、一溶劑與一催化劑之一液體反應物進料至該反應室；一回流輸送管，用以將一回流進料至該反應室；一產物排出管，用以將一產物在反應後排出至該外側；一氣體排放管，用以將所產生的一氣體在反應後排出至該外側。 The oxidation reactor of claim 2, further comprising: a gas delivery tube for injecting gas from an outside to the reaction chamber; and a reactant delivery tube for including a reaction material, a solvent and a liquid reactant of one of the catalysts are fed to the reaction chamber; a reflux delivery tube for feeding a reflux to the reaction chamber; and a product discharge tube for discharging a product to the outside after the reaction a gas discharge pipe for discharging a generated gas to the outside after the reaction. 如申請專利範圍第9項所述之氧化反應器，其中該氣體輸送管、該反應物輸送管以及該回流輸送管係分別被定位於該第二攪拌器之一半長度之內，其方向為由設置該第二攪拌器之一虛擬(imaginary)水平表面向著該垂直軸的方向。 The oxidation reactor of claim 9, wherein the gas delivery tube, the reactant delivery tube, and the return delivery tube are respectively positioned within one half of the length of the second agitator, the direction being An imaginary horizontal surface of the second agitator is disposed in a direction toward the vertical axis. 如申請專利範圍第9項所述之氧化反應器，其中該氣體輸送管、該反應物輸送管以及該回流輸送管係沿著該攪拌器的旋轉方向彎曲分別將該氣體、該反應物與該回流進料至該反應室。 The oxidation reactor of claim 9, wherein the gas delivery tube, the reactant delivery tube, and the reflux delivery tube are bent along a direction of rotation of the agitator, respectively, the gas, the reactant, and the The feed is refluxed to the reaction chamber. 如申請專利範圍第9項所述之氧化反應器，其中該產物排出管設置的位置是在使該產物排出管的一末端相對於該垂直軸係定位於該第一攪拌器之上方。 The oxidation reactor of claim 9, wherein the product discharge pipe is positioned such that an end of the product discharge pipe is positioned above the first agitator relative to the vertical axis. 如申請專利範圍第9項所述之氧化反應器，其中，至少一氣體輸送管、至少一反應物輸送管以及至少一回流輸送管，由該氧化反應器上方觀之，係以相等間距規律地設置。 The oxidation reactor of claim 9, wherein at least one gas delivery tube, at least one reactant delivery tube, and at least one reflux delivery tube are viewed from above by the oxidation reactor at regular intervals. Settings. 如申請專利範圍第1項所述之氧化反應器，更包含：一擋流器(baffle)，其設置於該反應室之一側壁以阻擋一液體的流動。 The oxidation reactor of claim 1, further comprising: a baffle disposed on a side wall of the reaction chamber to block the flow of a liquid. 一種製造芳香羧酸的方法，係經由將一含氧氣體、一烷基芳香化合物、一溶劑、一催化劑與一回流(reflux)注入如申請專利範圍第1項所述之氧化反應器進行一氧化反應，其中該含氧氣體、該烷基芳香化合物、該溶劑、該催化劑與該回流係進料至該氧化反應器之下方部份，以及該反應產物係由該氧化反應器之上方部分排出。 A method for producing an aromatic carboxylic acid by injecting an oxygen-containing gas, an alkyl aromatic compound, a solvent, a catalyst, and a reflux into an oxidation reactor as described in claim 1 The reaction wherein the oxygen-containing gas, the alkyl aromatic compound, the solvent, the catalyst and the reflux are fed to a lower portion of the oxidation reactor, and the reaction product is discharged from the upper portion of the oxidation reactor. 一種利用一氧化反應器製造芳香羧酸的方法，該氧化反應器由相對垂直於一垂直軸之一中間部分的一虛擬平面，劃分為上方部分與下方部份，且包括一第一攪拌器與一第二攪拌器分別以輻射狀地設置於該上方部分與該下方部份，以垂直於該垂直軸，其中 各攪拌器包括複數攪拌翼，各該攪拌翼具有至少兩個曲面部分或至少兩個彎曲部分形成於各該攪拌翼的末端，其中一液體反應物包括一含氧反應氣體、一烷基芳香化合物、一溶劑、一催化劑與一回流，該液體反應物係進料至該氧化反應器之該下方部份，以及反應後之一產物與該反應後之一氣體係排出於該氧化反應器之上方部份。 A method for producing an aromatic carboxylic acid using an oxidation reactor, the oxidation reactor being divided into an upper portion and a lower portion by a virtual plane relatively perpendicular to an intermediate portion of a vertical axis, and comprising a first agitator a second agitator is radially disposed on the upper portion and the lower portion to be perpendicular to the vertical axis, wherein Each of the agitators includes a plurality of agitating blades each having at least two curved portions or at least two curved portions formed at the ends of the agitating blades, wherein a liquid reactant comprises an oxygen-containing reaction gas, an alkyl aromatic compound a solvent, a catalyst and a reflux, the liquid reactant is fed to the lower portion of the oxidation reactor, and one of the products after the reaction and one of the gas systems after the reaction are discharged above the oxidation reactor Part. 如申請專利範圍第16項所述之方法，其中該回流的溫度係低於該氧化反應器之一內部溫度。 The method of claim 16, wherein the reflux temperature is lower than an internal temperature of the oxidation reactor. 如申請專利範圍第16項所述之方法，其中該烷基芳香化合物的氧化反應係於該溶劑的氧化反應之前進行。 The method of claim 16, wherein the oxidation reaction of the alkyl aromatic compound is carried out prior to the oxidation reaction of the solvent. 如申請專利範圍第16項所述之方法，其中該反應器之該產物的排出係於該氧化反應器中之一液體的表面進行。 The method of claim 16, wherein the discharge of the product of the reactor is carried out on the surface of one of the liquids in the oxidation reactor. 如申請專利範圍第16項所述之方法，其中，相對接近於該氧化反應中之該液體表面，一未反應烷基芳香化合物排除一不可凝氣體元素(non-condensable gas element)之濃度為0.01重量%或更少。 The method of claim 16, wherein the unreacted alkyl aromatic compound excludes a non-condensable gas element concentration of 0.01 relative to the liquid surface in the oxidation reaction. % by weight or less. 如申請專利範圍第16項所述之方法，其中，於該氧化反應器之一氣相區域(gas phase area)中，一未反應烷基芳香化合物排除一不可凝氣體元素之濃度為0.02重量%或更少。 The method of claim 16, wherein in the gas phase area of the oxidation reactor, an unreacted alkyl aromatic compound excludes a concentration of a non-condensable gas element of 0.02% by weight or less. 如申請專利範圍第16項所述之方法，其中該反應氣體、該液體反應物以及該回流係輸送至該第二攪拌器。 The method of claim 16, wherein the reaction gas, the liquid reactant, and the reflux are delivered to the second agitator. 如申請專利範圍第16項所述之方法，其中，該烷基芳香化合 物的濃度與雜質的濃度係隨著該烷基芳香化合物與該雜質接近該氧化反應器之上方部份而減低。 The method of claim 16, wherein the alkyl aromatic compound The concentration of the substance and the concentration of the impurities are reduced as the alkyl aromatic compound and the impurity are close to the upper portion of the oxidation reactor. 如申請專利範圍第16項所述之方法，其中，該溶劑之氧化速率係隨著該溶劑接近該氧化反應器之上方部份而減低。 The method of claim 16, wherein the oxidation rate of the solvent is reduced as the solvent approaches the upper portion of the oxidation reactor.
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