TW469269B - Process for the production of terephthalic acid - Google Patents

Abstract

An aromatic carboxylic acid such as terephthalic acid is produced by the liquid phase oxidation of a precursor thereof, the oxidation being carried out in such a way that substantially all of the aromatic carboxylic acid produced in the course of the reaction is maintained in solution during the reaction.

Description

4 6 9 2 6 9 'A7 __ £ 7__ 5. Description of the invention (/) The present invention is like an aromatic carboxylic acid that is freshly dissolved in acetic acid and water. It is an indispensable medium in the production method of myrionic acid polyacetate polymer, and polyester polymer 酣 is mainly used in the production of fiber and the production of bottles and cans. As far as the typical method for making mysterious acids is currently prevalent, the steps are mainly in the case where a promoter is contained, for example, a dissolved heavy metal in which bromine is contained. The toluene feed is placed in a carboxylic acid solvent composed of lower-order C2 ~ C6 aliphatics for a liquid-phase gasification treatment. This liquid-phase reaction method is pseudo-high temperature and pressure conditions. Generally speaking, At a temperature of about 150 ~ 250 X: and a pressure of 6 ~ 30 bar, β is performed in a stirring container or in several stirring containers. At the same time, air is sprayed into the reactant, once The yield of the finished product of p-arsenic acid is quite high, at least above 95¾. The solvent is allowed to evaporate, and the water generated during the reaction can be condensed with the steam generated in the isothermal reaction conditions in the tritium container, and then refluxed into the reaction container. As far as the traditional method for making tartaric acid is concerned, since the tartaric acid is dissolved in the solvent, the proportion is extremely limited, and most of the products will sink to the temple during the reaction process, resulting in a 4-CarboxJ ^ ] 3eίlz '£ ll ¢ ^ ehyde (4-- · ++ _ · _- 一 —CBA-) _ and --color-quality--of-and --- pair-secret-acid " -same-i ^ _Shen Dian, thus producing a crude product, this crude product. In order to meet the specifications of most polyester manufacturers, a purification treatment must be performed to remove the impurities. Taking a purification method as an example, the edible step is to dissolve the crude product in water, and contact it with hydrogen under the condition of high temperature and high pressure, and then use the purified acid to reuse the station acid. Recycling by crystallization and solid-liquid separation technology. Quickly use China National Standards (CNS > A4 size (210X297 mm) for this paper size) ------------ (锖 Note f on the back of M1 # before filling out this page) Order · 269 9269 A7 B7 V. Description of the invention () The purpose of the present invention is to provide a production of epithelial acid which has sufficient purity and can be used for post-setting without having to rely on an additional purification treatment method. In terms of a first aspect of the present invention, the provider provided a pseudo-borrowing of a pair of acids, the acid treatment, is in the domain, and the most or two boiling molds are limited to this, the furnace The internal precursor is placed in a solution in which the reaction method can be controlled in the solution to make the At acid side so that the reaction medium can be carried out in a row. Well, the reaction vessel is more than one plug flow reactor type operation is It ’s appropriate, but a type of flirting reaction method can be implemented. It can also be a reaction printed by one or one printed by the Central Oaks Bureau of the Ministry of Economic Affairs and Consumers ’Hehe. When you stop in a batch, you first look at the so-called adult things in the system. In the mode retention time, even the points of the present invention are combined to produce a reaction furnace that can synchronize the extraction and continuous continuous tether extraction like a seat or more than one. In 10 minutes, it can be shortened to a second view. However, it also contains the precursor and a solvent of the reaction medium to oxidize all pairs generated in the reaction zone, and perform a liquid phase oxidation method with gas. Its special feature is: the gasification reaction method is entangled flow reaction Under the mechanism, the reactor is connected to a flow-type reactor or an integrated bar composed of two blocks through a reaction zone. Moreover, it is necessary to point out that the implementation of the present invention is not limited to the reactor, and it will be described in advance. .For example, the operation effect of a series of non-boiling entangled flow agitation anti-linking ore plugging mechanism, or the combination of the non-boiling gangue pseudo-motion reactor and the furnace, regardless of the ordering mechanism ν refers to a reaction furnace in which the reaction of the reactants is continuously performed. It is different from a general one. In general, the skin medium is in the reaction area, preferably less than 3 minutes, but 5 minutes, or even 3 minutes. In terms of, its It can be administered alone, although the embodiments of the present invention. It will be a provider system (Read back surface of the refill socket Page} Note

The paper size applies to the Chinese National Standard (CNS) A4 specification (2 丨 0 × 297 mm) -5 ^ Printed by the Industrial and Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 46 926 9 A7 ____B7_ 5. Explanation of the invention (+) A pair of precursors The substance is placed in a reaction medium containing the precursor substance and a solvent. In the case that almost all of the counter-acids generated in the gasification reaction region in the reaction method can be maintained in the solution, the solution is reacted with chlorine. Citrus gasification is a method for producing p-acid acid, and its special feature is that the gasification reaction method is performed when almost all the gas is dissolved in the reaction medium. Therefore, from the viewpoint of the present invention described later, the implementation of the liquid-phase gasification reaction method is intended to: maintain almost all of the acid produced in the reaction period in the solution to reduce the reaction method The main impurity produced in 4-CBA is a method for contaminating the recovered & acid due to the simultaneous precipitation effect. When this aspect of the present invention is implemented, the gas used in the reaction method is almost All can be dissolved in the reaction medium. After the dissolved gas is used in the reaction medium, the gas can be more uniformly distributed in the medium. In this way, there can be no worries about the existence of gas-deficient parts in the medium, so that adverse reaction products such as benzene (1,2,4 > rime acid (Trime 11 iticacid), benzoic acid (B e η ζ 〇ieacid > and color quality, etc. In general, this method can produce low-pollution finished products, and can avoid unnecessary solvent combustion effects, thus avoiding the high-quality polyester for general high-quality polyester manufacturing. The purification method used in the production process for mysteric acid. Although from the viewpoint of the present invention and other aspects of the present invention, it is preferable that all the para-acids generated during the reaction can be retained in the solution. However, during the reaction, it is still possible that the weight percentage relative to the parasite acid produced is below U, usually below 5¾, and the total precipitate will not be formed above 10¾. Best, the reaction The medium is based on the paper size of at least two separated liquid oranges, and the national standard (CNS) A4 specification (2 丨 OX 297 mm) (please read the note $ on the back before filling this lamp)

T 469269 Central sample of the Ministry of Economic Affairs—Gongxiaojinghe A7 B7_ V. Description of the invention (屮) It is generated by mixing, and before mixing in this way to form the reaction medium, it is better to add a part of the oxygen to the Dissolved in one or more liquid components. For example, the separated liquid phase component may include a component composed of precursors and another component composed of the aforementioned solvents, and at least a part of the oxygen necessary for the reaction method may be added to The aforementioned second component is dissolved in order to allow the reaction method between oxygen and the precursor to be carried out after the two components are mixed and a reaction medium has been formed before it can proceed. In principle, the solvent component is mainly an aliphatic Monocarboxylic acid (which preferably contains 2 to 6 atoms) and can be derived from acetic acid, propionic acid, butyric acid, isobutyric acid, n-valeric acid, trimethylacetic acid, hexanoic acid, and any of the above A mixture of acetic acid and water, and this is a mixture formed during the reaction. At this stage, the preferred solvents are acetic acid and water. However, I also do not rule out the possibility of using other solvents, such as benzoic acid or a mixture of benzoic acid and water. Β In the traditional way, the liquid phase gasification reaction of p-xylene is used to make p! Acid. The component of water used in it is estimated by weight ratio, which is approximately equivalent to 3¾ ~ m of the mixture of carboxylic acid and water lost to the solvent in the reaction area. As far as the different perspectives of the present invention listed herein, they have a common feature: the water content used in the method can be much larger than in a traditional method of making tartaric acid. The water component β in the total feed to the reaction zone. From the different perspectives of the present invention illustrated herein, the reaction medium component at the beginning of the reaction process, wherein the proportion of the water component is estimated by the weight ratio, Approx. 32 to 30 × ^ Zhang scale is applicable to China National Standard (0 Division) 8 4 specifications (21 (^ 297 Gong > X) (Please read the precautions on the back before 1 ^ this page}

A7 B7 The Central Government Bureau of the Ministry of Economic Affairs, Work and Consumption Cooperation, Du Yin ». 6 9269 V. Description of Invention (丄), or 12¾, or between 10¾ ~ 30¾. The reason why the increase in water content is feasible is because the ratio of the solvent to the precursor used in the method of the present invention is quite high. This is to ensure that almost all of the produced acid is able to react during the reaction process. Retain in solution. For example, in the case where the precursor is para-xylene, the solubility of the para-xylene in an acetic acid / water mixture will greatly decrease due to the increase in water content, which will be limited to The amount of water that can be stored in the reaction medium can be stored in the acid production method. This is because the ratio of the solvent " p-xylene to p-xylene is very low, usually between 4: 1 to 7: 1. In terms of the inventive method, an increase in the amount of water is one thing that can be tolerated. Generally speaking, the ratio of solvent to precursor is at least 3 G, 1 level, or at least 50: 1 level. In actual operation, the ratio value can be much greater than 50: 1, for example, as high as 150: 1 or even 200: 1 level β. When referring to the ratio of solvent to precursor, it must be noted that in the reaction medium The water content in the medium is a part of the solvent, and it must be calculated as such when estimating the ratio of the solvent to the precursor. As far as a third perspective of the present invention is concerned, although this third perspective can be used in combination with the aforementioned first or second perspective of the present invention, it can also be used independently. The non-acid precursor is placed in a reaction medium in which the precursor and a solvent are contained. Once the reaction is completed, almost all of the acid generated in the reaction zone is left in the solution and is carried out with oxygen. Liquid-phase oxidation reaction to produce g acid is characterized by the following: the reaction method pseudo-generates a reaction medium flow from an inlet end through an anti-hall area to an outlet end, and establishes a temperature along the flow direction of the reaction area Distribution mode so that the temperature of the reaction medium at the exit end is greater than the paper size of the Chinese paper (CNS) A4 size (210X297 mm). page)

46 9269 a? B7 Liji? Printed by the Offshore Consumer Cooperatives of the Central Bureau of Quasi-Bureau 5. Description of the invention u) The temperature of the reaction medium at the inlet. A method of making a log-k acid by using a precursor that is relatively acidic-a reaction method with high exothermic properties. As far as the traditional technology is concerned, after allowing the reaction solvent and water to be vaporized and removing the water generated from the process from the reactor, a substantially isothermal condition can be maintained in the reaction furnace. For the method implemented in this aspect of the present invention, the reaction is carried out under non-isothermal conditions. Therefore, the heat generated by the reaction can be eliminated or less rubbed. Therefore, the temperature image in the reaction zone shows a distribution pattern that gradually increases from the inlet end to the outlet end. Generally speaking, the step of recovering K-acid from the skin medium and the cooling medium is performed to sink the reaction product, and then separate it from the mother liquor generated, and then return the mother liquor. To the reaction area. After the temperature of the reaction medium is gradually increased during the passage through the reaction zone, the temperature of the mother liquor is sufficient to prevent the mother liquor from being heated again before being returned to the reaction zone, even if necessary, warming The extent is also extremely limited. So, for example, the difference between the temperature of the mother liquor recovered after acid precipitation and separation and the temperature at the inlet end of the reaction zone can be maintained within 3ITC 犮, especially at 2 (TC or so). It must be noted that during the reaction, the temperature of some parts in the direction of the process may not be sufficient to maintain a nearly completely dissolved state, resulting in the precipitation of #acid from the solution. This precipitation phenomenon can cause The temperature distribution pattern in the direction promotes at least a part of the precipitated pair of acids to be re-dissolved to be offset. In addition, the temperature distribution pattern can also be adjusted so that any of the liquid components delivered to the reaction zone are contained in the medium. Any particles of the #acid can be dissolved when at least a part of the reaction medium passes through the reaction area. These particles can be removed from the r-site of the reaction area (please read the note on the back first) (Please fill this page again) .. W · Order_line 丨 The paper size used in the national standard (CNS) A4 now (210X297 mm) 46 9269 A7 B7 Consumer cooperatives Description of the invention (γ) In the process of recovering parathionic acid in the reaction medium, the liquid substance introduced by the separation is refluxed and introduced. The temperature distribution mode can be controlled by allowing the temperature of the reaction medium to rise, or control the reaction process. The temperature rise caused by the released heat is established. The reaction area can be formed by a single container or pipe, or composed of a series of small areas, a small area consisting of a single container or pipe, or It consists of independent compartments located in a single container. The temperature distribution from the inlet end to the outlet end can be a continuous increasing mode along the flow direction, or a step-temperature increasing mode. For example, in the reaction area is In the case of a series of small areas, at least one of the small areas must be equipped with the necessary heat removal or heating configuration mechanism to establish a pair that is best able to remain in solution throughout the reaction area. The temperature distribution pattern of the acid step is consistent. The reaction zone can be set more than-値, for example, two or three reaction zones can be set parallel to each other.反应 Reagents and solvents are loaded in each zone, and if necessary, the generated streams from each multi-reaction zone can be combined to form a single generated stream. 0 or one or more of them are generated from the reaction zone. For the operation of removing reaction heat in a small chest area, it can be taken from the mode in which the reaction medium transfers heat to a heat sink via a heat exchange surface (for example, heat exchange with W heat receiving liquid). It is also possible to add a quenching liquid agent such as a solvent or a precursor, or an inconsistent liquid (more details later), along the flow direction of the reaction medium flowing through the reactor, and add one or more In the case of using a heat-receiving liquid, the liquid can be passed through one or one ----------- ^-< Please read the precautions on the back first (Fill in this page again) Remarks: This paper uses China National Standards (CNS) A4 (210X297 mm) standard 4 6 9 2 6 9 Printed by the Central Ministry of Economic Affairs ϋΗξΊβίIndustrial Cooperative Cooperative «. 5. Description of the invention ( $) Or more channels with wall sections on them, Exposure to a reaction medium in the domain of the reaction plaque. For example, the heat-receiving fluid can flow through a coil or several of these coils that are immersed in the reaction medium. Alternatively, the reaction 采 can also adopt a shell-and-tube-type heat exchanger shape, so that the reactants and solvents pass through the shell portion, and the heat receiving liquid passes through the tube body located inside the shell portion. However, it can also be performed if heat transfer is performed in other ways. For example, the heat receiving fluid can be passed through a jacket β which can at least partially surround the application area. The principle of arrangement is to allow the reactants and solvents to flow through the pipe section, and the heat receiving liquid to flow through the shell section. The heat-receiving liquid can be in the same direction as the reaction medium flowing through the reaction area, in a countercurrent direction, or in a co-current situation, crossing the reaction area. It is best that the heat-receiving liquid flow path passes through the interior of the reaction. While extending. Preferably, the heat-receiving fluid after heat exchange with the reaction medium should be treated to recover the thermal, mechanical, or electrical energy released by it. At least one portion of the energy child thus recovered can utilize the action of a suitable compressor. The air or gas is pressurized, and then it is delivered to the reaction method as a gasification agent. For example, the thermal energy transferred to the heat receiving fluid can be converted into mechanical energy or electrical energy utilization in an energy recovery system. An applied method is to generate water vapor by using a heat-receiving liquid, and then perform a heat treatment on the water vapor, and then send the water vapor to a steam turbine to collect energy sharply. The heat-receiving liquid may be subjected to a pre-heat treatment before passing through the reaction area, in the form of heat exchange with water vapor generated by the gasification reaction. Preferably, the heat sink used is water or oil, such as mineral oil. Alternatively, the heat-receiving component may be a reaction medium, or one of its components, such as a solvent or a precursor thereof. For example, the heat released during the reaction, (please fill in this page with the notes on the back first) • W · Order i This paper size uses the country's home rubbing rate (CNS) Α4 size (210X297 (Mm) Printed by the Central Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives 4 6 9 2 6 9 Α7 Β7 V. Description of the Invention (I) One part may be used to preheat the imported reaction medium, and the other Part of it is used to increase the temperature of the reaction medium as it passes through the reaction zone, so that para-acid can be almost completely retained in the solution β. The starting temperature at the beginning of the reaction must be high enough to ensure that the beginning of the reaction is not hindered, but The magnitude of the rise in the temperature of the posterior loop caused by the non-response process should not cause excessive combustion of solvents and aromatics. The ideal starting temperature range is between 80 ° C ~ 200 ° C, or between 120 ° C ~ 180 ° C, especially between 140 ° C ~ 170 ° C. The temperature of the water vapor flow generated in the self-leveling field must be greater than the temperature at the inlet end, which can be between 1 8 CTC ~ 2 50eC_, and especially between 180 ° C ~ 23Q ° C, or even at 190-C ~ 220T: more suitable between a. After crossing the reaction area, almost all of the paraacids are in the solution. This solution may contain a catalyst, and a relatively small amount of a medium, such as p-phenylacetic acid and 4-CB A, and accompanying products, such as color quality and carboxylic acid β of benzene (1,2,4). The desired product, with respect to 0, can be precipitated in a manner that allows or allows it to crystallize from the solution in one or more stages, and then the generated mud can be re-treated in one or one. In the above stages, a solid-liquid phase separation process is performed. Before the precipitation and crystallization are buried, once the acid and other components of the gold portion are still in the solution, the reaction medium can be treated to exclude certain components. Off. For example, the reaction medium can use a cation exchange resin for an ion exchange treatment or use an ion exchange membrane to perform a treatment by electrodialysis to remove catalyst metal ions. In view of the solvent-to-precursor ratio used in the method of the present invention (please read the precautions on the back before filling this page) Order _ -i This paper size is in accordance with China National Standards < CNS) A4 size (210X297 (Mm) 4 6 9 2 6 9 A7 ___ B7 ^ _ 5. Explanation of the invention (b) The example value is quite high, so the product / mother liquor slurry obtained from the precipitation and separation stage is relatively thin, the best, can The product is subjected to a concentration treatment at the upstream portion of the solid-liquid phase separation. As for the thickening of the mud part, 刖 can be implemented with one or more cyclones at the downstream part of the crystallization method, or, during the crystallization method, an integrated crystallization / concentration device can be used. Implementation. Following the solid-liquid phase separation method, the commercially available solvent-based mother liquor, although it may contain it, may not necessarily contain the dissolved catalyst component. It is best to be recycled to the gasification reaction zone. The recovery can be achieved by the traditional crystallization technology, which involves the decompression process β of the reaction medium. However, this decompression process is bound to require the mother liquor to be recycled to the reaction system to be repeatedly pressurized. -In terms of viewpoint, although it can be implemented concurrently with the aforementioned viewpoint of the present invention, it is not necessary to do so and to implement it. In terms of another viewpoint of the present invention, its provider will all have In a reaction medium in which the precursor is contained, under the condition that almost all the g-acids generated in the gasification region during the reaction can be kept under control in the solution, liquid-phase oxidation treatment with oxygen is performed to The method for making the acid is described as follows: the reaction medium can be recovered by precipitation treatment without the need for significant decompression of the reaction medium, so that the mother liquor can be roughly the same as that of the reaction furnace. Working pressure Orange with or not far from the pressure F, for example, in Article 5 bar lower than the reactor system operating pressure, even under pressure in the low 2 Palestinians and Israelis, to be recycled. Regardless of what is shown above, or in each of the Xiao Shi viewpoints of the present invention disclosed by Lu Yi later, before the mother liquor is reintroduced into the oxidation reaction area, it can be applied to the Chinese National Standard (CNS) A4 specification (210X297). (Mm) ---------- 赛-(please read the note f on the back before filling in this).

0 -line I 469269 Printed by ABC B7 of the Central Economic Cooperation Bureau, B7_Fifth, invention description (< 丨) After the reaction medium leaves the reaction zone, or is still in the process of passing through the reaction zone, heat with it The exchange process is heated to cool the reaction medium. -In general, the 4-CBA contained in the precipitate thus formed is best if the weight percentage is less than 50,000 ppm β, which is the acid of life which is precipitated in the media. -CBA, its weight percentage is below 3000 ppm, especially below lf100 ppm. It is more advantageous if it can be suppressed to 50 ppm, or even within 20 ~ 300 ppm. It is best that the cooling treatment of the reaction medium and its subsequent effect on the precipitation of the acid are controlled at a temperature sufficient to suppress the generated slurry that is undergoing solid-liquid phase separation to 120 ° C ~ 180 ° C, or more ideally controlled within 130 ° C ~ 175 ° C, or even 140 ° C ~ 170 ° C Although the solid-liquid phase separation treatment performed at such a high temperature will cause a considerable amount of existence in the solution, it was found that the main impurity components in the recovered product will self-react with the temperature. The initial temperature when the medium starts to leave the reaction zone decreases and decreases, but it will increase after the temperature further decreases. As far as another aspect of the present invention is concerned, although Huang Shi can be carried out simultaneously with other aspects of the present invention, it can also be implemented separately. Its provider can clean up a pair of #acid precursors in one of them. In the reaction medium having the precursor and a solvent, in the reaction process, almost all the acid generated in the gasification reaction area can be controlled in the solution, and the liquid phase oxidation treatment is performed with the gas to produce a pair of # 酸 的 方法。 Acid method. After that, the reaction medium is subjected to a cooling treatment so that the pair of (§ epiic acid can be precipitated and formed, and then the solid-liquid phase separation step is used. The paper standard is quick to use the Chinese national standard (CNS > A4 size (210 × W7 mm)) (please first Read the notes on the back and fill in this 肓)-, ¾. -Order _ 469269 A7 B7_ V. Description of the invention (θ) is recovered in a step. At a temperature of C, or at a temperature of about 130 ° C ~ 175 ° C, it is even more advantageous at a temperature of about 14 ° C ~ 17 ° C. Another aspect of the present invention is to observe the viscosity. In terms of implementation, although it can be carried out simultaneously with other aspects of the present invention, it can also be implemented separately. The provider is a reaction in which a pair of g acid precursors are placed in a reaction in which the precursors and a solvent are contained. In the medium, in the case where almost all of the acid generated in the oxidation reaction area during the reaction can be controlled in the solution, the liquid phase chlorination treatment with gas is performed to produce a method of @acid, which is characterized by: Gasification agent 徭 flows towards an inlet of the reaction medium along a self-reaction area Two or more parts of the mouth portion are arranged in isolation and are introduced into the reaction area. This aspect of the present invention is applicable in the case where at least a part of the reaction area is constituted by a plug flow reactor. ; And in the form of oxidant that can be described as pure chlorine or an oxygen-added gas, the configuration of the β epithelium is particularly favorable, compared to the largest solvent and reactant flowing through the gasification area, which is extremely advantageous. Advantageously, so that the gasification agent can be attracted from a starting position and at least one position located downstream of the starting position. The gasification agent can be introduced into the reaction zone in a skeletal mode in general. Or a small area of the reaction medium process; for example, the gasification agent can be introduced through a perforated pipe immersed in the reaction medium and extending in the direction of the process. The number, spacing, and distribution of perforations are based on the oxidant It can be introduced at all points along the length of the anterior epiphyseal application region or a small region. The gasification agent used in the foregoing aspects of the present invention is a molecule It is suitable, for example, almost pure air, air or other gas containing gas (regardless of the size of the paper, the Chinese Illustrator (CNS) Λ4 specification (2 丨 0X297 mm, -ΜΓ {Please read the ¾¾¾ copy on the back first) Page) _ Therefore · Nail line ο A7 B7 6 9269 V. Description of the invention (丨 >) What is the proportion of oxygen), or gas dissolved in liquid 〇 The obvious benefit of using almost pure oxygen as a gasifier is that it can target When performing intensive reaction treatment under mild operating pressure, avoid gas vacuum and interference with the plug flow pattern ^, and achieve a high gas volume transfer rate. Gas can be combined with a diluent gas (such as sulfur dioxide) because the two gasification. Sulfur has a better solubility in solvents than diluent. Diluent gas, for example, can be derived from the exhaust gas generated in the oxidation reaction. The exhaust gas should be treated first, for example, using a high-temperature catalyst combustion method. Do a treatment to convert any existing methyl bromide to Br and Br2, and at least one partial reflux treatment without losing its HBr composition, because HBr can be used in the gasification reaction as One Use of catalyst components. For example, after the conversion of He8r to IfBr and Br2, a part of the exhaust gas can be biased ^ to dilute the gas feed to the reaction method, and the remaining part can be further processed, such as a liquefied medium. For the purpose of carrying and transporting. The deflected portion of the treated exhaust gas may be subjected to a cooling treatment (for example, heat exchange treatment with the exhaust gas located upstream of the conversion stage of MeBr), and before or after blending with the oxygen feed. A sufficient amount of recompression treatment so that it can be reintroduced into the oxidation reaction process. The remaining exhaust gas treatment methods may be sent to an energy recovery system, such as an expander and a scrubber located upstream or downstream of the expander to remove all residual pollutants such as H Br and B r 2 is excluded. Instead of using molecular gas, the gasifying agent can be replaced by atomic gas, such as a compound, for example, a compound containing one or more gas atoms in each molecule that is liquid at room temperature. For example, hydrogenated gas is a suitable compound. The size of this paper is based on the national standard (CNS) A4 specification (210 > < 297). (Please read the note on the back ^^ ^ Write this page) / · Line 'Printed by A7 B7 469269 of the Central Consumer Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 5. Description of the Invention (arsenic) In addition to the ratio of the solvent to the precursor, other relevant parameters, such as temperature and water content It must also be taken into consideration to ensure that during the reaction, all of the g-toluic acid produced can remain in the solution. The higher pressure conditions necessary for the reaction operation are selected based on the principle that the reaction medium is During the reaction period, it can be retained in the liquid phase. It is also in a non-boiling state. Generally speaking, the reaction method is performed at a pressure of 10 to 10 (1 bar, or even at a pressure of 20 to 80 bar, depending on Depending on the nature of the gasification agent. For example, in the case where the reaction is carried out with a dissolved gas, 'if the used is almost pure oxygen, the reaction pressure is about 60 to 80 bar, but at The gas and a diluent used are dissolved in the reaction In the condition of qualitative conditions, the reaction pressure is above 100 bar. C As far as another implementation viewpoint of the present invention is concerned, although its implementation can be carried out simultaneously with other viewpoints of the present invention, it can also be implemented separately. One is to place a pair of #acid precursors in a reaction medium in which the precursors and a solvent are contained. During the reaction, almost all of the pairs of acids generated in the gasification reaction area can be controlled in solution. In the case of internal gas, the liquid phase oxidation treatment with gas is used to make the #acid method. Its to be emblematic is the total volume of the gasification reaction A with the reaction zone orange, the unit of which is cubic meters, recovered For acid 4-CBA component B, its unit is the ppm value (parts per million) of west cents by weight, and for the acid C, which is recovered from the oxidation reaction, the unit is te per hour For #acid amount, the relationship between each other can be expressed by the following formula: (AAB) / C < [0 0 0 The total volume of 〃 gasification reaction 〃, refers to a single reactor or parallel, series and juxtaposition The total volume of several reactors, that is, the entire reaction area, plus the reactors The paper size for steaming / liquid phase separation in this paper is suitable for China National Standards (CNS) A4 specifications (210X297 mm). (Please read the note f on the back before filling this page) Order-line. A7 B7 Printed by the Central Government Bureau of the Ministry of Economic Affairs I Industrial Consumer Cooperatives 46 92 6 9 V. Description of the invention (<) Steam head space is included.. The upper switch type may be rewritten as the following formula is more practical: {^ B ) / C < 3,000 In general, according to the implementation point of view of the present invention, the content of 4-CBA in #acid recovered in the weight percentage value shall not be greater than .5, 0 0 0 ppb , Not even greater than 3, 001) ppm, or even greater than 1,000 ppm, or even controlled below 500 ppm, or even within the range of 20 to about 300 ppm. Generally speaking, the production rate is more than 20 te per hour. Β This aspect of the present invention can be performed simultaneously with the implementation of the acid production method implemented by other aspects of the present invention. For example, it can be used in non- Under boiling conditions, a gas supply with sickle flow or nearly plug flow law. For example, a single plug-flow reactor provided with near pure oxygen according to the present invention, when it is decided to produce a pair of acids at a rate of 60 te per hour, accompanied by a 4-percent by weight of 250 ρρ * 4- In the case of CBA composition, it can be performed with a reaction strip having a rated gasification reaction volume below 160 cubic meters, and in this case, (A # B) / C < 1,000. However, as far as a conventionally designed gasification reactor is still used in the industry, if its designed crude crude #acid yield is 60 te per hour, and the weight percentage of 4-CBA produced is about If it is 2 500 ppm, the total volume of the necessary chlorination reaction must be at least 400 cubic meters or more, so in this case, (A < B) / C > 丨 6 ί) I) 0, it is obvious from this In the case of using the embodiment of the present invention, it can be shown that the volume of the reaction volume can be reduced. As for a traditional single-stage gasification method using multi-stage reaction 泸, under high catalyst concentration and high temperature conditions (the degree of combustion of acetic acid is bound to be 髙) This paper uses the Chinese National Standard (CNS) Α4 Specifications (2 丨 0X297mm) (Please read the precautions on the back before filling in this page)

469269 A7 B7 Printed by the Central Government Bureau of the Ministry of Economic Affairs, Consumer Affairs Cooperative, Co., Ltd. V. Description of Invention (IV), if you want to make fiber-grade pair #acid at a pace of 60 hours per hour, and accompany. For the CBA component, the total volume required for the gasification reaction is about 800 cubic meters, and the data value calculated according to the (〆B) / C off pseudo-type is greater than 66 Ot). In terms of a related implementation of the present invention, a liquid acid oxidation of precursors of & acid is used to make a plant of #acid, in the trimming mechanism, starting with a production step of at least 20 te per hour In the case of producing p-bisphosphoric acid accompanied by 4-CBA with a weight percentage of less than 5000 ppm, the total volume of gasification reaction of the reactor in which the oxidation reaction is performed is A cubic meter, which can meet the following conditions:

A < (4,0000 / B) Any implementation viewpoint of the present invention mentioned in the foregoing, when it is actually implemented, generally, it must be implemented in the presence of a gasification catalyst. The catalyst used must be Soluble in a reaction medium composed of a solvent and an acid precursor, otherwise a heterogeneous catalyst should be used, whether single-phase or multi-phase, which contains one or more heavy metal compounds (such as cobalt or manganese compounds) Composition) and may be included in a gasification promoter (such as bromine or acetaldehyde) ^ For example, the catalyst can take any form used in the liquid-phase oxidation of the precursor acid, such as in fat Groups of carboxylic acid solvents, such as bromoalkanoates or Alkanoates (usually C1-C4 Alkanoates, such as acetate) of bromide, cobalt or manganese ^ Other heavy metal compounds, such as vanadium, complex, molybdenum , Iron or lanthanide rare earth elements, such as cerium, pins, thorium or thorium, can also be used instead of cobalt or manganese. Β is best, and manganese bromide (MnBr2) can be included in the catalytic system. National storehouse rubbing standard (milk milk) 8 4 specifications (210 father 297 mm > Λ- (please first read the note f on the back and then fill out this page) ^ • Bu 7 469269 Department of Central Rubbing Standards, Ministry of Magnetic Affairs Industrial and Consumer Cooperatives Co., Ltd. Yinli A7 _ _B7 _ V. Description of the invention "?) Β gasification catalysts can be selected from platinum, aluminum, etc., or one or more precious metals or their compounds, instead, or add additional ingredients Its shape can be highly cut or a metal sponge shape. If an oxidation accelerator is used, elemental bromine and ionic bromide can be used, such as HBr, NaBr, KBr, ΝΗ4ΒΓ or organic bromide, such as bromobenzene, Benzyl bromide, mono- and dibromoacetic acid, bromoacetamido bromide, tetrabromoethane, vinyl-di-bromide, etc., or monoketones such as methyl ethyl or Aldehyde, such as acetaldehyde. Under the condition that the catalyst used is heterogeneous, it can be appropriately placed in the reaction area to achieve a close connection between the continuous flow reaction medium and the catalyst. Here In the case, the catalyst can be appropriately supported and restricted in the reaction area to prevent In the case of a constricted flow to the cross section, this combination β is achieved. For example, a heterogeneous catalyst can be applied or otherwise applied or contained in a static element (for example, forming a Open structure element group) or above, so that the reaction medium can float on it. These static elements can be used to enhance the mild effect of the agent when passing through the reaction area. Or the catalyst can also Use the necessary equipment to make movable particles, particles, and metal sponge shapes to set them in the reaction area, so that the catalytic particles can be suspended or immersed in the reaction medium flowing through the reaction area during operation. By using heterogeneous catalysts in any of the above ways, the catalytic effect can be limited to a precisely defined area, so that after the reaction medium has passed through the area, further post-gasification methods can Keep pace, or suppress it effectively. This also eliminates the need for catalyst recovery. The support of the gasification catalyst can be made of a material with less catalytic activity, even (锖 read the precautions on the back before filling in this page) / order i This paper size uses the Chinese national kneading string (CNS) Α4 size (210X297 (Mm) — yv ^ 469269 A7 B7 The Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, Ltd. V. Description of the invention (\?) Compared to the chlorination reaction, the support body of the material that has no effect at all can be formed with holes. . In general, the catalyst support must be resistant to corrosion and, under prevailing conditions, have a gasification resistance. Therefore, depending on prevailing conditions, the catalyst support material can be selected from, for example, titanium, δ, bauxite, silica-alumina, α-alumina, y-alumina, d-alumina, π-alumina, niobium-rich andalusite, Spinel (Spinel), as well as supporting materials made of β but especially made of materials such as cr alumina, y alumina, silicon, or sand aluminum. The supporting material of the oxidation catalyst is a single pure material or a composite material. When considering that the catalyst should be given ideal physical or chemical properties, composite materials should be used. For example, the gasification catalyst can be selected from a substrate having high abrasion resistance and a surface film substrate having a high surface area. The production of these substrates can also be made by using the immersion technique. Materials used as substrates must, in general, have considerable corrosion and gasification resistance under prevailing conditions. Therefore, with reference to prevailing conditions, the substrate can be taken from alpha alumina, mullite, and Spinel (spinel). Membrane materials that can be used as composite substrates include silica, alumina, titanium, hafnium, α-alumina, y-alumina, ί-alumina, and π-alumina β The figure illustrates the case. The figure is as follows: Figure 1 is a block diagram of the overall gasification method of the present invention_e Figure 1A is a method diagram of combining different feeds to form a reaction medium_. Fig. 2 is a schematic diagram of a gasification reaction furnace scheme using nearly pure gas or aerated gas as a gasifying agent to implement one of the methods of the present invention. FIG. 3 is an improved embodiment of the gasification degree shown in FIG. 2. (Please read the note on the back before filling in this page) ’Order · i

I This paper size is applicable to the Chinese National Standard (CNS) A4 * MS · (210X297 mm)-Λ Printed by the Central Bureau of Standards of the Ministry of Economic Affairs and Consumer Cooperatives 469269 A7 _B7_ V. Description of the invention (η) Figure 4 shows the reaction method. In the case of using a continuous M-type reaction tank. An alternative embodiment β FIG. 5 is a flow chart of an example for crystallization and recovery of paper acid. 〇 FIG. 6 is made by a free crystallization method. Flow chart of the rectifier for recovering the solvent and water in the rapidly boiling steam. Fig. 7 is a flow chart of a system for recovering a product by a crystallization and concentration method in the same container. Fig. 8 is an embodiment of a plug flow reaction embossing system in which a heat removal body is provided. FIG. 9 is a schematic diagram of laboratory equipment used for implementing the embodiments mentioned herein. Symbol description of the graphical elements: 10: reaction system 12: preheating stage 14: feed streams 16, 17, 18: path 20: crystallization stage 22: concentration stage 24, 26: path 28: solid-liquid phase separation Stage 32: Path 34: Solvent Recovery Stage 1 35: Path 38: Path 40: Ventilation Treatment System 42, 44, 46: Path 60: Adiabatic Galvanometer Reactor 62: Path 64: Female Recirculation Feed 66 : Reservoir / Certificate 68: Calendaring machine 70: Path 70A, B, C: Input point 74: Recovery site 76: Recycled injection product 78: Water 80: Mother liquor 82: Mother liquor net flow 84: Path 86: Ventilation Gas flow 88: Heat exchanger 90: Path 32: Furnace 94: ms 170A, B, C. · Stirring stirring tank 172: Small plug flow reactor 171 Mixer / preheater Π6: Inlet end 178, 180. The paper size of this paper uses Chinese National Standard (CNS) Α4 specification (2Ι0 × 297 mm) One H One (Please read the precautions on the back before filling this page)

A7 B7 i 92 6 9 Printed invention description for printing by the Central Government Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 182: Path 184: Compressor 1S6: Path 190A, B, C: Condenser 192: Product / solvent recovery 鈒194: recovered paraquat acid 196: water 198: job 200: mother liquor net flow 202: ventilation air flow 204: condenser 206: path 209: high pressure absorber 210: preheater 212: device 214: extender 216: nitrogen Gas flow 220: reaction furnace 222A: first stirring crystallization container 222B: second right stirring crystallization container 224: path. 226: pump 228: hydrocyclone 230: thickened down stream 232: up stream 234: power drop vessel 236: Gyrovac 238A, B: condensers 240, 242, 244: path 246: solvent recovery stage 248, 249: path 250: steam stream 254: path 255: mixed feed stream 260: path 300: generated stream 302A, B: Vessel 304: Condenser 306: Paths 308, 309, 310: Path 312: Fractionation / rectification columns 316, 318, 320, 322: Path 324: Steam condensation turbine 326: Path 330: Heater 332: Device 334, 336: Path 338: Exit 34 端: Path 342: Heat exchanger 400 : Path 401: Mixer 404: Mother liquor feed 406: Feed 408: Path 410: Peel furnace 412: Crystallizer 414: Pump stirrer 415: Path 416: Steam condenser 4J8, 420, 422: Path 424: Path 426: Precipitation area 430: Path 432: Elutriation base 43S: Path buckle 8: Sudden boiling crystallization vessel 440: Condenser 442, 444: Path 446: Product separation stage (Please read the precautions on the back first Refill this page.) This paper size applies Chinese National Standards (CNS) A4 specifications (210X297 mm) A7 B7 Printing policy of the Central Consumers' Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 469269 V. Description of the invention (M) 448, 450: Path 452 : Path 500: Reactant 502: Solvent 510: Reaction medium 512A 'B, C: Heat exchange device 514' 518: Path This case is explained in detail: Referring to Figure 1, the one shown is in the case where a catalytic system is involved. A method for preparing a para-acid in the reaction system 10 by using a precursor of a para-acid (for example, para-xylene) in a solvent (for example, acetic acid) and liquid-phase gasification. The reaction system (It) can adopt a variety of different modeling modes. For example, it can be a single plug-flow reactor, two or more plug-flow reactors connected in series, one connected with one or more. Burma Stirring reaction combined with a plug flow reactor, or one or more serially connected tandem skin mixing furnaces. 'To achieve the plug flow effect β The following will illustrate some possible reaction system configurations. Precursors, supplementary solvents, supplementary catalysts (such as cobalt and manganese compounds plus a gasification accelerator bromine), and the recovered mother liquor and solvent components are placed in the mixing and preheating stage 12 and mixed together to produce a The ratio of the solvent (fresh and grazing) to the precursor in the mixture is significantly larger than that of the reaction medium used in the conventional method for gasification treatment of p-xylene to acid using liquid phase gasification. If necessary, at least a part of the preheating can be provided by the mother liquor and solution recovered under the stable operating state of the system. The heat provided by the recovered mother liquor may be sufficient to eliminate the need for an external heat source in a stable state, but in this case, an external source is still required at startup. In general, the ratio of the solvent to the precursor is about 70: 1 (. The weight ratio is based on the mixture being sent to the inlet of the reaction system via path 14 and the temperature of the mixture of the reaction system. Generally speaking, , About 15 (TC, and pumping to--appropriate pressure to ensure that the size of clothing and paper standards (CNS > Α4 specifications (210X297 cm)) (please note the first item before filling the nest This page}

-469269 A7 _B7_. 5. Description of the invention (> (Please read the note on the back before filling in this page) During the reaction, you can generally prevent the boiling of the reaction medium or change it. Mode, not in the mixer 1 2 The liquid phase components are mixed, preheated, and kept isolated until introduced into the reaction system (in this case, component 12 can be a simple preheater only), and two or two The shape of the feed unit 14 above the strand is mixed in the inlet of the reaction system 10 and then input into the reaction system 10 (for an example of this mechanism, refer to FIG. 1A). Oxygen is input via the path 16. The oxygen source may be Use a variety of different modes, including near pure gas, air, aerated air, $ with gas, and a diluent (such as nitrogen or two-gas chemical, etc.). The single path 18 in the system represents that factors such as the oxygen supply and transportation mode and the degree of oxygen feed are full of variables, which will be further explained in the embodiment described later. Also, although shown in the drawings The oxygen feed source is pseudo-independent of the solvent / para-xylene reaction medium, in addition Separately into the reaction system, but it is preferably at least partially (Li Yue path 17) pre-dissolved in the reaction medium or located in the reaction system or one of the upstream positions of the mixer / preheating device 12 The above ingredients (such as acetic acid or mother liquor recycling fluid), regardless of the oxygen source used, and especially the user is almost pure gas, or gas diluted with an inert gas. The solvent / precursor / catalytic reaction medium printed by the quasi-stationary consumer cooperative is best in the form of a plug flow or near plug flow. The inlet of the self-reaction system reaches its outlet, and there is a generated logistics at the outlet. Via path] 8 Outputs should be carried out under the condition that almost all of the para-acetic acid formed during the passage of the solvent /, precursor mixture through the reaction body, in order to make intermediaries such as p-phenylacetic acid and 4-CBA During the reaction period, the substances can be kept in the solvent, so as to facilitate the implementation of the reaction method. Β, so that one of the 4 ~ C Β Α components with a very low raw paper size standard (CNS) can be obtained. ) A4 size (210X2 97 mm) Α7 Β7 46 9269 V. Description of the invention (> >) The product. The product stream passes through the route 18 to a crystallization level 20, where the product and the paper acid are precipitated. A thin counter-flowing dragon plasma stream β crystal is formed in the mother liquid composed of the used solvent and some water, the dissolved catalytic components, the opposite region & medium and the accompanying products formed in the reaction method. The chemical method involves decompression and temperature reduction. At the end of the method, the pressure of the mud pressure can be lower than the atmospheric pressure and higher than the atmospheric pressure, which is especially suitable for the latter. The temperature is selected based on the principle that the temperature of the mother liquor recovered after the mud is at a level sufficient to ensure that when the mixed stream is mixed with the supplemental solvent and the precursor, its predetermined temperature level is equivalent to the rationale inlet of the reaction zone. temperature. There will be water generated in the oxidation reaction. One method to remove at least a part of the reaction water is: using a pressure rectifier / distillation column in the crystallization stage, for example, Under the condition of high temperature, the sudden boiling steam of the crystallization vessel is directly sent to a distillation column to separate the product solvent at the bottom end from the product at the top and water vapor. Thereafter, the pressurized steam at the top can be used by a steam condensing turbine in a power recovery system. Hereinafter, an embodiment of this mode will be described with reference to FIG. 6 for a further two steps. In the case of acid, the pressure of the steam produced by the oven should be reduced to a value below its saturated water vapor pressure, and the crystallization method to guide the removal of the solvent and make it precipitate using the step of boiling and solvent cooling After recovering enough acid, at least the whole residual mother liquor is recirculated to the reactor after repressurization. Another focus is on avoiding the need to recirculate and pressurize the mother liquor. CNS Α4 size (210X297 mm) —> 4 1 (Please read the notes on the back before filling in this page) Revision 丨. Bu. Μ Central Ministry of Economic Affairs Bureau BKK: Printed by Industrial Consumer Cooperatives Crack A7 B7 469269 V. Description of the invention (called) (please read the “Notes on the back side and then fill out this page”) For the example, the acid can be used to make a flow to the reactor without reducing its pressure. Precipitation is carried out in the form of cooling treatment. Then, hot mash can be removed through a heat exchange surface. It can be used for steam generation or method heating. In terms of this layout, #acid tends to contaminate the surface of the heat exchanger / converter after cooling, thus causing its efficiency to slide down. This pollution can be rampant. One surface scrapes the heat exchange device to treat it. The other focuses on In the embodiment of reducing the need for repressurization of the mother liquor circulation, the main method involves the use of solvent removal without precipitation of the solvent to precipitate the acid from the reaction medium. Solvent can be eliminated by forcing it to pass through a semi-permeable membrane (referring to resistance to acetic acid and water, conditional resistance to catalysts and reaction impurities, but not resistance to #acid). When the solvent is eliminated, it will begin to precipitate on the acidic acid, which is enough to cause the membrane hole contamination of the membrane efficiency, which can be achieved by cutting the shear force of the membrane surface or placing the membrane and crystallizing effect. The design of the intermediary container in series was resolved. Due to the limited pressure drop of the membrane skin system, the cost of oil 循 ows in the circulation of the mother liquor can be reduced & acid, this is due to the higher ratio of solvent to precursor. Therefore, it is better to complete the concentration of the slurry before performing solid-liquid phase separation. Β 瑄 can be implemented downstream of the crystallization stage of a concentration stage 2 2. This stage, for example, can be operated by one or more hydraulic forces. The cyclone is formed to generate a thickened down stream composed mainly of mud and mother liquor (§ !; acid crystals), and an up stream composed of mother liquor with acid particles suspended in it. With one or more hydrocyclone to thicken the mud, it is very advantageous due to the low cost. However, this paper scale is not suitable for the National Standard (CNS) 8.4 (ϋ X 297 mm)- A7 B7 469269 5. Description of the invention (ο other devices, such as one or more centrifuges (nozzles, decanters, etc.), filters (including cross-section flow through the filter element), or gravity clarification (Please read the note $ on the back before filling in this card) / Thickening device can be used regardless of whether it is an S external tube alone or incorporated into the body of the crystallizer (see below for details). «Central Ministry of Economic Affairs Kneading Bureau Shellfish Consumer Cooperatives printed from concentrated The upstream of stage 22 is passed back to mixer / preheater 12 via paths 24, 26. The concentration is transported to a solid-liquid phase separation stage 28 where acid crystals are separated from the mother liquor and the solid and liquid phases The separation treatment can be performed in one or more than one shovel filter device at higher or lower than atmospheric pressure or under atmospheric pressure conditions, which may or may not be equipped with flushing equipment, as previously published by the applicant The international patent applications Nos. W093 / 24440 and WO 94/17982 are shown, the entire contents of which are incorporated herein by reference. So, for example, the integrated solid particle separation and water washing device can be It consists of a centrifuge, a belt-type concrete implement, and a conical cone filter element. When the mud side is under pressure, or a barrel-type filter element (such as a number of mud receiving chambers) BHS-Fest. Pressure filter cartridge, in which the mother liquor is removed from the filter cake using the hydraulic pressure delivered to the receiving chamber). After the mud is filtered, the recovered acid can be dried. In the case where it has not yet reached atmospheric pressure Filtration Can be moved to a low pressure area (for example, at atmospheric pressure) to take advantage of a suitable pressure drop device, such as a lock funnel configuration, a rotary valve, a tamper-type pump, a screw feed device, or a progressive Feeding device, such as a cold slurry type progressive cavity pump for pumping high particle content, for a drying process. The separation temperature and the degree of washing depends on the amount of impurities generated in the reaction and the required products. It depends on the specifications. Although, generally speaking, it can produce the acid for It which is pure enough to avoid further purification treatment (for example, for this paper size, use the Chinese National Standard (CNS) A4 specification (210X297 mm))雉 m 消 f cooperatives 4 6 9 2 6 9 A7 ____ B7 _'_ 5. Description of the invention (K): The monoacid solution of #acid is oxidized or hydrogenated to convert 4-CBA to p-acid or p-benzene Acetic acid), but I do not rule out the possibility of performing this purification treatment according to the method of the present invention β After the solid-liquid phase separation, the product can be recovered through a diameter of 30, dried, or without intermediate chemical purification method Using one or two The olefins, such as ethylene di-esterase, are used for monoesterification. The drying of β products for downstream production of polyesters can be carried out in a wine rotary steam tube dryer or in a liquid bed dryer. The mother liquor filtrate obtained from the solid-liquid-liquid phase separation stage 28 is recycled to the mixer / preheater 12 via paths 32, 26. The mother liquor may contain a solid phase that is dry and withdrawing particles. The acid withdrawing component can be partially redissolved in the reaction medium at least as a result of preheating or in the reaction system. Zhu Neng can still dissolve when passing through the reaction system, which is generally tolerable, because these fine-grained ingredients have a relatively low purity compared to the microparticles made by the traditional acid-making method. Although not shown in FIG. 1, the mother liquor recovered through the paths 32 and 26 can be heated by a heat exchanger before returning to the mixer 12 to promote the heat transfer of the steam product on the path 8 Into the mother fluid circulation. Alternatively, in the case where the mother liquor can be used as a pre-dissolved gas carrier, it may be appropriate to perform a cooling treatment on the mother liquor. In this case, the mother liquor may be heat exchanged with a feed 14 of the reaction furnace system to Contributing to the heating effect of the feed stream. The solid particles recovered from the downstream part of the crystallization method. At least a part of them can be returned to one or more crystallizers to promote the solution and the nucleus or the growth of the particles. For example, to achieve this, a part of the upstream or thickened bottom stream containing the particles taken from the concentration stage can be fixed into the crystallization process. (Please read the notes on the back before filling the booklet I). Elephant · Order · -line ο The paper size is applicable to the Chinese Standard for Household Standards (CNS) Α4 (21〇 × 2ί »77) 46 926 9 A7 ___B7_ 5. Description of the invention (> ")) The crystallization method generally involves the sudden boiling off of the solvent and water in the mud, and the water is the water vapor generated by the accompanying product D and / Or the condensate is passed to a solvent recovery stage 34 through path 35. The solvent recovered in the solvent recovery stage is sent to the mixer / preheater 1 2 via paths 38, 26, and the gas and other volatile substances, including self-reaction systems or self-crystallized via path 44 The unreacted oxygen recovered from the chemical stage is transported to a ventilation treatment system 40 via path 42 together with other gases and volatile substances. In the case where the reaction furnace system is operated under a relatively high pressure condition to obtain a single phase mechanism throughout the reaction process, no exhaust gas will be obtained from the reaction furnace system, but when the gas component self-crystallizes When the solution in the chemical stage is decanted, remove it by ventilation. The water separated from the solvent in the solvent recovery stage 34 is passed through the path 46 to the first-class effluent treatment plant. There are more than one method for introducing gas into the reaction system. According to an ideal embodiment of the present invention, oxygen or a gas containing gas is introduced into the reaction medium when it is almost completely dissolved in the reaction medium, so that the reaction can be performed with these components under single-phase conditions. And if these components are processed under a traditional method for acid production, they must be carried out in the vapor phase, and the solid phase must exist in the liquid skin medium in a dissolved form. This method is shown in the following figure], A. In this method, the following liquid phase components are built in Anti-Axial 11) Α: A · p-xylene and acetic acid solvent (liquid orange). B. Complementary catalyst (liquid phase) placed in acetic acid solvent ^ C. Mother liquor (liquid phase) solidly collected from the method, and D. Oxygen or gaseous gas (vapor phase). This paper size is applicable to China® furniture standard (CNS) A4 scale (210X297 mm) (Please read the precautions on the back before filling this page) 469269 A7 B7 _ ^ _ 5. Description of the invention (4) Phase with the feed C In contrast, the smaller feeds A and B are first oiled to the system pressure, and then preliminary mixed in the mixer M 1, and if necessary, before, after, or during the mixing A pre-heat treatment was performed to produce a mixed feed E. The feed E is delivered to the inlet 1 of the reaction system. Oxygen in excess of the stoichiometric amount required for the reaction is added to mother liquor feed C under system pressure via feed D, and if necessary, after the oxygen addition feed is preheated, and the resulting oxygen-containing liquid 2. Feed F is introduced into the inlet 10A before processing the gas in excess of the stoichiometric amount required for the reaction. Gas, for example, can be added as a single jet into the mother liquor recirculation stream located immediately upstream of a static mixer M2. The design focus of the static mixer M2 is: to ensure continuous mixing through the mother liquid stream, and there is no phenomenon of high-concentration gas accumulation in the chi part in the solution, and the maximum volume of the bubble can be controlled by preventing the condensation of the bubble, And the foam can be evenly distributed in the mother liquor recirculation flow, so as to minimize the time taken for all vapors to dissolve in the liquid phase flow. A mixing device M3, such as a static mixer, is contained in the inlet portion 10A to ensure sufficient temperature search of the feed E and the feed F to form a reaction medium. The operating pressure, which is the pressure at which feed E and feed F are pressurized, is selected as follows: before the reaction medium is prevented from boiling, all the introduced gas or chlorine-containing gas can enter The solution enters the liquid-phase reaction medium. In the case where pure oxygen is used as the oxygen source, the operating pressure of the system is generally above 6 Q bar. Once the diluent is interposed, the pressure value will increase in equal proportions. For example, in the case where gas is input in the form of a gas containing a ratio of 80¾ gas and 20¾ gas, the system operating pressure is generally about 75 bar or more. In principle, feed E and feed The temperature of F is based on the paper standard (CNS) Α4 size (210X297 mm) (Please read the precautions on the back first ^ write this page) · 7 Printed by Zhengong Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs M. Central Ministry of Economic Affairs, Department of Industrial and Consumer Cooperatives, India 469269 5. Description of the invention (called) The two must be mixed at the inlet of the reaction system 1Q to achieve an ideal suitable for initiating the gasification reaction. The temperature of the reaction medium, for example, the ratio of acetic acid to p-xylene at 150 ° C 0 can be determined jointly by the solvent introduced through the feeds A and B and the acetic acid refluxed through the mother liquid feed C. The determining principle of this ratio is: the reaction medium will gradually drive into the outlet of the reaction system 10B 畤, there will be a progressive increase in the formation of @acid, and because the reaction system will proceed in a non-isothermal state, resulting in The temperature increases from the inlet 10A toward the outlet 10B, which in turn leads to an increase in the temperature of the reaction medium. After considering these factors, it is necessary to ensure that all of the acid produced in the subsequent reaction method is retained in the tidy reaction area. The temperature curve achieved by the solution β can be trimmed, and a feasible temperature curve control method is to introduce the feed F in a phased manner instead of pouring it from the inlet 10A to the inlet ί 〇 Α. Response system〗 0. Therefore, as shown by the dashed line in the plaque U, the feed F can be divided into several feeds F, F 1, F2, ..., the feed F is introduced from the inlet 10A, and the remaining feeds FI, F2 ... Several fixed points along the path of the reaction medium flowing through the reaction system are put into the reaction medium in the form of quench feed. Appropriate mixing devices M4, M5 can be provided at each input point to ensure that the input liquid agent is fully mixed with the remaining reaction medium. In the case that the system should be composed of two or more reaction vessels, the feeds F 1, F2 ... can be smoothly put into the reaction medium at the intermediate positions of the two reaction vessels. In the inter-spring operation, the mother liquid feed C pseudo-introduces oxygen into the reaction body 糸, the most suitable donor, because it is under steady-state operating conditions. It can constitute the main body of the reaction medium; however, I do not rule out gas Or more than one batch of responses: This paper size is applicable to China National Standards (CNS) Α4 size (210X297 mm) (Please read the precautions on the back before filling this page) r · Order 'Economic 4M-Central Standards Bureau Shelley Consumer Cooperation Du Yinhe 4 6 9 2 6 9 Α7 Β7 V. Description of the invention (") Other feeding methods of the system to replace the mother liquid feed, or as an additional feed other than the original mother liquid feed Reference is made to the possibility of the system. Referring again, the one shown in the embodiment of the method of the present invention is described in ®Photograph 1, where the reactor furnace system adopts an adiabatic plug flow reactor mode 6 Q, there is an inlet for mixing with the leptin. The liquid orange reaction medium consists of para-xylene, fresh solvent and supplementary catalyst input from the mixer / preheater 66 via path 62, and via path 64. The reflux mother liquor is fed and combined to produce. In one embodiment, the chlorinating agent composed of almost pure gas can be supplied through the compressor 68 and the path 70, and mixed with the mother liquid reflux feed 64. The reactant is subjected to appropriate strong pseudo-mixing to generate a mash. One phase, while oxygen is dissolved in the liquid phase ^ Generally speaking, the liquid phase reaction medium is pumped to a pressure of about 60 bar, and the gas is compressed to a pressure level above 60 bar to facilitate its introduction into the liquid phase As in the case of the embodiment shown in 圔 1, the reaction medium contains p-xylene (PG), a solvent-based mother liquor, a solvent recovered from the downstream portion of the reaction furnace system, a supplementary solvent, and a supplementary catalyst. In general, the temperature of the reaction medium / oxidant mixture delivered to the inlet 62 of the system should be about 15 ° C. In the case of acetic acid as the solvent, the single-phase operation of the reaction furnace system It has the function of reducing and inhibiting the formation of methyl acetate, and compared with the traditional reaction furnace, the degree of solvent combustion is relatively low β In addition, the use of gas without air can be used in the subsequent crystallization method To promote ventilation The total gas feed required for the reaction method can be introduced in the inlet area of the anti-Sassin system d 0. In this case, in order to achieve a single phase condition in which the gas is dissolved in the liquid phase, the reaction furnace must be between 60 and Operation under high-pressure conditions of 100E β If this paper size is applicable to Central European countries (CNS > Α4 size (210X297 mm) (Please read the note on the back w-item before filling in this page) 嚷. • Order 4 6 9 2 69 A7 ___ B7 __._ 5. Description of the invention (M) Necessary, the pressure in the reactor can be reduced by distributing the oxygen feed along the flow direction through the reactor 60. Therefore, as shown in Figure 2 It is shown that a part of the gas feed is supplied by the path, and the rest is through N input points 70A, 7QB, and 70C. The value can be 1 or greater than 1). (Appropriate strong mixing is used to achieve single-phase conditions) "As for another alternative embodiment as shown in Figure 3, the distribution of the gasification agent can be obtained by passing the inside of a longitudinal direction along the reaction 燫 60. The introduction of an extended f-hole channel or similar structure, and Mode. After the gasification agent is gradually introduced according to the method shown in FIG. 2 or FIG. 3, the amount of gasification agent input at a certain point can be adjusted according to the demand for gas at the certain point, and it can be ensured in the reaction furnace. There is no lack of gas in the area. In addition, the pressure of the reaction plutonium can be reduced, and the plutonium must be at a level sufficient to prevent the boiling effect of the reaction medium during the reaction. In the case where the ratio of the solvent to paraxylene fed to the inlet of the reaction furnace 60 is about 60: 1, the adiabatic temperature rise during the reaction is about 7 (TC ^ released during the reaction The heat can be eliminated by raising the temperature of the reaction 5 5 G ° C from its inlet end 2 G to about 2 2 (TC) at its outlet end, so that it does not need to be transferred by indirect heat transfer. , Or by introducing a cooling liquid to quench it (for example, by introducing a reaction medium or a heat-wearing body). However, it must be noted that the present invention includes a spring embodiment as shown in Figure 2, The way in which the released heat is removed is not limited to a mode that makes the temperature's reflexive inlet end rise to its outlet end. At least a part of the reaction heat can be removed by any suitable heat removal method. The generated logistics output from the outlet end of the self-bolt flow type furnace 7 2 is applicable to the Chinese National Standard (CNS) A4 specification (2 丨 0X297 mm) on a large paper size (please read the precautions on the back before copying this page)

Printed by the Central Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, ρ 46 92 6 9 Α7 Β7 V. Description of the invention (p) It is equivalent to the parts 2Q, 22, 28, and 34 of the factory described with reference to FIG. 1. And the solvent recovery part 74 is processed, and the recovered product, water, and mother liquor, and the net flow of the mother liquor are marked with code 76, 78, 80, and 82, respectively. As for this embodiment, the near-pure gas used is a gasifying agent, and nitrogen or other inert gas can be transported into the crystallization method through the path 84 to ensure that the ventilation gas recovered through the path 86 does not have easy Flammability. Generally speaking, nitrogen is at least transported into the head space of the first container in the crystallization sequence, that is, the head space of the highest temperature and highest pressure crystallization container. The ventilation gas flow 86 passes through the heat exchanger 88, where it is preheated with the heat-treated ventilation gas transported through the path ί) 0, and then heated in the furnace 92, and then subjected to a catalytic combustion treatment in the device 94. To destroy contaminated substances such as primary gas sulfonate and organic matter that can be converted into secondary gas sulfonate and water. The treated gas, after reaching the heat exchanger 88 through the path 90, may be removed after being wiped with water or alkali if necessary to remove any methyl bromide present in the ventilation air flow 86. Residual pollutants generated by catalytic combustion, such as bromine and ίBr are eliminated. As an alternative to the embodiment shown in FIG. 2, two or more plug-flow reactors can be connected in series, preferably in one or more of these series-connected pan furnaces as necessary. Put in several batches of oxidant. For example, the stream containing the product from the first reactor can be directly sent to the sub-reactor (if more than one plug-flow reaction is provided, do so). A quenching medium can be introduced into one or more reactors downstream of the first reactor to control the temperature distribution curve of the entire reaction system so as to synergistically promote the formation of almost all of the #acids in the solution. Synchronization within. Quenching medium, in general, contains the paper size used in the application process. ® Standards for Home Furnishing (CNS) A4 (210X297 mm), 3 Canton (please note the item f on 09¾ before filling the nest) (This page)-ordered. Dv · A7 B7 Printed by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 46 92 6 9 V. Description of the invention (6) Solvents used (as shown in the mother liquor of Xuye in Figure 1A), or one of them There is a gas pre-dissolved in it. According to another alternative embodiment of the present invention, the thermal control medium introduced into one or more reaction furnaces downstream of the first reaction susceptibility may pass through the temperature curve pattern of the reaction susceptibility system, and react to the reaction from the previous one. The generated stream in the furnace transfer is heated instead of cooled. As far as the embodiments described above are concerned, the catalyst used is dissolved in the solvent medium delivered to the gasification reaction method; however, as mentioned above, a heterogeneous catalyst may also be used. It is best to incorporate zirconium in the catalyst system. For example, 15% by weight of cobalt supplementation has been proven to achieve a 4-CBA content in the same conditions as those with the same residence time, feed composition, and temperature, but without this supplement. The level of light emission is reduced, and the content of 4-CBA is about 0 0 ppm if there is any interference in the catalytic system. If there is no feed in this system, the content of 4-CBA will be higher than 2 50 ppm. For the example shown in Figure 2, the gasification reaction is a plug flow reaction at one or more In the furnace. Shown in Fig. 4 is an alternative scheme in which the reaction area is pseudo-contiguously composed of a series of continuously agitated reaction tanks 17 0 A, 17 0 B, and 17 0 C, and it is preferable that a small plug flow reaction is further provided therein. (1 7 2 β) In this embodiment, the operation of the plug flow mode can be completed by Lipper's CSTR. The more CS TRs are used, the closer the system operation is to the plug flow mode, so The more favorable the relationship between combustion and 4-CBA ft is.

The reaction medium originating from the mixer / preheater 1 7 4 has the same composition as the one explored in the embodiment taught with reference to FIG. 2 and is subjected to a pressure treatment to pump to the inlet end of the reaction system. 176, which is the inlet of the first barrier class CSTR 1.7f) A, the reaction medium is falsely pressurized to an appropriate margin to prevent it from using the Chinese national standard for each c STR paper standard {CNS > A4 size (210X297mm) (锖 ^^ read the note on the back and write this page)

Printed by the Central Government of the Ministry of Economic Affairs and the Industrial Cooperative Cooperative A7 469269 B7 V. The level of the invention that causes obvious boiling effects, such as a pressure of about 25 bar. The effluent of each CSTR is sent to the next stage through paths 178 and 180, and to the plug flow type skin pump 172 (if provided) via path 182, which is stored in a dilution gas, such as two gas The air or gas inside is compressed by the compressor 184 to a pressure of about 32 bar, and is sent to the first CSTR through the path 186, and the plug-flow anti-rattan furnace 172, if provided. For an improved embodiment of the present invention, nearly pure oxygen can be delivered to the CS TR or plug flow reactor as an oxidant, but it must be aimed at potential risk factors caused by a large amount of gas intervention in the system. Take appropriate precautions first. For example, the feed of a CSTR may be air, and the feed of a plug flow reactor may be near-pure gas, or a single gas source, such as a gas added with a dilute gas such as carbon dioxide or nitrogen gas. Regardless of the form in which the gas is supplied, the input air / oxygen flow of each CSTR is preferably controlled on the gas output to the CSTR to ensure that it does not run out of gas.

The temperature of the reaction medium in the reaction zone must be adjusted so that almost all of the para-acid generated after the para-xylene gasification through the reaction medium in the reaction zone can remain in the solution ^ In this regard, it is worthwhile It is mentioned that there may be some solid phase #acids in the circulating mother liquor in the form of undissolved penetrating particles (as described above). Therefore, in the case where the temperature of the reaction medium delivered to the inlet of the reaction zone is about 15 ° C, the first stage CSTR 70A can be operated at a temperature of about 8 ° C; the second stage 刖 is about Operate at a temperature of 200 ° C; the third stage operates at a temperature of approximately 2100 ° C, thus achieving a temperature distribution situation sufficient to retain all the generated pairs in the solution. In other words, With the advancement of the reaction process and the formation of more and more #acids, the reaction medium will pass through the CSTR of the next level. This paper size applies to China's national standard < CNS > A4 specification (210X297 mm) (Please read the note $ on the back before filling this page) • WV · Order A6 9 26 9 A7 B7

V. Description of the invention UO, the temperature here is sufficient for the formed acid to remain in the solution. The same pressure β, including those formed in the relevant CSTR, can prevail in each CSTR, but We do not rule out the possibility of operating the reactor system before the pressure is increased from one CSTR to the next CSTR. Β The exhausted air passes from each CSTR 1) A, B, and C through a passageway. The top flow of the condensers 19 0 A, B, and C was eliminated. These condensers are not used for a large amount of boiling and evaporation, and are different from traditional designs, because CSTR operates under a non-boiling mechanism; on the contrary, the role of the condenser is actually to knock back some of the steam or The shape of the water droplets infiltrates the solvent in the exhausted 'air stream. The retention time of the reaction medium in the first C STR is about 30 minutes, which is significantly shorter than the retention time of the conventional production-to-soft acid CSTR mechanism, which is about 30 minutes. Generally speaking, the residence time in each CSTR] 70A, B, C is about 2 minutes per CSTR]. The produced stream extracted from the last CSTR 170C can be directly passed to the product / solvent recovery stage 1 92, but in the case of wanting to obtain a low 4-CBA component of the acid product without excessively burning the solvent, A small plug flow reaction i 7 2 can be used to further reduce the 4-CBA component and other impurity components in the output from the last stage CSTR 1 7 0 C. The volume of the plug-flow reactor used for this purpose can be compact. For example, if the volume of the CSTR is about 100 cubic meters, the volume of the plug-flow reactor 172 is only 10 to 20 cubic meters. Β can be achieved between meters, so, for example, most of the acid obtained during the gasification reaction, which accounts for more than 75%, can be produced in CSTR, and the rest is in the plug flow. Made in a reaction furnace. Product / solvent recovery grade 1 9 2 is roughly similar to those described with reference to Figure 2 and Figure 2 0 Segments 9 4 1 9 6 1 38 and 2 f) G represents the paper size obtained from the paper逋 Use Chinese National Standard (CFS) A4 wash case (2Ϊ0 × 297 mm) (please note the $ item on the face before filling in this page) Order ·

AJY Central Labor Department of the Ministry of Common Carriage and Consumers & Co., Ltd. & Co., Ltd. *. 469269 A7 B7 V. Description of the invention (★) For #acid products, water. Circulation to the mixer / preheater 1 7 4 Select liquid, and net flow of mother liquid. The depleted air flow of the source forced condensers 130, A, B, and C has a relatively high pressure, about .25 to 30 bar, and there are still residual gas, monosulfurized sulfur, and disulfurized sulfur, which are quite large. Nitrogen, solvent, and other organic matter, such as methyl bromide and methyl acetate β, a ventilated air stream 202 is further cooled in the condenser 204, and the main component of the condensate is the solvent. Path 206 is routed to the solvent recovery stage. The cooled ventilated air flow is then brought into contact with the washing liquid in the high-pressure absorber 209 to further remove organic matter. The scrubbed ventilation gas is preheated in the fuel ignition preheater 210, catalytic combustion is performed in the device 2 1 2 and finally passed through the extender 2 1 4 to recover energy β from the extender 214_ and receive The obtained nitrogen-containing gas stream 2] 6 can be further processed by using water or tincture to remove pollutants such as bromine and HBr, and then discharge or use it for other purposes in the production plant, such as chemistry For processing. The ventilation air treatment method can be substantially the same as the method shown in published international patent application WO 96/39595. As an alternative to the embodiment shown in FIG. 4, there is a plug flow in the deployment. In the case of a type reactor, one unit of one unit can be used instead of an inline deployment as shown in the figure. The deployment principle is, for example, an acid product obtained from the overall reaction process. Most of the reactions are carried out in the CSTR at least 75% of the time: the rest are produced in a plug flow reactor. For another alternative, each C ST 卩 can be supplied with nearly pure nitrogen or an aerated gas f as shown in US-A -5 37 U8 3, where the oxygen cross-section is greater than the oxygen in the air Concentration of gas cross, for example, where the oxygen concentration is between 2 3¾ ~ 10 0 55), and a device for establishing a static area in the reaction furnace, so that the gas foam is confined to the circulating liquid, so that The paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm). (Please read the precautions on the back before filling out this page.) 92 69 The Central Ladder of the Ministry of Economic Affairs, Employee Consumer Cooperatives, Benben A7 _ B7___ V. Description of Invention (1) It must enter the top space of the reactor. As shown in US-A-537 1283 (the entire content of the case is Incorporated herein by reference), which can be achieved by baffles located in the area of the interface between the gas and liquid phases, or by using an inert gas hip (such as nitrogen) for the headspace in the furnace Achieved. In this way, Langco can easily confront the Qi component in the Qiqikuang Monitoring to prevent the risk of flammability in the headspace of the reactor. For the embodiment described above, in the case of using one or more plug flow reactors, the orientation is the same. The vertical axis extends horizontally. However, this is not important. The anti-kuang furnace can also adjust the seat to make the liquid flow in a generally vertical direction. Η As shown in Figure 1, Figure 2 and Figure 4. An exemplary embodiment of a product recovery stage is shown in Fig. 5 and explained as follows. The generated stream from the path 2 2 0 leading to the reaction system enters a first agitated crystallization vessel 222A, here Sudden boiling to a lower pressure and temperature conditions, resulting in the local precipitation of acid components in the generated stream, and the generation of water vapor containing components such as solvents and water. This generated stream is then passed through path 2 2 4 The second pseudo-mixing crystallization vessel 222B is suddenly boiled to a lower pressure and temperature, and a pair of g of acid crystals is further precipitated, and the solvent and water vapor are generated. Generally, it is on path 2 The temperature on 2 0 is between 2 I 0 ~ 2 2 () ° C As for the raw material, it can be boiled in the first crystallizer to a temperature of about 195 ° C and a boat force of 9 bar, while in the second crystallizer, it can be boiled to 1 5 1 巴 and 3 bar. status. Although shown in FIG. 5 is a crystalline embodiment of one or two stages, it must be pointed out that either an embodiment with more stages or an embodiment with only a single stage may be used. The resulting stream composed of acid-precipitated crystals that are stored in a solvent-based mother liquor is a rather thin mud plow, for example, which contains the paper paper scale, using the Chinese National Standard (CNS) 8-4 specifications (210X297 mm) Please read the note f on the back before filling in this page) W. -Order · / A7 B7 Five printed by the Central Government Bureau of the Ministry of Economic Affairs and other consumer cooperatives 46 92 69 You) have a solid percentage of resetting bb of about 3.5%. The mud is delivered to one or more hydrocyclones 228 through the pump 2 2 6 (there is only one shown in Figure 5. If more than one is used, it is usually either in parallel or in series ). The thickened mud in the hydrocyclone 228 generates a thickened down stream 230 with a percentage of heavy layers of about 30¾, and an up stream containing a solvent-based mother liquor in which acid particles are suspended. 2 3 2 ^ Downflow into a pressure drop container 2 34, where the pressure of the thickened slurry can be reduced to about 1 bar or lower, and the slurry is sent to the slurry receiving chamber of a rotary vacuum filter 2 36, so the # 酸 晶 卽It can be separated from the mother liquor in large quantities to form a filter cake on the conical filter cloth of the vacuum filter. After the filter cake is removed from the filter cloth, it is transported to a dryer 237 to generate a dry contrast acid crystal. The solvent can be recovered from the crystallization process in different stages. After recovering the water vapor containing the solvent and water from the container 22 2A and B, it is passed through the condensers 238A and B to generate the condensed tritium solvent, which is then cycled through the routes 240, 24, and 244. Mixing stage (see Figure 1, Figure 2, Figure 4). The upstream form of the solvent is recovered from the hydrocyclone, and is recycled through path 232, 2 4 4 β. The subsequent solvent can be recovered from the solvent recovery stage 24 f5. Month: It is recycled through path 248, 2 4 2, 24 4. The structure of the solvent recovery stage 2 4 6 may be a distillation column (not shown), such as an azeotropic distillation column, in which a feed stream composed of a solvent and water from different sources in the production method may be input, The solvent is separated from the water, and a part of the water is passed through a path 2 4 9 to a water phase effluent treatment system (not shown). For example, this feed stream can be obtained from the rapid boiling steam stream obtained from the crystallization vessels 2 2 2 A, B after the heat P recovery steps in the condensers η 8 A, B, and 2 5 2. This ―Steam stream 25G can also contain residual gas and inert gases such as radon, carbonized gas, carbonized gas and other inert gases. This paper is a national standard (CNS) A4 specification (210X297 mm) (please read it first) (Notes on the back write this page)

The sample cooperation between the Ministry of Economic Affairs and the Ministry of Economic Affairs of the People's Republic of China, the seal of cooperation 46 9269 V. Description of the invention (β) In the case where air is used as the oxygen source, β acetate will exist. In between. A solvent / water mixed feed stream consisting of a solvent / water mixed feed obtained by evaporation from a net stream drawn from a mother stream was passed to the distillation column for 255 cycles. The vapor phase components are separated from the top components generated during the distillation, and M is sent to the ventilation gas treatment site through the path 254 (for example, catalytic combustion, energy recovery through a spreader, and wiping treatment). In general, the solvents recovered from the distillation column are quite clean, and can be used for decontamination and washing. So, for example, a part of the solution flow 2 4 8 can be scattered into the tooth diameter 26 0 and used to wash the cake formed on the filter cloth of the rotary vacuum filter 236 if it is deemed necessary. Solution The filter cake formed on the filter cloth can be subjected to a countercurrent rinsing treatment. Although the one shown in Fig. 5 is a rotary type air filter, it must be noted that the solid-liquid phase separation method can be performed by other devices, such as a belt filter. The flushing does not necessarily require the use of a solvent, and water may be used instead. The embodiment shown in FIG. 6 is an example of recovering the solvent in the self-crystallization method. In this example, the energy source is collected by a condensing steam turbine, and the generated stream 300 from the reactor system is subjected to crystallization treatment. As shown in the figure, the crystallization method of the pseudo two-stage mode β in each container 3 02 A and B is performed in the manner described with reference to FIG. 5, and as a result, a step containing components such as steam and solvent vapor is generated. Boiling steam flow. The sudden boiling material from the container 3G2A is passed to a condenser 3 0 4 where heat is transferred and transferred to the turbine feed water fed through the passage 3 (36) to generate a low-pressure water vapor flow in the path 3 0 8 In order to use the β condenser for the production method, the role of the solvent is to knock back the solvent, and because this solvent is completely depleted, the acid content can be reached through the path 3 0 ί). Home Slope (CNS > Α4 Zhuge (210X297 public envy) ton 2- (please note the $ item before filling in this page)

46 92 6 9 V. Description of the invention (ψο) (Please read the note on the back before filling in this page) Agent return path 3 1 0, and finally to the mixer / preheater crosslinked with the reaction sickle, and It is not circulated into the second crystallization container 302B. The solvent-free quenched boil that has condensed passes through the path 3 0 5 to the second crystallization vessel 3 0 2 B, where it is combined with the quenched boil from the vessel and directly passes to a fractionation / refining facility.柱 312。 312. Alternatively, the sudden boiling material from the path 305 can be directly sent to the ventilation unit, as described below. The pressure of the sudden boiling steam from vessel 302 B is usually around 3 bar. «In principle, the deployment of the steam column 312 is to withstand the last crystallization stage from the use of a crystallization stage with one row; however, I do not rule out the possibility of coupling the distillation column to one of the several crystallization stages located upstream of the last stage. The mud from the container 3G2B is sent to the solid particle recovery method indicated by the code 3 1 4 to generate dried acid crystals on the path 3 1 6 and to generate the circulating mother liquor on the path 3 〖8. The ladder is the bottom end product (path 320) generated on Λ Η consumer cooperative Yindongzhu 31 2, and its composition is a solvent containing a small amount of water, and the top end product is generated, of which a larger amount Water and Ruoxian solvent (path 322). The bottom product containing more solvent is returned to the reaction furnace system through path 310, and the top product is processed by a bismuth-steam condensing turbine 324 to recover energy. This turbine 324 can accept the input on the path 326. Water vapor, for example, obtained from Lu Zhi 308, and lower pressure water vapor derived from the top product (path 3 2 2). The air stream composed of organic residue, residual gas, nitrogen, and water vapor forming the top product of the path 32 2 passes through the heat exchanger 328, and a preheated heat treatment is performed by using the ignited heater 330. This air stream Then, a catalytic combustion process is performed in the device 332 to eliminate the pollutants if the insects are soluble. The generated high-pressure, high-temperature airflow on the path 334 (the temperature value after catalytic combustion is about 4 50 SC 犮). The paper size is in accordance with China National Standard & CNS A4 size (210X297 Mm) 1 t 4 6 9 2 6 9 A7 B7 The central standard of the Ministry of Economic Affairs is the printed policy of Zhengong Consumer Cooperative. V. Description of the invention (屮) In the way of the airflow moving to the top of the inlet on path 322, A cooling process is performed in the exchanger 328 to adjust its temperature to a level that is in accordance with the 3, 4 step adjustment of the condensing steam turbine that is turned by the path 336, so as to achieve a temperature of about 12 at the turbine outlet 338. % Wetting. The output air stream of the turbine 338 is subjected to a cooling treatment in the heat exchanger 342, and a part of it can be used as the turbulent flow (path 340) of the distillation column 312. The remaining water component recovered from the turbine 324 can be used for other parts of the production method or used for treatment of discharged water. For example, it can be fed to the condenser 304β as a vortex water feed, as shown in the distillation device shown in FIG. 6 According to a modified embodiment of the invention, all the sudden boiling materials from the first crystallizer 3D2A can be directly advanced into the second crystallizer 302B. As mentioned earlier, the mud obtained during the crystallization process is very thin, which means that the product should be subjected to a concentration treatment with respect to the mother liquid component before solid-liquid separation. The device shown in Fig. 7 is a device for ensuring a concentration level in a crystallization processing method using an integrated crystallization and concentrator device. As shown in FIG. 7, the crystallization / concentration stage is composed of a ventilator baffle (D T B) type crystallizer. In Figure 7, for simplicity and clarity, other parts of the plant, such as solvent dehydration, solid pellet drying, net flow buried equipment, pumps, and control valves are omitted and not shown. The structure principle of this unmarked part is not different from that adopted by the traditional industry. Under pressure, the gas input via path 40ϋ and the hot stream mother liquid transported via path 40 2 are mixed in mixer 4 f) 1 to pre-dissolve the gas and produce a gas-based mother liquor feed 404. At the feed α end of the plug flow reactor 4], feed w 6 containing fresh para-xylene, catalyst and acetic acid solvent was mixed with gas-based mother liquor feed 4 G4, and the reaction was carried out. The heat released by the reaction results in an increase in the temperature of the reaction furnace 4 i 0. This fact, together with the reaction medium (please read the note f on the back before filling this page)-r · Order ·

T

M This paper is in Chinese standard (CNS) A4 size (2 丨 0X297 mm) 1 w 469269 Α7 B7 V. Description of the invention U >) The proper selection of the solvent to paraxylene ratio can ensure the produced The acid can remain in the solution during the reaction. The product of the oven is fed forward through a path 408 to a DTB crystallizer 412 whose pressure and temperature are controlled. As the feed enters the central vent pipe 413, it will boil locally. Since the density of the two-phase flash boiling feed is less than that of the whole mixture, a circulation flow can be established in the crystallizer 412 (if necessary, the circulation flow can be further stimulated by an upwardly-extracting agitator 4 14). Water vapor is released from the liquid surface, and passes through a path 415 to a steam condenser 416, where steam is generated for heating and energy recovery by the method. After the solvent has condensed, most of it rides along with the mother liquor through the path 4 1 8, 4 2 (1 and 4 0 2), but also a small part is guided to the solvent dehydration treatment group through the path 4 2 2 Yuan. A small amount of gas ventilation flow from the condenser 41.6 (the gas to be reacted, plus large vapors and low amplitude volatile organic matter) is input into a ventilation gas treatment method through path 4 2 4. Central Standards Bureau | Ministry of Economics | Engineering Consumption joint # '社 印 箪 (please read the note f and read the second copy of the book)--DTB crystallizer 4 12 is provided with a precipitation area 42 6 to extract roughly no solid The mother liquor of the granular component (which contains some crystals to withdraw particles) is recycled through the path 43. The resulting slurry has a higher mud strength, for example, the particle weight M |: b. The mud strength is about 30%. The crystals extracted from β in the elutriation base 432 in the analysis base 4 3 2 can be washed counter-currently by the cleaning solvent supplied through the path 434. A large amount of solid slurry is advanced through the path 4 3 6 to borrow a single step. Boiling crystallization vessel. 4 3 8 or several crystallizers connected in series, one to one The slurry is cooled and decompressed. The hot water is discharged to the cooling water or the heat is recovered through the condenser 4 4 0. The generated non-discharge residue is passed to the ventilating gas treatment unit through the path 4 4 2, 424, and condenses. The product passes through path 444 to paths 420 and 402. The cooled and decompressed mud is then forwarded to the product separation stage 4 4 6 through path 4 3 5. For example, using a paper scale suitable for China National Standard (CNS) A4 specification (2 丨 0X297 mm) 咄 广 4 6 9 2 6 9 B7 V. Description of the invention (6) Rotary or belt filter or a centrifuge, at or above atmospheric pressure The β-wet solid particle product thus transported under the pressure is recovered via path 448 for a drying process. The secondary mother liquor is recovered from path 4 5 f) from the separation component 4.4 6 and the β is extracted from path 4 5 2 -Children's The mother liquor is cleaned to remove soluble impurities from the process. The net flow frame shown in the figure is taken from the product separation liquid, but it can also be taken from other sources, for example, the primary mother liquid flow 4 3 Ο β from the mother liquid net flow 4 5 2. The product drying flow, solvent dehydration flow and all The solvent recovered from the condensing component of the condensing unit of the crystallizer is even combined with the catalyst. If necessary, it is mixed with the initial circulating mother liquor 4 30 after preheating with a heater 4 5 4. During mixing, all the particles in the primary mother liquor have a tendency to dissolve (a microparticle dissolution container can be provided to provide a residence time for this dissolution). When the temperature of the solvent rises, the remaining undissolved particles tend to enter the solution in the reaction furnace. Printed oxygen by the Central Laboratories of the Ministry of Carriage of the People ’s Republic of China. (Read the note on the back ^ • item and then f this page.) As mentioned earlier, after the reaction, for example, the temperature of a single plug flow reactor The curve can be trimmed as needed, especially because the source is based on the principles of chemistry and chemical engineering, and the constraints that must be faced. For example, in general, the inlet temperature of the reactor can be as low as possible, and R should not be lower than the starting temperature of the reaction. Preferably, the inlet α temperature is equivalent to or very close to the temperature when the acid is separated from the mother liquor. This is because the cooling or heating treatment of the mother liquor is extremely expensive due to the extremely high flow rate involved. Because-the known fact is that the quality of the product is greatly affected by the temperature of the solid-liquid phase separation. From the above considerations, it can be seen that the inlet temperature of the reaction furnace is 1 2 0 ° C ~ 1 8 (TC is It is more suitable, especially at 1 4 (rc ~ 7 (TC). The temperature of the outlet end of an adiabatic reactor without external heating or cooling is related to the temperature of the inlet end of the reactor and the solvent ratio. However, the outlet The temperature at the end is still subject to the following factors: The national standard of this paper (CNS) A4 * t grid (210X297 gong) One call one 469269 付 A7 Β7 The central government of the Ministry of Economy seeks to print for employee consumer cooperatives Explanation of the invention (called) The combustion of solvents and precursors (that is, the combustion of acetic acid and para-xylene as CO / C) must be minimized, so the temperature at the outlet end of the reactor should be below 2 30 ° C, for example To operate at a level of 2 1; once the proper combination of outlet temperature and outlet solvent flow must be used to ensure that the produced #acid can almost retain the gold part in the solution β at the inlet temperature is 16 (TC ~ 1 70 ° C and outlet temperature at 2 1ITC In the following cases, the ratio of the solvent to the precursor that must be possessed by a simple adiabatic reaction must be at least 10Q: 1. This ultra-high solvent ratio is important for the reaction, crystallizer, and product recovery. In terms of equipment and backhaul systems, both the capital and the operating costs are extremely impressive. This high ratio of solvent to precursor can be eliminated by removing a part of the reaction heat in the range between The way in which the reaction system is operated under adiabatic and isothermal conditions is avoided. The heat thus removed can be used to generate a steam stream to recover energy or perform heating functions. It will be possible to achieve an ideal In the case of the temperature of the reaction 垆 exit end, the method of simultaneously removing the reaction heat is shown in Figure 8. In this embodiment, the reactant / solvent / recycling feed 500, 50 2 degree furnace The non-adiabatic / non-isothermal mode operation of the system 510 can be performed by using one or more heat exchange devices 512A, 512B, 5 12C for internal cooling, and within the reaction furnace system, there is a Appropriate coolant, such as via The vortex supplied by the diameter 514 is fed with water or mineral oil, and flows through it. As shown in the figure, the heat exchanger is probed into a row of tubes and the coolant flows to react with the flow through the reaction system. If the medium is co-current, or relatively countercurrent, it circulates in the tube array. If the coolant contains water, the coolant can be removed in the form of a steam flow through path 5 18. Alternatively, the coolant used can be stupid The paper size is applicable to the Chinese national sample rate (P «) Α4 specification (2 丨 0 > < 297 mm) (please read the note $ item $ on the back page first to write this page). Γ- -Demarcation"-A7 B7, 45 9 2 6 9 V. One of the multiple liquid streams used in the description of the invention (UJT) system, for example, can be a para-xylene feed (before or after aeration, and before and after dissolution) circulation Mother liquor, so that the recovered heat can be used, for example, to raise the temperature of a batch or more of the feed to the inlet of the reaction furnace. Number, size and location of tubes, solvent-to-precursor ratio, solvent operating temperature, steam generation temperature Flow mode, then make an appropriate selection is avoided. In the embodiments described below, the cold heading agent can flow co-currently or in a counter-current flow with the reaction coal, but it is more advantageous to use co-current mode. The reaction furnace system shown in Figure +8 can adopt a single plug flow reaction 垆 or two or more plug flow reaction 燫, one or more of the reaction 配置 is arranged in the A heat exchanger as shown previously to adjust the temperature. Although the embodiments of the present invention described above with reference to the drawings use para-xylene as a precursor of para-acid, it must be pointed out that other precursors can also be used instead or used in combination, such as 4-tolualdehyde & 4-benzene Acetic acid beta Example: Experimental verification was performed using a plug flow type reverse furnace system as shown in FIG. 9. In the container D3 02, a quantity of p-toluene β which was stored in an acetic acid / water solution was charged into the container D301, and a quantity of a liquid catalyst which was also stored in an acetic acid / water solution was charged. Air from the A S feed source enters the dripper via valve V2 0 and is simultaneously introduced into D 3 [) 1 and D 3 D 2. The reason for setting the system power is to ensure that the required gas (greater than the amount of para-xylene that is determined based on the stoichiometric principle) actually enters the solution. After the gas is dissolved, 阙 V 2 1 paper scales are used in the Central and South China countries (CNS) Α4 size (210X297 mm)-卩 一 (please read the note $ on the back before filling this page) Order-印 Printed A7 B7 ^ 69269 by the Central Government Bureau of the Ministry of Economic Affairs and Consumer Cooperatives V. Description of the invention (4) 卽 Turn on and the differential pressure (JP) controller DCP will be set to the D301 / D302 and downstream containers Establish a constant pressure between them. After the liquid flow starts to be established later, a fixed pressure difference can determine the residence time of the reactor. After the valves V23 and V25 are opened, two feed vessels D301, D 3 0 2 The cross-connection is conducted, and the valves V27 and V28 are kept open and closed to prevent fluid from flowing through the RC shape of the reaction coil, and the plug-flow reactor that was originally filled with acetic acid. The containers D3Q1, D302, and the reaction pan are immersed in an oil bath In B, the oil bath B can preheat the contents of the containers D301 and D 3 0 2 to the required depreciation temperature. Once D30 1 / D 3 0 2 reaches the fixed temperature, the valve V28 can be opened. Start entering the reaction method to promote flow through the reaction coil into the # off-specification container and the acetic acid The reaction coil is drained into the Off-Spec container OSV. After a preset time, the valve V2 7 can be opened, and then V28 is closed to switch the generated stream from the Duo Coil to In the sample container SV. Β, the generated stream from the reaction coil RC is then switched to the isolation specification container 0SV. At the end of this experiment, all the containers are cooled, and the path is made via the path AV. Ventilate, clean, and discharge the solid and tritium components in the β sample container through the exclusion path D to recover, weigh, and analyze them. The components of the reaction solution separated from the reaction coil are estimated inversely. Table 1 Shown are the concentration values of the medium, Paratolualdehyde (PT0ULD), p-phenylacetic acid (PT0L), and 4 Carbojcybenza: dehyde (4-CBA) obtained in experiments with different reaction retention times. As used In terms of the preparation of small-scale devices, the reaction method is carried out under nearly isothermal conditions, and the temperature is very close to the temperature of the oil bath throughout the entire period. 2 The example shown in 0eC β clearly shows the retention Time alignment In the use of this paper, «Family Standard (CNS) Α4 Specifications < 210 × 2ί > 7 mm) (Please read the note on the back before filling in this page) / Λ. 钟 钟 济 部 中心 # 率Printed by the Industrial and Commercial Co-operative Cooperatives, and printed by the Central Government Standards Bureau. "Printed by Industrial and Cooperative Cooperatives, 41 9269 A7 B7. 5. Description of the invention (β) Effect of qualitative concentration. In terms of a retention time of 4.86 minutes, the conversion rate of p-xylene to the medium in the reaction is 0.5% or less, and when the retention time is 1.28 minutes, the conversion of p-xylene to the reaction medium is The quality single-pass conversion rate is about 16% a. However, it is worth noting that during the tilting reaction mechanism, para-xylene is converted into 4_CBA (a medium that has a tendency to co-spatter with the product's acid). ) Conversion rate is below 1% or 13 ^. Table 1: Plug flow reactor-gasification results. In all the experiments, its composition parameters have remained unchanged, and its weight percentage data values are shown below: solution water 5%, acetic acid 95¾ paraxylene 0.535 ( 2 0 0: 1 solvent ratio) Catalyst Co 632 ppm Μη 632 ppm B r 1 2 6 4 PP b + 2 r 9 6 ppm

Oil bath temperature 210 ° C 11 II Time (min) VA soluble P t 〇1 a 1 π (ppm w / w) Storage solution internal protection pt.ol (ppm w / w; Relay capacity 4 CBA (ppm w / w ) 1 1.28 228 687 76 2 1.78 55 4 11 51 3 2.28 132 312 42 4 2.31 99 192 38 5 3.23 15 82 6 6 4.86 1. 7 27 _ • One &0.1; National Standard (CNS) ) A4 size (210X297mm) -----.------ ['1 -------- 130,-(please note the f item on the HIKSIC side before filling out this page) 4 carp Printed by the Central Ministry of Economic Affairs of the Ministry of Economic Affairs of the People's Republic of China. 9269 _B7_ V. Description of the invention (1 ^) 2 · Crystallization / heat filtration experiments at a high temperature of 2 10 ° C and a sufficient temperature to maintain a liquid phase Under pressure, it was obtained that the weight ratio of the west cents to the ratio of M to the acid (TΛ), 125 ppm of 4-CBA, 175 PPB Pto], and other gasification media were placed in a 5% by weight proportion. A solution consisting of water and acetic acid solvent with a weight ratio of 95¾. This solution is entangled through a pressure reducing valve to enter a pressure and temperature are adjusted to be sufficient to make TA precipitate from the solution. Out of the crystallization vessel. The mud generated in this crystallization vessel Lead to the subsequent crystallization vessel, where the pressure and temperature are reduced to the peripheral conditions, and more TA sinks out. During the experiment, the crystals from the first unitary crystallizer (thermal filter TA) Recovered and analyzed the 4-CBA and ptol components and average particle size (analyzed by -Coulter LS23G laser refraction psd analyzer) ^ Crystals from the downstream container (cold filtration TA) were also recovered The results are shown in Table 2. The thermal filter TA / 4- for the experimental group with different temperature, residence time and stirring speed of the first crystallizer in each of them is shown in Table 2. The CBA composition and the average particle size data value of the particle are for reference only. An analysis for cold filtration TA is also included. From the phase comparison data shown in experiments 7, 8, and 9, it can be seen that hot filtration In terms of TA, the 4-CBA and Ptol components decrease with the filtration temperature from 19finC to 1 48 ° C. This data also shows that the average particle size of the particles increases when the temperature T decreases. Experimental Examples 10 and 11 were performed. In terms of A, when the filtration temperature is reduced from 15 ° C to 126nC, the amplitude of 4-CBA will increase, and the level of Pto] and the average particle size of particles will be reduced. Standard (CNS) A4 specification (210X297 male i) (Please read the note on the back before filling in this page) Order-Final, 469263 A7 B7_ V. Description of the invention (β) From Example 7 to Example 11 In other words, regardless of the structure of the medium or the average particle size of the particles, the ideal first crystallizer temperature is about 150 ° C ± 25 ° C, especially between 140 ° C ~ 170eC. Examples 1 and 2 and 3 show that after the residence time of the first crystallizer was extended from 9 minutes to 18 minutes, it was beneficial to the structure of the medium and the average particle size of the particles. After comparing Examples 14 and 15 with reference to Example 10, it can be seen that after increasing the rotation speed of the first crystallizer mixer from 270 γρβι to 1000 rpiH, there is no significant effect on the average particle size of the particles, but it can reduce the medium Structural. Table 2: Crystallization / Heat Filtration Results In all the experiments, its composition parameters have remained unchanged, and its weight percentage data values are shown below: Solvent ° Water 5¾, Acetic acid 953:

Aromatic ingredients in feed solution ΤΛ 2%, 4-CBA 12'5 PPIB ptol 1.75 ppm

The temperature of the feeding solution 2 1 0 ° C {Please read the notes on the back before filling in this I) Order 11 (min) Isil (rpm) The first crystallization temperature rc ) 4-CBA Ingredient (ppra) ptol, Ingredient (ppm) ill ^ (Micron) 7 12 .1,0013 196 2,360 345 59 8 12 1,000 176 1,04 0 218 114 9 12 1,000 148 670 89 134 10 18 1,500 1Γ ) 1 710 J38 96 11 18 1,500 m 1, 060 117 86 12 • 18 1,000 173 980 150 106 13 9 “000 179 1,140 217 96 14 12 270 152 930 123 139 15 12 500 150 790 106 135 11 12 1,000 148 2,340 ( (Cold filtration) 281 (Cold filtration) 102 *, (Cold filtration) This paper size is applicable to China National Standard (CNS) M specifications (210X297 mm) pcs.

Claims (1)

6 9 2 6 Reference No. 871〇2849 Patent Application A8 B8 C8 Chinese Patent Application Scope Amendment (April 1990) DS Printed by Shellfish Consumer Cooperative of Central Standards Bureau of Ministry of Economic Affairs 6. Scope of Patent Application -... 1 1 The method for preparing S acid is that at the beginning of the reaction, the ratio of the solvent to the precursor is at least 30: 1 or more, and during the reaction, substantially all of the acid deficiency generated during the oxidation reaction can be retained in In the case of a solution, liquid phase oxidation is performed in a reaction zone using a precursor of S-toluic acid and oxygen in a reaction medium containing a precursor of p-phthalic acid and a solvent. The reaction zone includes at least one The agitation tank reactor (CSTR) and at least one tethered reactor in series are characterized in that the oxidation reaction is carried out under the condition that the reaction medium passes through the reaction zone under a continuous plug flow reaction mechanism. 2. The method according to item 1 of the scope of patent application, wherein the oxidation reaction is carried out with substantially all the oxygen dissolved in the reaction medium. 3. The method according to item 2 of the patent application park 'where the reaction medium is generated by combining at least two or more separate liquid phase components, and before these components are combined with each other to form an oxidation medium, at least Ά ..., a part of Yin oxygen is dissolved in one or more of the liquid phase components mentioned above. 4 · The method according to item 2 or 3 of the patent application park, wherein after the completion of the reaction method, oxygen is added to the mother liquor circulating liquid recovered from the reaction medium and dissolved. 5. According to the patent application Fanyuandi! In the method of item 2, the weight ratio of water in the reaction medium at the beginning of the reaction method is between 5% and 30%. This paper size is in accordance with China Gujia Standard (CNS) A4 (21〇 < 297 mm) -i- In 1 ^ 1 I · Ι I -J clothing—i ^^ 1 ^^ 1-I (谙 先Please read the notes on the back of the page and fill in this page again) 46 92 6 9 ABCD 、 Applicable patent scope 6. According to the method of patent application park No. 1 or 2, the temperature of the reaction medium at the beginning of the reaction method is 120 ° C ~ 200 ° c, and the temperature of the reaction medium when it leaves the reaction zone is between 180 " c ~ 250, c D 7. According to the method of patent application No. 1 or 2, the oxidation reaction is D in the presence of a catalytic system including the recording D 8. Method according to item 7 of the scope of the patent application 'where the catalytic system is dissolved in the reaction medium. (Please read the note ^ on the back before filling out this page) " Order Printed by the Consumers' Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs -2-This paper size is applicable to China National Standards (CNS) A4 greetings (210X297 public epidemic)