TW457112B - Process for recovery of hydrogen bromide from alkyl bromide compounds - Google Patents

Abstract

Processes are disclosed for recovery of hydrogen bromide from one or more alkyl bromide compounds by hydrolyzing the alkyl bromide compounds to hydrogen bromide and corresponding alcohols, and simultaneously separating at least the alcoholic products of hydrolysis from aliphatic monocarboxylic acid solvent component. Also disclosed is a process for preparing aromatic carboxylic acids by the exothermic, liquid-phase oxidation of an aromatic feedstock compound wherein the energy produced by the exothermic oxidation is efficiently recovered, and uses of water produced during the preparation of aromatic carboxylic acids are efficiently integrated into the process.

Description

4 57 1 ϊ 2 A7 B7 V. Description of the invention (referred to in the case of the present application, the United States provisional application filed on February 11, 1998 \ C 60. The reference number of the test number is incorporated and completed This is in its right to prioritize and deal with the benefits of the method of physical modification of the bromoalkane J-to deal with the species 1 Yu Shangming hair from the gaseous species of the hydrogen phase of the liquid into bromine, Guan or hot strip liberation of the Ming The water phase is borrowed from the liquid phase, and its acidic land, the carboxylated French fangfangfang is C hydrogen to form the compound to produce bromine, and the recovered product is returned to the assimilation group of the cobromoaryl group, such as the alkylation. The fraction of the acid that forms the carboxylic acid is a family of soluble aromatic acids that can be used to prepare a single-race mono-lipid from carboxyl. From the beginning to the end of the day, it will have the same effect as the alcohol. The acidified carboxylic gas phase aromatic liquid is made by the amount of water, heat and radiation, and can be combined to make the material. The evolution of the entire family of gas, aromatic and thermal effects is released by borrowing and used to return to the French side. Hehua LU / 1 It is widely used to make Λ3 with some things. ------ 装 — (Please read the notes on the back before filling in this page) Orders that are over 00 years old o 'Every 10 years of making the world can be made every year in every acid preparation, making As an example, ο ο the raw material and the quantity of the material are over 100 billion yuan, which is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The use of textiles to make the original material of the film cool V poly pair is used as it is, the container is compatible with the material and gas to the poly bag 0 »备 ί Β Manufacturing services and the family's fragrance is suitable The phthalocyanine is a beta or gaseous chemical compound. It belongs to its gold or heavy gas type. It can be used for multiple purposes or in one. Benzene, methyl, and two doses of chemical gas are used as sources to release high pressure. 1 Promote chemistries to promote ci species, or this paper size is applicable to China National Standards (CNS) A4 (210X297 mm) 457112 A7 Employees of Intellectual Property Bureau of the Ministry of Economic Affairs, Cooperatives and Indus B7 5. Description of the invention (>) Oxidation manufacturing. Use such as liquid phase oxidation gasification Methods for para-xylene and other aromatic compounds Bi is known in the art. For example, US Patent No. 2,833,816 to Saffer shows a method for gasifying an aromatic feed compound to its corresponding aromatic carboxylic acid. The main method of the group carboxylic acid method is to use a specific amount of water in a liquid phase reaction mixture including a low molecular weight monocarboxylic acid such as acetic acid as a part of the reaction solvent. Also present in the gasification reaction are solvents and water is also formed as a result of the gasification reaction. Although various methods can be used to control the temperature of the highly exothermic oxidation reaction, it is usually most convenient to remove the heat by evaporating the solvent during the oxidation reaction, simmering, and boiling. The gaseous dissolution from the gasification reaction usually comprises steam, monocarboxylic acids, their esters, digassing, osmium monoxide and bromine, depending on the aromatic feed compound used, mainly one or more alkanes In the form of methyl bromide, such as methyl bromide. Methyl bromide is toxic. If it is released into the atmosphere, it is believed to cause consumption of atmospheric odor. Therefore, it is important to avoid the release of methyl bromide in the atmosphere. In addition, when compressed air is used as the source of the two gasification, the gaseous eluate contains radon gas and unreacted gas. The evaporated solvent, which is generally a mixture of low molecular weight carboxylic acids, has hitherto been condensed in one or more thorium tower condensation units and condensed back to the anti-thorium mixture. However, due to the presence of water, at least part of the injured condensate is usually directed to a separation device, which is usually a distillation column to separate water from a low molecular weight aliphatic acid solvent, so that the water concentration in the reactor is maintained at a fixed level. The components of the non-condensing gaseous leachate are generally oxidized by vapor phase i,? R—'c (Please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 (210X297) %> 4 5 7 1 1 2 at B7 V. Description of the Invention (^) The unit burns volatile organic by-products and forms environmentally acceptable leachables. The high-pressure exhaust gas contains a large amount of energy. Exhaust gas passes through, for example, an expander or turbine, and to some extent uses some of the energy contained in the exhaust gas, the prior art method does not fully utilize the energy available in this high pressure exhaust gas. In the prior method, the heat of the reaction mixture is removed It is completed by condensing a part of the reaction overhead vapor to produce medium pressure steam. Part of the medium pressure steam is used to recover energy by a steam turbine, and part of it is used to separate water and acetic acid by distillation. In W09 6/39595, International Application No .: PCT / GB96 / 01261 Patent proposes a method for recovering energy from eluent gas derived from the production of osmic acid, which catalyzes the combustion of the eluent gas to vaporize methyl bromide (please (Please read the notes on the back and fill in this page again.) The printing power of employees' cooperatives in the Intellectual Property Bureau of the Ministry of Economic Affairs, the hydrogen extraction of bromine mixed objects and the vaporization of roller C, prevent alcohol in vortex condensate, bromine 02 After the ester-a fluid condenses, you can decompose the 1st gas into the gas, and the 35 acidolyze, such as bromine and osmium gas, 2 into the hydration-or in the middle of the W phase. \ Yes From its neutralization, it is possible to measure the environment 01 in the equipment and other areas, urging the hydrogenation to specialize its energy ring 3, acid, conversion, oxygen, and the amount of bromine agent in the 11th column after passing through the 11th column. Management can be stopped for trial storage. Cases of low profit return or lack of anti-corrosion can be used in the degradation of the ester tower, and the condensate is applied in the same country. B's energy conversion request. Or, it can be applied by touching one's own property and system transfer, and then the production and control amount is the natural reason. ^: The energy bromine that can be solved by the law. Hydrogen. A single amount 1 Hi The degree of hydration and the chemical production of Sinopec contain PA species containing hydrogen and bromine to wash bromine in one gas and the quality of the compound. For the purpose of this paper, Chinese national standards (CNS > A4 specifications ( 2i〇X297 mm ) 457 1 1 2 A7 B7 5 'Invention Description U) (Please read the notes on the back before filling out this page) Acetic acid. Advantageously, in catalytic steaming, use hard, cellular stone or coated with catalytically active substances It is hard, cellular stone or catalyst-filled material coated with catalytically active material. Preferably, the cellular stone is a ceramic honeycomb stone. Importantly, US Patent 5,113, 015 and The 5,235, 102 and W096 / 3 9 5 9 5 patents do not contain references to any possibility of recovering hydrogen bromide from alkyl bromide by hydrolyzing the alkyl bromide to hydrogen bromide and the corresponding alcohol. . However, various natural and synthetic molecular sieve compositions of the past have been found to be useful in many hydrogen conversion applications. It is alkylation, aromatization, dehydrogenation and isomerization. The used sieves are A, X, Y, and MFI crystal structures, as shown in the "Zeolite Structure Type Map", second updated version 1 987, which is sold on behalf of the International Zeolite Association Structure Committee and incorporated here as Reference. The most recent representative is ZSM-5 and AKS borosilicate molecular sieves. Advances in technology development have produced the formation of many synthetic crystalline materials. Crystalline aluminosilicates are the most popular and are used in patent literature and published journals. Printed by the Bayer Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, or by other convenient symbols. Examples of these substances are zeolite A (US Patent No. 2,882,243 to MiUon), zeolite X (US Patent No. 2,882,244 to Milton), zeolite Y (Brecfc US Patent 3,130,007), zeolite ZSM-5 (Argauer et al. US Patent 3,702,886), zeolite ZSM-ll (Chu U.S. Patent 3,709,979), zeolite ZSK-12 (Rosinski et al. US Patent 3,832,449), and the like. Therefore, this technique requires an improved method for the treatment of alkyl bromide, which exotherms when the aromatic feed compound becomes an aromatic carboxylic acid, and the liquid phase is oxidized. The size of this paper is applicable to China National Standard (CNS) A4. 210X 297 mm) 457112 kl B7 Ministry of Economic Affairs Intellectual Property Office HIGHLAND consumer cooperatives printed

V. Description of the invention (^ *) II. 1 Manufactured as a by-product. II. I hope that this improved method should be g. Bromide recovery such as hydrogen bromide II. Bromine, which is a bromine form that can be used in the liquid phase gasification reaction mixture. r ~ ^ Please I first I In addition) Because hydrogen bromide and bromine are likely to produce corrosive reagents 9 Especially read I in the mixture with the condensate, do not need it-a kind of recycled hydrogen bromide straight back II 6 I connection Improved method for recycling to liquid-phase oxidation. Note II Advantageously »This improved combination effectively recovers the exothermic gas in the method for preparing aromatic carboxylic acids by the exothermic reaction of aromatic feed compounds > Fill in this \ Energy of Manufacturing »and the use of water in the preparation of aromatic carboxylic acids has page II effect Integrate into the method. II. The present invention provides this improved method. I. I specifically order the present invention to be a method of collecting argon bromide I by using more than one type of bromide. ≫ Hydrolyzed or bromide-based bromide and corresponding II enzymes> At the same time, at least at the same time, hydrolysis and hydrolysis of fatty monocarboxylic acid solvent components to produce product I. For example, 9 hydrolyze methyl bromide to hydrogen bromide and methanol at the same time. The acetic acid is separated from the hydrolyzed methanol product grade 0 | The method of the present invention includes the high-efficiency separation device in the presence of solid hydrolysis f I to promote the presence of a catalyst substance * The bottle is contained in an aqueous liquid phase countercurrently containing two II oxygen and two oxygen Sulfur oxide vapor S 2 to about 6 strong atoms II aliphatic ac3 early carboxylic acid S with 1 to about 5 sulfonic atoms or more I! Gas flow of compounds »to form a hydrolysate containing alcohol and hydrogen bromide and II In a high-efficiency separation device, aqueous bromine II is separated from a less volatile aliphatic early carboxylic acid 7 by a volatile white than a volatile alcohol. 9 Water-based hydrogen bromide and aliphatic tat * early carboxyl IIIIII This paper size applies to China's national sample rate (CNS > A4 size (210X297 mm) 457 1 1 2 at Β7 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs Description of the invention (fc) ί I acid is contained in the aqueous liquid phase »and the alcohol is taken away from the separation device in the gas stream to be hydrolyzed II and the separation coexists in the separation device. Ⅱ In one state of the invention * 髙 Efficiency separation device For high efficiency, please firstly distill the column * It is preferred to have at least about 30 theoretical plates > and solid state reading. The hydrolysis-promoting catalyst substance is in the form of a steamed column packing. The back I of A I 1 is in another M state of the present invention > solid state water m promotes the catalyst substance. Note that I | includes an essentially hydrogen form with a H F I crystal structure, a crystalline molecular sieve. General matters I | Re {»This solid water A7J m catalyst-promoting substance also includes-^-or more binders. Fill in this package. 0 is better 9 The solid hydrolysis-promoting catalyst substance page used in accordance with the present invention I 1 includes binder substance or matrix substance which contains at least one choice i Includes II Gasification energy t Oxidation junction * Silica >% Stone-alumina, C t-Gasified aluminum False I Fibrous alumina tmm-shaped alumina 9 Ύ-alumina, and / or optional fluorocarbon resins and gas mixtures including gaseous hydrocarbons, nitrogen hydrocarbons, fluorocarbons, fluorine resins, and mixtures thereof. Preferably, silica-silica-gasified aluminum is used. Or II, such as tetrafluoroethylene, a fluorosulfonic resin as a cobalt mixture. Ⅰ Another state is the method according to the invention »wherein the gas stream is the high m tower top of the gasification zone in a continuous process for the preparation of 1 aromatic dicarboxylic acid. flow 9 its I by) in the presence of high temperature and pressure and in the presence of a gaseous catalyst containing heavy metal components and bromine sources t 1 in a solvent containing an aliphatic 0D early carboxylic acid 9 in a non-phase 1 I adjacent position has two Gasizable or fluorenyl ring substituents or oxidizable phenyl compounds corresponding to 1 1 group and fluorenyl ring substituents or having two oxidizable 1 1 > alkyl or m-based ring substituents Or the pair 1 1 of an oxidizable alkyl group and a fluorenyl ring substituent should be gasified using a liquid phase containing a digas. 0 Advantageously, according to the present invention, the oxidized benzoyl compounds are p-xylene and aromatic. Group dicarboxylic acids are terephthalic acids. -8-1 1 1 1 1 1 This paper size applies to Chinese National Standard (CNS) A4 (2 丨 0 X 297 mm) 457112 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (,) 1 1 Another state is the method according to the present invention * wherein the aliphatic monocarboxylic acid 1 1 is acetic acid 9 and the top stream of the white oxidation zone contains two gases, one gaseous sulphur, two 1 1 methane vapor acetate methyl acetate and at least Methyl bromide »And I ask the first one. Methyl esters and methyl bromide both promote the presence of catalytic substances by hydrolysis in the solid state. Read 1 'Hydrolysis to formic acid with acetic acid or hydrogen bromide in contact with aqueous liquid phase Back A 1 [(The present invention is also a method for preparing aromatic acids from the corresponding methyl substituted aromatic compounds Note 1 I continuation method > its m by the high temperature and pressure and in the matter containing heavy gold 靥 components 1 | In the presence of a gasification catalyst derived from bromine source t, a solvent containing a low m aliphatic monocarboxylic acid filled in this VA is used to catalyze liquid phase gasification of a methyl group containing a digas amt, t this page'- -> 1 I method includes 1 1 (a) in the manufacture of aliphatic carboxylic acids containing two gases, one gasification m, two gasification sulphur vapors 2 I to about 6 fluorene atoms and one or more volatility Organic bromide gaseous tritium under the reaction conditions of r in the presence of water X 2 1 to about 6 aliphatic atoms of aliphatic on early carboxylic acid, containing heavy gold rhenium component and bromine to 1 1 獠 and gasification of two gas sources The catalyst liquid is opposite. In the mixture, the methyl 1 I-substituted aromatic compound is vaporized to an aromatic carboxylic acid (b) in the state of solid state hydrolysis to promote 1 Γ in the presence of a mediator 9 which is used in a separation device. Do not decompose within the next m months » In the efficiency separation device, the aqueous liquid orange is contacted with 1 I gas stream countercurrently to form a hydrolysate containing alcohol and hydrogen bromide 9 and in a high-efficiency 1 t separation device, the volatile quotient separates the aqueous hydrogen bromide from 1 1 Non-volatile aliphatic aa Early carboxylic acid I Aqueous desert hydrogen and aliphatic carboxylic acid are contained in quotient 1 [In the aqueous liquid phase extracted from the liquid bottom of the separation device > and the alcohol is removed in the gas stream 1 1 In the separation device y, hydrolysis and separation are performed in the separation device. ί [In the state> The present invention 9 is a kind of carboxylic aromatic acid prepared 1 1 1 1 1 1 This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) 457 1 1 2 B7 Ministry of Economic Affairs Printed by the Intellectual Property Bureau's Consumer Cooperatives on the 5 'Invention Description (J) 1 1 The entanglement method is performed in the presence of a high temperature and m-force and in the presence of a gasification catalyst containing a heavy metal component and an i 1 bromine source in a solvent. 9 In non-adjacent positions 1 1 with two fluorinated radicals or fluorenyl ring substituents or oxidizable radicals and 醯 / —. Please 1 p-m phenyl j or t Can be gasified or aldehyde-based ring corresponding to ik 1 substituent or oxidizable alkyl and m-based ring substituent Cai Cai using a liquid phase gasification containing two back A 1 I 1 oxygen gas This method contains • (a > In the manufacture contains two gases, note 1 I carbon dioxide nitrate m gas Aliphatic monocarboxylic acid with or more matters 1 1 re / species 1 to about 5 large atomic alkyl bromide gaseous high pressure flow inversely filled under conditions I should include in water 2 to about 6 health atom Aliphatic early carboxylic acid page 1 I, a liquid 1 1 containing heavy gold tincture component and a gasification catalyst of bromine source and digas source in the reaction mixture 9 to oxidize the substituted aromatic feed compound to an aromatic I carboxylic acid; (b) In the presence of solid-state hydrolysis-promoting catalyst substances »It is used under the conditions of a separation device ™-not decomposed within one month In a high-efficiency separation device 1 the aqueous liquid phase is counter-currently contacted with air flow to form Hydrolysate containing alcohol and brominated 1 I hydrogen, and a more volatile 1 in a high-efficiency separation device | Separation of aqueous hydrogen bromide and less volatile aliphatic ΗΕ by an alcoholic alcohol »Early carboxylic acid > Waterborne 1 J Hydrogen Bromide and Fat Early carboxylic acids are contained in the aqueous liquid phase I * extracted by the white separation device and the alcohol is removed from the separation device in the gas stream »Hydrolysis and separation are performed in the separation device \ 1 I (C) White oxidation reaction mixture in the liquid phase In the 1 1 anti-m mother liquor separation step (a) produced at the time, an aromatic dicarboxylic acid is formed * to form a crude aromatic 1 I group carboxylic acid; ⑷ in a water-containing purification solvent i at high temperature and m force pure 1 1 J · Hydrating the aromatic carboxylic acid 以 to form a mixture of purified aromatic carboxylic acid and a purified mother liquor 1 1 containing water, and (e) separating the purified aromatic carboxylic acid from the purified mother liquor formed in step (e) and Follow through at least a part of the purified mother liquor to high efficiency 1 -1 0-i 1 1 1 This paper size applies to Chinese National Standard (CNS) A4C (2IOX297 mm) 457 1 1 2 A7 B7 Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by Consumer Cooperatives V. Invention Description (? : 1 1 rate steaming tube column 0 1 1 For a more complete understanding of the present invention 9 Reference should now be made to the detailed 1 1 description in the drawings and the specific embodiments described below by way of example of the present invention. 1 1 1 Simple. _ Say 1 Read [The attached string asks the scope of patents to describe the novel features that characterize the invention [I of 1 0] However, the invention itself and its m points can be referred to the following with BUM m implementation note 1 A brief description of the example is best understood in conjunction with the drawings »where matter 1 I is reloaded Figure 1 is a connection configured to comply with the present invention to provide sufficient backfill for the application and maintain an excessive reaction temperature Simplified schematic diagram of the preferred method of operating the method page V * 1 1 of the present invention and 1 I Figure 2 is used In the presence of solid-state hydrolysis-promoting 6m of media, 9 High efficiency of contacting airflow countercurrently with 1 aqueous liquid phase > Building separation device 1 Simplified schematic diagram 1 Brief description of the invention 1 | In the present invention In the process »Aromatic feed compounds are exothermic) Liquid-phase oxygen 1 I is oxidized to aromatic carboxylic acids in the reaction mixture * and efficiently recovered and used 1 1 The energy generated by this highly exothermic oxidation, such as generating electricity or other forms of I Available and transportable energy. 0 1 1 I The aromatic feedstock used in the process of the present invention is any aromatic compound having a gasifiable substituent that can be oxidized to a carboxyl 1 acid group, such as 9 oxidizable The 1 I substituent may be an alkyl group such as methyl, ethyl, or isopropyl. It may also be a partially oxidized alkyl group such as an alcohol group, an m group, or an aryl group. The aromatic moiety of compound 1 may be a benzene nucleus or it may be a bi- or polycyclic ring such as a t-nucleus. 0 1 I%-Group feedable Π The number of gasifiable substituents on the aromatic moiety of the compound may be equal to 1 1 -1 1-1 1 1 1 This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 4 5 7 112 A7 B7 V. Description of the invention (,. ) The number of positions available on the aromatic portion of the aromatic feed compound, but usually less. Β is preferably from about 4 to about 4, more preferably from 2 or 3. Accordingly, examples of suitable aromatic feed compounds for use in the present invention include toluene, ethylbenzene, m-xylene, p-xylene, 1-methylfluorenyl-4-methylbenzene, and methylolmethyl. 4-methylbenzene, 1,2,4-trimethylbenzene, methylphenidyl-2,4-dimethylbenzene, 1,2,4,5-tetrasylbenzene, alkyl, methylol And fluorenyl, and fluorenyl substituted fluorene compounds, such as 2,6- and 2,7-dimethylnaphthalene, 2-fluorenyl- (5-methylfluorenyl, 2-methylfluorenyl-6-methyl Lai, 2-methyl-B-ethyl Lai, p. Such as naphthalene, acetylated dioxo 6-benzyl diisophthalic acid phthalate to make benzoic acid into the aromatic group. The second reaction is 6-gas 2 'to catalyze the production of naphthalene gold stilbene. The two-phase 6-liquid 2' is used to make acid phthalate differently. The intellectual property of the national family Meifang should be equal to er, f, and gas. The knowledge of this has been 0. For example, the method of exposing his country is 4 US. 93 in 2 and 29. 5 ' _ * 利 5 9 The special acid carboxylic acid I 6 2 into chemical gas naphthyl methylenediate exclusive country $ 寒 于 示 掲 式Good time usually contains I ^ Order-r ^ (Please read the precautions on the back before filling out this page) The Intellectual Property Bureau of the Ministry of Economic Affairs has a number of printed gold printed by the consumer co-operative society as the original agent. 2, 〇〇 of about better than ^ 1 2 0 The material has a mixed manganese-clad medium that is cobalt-coated to gas and argon gold, which belongs to M. 0 or its combination, mixed acid carboxyl It is low in the content of the family acid ester B or the content of the sub-acid, and its W is the sub-quality of the sulfonate. It is compared with the sulfonate. On the contrary, there is a child and a primordial, such as the degree of sulphur, and the temperature should be reversible by inclination of G. Below i P, there are 35 pieces with 2 Θ phase or liquid _ in the amount of 14 and the amount is about _ Type

To P This paper size applies to China's National Standards (CNS) A4 specification (210X297 mm) A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description ('')! Promotion of I 〇 You can also use this Known bromine accelerator compounds, such as 1 1 hydrogen bromide molecular bromine, brominated bromide, etc. 0 also need a source of molecular gas, and 1 1 It is generally air 0 In order for para-xylene to be converted into terephthalic acid, Divide the molecular gas content of the first gas source from 10% molecular gas to oxygen. The empty reading of 1 gas is the preferred molecular gas. In order to avoid the formation of explosive mixtures, I 1 of 1 »gas-containing gas m QUiV fed to the reactor provides 0.5 to a volume% oxygen. Note 1! Exhaust gas-vapor mixture (measured on a solvent-free basis). For example, it is sufficient to note 1 1 (provide a feed rate of 1.5 to 2.8 moles of oxygen-containing oxygen for each m of methyl). Fill in this \ Filling rate. Whose overhead gas-vapor mixture provides this 0 5 to 8% by volume of s_- · 1 I oxygen (measured on a solvent-free basis) 〇! 1 The catalyst used for the gasification step of manufacturing crude to m acid preferably includes cobalt, manganese and bromine components f And may additionally contain known accelerators of this technology. Liquid 1 The phase-to-phase catalyst gasification of the cobalt component of the cobalt component of cobalt (calculated as 1 for elemental cobalt) is suitably a pair per gram mole. Toluene in the range of about 0.2 to about 10 milligrams of original 1 Ion (1 ga). In the liquid phase gasification of the catalyst, the cobalt component of the catalyst is 1 fcb. The ratio (calculated as elemental manganese 1 1) is suitably in the range of about 0.2 to about 10 0 ga cobalt per H1 ga 0 liquid I cobalt and manganese components of the catalyst in the citrus gasification The ratio of middle catalyst to total cobalt and manganese (e.g. 1 elemental cobalt and elemental manganese calculated > the bromine weight ratio of bromine component (e.g. element 1 1 bromine calculated) is appropriately about 毎 B ga total cobalt and manganese about 0 2 to about 1.5 iga 1 [Range < 0 [Each cobalt and iron component can be provided in the solvent of the reactor in any known ionic or combination form of cobalt, manganese, and bromine. 1 For example 1 When dissolving 1 I agent in acetic acid medium, cobalt acid and / or acetic acid, tetraacetic acid tetrahydrate can be used. 1 t -1 3-1 1 1 1 This paper size applies to Chinese National Standard (CNS) A4 specification (210 X 29 " ? Mm) 5 7 t 12 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, 5. Description of invention (\ >) compounds, and / or bromine. H ·].. 0 to 1.5: 1 0 § The ratio of point bromine to total uranium and manganese in milligrams is provided by the appropriate bromine source. This bromine source includes elemental bromine (B Γ 2 > or ionic bromine (eg, ii B r, Na B r, KB r, N Η 4 B r, etc.), or is known to provide bromine at the operating temperature of the gasification Ionic organic bromides (for example, benzyl bromide, mono- and dibromoacetic acid, bromoacetam bromide, tetrabromomethane, ethylene-dibromide, etc.) The total bromine in molecular bromide and ionic bromine is used to determine 0.2: 1.0 to 1.5: 1.0 elemental bromine satisfies the total cobalt and manganese mg tb. The bromine released from the organic bromide at the oxidation operating temperature is easily determined by known analytical methods. In order to oxidize p-xylene to terephthalic acid, the oxidation reaction The minimum force maintained by the reactor is generally the pressure to maintain a large amount of liquid phase of para-xylene and the solvent. When the solvent is an acetic acid-water mixture, the appropriate gauge pressure in the gasification reactor is about 0 kg / cm2 to about 35 kg / cm², and denier is generally in the range of about 10 kg / cm² to about 20 kg / cm². The temperature range in the gasification reactor is usually from about 12 ITC, preferably about 150 ° C, To about 240-C, preferably to about 2 3 fTC ^ in a gasification reactor The solvent residence time is usually about 20 to about 150 minutes and §_ is preferably about 30 to about 120 minutes. The processing conditions for the gasification of para-xylene to terephthalic acid can also be used to meta-xylene gas. Formation of isophthalic acid ^ For the gasification of 2, fi-dimethylnaphthalene to 2,6-dicarboxylic acid, the deterrection ratio of the monocarboxylic acid solvent to 2,6-dimethylnaphthalene is preferably about 2: 1 to about 12: 1, the manganese to cobalt mga ratio is about 5: 1 to about fl.3: 1, bromine to total cobalt to manganese mga ratio is about 0.3: 1 to about 0.8: 1, and total cobalt Manganese, such as,, i crack. Order (please read the precautions on the back before filling in this education) This paper size applies Chinese national standard (〇 Chan) 8 4 specifications (210 father 297 mm) 457 1 1 2 A7 B7 Printed by the Shelley Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (㈠) 1 i Calculated by elemental cobalt and elemental manganese > Based on the weight of the solvent is at least about (κ 4 [丨 heavy 1 i amount% * and oxidation reaction The latent temperature is about 18 5 ° C to about 220 ° C. 0 Acetic acid is the most suitable solvent for the oxidation of 1, 2-6-dimethylcyanide with 1 1. First 1 Reading for liquid-phase oxidation of aromatic feed compounds to aromatic carboxylic acids. 1 The reaction vessel is any reaction vessel used for liquid-phase gasification reactions. These are the opposite 1 1 1 reactors ... Consist of inert materials such as titanium »or with inert materials such as glass or titanium Note! I-type material pads if the gasification reaction is performed at high m. The reactor must be subject to the matter 1 I and t withstand the M force for the oxidation reaction. Composition 〇 Reactor can also be equipped with _ * or filled% more stirrers 〇 Normally »The reactor has a round design and is arranged in a vertical page 1 I. 1 1 As mentioned above, it is generated during liquid phase oxidation The heat is dissipated by evaporating the reaction solvent with 1 1 of the water-white reaction compound present in the reaction mixture. Order by 1 The temperature at which the liquid boils and the force related to the gasification reaction can be controlled by 1 controlling the reaction pressure 0 to about 7 to about 2 1 kg / cm 2 1 anti-pressure 9 anti-blind mixture using acetic acid as a solvent »And the temperature of the steam produced by it 1 1 is about 170 ° C to about 2 10 ° C. Therefore, the high temperature produced by the liquid phase gasification 1 y reaction, high pressure steam is the main source of energy 9 especially L · 1 Large quotient producing 20,000 to 750,000 metric tons of aromatic carboxylic acid per year 1 1 Le equipment considers this amount of vapor 0 1 1 In the method of the invention ί evaporated reaction solvent 9 It is generally low in fractions. T The hydrazone aliphatic carboxylic acid is guided by the water produced during the gasification reaction to a device capable of separating the solvent. 9 Such as a high-efficiency distillation column. The device for separating water and solvent must be It can make the vapor gas at least about 95% in the reaction stream * more preferably about 98% and most preferably at least l -1 5-1 1 1 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 457 112 A7 B7 Printed by Shelley Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of Invention (i 1 I Approx. 99 weight: 1% bb Low-molecular-weight carboxylic acid solvent removal separation. Therefore 1 1 leaves the separation device The gas stream has a very low reaction solvent content * and except for 1 1 the carbon gas 9 nitrogen and gas and any by-products »it is mainly high pressure steaming please 1 first 1 gas. For example, in the anti-fluorescent solvent is a low molecular weight carboxylic acid such as acetic acid When the acid is j, read 1 The vapor entering the separation device contains a mixture of acetic acid and water »where the proportion of acetic acid to the water on the back f I is about 20] to about 3 · 1, and leave the separation device Note that 1 I vapor m is usually less than about 0.5% by weight of acetic acid, more preferably less than about C. 1 Matter 1 I again weight 鼍% of acetic acid. The best is less than about 0.5% by weight The percentage of acetic acid is 0. Although the device used to perform this separation can be any device that can separate water and reaction solvents, page 1 I * The preferred device or method for performing this separation is distillation column 1 I 1 is preferably For high-efficiency M distillation column, what high-efficiency distillation column I can be used. However * the preferred gas distillation column is the one containing rhenium efficiency packing t such as Ko ch I order F 1 e X ip ac etc. S or containing sieve Or bubble cap gate 0, preferably 9 distillation tube 1 column with at least about 30, if theoretical plate number »more preferably at least about 50 theoretical plates 1! Num 0 m distillation tube column must be manufacturable to vaporize the top of the m gas column 95% less in the reaction stream, more preferably about 98%, and M is the best Is at least about 99% by weight than 1j. The separation of the low-molecular-weight carboxylic acid solvent removed is as above »in the top 1 stream * as the low molecular weight DtT of early carboxylic acid to water by acetic acid-generally 1 1 1 about 2 0 1 to about 2 1 0-1 1 is a separation device designed to produce a reaction solvent and water at a high temperature 1 I separation. 0 The separation device is preferably at or below the liquid phase gasification reaction. The working pressure of the exposed force can be used to guide the m gas produced by the liquid phase gasification reaction to the separation 1 I device. 0 For example, a pipeline or other appropriate conduit can be used. In addition, 1 1- 1 6-1 1 i 1 This paper size is in accordance with Chinese National Standard (CNS) A4 (210X29? Mm) 457 1 12 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (1 sr 1 i Μ Separation of split pipe columns Can be directly connected to the reactor vessel for liquid phase gasification reaction 1 i 〇1 1 The general term “molecular sieve” includes a wide variety of natural and synthetic types, please refer to the first TF-containing material. It is usually special Although the crystalline aluminosilicate y is read 1, other crystalline materials are included in the broad definition. C The crystalline aluminosilicate is composed of a four-body network of 1 Si fl 4 and A 1 0 Δ in II. Among them, silicon and aluminum Atom attention i | U is cross-linked by common hydrogen atoms 0 The electricity price of aluminum atoms is balanced by the use of positive ions 1 | re r > For example 9 alkali metal or aging gold cation 0 1 \ Installed here Natural and synthetic zeolite materials have proven to be useful in the past! I Multi-hydrocarbon treatment has catalytic capabilities. Zeolite materials often referred to as molecular sieves are 1 1 Ordered porous crystalline aluminosilicate with finite structure ♦ It has large and small pores connected by 1 channel. All pores and channels of the crystalline material are usually large i order small and uniform * for selective separation Hydrocarbon 0 results * These materials are classified in many cases of this technology 1m into molecular sieves 9 and in addition to selective adhering treatments »1 I for pending catalytic properties. The catalytic properties of these materials are also in— " to a certain degree II subject to molecular size Influence * It can selectively penetrate the crystalline structure * It is expected to be connected to the active catalytic site within the ordered structure of these materials fm 〇I The molecular sieves used in the present invention can be derived from the cation source r 1 under controlled pH > Aluminium gaseous substance Ϊ Gaseous substance 4 and organic sample compound aqueous 1 1 m compound crystallized and m prepared 0 1 IZS M substance production and use mixed The system, which contains aluminate and 1 l of substance and sodium hydride and organic m * such as tetrapropyl m hydroxide and tetrapropyl 1 f bromicide are mixed together under the specified reaction conditions to form crystalline aluminum 1 I silicon Acid salt 〇1 ~ 1 7-1 i 1 This paper size is applicable to China National Standard (CNS) 8 4 specifications (210X297 mm > A7 B7)

V. Description of the invention (1 1 1 In general »The M ear tb of various anti-m substances can be changed to produce the crystal aluminosilicate C of the present invention 1 1 In particular 9 the mole ratio of the initial reactant concentration 1 1 case Represented below; please 1 first 1 anti-m matter is better and best read 1 Si 0 2 / A) 2 〇3 5 ^ A 00 1 0 -1 5 0 4 0-120 back 1 I of it! Κ2〇 + / [Κ · 2〇 ^ + M2 / nPl 0 * 1 -1 .0 0. 2-0. 9 7 0. 2 -0. S I 1 filial 1 Of — / S i 0 2 0 * η 1 " 11 0. 0 2 -2 0 .C Item 3-1 I (Η 2 0/0 Η 1 1 0- 4 0 0 0 1 0 -5 0 0 1 0- 5 0 0 Fill in i where R is organic η and Η are at least— * 1 page with vaporized state η '• w ·· 1 1 cation 9 such as alkali or earth metal cation or oxygen 0 m aluminum content (such as reaction! AJ 2 in the compound Represented by 3) Adjustment * The molar ratio of Si in the final product can be changed to 1 / α1 2 0. 1 can be changed more specifically »The sieve material used in the present invention can be used in water (preferably 1 is steamed or deionized). ) Mixing the base, aluminum vaporized source, and organic sample II compound to prepare the Q addition usually does not qualify »Although the typical step is 1 dissolve m with sodium aluminate in water and then add the sample compound. Generally, gas 1 1 Ί I After adding silicon compound, add it in a strong mixture. * For example, in the Waring ng blender, and the resulting slurry is transferred to a closed crystallization container for an appropriate time. 1 1 1 The crystalline product formed after crystallization can be Filtration, washing with water, drying, and calcining. 1 1 Preparation. Acidic conditions should be avoided. 0 When using alkaline gold m hydride 1 > 0Η / S i 0 shown above. The ground is about 9 to about 13. 5 1 1% of the range in the garden. PH supply. 0 Beneficial reaction% The range of pH is in the range of about 10 to about 11. 0-1 8 ~ 1 1 1 I This paper size applies Chinese national standards (CNS > A4 Specification (2H) X297 mm) 457 1 12 A7 B7 Printed by Hao Gong Consumer Cooperative, Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention () 1 1 Examples of materials for providing silicon oxide used in the present invention include silicon silicate 1 1 I acid pin S tetraalkyl silicate and A e Γ 0 si 1 " 3 8 0, D eg US sa AG Company 1 1 Product 0 Generally speaking, the oxide of 9 m source is sodium aluminate. Please go to II first 1 The cations used for crystalline silicate formation include alkali metals and alkaline earth metals. 1 I is a cation 9 such as sodium potassium lithium calcium and m 〇 Ammonium cations can be used alone or back ft 1 I 1 This combination of gold cations is used. Crystals of Invented Molecular Sieves Important / Ideas 1 Matter 1 Basic conditions i The source of this cation is usually the hydroxide item such as sodium hydride and 1 (for I). If a base such as ethylenediamine is used »A sieve in the form of M can be produced directly 0 Complete this Organic samples used to prepare crystalline aluminosilicic acid include academic aluminum cations or S. 1 1 precursors such as tetraalkylaluminum compounds f to be tetra-n-propyl-m compounds 0J 1 I The available organic samples are four 7E Acrylic compounds. Diamine 9 can be used, such as 1 1 monoamine. 1 In the better description of the typical preparation of the present invention, an appropriate amount of sodium hydroxide 1 is strongly and mildly dissolved in distilled or deionized water 9 and then an organic sample. Addition of 1 〇 Sodium aluminate and then slowly add OH PH adjusted with 1 compatible acid or base such as sulfuric acid to about 10 * 5 + /-0. 0 5 〇1 or M is more preferably 9Can be crystallized from a gas mixture of silicon, aluminum oxide K 1 and a source mixture of an ammonium compound and ethylenediamine »so that the initial reactant Moore tb of water to 1 I ranges from about 1 to about 2 0 * It is preferably about 1 1 to about 10 and more preferably about 4 to about 6, and the crystalline aluminosilicate fraction 1 | 1 bh cases range from about 4 to about 15 0, more preferably from about 5 to about 120 and most preferably 1 1 is from about Γ) to about 80 mol. The mole fcb of ethylenediamine on silicon gas should be higher than about 0.0 ! I Λ is generally lower than about 11, preferably from about 0.01 to about 2.0, and & the best is 1 1 I -1 9-1 1 1 1 This paper size applies Chinese National Standard (CNS) A4 Specifications (21 × 297): Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 4571 1 2 A7 B7 V. Invention Description (d) About 0.02 to 1. Aluminium alkyl compounds, such as tetra-n-propylammonium bromide, have a molar ratio of silicon to gasified silicon ranging from 0 to about]. Or more, generally higher than about (1.005, preferably about Q.G1 to about 0.1, More preferably about 0.01 to about 0.1 and most preferably about 0.002 to about 0. (18. The resulting slurry is transferred to a closed crystallization vessel and typically ranges from about 10 frc to about 250 ° C, preferably about 1 2 5 Ό to about 2 I) 0 ° C, a time sufficient to crystallize at a pressure of at least the vapor pressure of water, which is usually about fi. 2 5 to about 2f) days, generally It is about one to about ten days and preferably about one to about ir days. The crystalline material can be stirred or agitated as in a shaking comb. Preferably, the crystallization temperature is maintained below the decomposition temperature of the organic sample compound. Optimal conditions are about two to five days of crystallization at about 15QO. Samples of the substance can be removed during crystallization to check the degree of crystallization and determine the optimal crystallization time. The formed crystalline material can be separated and recovered by known methods such as filtration and aqueous cleaning. Plutonium can be gently dried at different temperatures for several hours to several days, generally about 50 ° -225 ° C, to form a dry block, which can then be crushed into powder or small particles and extruded, granulated, or prepared Into a form suitable for its intended use. In general, the material prepared after gentle drying contains organic sample compounds and hydrated water in solid blocks, and subsequent activation or calcination steps are required. Generally, the mildly dried product is calcined at a temperature ranging from about 2 fi 0 ° C to about 850 ° C and preferably from about 4 25 ° C to about 600 ° C. The drying temperature or prolonged crystallization time at the end of the end proves to be harmful to the crystalline structure, or it can be completely destroyed. Generally, it is not necessary to raise the calcination temperature to above about G0 ° C to remove organic matter from the crystalline matter that was originally formed. Generally speaking, molecular sieve substances are dried in a powerful ventilated oven at 2 n ° c-20- (Please read the precautions on the back before filling out this page) The X degree of this paper applies the Chinese National Standard (CMS) A4 specification (210X297 mm ) Kl 457112 B7 V. Description of the invention (〇) (Please read the notes on the back before filling in this page) Dry for about 16 hours, and then calcined in the air so that the temperature does not exceed 1 hour) 2 5 ° C Until the temperature reaches about 5 5 (TC. Calcination at this temperature usually lasts about 4 to] (5 hours. A useful molecular sieve of a comparative species according to the present invention is the United States commonly assigned to Marvin R. Klotz Patent 4,268,420, U.S. Patent 4,269,813, U.S. Patent 4,292,457, and the crystalline borosilicate molecular sieves shown in U.S. Patent 4,292,458, all of which are hereby incorporated by reference in their entirety. Alternatively, the crystalline boroborate osmium molecular sieves of the present invention may be borrowed. Crystals from controlled pH, cation sources, boron vapors, silicon oxides, and organic sample compounds described in Muin S. Kaddad US Patent 5,053, U1, which are specifically incorporated by reference in their entirety. An aqueous mixture is prepared. In a broad sense, a crystalline borosilicate suitable for use in accordance with the present invention is a molecular sieve material comprising a composition having the following mole ratio with respect to oxides: 0.9 ± 0.2 Μ 2 „0: Β 2 t ) 3: YS i 0 2: ZH 2 〇, where M is at least one cation with η valence, ΐ is 4 to about 600, and Z is 0 to about 1 fi 0. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A specific example of osmium borosilicate is prepared by a method that includes: U) preparing silicon-containing oxides, boron vapors, metal or alkaline earth metal hydroxides, alkylammonium cations, or alkane A precursor of the ammonium cation, and a mixture with water; and (2) maintaining the mixture under appropriate inverse conditions for the formation of the borosilicate, the inverse conditions comprising about 2 5 ° C to about 3 The reaction temperature within the range of 0 n ° c, at least the water is reacting-2 1-This paper size applies to China National Standard (CNS) A4 (210X297 mm) 4 5 7] 12 A7 B7 Intellectual Property Bureau, Ministry of Economic Affairs Printed by employee consumer cooperatives 1 1 Repeated pressure of temperature and sufficient reaction time for crystallization 1 1 Catalytically active metal m Ion exchange S Impregnation of its combination i or other suitable 1 1 When the contact method t is placed on a crystal gold silicate sieve. After the catalytic activity, the first metal is placed on the aluminosilicate m or borosilicate sieve, J- 刖 t hopes that the metal silicon is read. 1 The acid sieve is in the hydrogen form. Like hydrogen on the back 1 I 1 Sodium oxide * Hydrogen form-general M is manufactured by exchanging one or more salts with m Note 1 1 i which-generally uses nitric acid m, m and dried and calcined as above 0 Ion boxing term 1 I The technique of exchange and immersion is known * As known to those skilled in the art, fill in this book on the catalyzed gold catalyst on a borosilicate sieve > such as platinum > can be individually Page • wi I from about 0.1 1% to about 5% by weight > generally about 0.1% to 1% to about 1% by weight 9 and most preferably 0.1% to D. 5% by weight 〇1 With or without active gold scraping load »The crystalline molecular sieve used in the present invention can be mixed with 1 or combined with each rhenium binder or matrix substance depending on the processing purpose of the graph. 1 crystalline aluminate m sieve and / Or crystalline borosilicate sieves can be used together 1 1 to bind the active or inactive materials of crystalline molecular sieves, synthetic or natural hair 1 I zeolite * and inorganic or organic materials 0 appropriate binders or matrix materials 1 J including silicon Stone-vaporized aluminum, oxide m, vaporized titanium \ vaporized junction, vaporized aluminum k. I mm S hydrated alumina such as borax or kaolin clay S such as gas polymerized 1 Γ t m-based resin or this technology m other known adhesives 01 1 In general, The silicate is incorporated into the matrix material by dissolving the matrix material and the gel 1 to form an η compound, and the solid particles of gold 靥% acid and the matrix material 1 can also be physically blended. In general) the metal silicate 1 1 composition can be granulated or extruded into a usable shape. The crystalline metal silicate containing i I-鼍 can be a number of up to 100% by weight. The catalytic composition may contain about 1 -22-1 1 1 1 This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 gong) 457 1 12 A7 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs B7 V. Description of the invention (≫ 丨) 0.1 to about 100% by weight of a crystalline gold tincture silicate material, and preferably about 10% to about 35% by weight of this material, and the best. It is about 20% by weight to about 80% by weight of the substance. Fluoropolymers are a family of known polymers based on organic fluorochemicals, which include fluorocarbons, chlorofluorocarbons, gas fluorocarbons, gas fluorocarbons, and fluorocarbon resins. For example, see Polymer Technology of nC Hies and JH, Bristion, Chemical Publishing Company, New York, 1979, pp. 357-370, or CAHarper's Handbook on Plastics and Elastomers, M. (Uaw-HU) Company, New York, 195, pp. 1-75 to 1-78. The original, basic fluorosulfonic resin, and a representative of this family, is tetrafluoroethylene (TFE). Other widely known fluoropolymers Bio-resins include, for example, fluorinated ethylene propylene (FEP), ethylene-tetrafluoroethylene copolymer (ETFE), perfluoroalkane gas group (PFA), gas trifluoroethylene (CTFE), ethylene-atom-trifluoroethylene copolymer (E-CTFE), polyvinylidene fluoride (PVF2), and polyvinyl fluoride (PVF). Hydrolysis in the presence of the above-mentioned catalysts is performed by gaseous mixtures under the conditions of temperature and pressure, which are suitable for borrowing. Volatile separation and gasification counter-clockwise water and the low-molecular-weight aliphatic carboxylic acid component of the gasification reaction solvent, the β reaction in high-efficiency separation equipment usually occurs under high pressure, but the danger can be about 1 bar About 30 bar, more preferably in the range of about D bar to about 15 bar < reaction uses about 1 second to about 1000 seconds, compared with It is preferably about 2 seconds to about 5 (] seconds, and more preferably, the surface residence time of about 2 seconds to about 10 seconds is properly completed. In this way, the vapor produced by the liquid phase gasification reaction and the result of oxidation are formed Any by-product gas, any radon gas formed during gasification, such as -2 3-(Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) Α4 specification (210 × 297) (B) 457112 A7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, B7 V. Description of the Invention (0) If air is used as the source of molecular gas, and radon is passed through the separation device to remove most of the reaction solvent, it leaves the separation device The gas usually contains water (M gas), a large amount of gas, nitrogen, any unreacted molecular gas, and the side reaction of gasification reactions such as methyl bromide. Importantly, the gas skeleton leaving the separation device is still under high pressure. Therefore, It is a valuable energy source. Although the exhaust gas from the β separation device can be sent to a device that recovers energy, for example, an expander, it is preferable to firstly guide the draft expander or other device that recovers the most energy. High-pressure exhaust gas removes corrosive and / or by-products from combustion parts. "Although a device for removing combustion-part material from exhaust gas is suitable, for example, a thermal gasifier, the preferred method is to use a catalytic oxidation device in which the exhaust gas is in the air or other molecular gas sources. In the presence of high-temperature and high-pressure radiation, the catalytic substance Cao and the corrosive and combustible by-products in the exhaust gas are catalytically gasified into environmentally compatible substances. This catalytic gasification unit can be reduced or eliminated by gasification. Any residual oxidation reaction solvent present in the gas and its by-products that can be oxidized, such as methyl bromide. However, in the method of the present invention, the separation device used removes most of the reaction solvent from the reaction gas. Due to thallium, the exhaust gas entering the exhaust catalytic oxidation unit has a low-reaction reaction solvent, so the load on the catalytic oxidation unit is small. • Otherwise, the high-reaction solvent on the exhaust catalytic oxidation unit is loaded on the catalytic gasification unit to generate excessive temperatures. Increasing β In addition, the combustion of the reaction solvent is a large economic loss because it is desirable to store and recycle as much of the gasification reaction solvent as possible. Generally, the leachate from the catalytic gasification unit is directed to a scrubber to remove any acid parts, inorganic materials such as bromine and hydrogen bromide. Bromine and hydrogen bromide are formed by the catalytic oxidation of methyl bromide. The gasification catalyst used for the gasification of this exhaust gas can be obtained from -2 4-(Please read the precautions on the back before filling out this page) This paper Αdegree is applicable to China National Standard (CNS) Α4 specification (2 丨 〇 X 297 (Mm) 457 112 A7 B7 Printed by the Anti-Poverty Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

V. Description of the invention (> 1 1 For example, En ge 1 har (i company, ϊ 〇hns 0 DN att, h ey, or apply times 1 1 | No. company 0 1 1 gaseous state?) White catalytic gasification C10 early The high-pressure eluate of the element and the scrubber is better t > please 1 first 1 to lead to the preheater to raise the temperature of the exhaust gas so that any readings present 1 r condensate water is converted to steam 0 leave the preheater to dry > High m airflow guide on the back 1 I of 1 1 crooked expander or other device to recover energy with g high pressure air flow. Note 1 thing 1 device for energy recovery from high mm gas such as > expander) proper item! connection pull Generators and / or other devices that require mechanical work ί Fill in ▲ Install I Shrinkers 〇 Electricity generated by generators can be used to produce aromatic carboxylic acids Page 1 The power supply of the equipment of the I equipment ♦ For example, it can be used as a m shrinking machine to add air 1 1 gas to the liquid phase gasification reaction and any electric energy can be transmitted to the local electricity 1 1 The production of p-xylene feedstock is the most capable of producing at least about 0.3 p-m of acid per pound and more preferably at least about 0.35 watt-hours per pound of sterilization produced in this hairpin. 1 After leaving the expander > Exhaust gas condensation and generated water is used for other treatments in the manufacturing equipment1 This water has a fairly high purity »It contains only a small amount of dissolved 1 L decomposed gas. For example > Condensate can be used as It can be used for refluxing the distillation column of the high-efficiency separation device iv-I used. 0 Condensation of exhaust gas. Water produced can also be used as a solvent for purification steps. Aromatic carboxyl of I 1 〇Therefore, 1 the water formed by the condensation of the reaction m gas can be used as 1 1 recrystallization mm or as a solution for one and more crude carboxylic acids chemical and 1 1 / or physical treatment _ 〇-this purification method Contains water m 1 I solution or slurry of crude aromatic carboxylic acid contacted with hydrogen at high temperature and force in the presence of a hydrogenated catalyst. This method is shown in U.S. Patent No. 3,584,309. -2 5- 1 1 1 I This paper size applies the Chinese national standard (CNS > A4 size (210X297mm) 457 U2 Α7 Β7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of invention) Purification as an example „This purification step is carried out in a fixed catalyst bed at high temperature and M force. Both downstream and upstream reactors can use purified crude phthalic acid dissolved in water or a mixture of water and other polar solvents, such as C r -C 4 aliphatic carboxylic acids. The reactor during purification, and thus the temperature of the terephthalic acid solution, can be in the range of about 10 (TC to about 3 5 trc. Preferably, the temperature is about 2 7 5 ° C to about 30 0 ° C Range. The pressure condition of the reactor depends mainly on the temperature at which the purification process is performed. Because the temperature of the impure terephthalic acid that can dissolve the actual 1 is substantially higher than the normal boiling point of the solvent, the processing pressure needs to be much higher than atmospheric pressure to maintain the aqueous solution. In the liquid phase. Generally, the reactor pressure during hydrogenation can be in the range of about 20 (1 to about 1 S0 (1 pound (psig)) per square inch hour meter, and is usually in the range of about 900 psig to about 1.2 finpsig. The hydrogen partial pressure is generally in the range of about 30 psig to about ZGOpsig. The catalyst used in this purification step contains one or more active hydrogenated metals, such as ruthenium, rhodium, rake or platinum, on a suitable support, such as sulfon or Titanium oxide. A suitable support is living carbon, which is usually derived from coconut coke in the form of particles of 600 square meters per gram to 150 (1 square meter per gram). The load of the metal on the support is suitably about 0.01% by weight to about 2% by weight of house 〇 Preparation of purified aromatic fluorene from fluorene aromatic carboxylic acid Appropriate substances for acids are shown in 511 (1, 61 ^ 3, U.S. Pat. Nos. 5,256,8,7, and 3 (; »111〇6 {^ 1 ', et al. U.S. Pat. Application No. 029,037. After purifying the aromatic carboxylic acid through the reactor, the solution of the aromatic acid in an aqueous solvent is cooled to precipitate to purify the aromatic carboxylic acid. The temperature at which the solution is cooled is -2 0--Binding J " (Please read the notes on the back first and fill in this page) This paper size applies Chinese National Standard (CNS) Α4 size (210 × 297 mm) R 7 〇 A7 B7 Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs ^)! I make most of the purified aromatic carboxylic acid crystallized 0 Crystallized purified η group carboxylic acid 1 1 Use FFJ-compatible solid-liquid separation device to separate from the mother liquor of water parts, such as centrifuge 1 1 or filter 0 Purified aromatic carboxylic acid blocks can be washed with pure water. 9 Dry and send to 1 Please store, pack, and ship. 1 Read 1 Water separation by centrifuge or subtraction. The liquid contains many impurities i. 1 of the product in the reaction. It also contains suspended and dissolved aromatic carboxylic acids. Note 1 in the prior method. This stream is sent to a waste treatment facility. However) In the method of the present invention, the Matter 1 I A further part of this mother liquor can be transported to the water produced during the white chlorination reaction to complete the separation device filled with the gasification reaction solvent. Therefore 9 Impurities »Reaction Intermediate Page 1 I and aromatic carboxylic acid products Return to the oxidation reaction mixture. Impurities enter— * Step oxidation 1 1 9 Intermediate products are converted into usable products 9 and the aromatic carboxylic acid is recycled to solid 1 and recovered. The mother liquor for hydrogenation reaction is recycled for self-oxidation. Reaction 1 It is especially useful when the separation device for separating the solvent and the water is a m-tube column. Return to the recirculating aqueous column of the 1-column column. The liquid is not only used as the reflux of the column. It is also used as 1 | It is an effective way to add the mother liquor from the purification method to the oxidation reaction mixture. Therefore, the method of the present invention provides the elimination of the main waste product stream. Stream to the waste treatment facility 0 Before the mother liquor stream is recirculated to the distillation column, it can be processed to remove any suspended matter if present 1 1 1 For example it can be filtered or centrifuged 9 or it can be passed through a water spin The reactor removes suspended matter by 1 1 before the suspended matter is removed. For example, 9 1 I mother liquor can be cooled to remove dissolution that may contaminate the distillation column. 1 1 1 Figure 1 shows the formation operation. A preferred embodiment of the method of the present invention I Example 11 0 Oxidation reactor m 0 mixed with m 1 1 in the presence of acetic acid and 1 -2 7-1 1 i 1 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 4 5 7 1 1 2 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention) 1 1 Water as a gasification solvent ♦ Cobalt contacts manganese oxide metal and one or more bromide 1 1 as an oxidation promoter 9 such as hydrogen bromide in contact with para-xylene with air. 1 1 The gasification reaction is carried out at a temperature in the range of about 170 ° C to about 2 1 0 ° C7 and at about 7 Please perform a force of 1 to about 21 1 kg / cm 2 in the range of plaque. 0 exothermic gasification Anti-reading im The heat generated by the reactor caused the reactor solution to wander. Evaporated solvent and methyl bromide I 1 to 1 methyl acetate m and other volatile Mi Μ compounds sulphur oxides.> Attention! I air gas t pack Aspirated reaction > and unreacted dioxygen pass through line 12 of item 1 I and then to a high m distillation column with about 4 5 m plate number 20 in the middle of 0 f this k in m »» acetic acid Solvents from the top of the reaction tower are separated from the leachate or the exhaust gas. Page 1 1 〇 Steam the tube pestle so that at least 93% of the acetic acid white top gas is removed. Acetic acid solvent I% The water is fixed to the reactor 10 through the tube 25, and the control agent I is controlled so that the excess reaction solvent is maintained in the oxidation anti-hVM * device. 1 According to the present invention, at least a part of the distillation column 20 has hydrolysis. Promote 1 1 catalyzed m-charged substances »where methyl acetate and methyl bromide are hydrolyzed into formazan and ethyl 1 I m or hydrogen bromide 0 1 j via line 3 8 leaving the top of the high-pressure distillation column column 20 Shao I I acetic acid at about Q-1%, and mainly vapor, but also contains nitrogen, 1 1 sulfide oxide * gas without m > and m compounds such as methanol volatility! 1 〇 来The eluate at the top of the pipe 3 8 is in the catalytic gasification oxidation αα unit 40! The reason is that the volatile organic 1 1 compounds such as methanol and many residual acetic acid are catalytically vaporized in the eluate at the top of the tower. 0 If acetic acid is not effectively gas Reverse 1 1 should be removed from the top of the tower to oxidize it in the early stage of catalytic gasification to generate economic losses I An η The gas leaving the catalytic oxidation unit 40 is led to the pipeline 4 2 〇1 1 -28- 1 1 1 1 paper Standards apply to Chinese national standards (CNS > A4 specification (210X297 mm) 457112 A7 B7 Printed by the Shelley Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (^) 1 1 According to the present invention, t is suitable for catalytic gasification. 〇 Early Yuan's solid gasification catalyst package 1 1 Contains the combustion-promoting metal disposed on the catalyst body 〇 When the oxidation catalyst 1! M am w. Including at least-members include gasification titanium > oxidation junction N gravel gravel-gas please first 1 alumina, a-gasified aluminum, pseudofibrillated alumina, fibrous alumina, read 1 alumina-alumina. Combustion-promoting metals can be used for this technology or--I have been known to be promoted in the presence of molecular gas-* Sulfur oxide becomes carbon oxide gas Note 1 I chemical formula 〇metal ΘΤ is combined Such as gaseous substances, not in the element 1 I and r states. Combustion of gold m may contain more than one type of physically or chemically filled catalytically active metal 0 Appropriate m for the method of the present invention · / Κ Burn-promoting III metal is a transition group element of the Periodic Table (I IIP AC), preferably V II Group I 1 1 Au 鼷 is preferably a precious metal and more preferably at least one member includes oxidation crane, gasification Absolute% gasification tin S vanadium oxide > platinum Λ harrow and ruthenium platinum are preferred due to their ability to maintain a high activity of oxidized m oxidation oxidized m1 added to the combustion of the gasification catalyst used in the present invention promote The percentage of metal fch is a function of the catalyst cost and processing effectiveness. 1 The better traceability of the promoter Jin I. I is the person who obtains the treatment purpose with the lowest catalyst cost. 0 Usually% The combustion promoter 1 l. Gasification catalyst is called ΓΠ Noble component 〇 Compared with 猿 metal ape degree and lower body L · 1 product use to reduce the cost of support and oxidation catalyst 0 The combustion promotion catalyst of the present invention 1 1 f appropriate gold Kg rm Concentration heavy house: l: b in the range of about 0.1 ρ P m to about 15,000 ppm 1 1 > more than about (K 5 P ρ Π) to about 10, 〇 PP Π1, and M for The best result 1 I fruit > more about 1 p ρ η to about 8, 0 0 Op PHI 〇1 1 Β describes many particularly m gasification catalysts 0 Example > United States special 1 Li 3, 37 8. 3 3 4, this note is hereby incorporated by reference in its entirety, describing r! A tenon containing up to about 5% of the catalytically active metal spherical catalyst particles fixed 1-2 9- L- 1 1 1 1 This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 2

A indicates that the media, the five media 3, and the 68 are 9 ο 5 suitable ο 4 body and 6 0 7 SVT; ο Fei, 4 4 5 ， 7 6 ίθ9 _h ¾ο sodium 4, Π Lili Ru The beauty of ruthenium is contained in C. The high pressure of containing B. The main reason is that C. The body of the body is 2 of 4 and the unit of the road is all in. The SSI is very large and it is from the middle to the defense. Ί G Use the feet to warm and predict the temperature. The heat of the RO ° G device 35 reaches the bow ο guides 20 55 to the tube heat. After the heat is added, the step gas is steamed into the exhaust gas,

Approx. Up to CC guide 70 for expansion and expansion, and input energy, 65 machine tubes, removed by CCF, MSJ, air and heat, self-expansion, expansion, condensation, and cold lending. 1 The device should be able to quantify the energy to the machine's air. The pressure is as small as C. The gas is sent to the pipe. 7δ The pipe of the waste road. The power arm of the road is driven to the ground by reference to the equivalent conductance and ground capacity. It can be equipped with a BS system made of gas generators. It can be used in the Ministry of Economic Affairs. It ’s part of it. Compared with 00DP, the machine ’s energy is from PT to this water to 50 channels in C, and 45 buckets of water are divided into 5 units. Cold skull gas forging capacity

Tube. The whole manager's disappointment and disappointment are 510 cold road10. Tube L can control the device. Expansion is inflated to the same level as the lead body of the guide. 2 5 4 4 The tube is condensed from the cold and will be accompanied by the free part to avoid the large or low part. (Please read the precautions on the back before filling This page) Installation. -1fl Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives, the condensate is cold and cold, and it comes in. The C and water 70 state liquid swells into a condensate, opens the cold, and leaves the gas. The pressure of the swell of the gas generator is low, and the 1-column barrel stream distillation is re-evaporated to the pressure leading to 2-9. The bow duct 00 is a water-passing In 90 pipe and the tap is used as water and water 00 column I tube to back to guide 5 ο H Lu Xiao Jing Yi Shui P ο bucket £ Π 来 流 no _ 11 times 丨 the device and the capacity of the container is m The paper size is applicable to China National Standard (CNS) A4 Specifications (210X297 mm) 457 112 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (&7;) Tantalum contains crude terephthalocyanine, water, acetic acid, catalyst metal, intermediate products of gasification reaction and The reaction mixture of the by-products leaves the gasification reactor 10 through the pipeline 1 1 5 and is guided to the container. 12 η, this gasification reaction temperature of the mixture was lowered to crystallize the terephthalic acid dissolved. Container 20 is optionally equipped with an aerator to hold the ore gasification reaction. The gas from the container 120 is guided through a line 125 to a pressure distillation column 20 having about 4 theoretical theoretical plates. The slurry from the container 120 is guided to the container 130 through the pipeline 128, where additional cooling and crystallization of the terephthalic acid occurs. The slurry from the container ΐ 3 (1 enters the separation device 135 through the line 132. The separation device 135 generally contains one or more centrifuges or filters. In the separation device 5, the crude terephthalic acid is self-gasified to react with the mother liquor. Separation. The gasified anti-dip mother liquor leaves the separation device 13 5 and enters the mother liquor tank 140 through the pipeline 1. 3 8. Most of the mother liquor containing catalyst and acetic acid is recycled to the gasification reactor 1 (1. 1. A part of the mother liquor is sent to the stripping device 150 via Ken Road 148, where the acetic acid is removed and guided to the draw vessel 13 via line 152 (U from the bottom of the stripper 150 and sent to the waste treatment through line 154. Self-gasification reaction The crude terephthalic acid separated from the mother liquid is transferred to the P ΐ A paddle bucket 1 1 (1 by conveyor 136, and the water condensed from the top of the tower gas leaving the top of the high pressure distillation column 20 is partially dissolved a laijun Slurry tank Η η 籾 phthalic acid and water slurry are guided through the pipeline i 5 8 hydrogenation reactor 16 In the hydrogenation reactor 160, the relative phthalic acid dissolved in water is at a high temperature, for example, about 2 6 (TC to about 2 9 (TC, and high pressure treated with hydrogen to purify by, for example, reducing the content of 4-carboxybenzaldehyde Phthalic acid from the Θ hydrogenation reactor 1 fi 〇 through the pipeline] β 5 into -3 1- (Please read the precautions on the back before filling this page) This paper rule and applicable Chinese National Standard (CNS) Α4 Specifications (210X297mm) / 1 K " 7 1 1 〇 "'1 ~ Α7 Β7 V. Description of the invention (W) Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperative Printed Device Capacitor Junction Device Holder ttft. tttt. 0 0 points to. Introduce 置 隹 隹 隹 0 0 ο SW 8 Κ 1 win _ Jin. 17 installed acid β Lny, a 丨 a 71 pure 2 road set

Path 1 Tube self-passing β-water 19 and back acid-guided phthalic acid by pure acidification of phthalic acid into pure form C filtered empty true rotation or device core 0 Included often through suspension and dissolution The tube of the liquid mother is mixed with the product and the product, and the product is in the middle of the product. The product is separated from the product and the product is separated from the product. Distilled high to 0 ring height 0Ί 楣 5 and then back to 0, the middle acid phthalate treatment facility will set the physical waste to waste transfer or waste or deoxidize it. The acid step of the step device should be against the noble value of the phthalate. The gas price should be as high as necessary to return to the animal husbandry cycle, and then the material or the column tube, 0, 0, and 0 will be described in more detail. The slightly water is a little bit, the middle product garden 0 2 Da Di Li is in charge of dissolving the water and promoting the state to dissolve the water. The c-shaped bed of Gu Chongduo has a pestle or tube 1 m at 0 in the storage 2. 2 The medium can be distinguished from the medium, the medium GIM 2 can be used as the medium. The medium is ί 2 and the medium 2 is the medium of the low quality. ¾¾ 3 榑 2 The upper plate of the zone 22 There is a medium touch 22, and the pass through the medium is urged to replace the high-quality material in the medium tube with 1 plate. Take 23 lg area sh under R or 21, and the area is filled with 区. When the chemical conformation is completed, or 〇 Saddle 23 or 0, the panic acid ester ethyl bromide and the agent evaporate the 3 Z zone of the steaming place and the C is used to lower the anti-evolutionary gas to two. The equipment should be self-reversing, the 10th carburetor, the oxygen reaction, the gas and the gas, and the gas from the machine, and there is a nitrogen gas, and it should be emptied with the acid. 2 Pestle tube in ο Fluid liquid Ren Ning I Cold Bow-2 of 1 ft Road 21) Pipe warp, ΐΠ gas to steam and touch the material (please read the precautions on the back first) Fill in this page again) Column tube 0 Steam 0 High ground flow is reversed. In this paper scale Chinese National Standard (CNS) A4 (210X 297 mm) 457 1 12 A7 B7 V. Description of the invention (W) A certain bromine is hydrolyzed to methanol and acetic acid or hydrogen bromide. N The less volatile acetic acid and hydrogen bromide maintain a liquid phase. It passes through the lower panel 2 3 and passes through the pipe 2S and is extracted from the column 2Π. Methanol is loaded with other gases and non-condensate through the upper panel 21 and leaves the column 20 through the pipeline 38. The following examples are used to describe the specific embodiments of the present invention shown here. However, the following examples It should not be construed as limiting the scope of the novel invention, because many changes can be made without departing from the spirit of the disclosed invention. As is familiar to those who know bismuth, the _JiL hydrolysis experiment is 2.5 inches in diameter. It is carried out with non-embroidered pin string of G Π British height, which has a gaseous feed preparation system, a reservoir of liquid reflux solution, a combined pump, sample point, steam generation system and the electric heating unit required to maintain appropriate conditions. ^ The column is operated as a trickle bed reactor where the gas It is connected countercurrently with the liquid in the catalyst material bed. The liquid reflux solution is introduced at the top of the column. The heated gaseous feed enters at the bottom of the column. The column is fixed at a temperature of about 3 4 and fixed at 1 8 5 P sig. _Force-operated beta catalyst is tested in the form of 1 G and the extruded product. N I n II f '* x ^ n ^ i ^^ 1 I -I- _- J3.-1 (Please read the Note: Please fill in this again. F) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. % Gas of gas two), 氡 about it and the methyl alcohol and bromomethyl formate's alkane 约为 about the mixture of the mixture --0 gas pipe of the pestle λ intake of 0 Mercury millimeters ο β 7 ο and 32 ° F, and the standard standard of the Irb article is in contact with gas when the material is in the in-phase state, and the surface of the paper is in accordance with the Chinese national standard (CNS) A4 Specifications (210 X 297 mm) 457 1 Ί 2 Α7 Β7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention description (#) ratio. More - for example - Shang: said means for performing the column as a hydrolysis experiment, except that the filling material (stainless steel) catalyst bed using inert substituents member "> substituted catalyst bed. The conversion time was determined using a concentration of water and two types of aqueous acetic acid in a liquid reflux to the column at a residence time of about 20 seconds. In Table 丨, it is proposed that methyl acetate and methyl bromide hydrolyze and convert α to three different reflux liquids. Table L Conversion of methyl acetate and reflux methyl bromide%%% «13.7 24.0 0. 8 1 4.3 2 2 .3 5. Π 2 0. 4 2 4 .3 Real .1 丄 Use hydrogen containing form with MFI crystalline structure, hydrolysis of crystalline aluminosilicate molecular sieve and silica binder to promote the vehicle, as described above A series of hydrolysis experiments. The amount of 1/16 inch extrudate used is selected to provide a surface gas retention time of about 5 seconds to about 57 seconds. The acetic acid concentration in the refluxing liquid was 0.8 wt%. In Table II, the hydrolysis conversion of methyl acetate and methyl bromide with different retention times is proposed. -3 4-This paper size is in accordance with Chinese National Standard (CNS) Α4 · ^ (210 × 297 mm) (Please read the precautions on the back before filling out this page). Packing. 4 ° 457112 A7 B7 V. Description of the invention (^ ) Table ... IL retention time Conversion of methyl acetate Conversion second of methyl bromide%% 5 9 5 16 10 97 2 8 4 0 94 6 9 57 94 8 1 Example-Example 1 Use of hydrogen with MFI crystal structure In the form, the hydrolysis of the crystalline aluminosilicate molecular sieve and silica binder promotes the catalytic substance, and a series of hydrolysis experiments are performed as described above. The scene of the 1 / 16-hour extruded material is selected to provide a surface gas residence time of about 40 seconds to about 57 seconds. The acetic acid concentration in the reflux liquid was 5 wt%. In Table III, the hydrolysis conversion of methyl acetate and methyl bromide with different retention times is proposed. (Please read the notes on the back and then fill out this page) Printed by S-UX Stop Methyl Acetate Conversion by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Conversion of methyl bromide%%% 4 0 84 R8 5 7 78 80 The upper bowl device is equipped with hydrogen containing MFT crystal structure, solid state hydrolysis of crystalline aluminosilicate molecular sieve and silica binder to promote the catalyst substance. The rat was extruded at 1/1 fih to provide a surface gas residence time of about 5 seconds. Water is a reflux liquid. The resulting hydrolysis is converted into 89.2% by weight. The paper size is in accordance with the Chinese National Standard (CNS) A4 (210 X 297 mm) 457 1 1 2 A7 B7 V. Description of the invention (corrected) methyl acetate and 1 5 8% methyl bromide. Fen JJ "_ The upper unit is equipped with a solid substance containing hydrogen in the form of M F I crystal structure, crystalline aluminosilicate molecular sieve and gasified aluminum binder U M S-18) as a catalyst to promote the solid hydrolysis. The web is selected from a 16-hour extrudate to provide a table with a time of about 10 seconds to about 40 seconds and a gas retention time. The reflux liquid was water. In Table IV, it is proposed that the hydrolysis time of methyl acetate and methyl bromide on different tables is different from the table. (Please read the notes on the back before filling this page) Conversion of methyl acetate Xtj m to methyl bromide%%% 10 68 2 7 4 0 9 0 6 9 For the purposes of the present invention > "predominantly" is defined as more than about 50% 〇 "essentially" is defined as sufficient The occurrence frequency or proportion of the measurable effect of the measurable scene effect in combination with the compound or% system is considered to be approximately 25% or higher. m "essentially" is defined as absolute, except that it does not exceed the negligible effect on the macroscopic quality a. The final result of m is small, which is generally about 1%. A spring case has been proposed. A hypothesis is proposed here to better To communicate The to-be-determined quotient of this invention 0 The scope of this invention is determined only by the scope of the attached patented patent park. B. The description of the wood, A. Please; -3 Γ)-This paper size applies to China National Standard (CNS) Α4 specification (2〗 〇297297 mm)

Claims (1)

571 4 '· ABCD 90. 4. 1 »Patent application No. 8S 1 0 1 960" Method for recovering gj d. Hydrogen from alkyl bromide "(revised in April 1990) A Patent application Scope: 1. A method for recovering hydrogen bromide from one or more alkyl bromides by hydrolyzing the alkyl bromide to hydrogen bromide and the corresponding alcohol, while separating at least from the aliphatic monocarboxylic acid solvent Hydrolyzed alcohol production_ (This method includes in a high-efficiency 1 continuous separation device, in the presence of a solid hydrolysis-promoting catalyst substance, in an aqueous liquid phase countercurrently contacting containing oxygen, carbon monoxide, carbon dioxide, steam, 2 to A gas stream of 6 carbon atom aliphatic monocarboxylic acid and one or more alkyl bromide compounds of 1 to 5 carbon atoms to form a hydrolysate containing alcohol and hydrogen bromide, and in a high-efficiency separation unit Separation of aqueous hydrogen bromide and less volatile aliphatic monocarboxylic acid from more volatile alcohols by volatile | Aqueous hydrogen bromide and aliphatic monocarboxylic acid are contained in the aqueous liquid phase, and the alcohol is taken away from the separation device in the gas stream Hydrolysis and separation coexist in a continuous separation device. 2. The method of the first scope of the patent application, wherein the high-efficiency separation device is a high-efficiency distillation column, and the solid hydrolysis-promoting catalyst substance is in the form of a distillation column column filling. 3. The method 1 of the second scope of the patent application The solid-state hydrolysis-promoting catalyst substance contains an essentially hydrogen form having an MF I crystal structure, a crystalline molecular sieve and a binder substance. 4. The method according to item 3 of the patent application, wherein the binder substance contains at least one member selected from the group consisting of oxidized phthalic acid , Zirconia, silica, silica-oxygen This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) ----------- installation -----.- order 1 I --14 ^ (Please read the notes on the back before filling out this page) Printed by the 8th Industrial Cooperative Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 457 1 1 2 Α8 Β8 C8 D8 VI. Patent application scope Aluminium 'α -Alumina, false Fibrous alumina, fibrous alumina, T-alumina, and fluoropolymer resin. 5. The method of claim 3, wherein the binder substance comprises at least one member selected from the group consisting of silica, silica-oxidation Aluminum, fluorocarbon resin, chlorine Fluorocarbon resin 'chlorofluorocarbon resin, and fluorocarbon resin = 6. The method according to item 1 of the scope of patent application, wherein the gas stream is the overhead stream from the high pressure column in the continuous process for the preparation of aromatic dicarboxylic acids, which By having two oxidizable alkyl groups or fluorene at non-adjacent positions in a solvent containing an aliphatic monocarboxylic acid under high temperature and pressure and in the presence of an oxidation catalyst containing a heavy metal-giving component and a bromine source. The corresponding benzene compounds of the alkyl ring substituent or the oxidizable alkyl group and the fluorenyl ring substituent, or the corresponding naphthalenes having two oxidizable alkyl or fluorenyl ring substituents or the oxidizable alkyl group and the fluorenyl ring substituent use Liquid-phase oxidation of dioxygen gas. 7. Method 1 according to item 6 of the scope of patent application, wherein the high-efficiency separation device is a high-efficiency distillation column, and the solid-state hydrolysis-promoting catalyst substance is in the form of a distillation column packing. 8. The method according to item 6 of the application, wherein the benzene compound to be oxidized is p-xylene, the aromatic dicarboxylic acid is terephthalic acid, and the aliphatic monocarboxylic acid is acetic acid. The overhead stream from the oxidation zone contains Dioxygen, carbon monoxide, carbon dioxide, vapor, acetic acid, methyl bromide, and methyl acetate, which are essentially in the form of hydrogen with an MFI crystal structure when they are contacted countercurrently in an aqueous liquid phase, a crystalline molecular sieve and a binder substance The solid-state hydrolysis promotes the hydrolysis of methanol and acetic acid in the presence of catalytic substances. This paper size applies the Chinese National Standard (CNS) A4 specification (2ί〇 × 297 mm) (Please read the precautions before filling in this page) Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs 0 Industrial Consumer Cooperatives A8 B8 C8 D8 457 1 1 2 VI. Application for patent scope 9. The method according to item 8 of the patent scope, wherein the solid hydrolysis-promoting catalyst substance is in the form of a distillation column column, and the molecule is selected from aluminosilicate and borosilicate The acid salt molecular sieve 'and the binder substance include at least one member selected from the group consisting of silica, silica-alumina, and fluoropolymer resin. 10. The method as claimed in item 9 of the patent application, wherein the molecular sieve is an aluminosilicate molecular sieve having a Si / Al ratio of at least 12. 11. A method for continuously preparing aromatic acids from corresponding methyl-substituted aromatic compounds, by using low-carbon aliphatic monomers at high temperatures and pressures and in the presence of oxidation catalysts containing heavy metal components and bromine sources The use of a methyl group containing a dioxygen gas in a solvent of a carboxylic acid catalyzes liquid-phase oxidation. This method includes: (11- a) In the manufacture of dioxygen, carbon monoxide, carbon dioxide, steam, aliphatic monocarboxylic acid, its methyl ester, and Under the reaction conditions of gaseous high-pressure flow of one or more volatile organic bromides, an oxidation catalyst containing water, an aliphatic monocarboxylic acid of 2 to 6 carbon atoms, a heavy metal component and a source of bromine and a source of dioxygen In the liquid-phase reaction mixture, the methyl-substituted aromatic compound is oxidized to an aromatic carboxylic acid: < 1 1-b) in the presence of a solid-state hydrolysis-promoting catalyst substance, which is used for one month under the conditions of a separation device Does not decompose internally • In a high-efficiency separation device, the aqueous liquid phase is counter-currently contacted with the gas stream to form a hydrolysate containing an alcohol and hydrogen bromide, and in a high-efficiency separation device, the aqueous bromine is separated from the more volatile alcohol by volatility. Hydrogen and less volatile aliphatic monobasic acid, water-based hydrogen bromide and aliphatic monocarboxylic acid contained in the self-separation device. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (2 丨 0〆297 mm) ^ Binding I Μ (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperative of the Wisdom and Time Bureau of the Ministry of Economic Affairs 4571 1 2 A8 BS C8 D8 VI. Patent application scope 'And the alcohol is taken away from the separation device in the top stream of the gaseous high pressure column, and the hydrolysis and separation are carried out in the separation device. 12. If the method of the scope of patent application No. 11', wherein the high efficiency separation device is a high efficiency distillation column, It provides the concentration of aliphatic monocarboxylic acid in the overhead stream of the high-pressure column below 1% by weight of the overhead stream. 'The solid-state hydrolysis-promoting catalyst substance is in the form of distillation column column fillings' and the catalyst substance contains a MFI crystal structure Essentially in the form of hydrogen, 'crystalline molecular sieve and binder substance. 13. Method according to item 12 of the patent application', which further comprises a device for directing the top stream of the high pressure tower to recover energy from the top stream of the high pressure tower. 1 4. Method 13 of the scope of patent application 'wherein the device for recovering energy from the second high pressure tower top mixture is an expander. 15. For method 1 of the scope of patent application No. 14 where the expander drives a generator. 16. If applied The method of item 12 of the patent scope further comprises a device for directing the overhead flow of the high pressure column to an apparatus for increasing the energy content of the high pressure column overhead flow by oxidation of alcohol. 17. The method of item 16 of the scope of patent application, wherein the oxidation is in Performed in the presence of a solid oxidation catalyst * which contains at least one member including titanium oxide, zirconia, silica, silica-alumina, alumina, pseudofibrous alumina, and r-alumina, and optionally at least one member includes oxidation Tungsten, oxide scale, tin oxide, vanadium oxide, and metals platinum, palladium and ruthenium. This paper size applies Chinese National Standard (CNS) A4 (210X297 mm) ^^ 1 ^ — »^ 1 I---m I— 1 ^ 11 ^^^ 1 ^^^ 1 ^^^ 1 nn J ·. · I _ _ _ _ (Please read the precautions on the back before filling out this page) Printed by the Consumers' Cooperative of the Wisdom and Time Bureau of the Ministry of Economic Affairs 457 1 12 A8 BS C8 D8 Printed by the Wisdom of the Ministry of Economy's Consumer Cooperatives 6 'Application for patent Fan Yuan 18 The method according to item 16 of the patent application range, wherein the oxidized methyl-substituted aromatic compound is p-xylene, the aromatic dicarboxylic acid is terephthalic acid, and the aliphatic monocarboxylic acid is It is acetic acid, and the overhead stream from the oxidation zone contains dioxygen, carbon monoxide, carbon dioxide, vapor, acetic acid, methyl bromide, and methyl acetate. * When it is contacted countercurrently in an aqueous liquid phase, it contains an MFI crystal structure. In its hydrogen form, solid-state hydrolysis of crystalline molecular sieves and binder substances promotes the hydrolysis of methanol and acetic acid in the presence of catalytic substances. 19. The method according to item 18 of the scope of the patent application, wherein the solid hydrolysis-promoting catalyst substance is in the form of a distillation column column filling, and the molecular screening is from aluminosilicate and borosilicate molecular sieves and binder substances. Contains at least one member selected from the group consisting of silica-silica-alumina, fluoropolymer resin. 20. The method of claim 16 in which the condensate derived from the overhead stream of the high pressure column is used as a solvent for the purification of aromatic carboxylic acids. 21. A method for continuously preparing a dicarboxylic aromatic acid, by using two solvents at non-adjacent positions in a solvent under high temperature and pressure and in the presence of an oxidation catalyst containing a heavy metal component and a source of bromine. Oxidized alkyl or fluorenyl ring substituents or corresponding benzenes of oxidizable alkyl and fluorenyl ring substituents, or those having two oxidizable alkyl or fluorenyl ring substituents or oxidizable alkyl and fluorenyl ring substituents For liquid phase oxidation of naphthalene using a dioxygen-containing gas, this method includes: (21-a) In the manufacture of dioxygen, carbon monoxide, carbon dioxide, steam, aliphatic monocarboxylic acid, and one or more 1 to 5 carbons Atomic ---- 7 ----- Packing ------------ Order ------ 4 (Please read the notes on the back before filling this page) This paper size applies to Chinese national standards (CNS ) A4 size (210X297 mm) 457112 AS B8 C8 D8 6. Application range of patent application: Gaseous high pressure flow of alkyl bromide under the reaction conditions, containing water, aliphatic monocarboxylic acid of 2 to 6 carbon atoms, containing heavy gold In the liquid-phase reaction mixture of the tritium component and the oxidation catalyst of molybdenum source and dioxygen source, Aromatic feed compounds are oxidized to aromatic dicarboxylic acids; (2 1-b) in the presence of solid-state hydrolysis-promoting catalyst substances, which do not decompose within one month of conditions used in a separation device, in a high-efficiency separation device The aqueous liquid phase is counter-currently contacted with the gas stream to form a hydrolysate containing alcohol and hydrogen bromide, and is volatile from the more volatile alcohols in a high-efficiency separation device. The aqueous hydrogen bromide and the less volatile lipids Group monocarboxylic acids, aqueous hydrogen bromide and aliphatic monocarboxylic acids are contained in the aqueous liquid phase extracted from the liquid bottom stream of the separation device, and the alcohol is taken away from the separation device in the gas stream, and the hydrolysis and separation coexist in the separation device. (21-c) forming an aromatic dicarboxylic acid from the reaction mother liquor separation step (21-a) produced when the reaction mixture is oxidized in the liquid phase to form a crude aromatic carboxylic acid; (2 1-d) containing water Purify the crude aromatic carboxylic acid in a purification solvent at high temperature and pressure to form a mixture of the purified aromatic carboxylic acid and a purified mother liquor containing water; and (e) isolate and purify the purified mother liquor formed in step (21-e) Aromatic carboxylic acid and recycled at least one Part of the purified mother liquor to high efficiency distillation column. 22. The method according to item 21 of the patent application, wherein the oxidized substituted aromatic feed is p-xylene, the aromatic dicarboxylic acid is terephthalic acid, and the aliphatic paper size is applicable to China National Standards (CNS) ) A4 size (210X297mm).-(Please read the notes on the back before filling this page) -1 ° Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy ABCD 4 5 7 1 1 2 VI. Application for Patent Scope The carboxylic acid is acetic acid, and the overhead stream from the oxidation zone contains dioxygen, carbon monoxide, carbon dioxide, steam, acetic acid, methyl bromide, and methyl acetate. When it is contacted countercurrently in an aqueous liquid phase, The structure is essentially in the form of hydrogen. In the presence of solid-state hydrolysis of the crystalline molecular sieve and the binder, the catalyst is hydrolyzed to methanol and acetic acid = 23. For the method of the scope of application for patent No. 22, the solid-hydrolysis-catalyzed catalyst is Distillation column column filled form, molecular screening from aluminosilicate and borosilicate molecular sieve, and binder material contains at least one member selected from the group consisting of silica | silica-alumina, fluorine polymerization物 材料。 Resin. 24. The method of claim 23, wherein the molecular sieve is an aluminosilicate molecular sieve having a S i / Λ 丨 ratio of at least 12 and the fluoropolymer resin is at least one member selected from the group consisting of fluorocarbons and chlorofluorocarbons. , Chlorofluorocarbon, fluorocarbon resin. 25. The method of claim 23, wherein the fluoropolymer resin is a polytetrafluoroethylene resin. 26. The method according to item 22 of the patent application, wherein the metal silicate molecular sieve is AMS-I B crystalline borosilicate molecular sieve in the form of hydrogen. 27. The method according to item 21 of the patent application, wherein the high-efficiency separation device It is a high-efficiency distillation column, which provides an aliphatic monocarboxylic acid concentration of 1% by weight in the overhead stream of the high-pressure column and a solid hydrolysis-promoting catalyst substance in the form of a distillation column column. 28. If the method of applying for the scope of the patent No. 21 ', wherein the purification solvent includes the Chinese national standard Xin (CMS) A4 washing grid (210 × 297 mm) applicable from the paper scale ----: ------ pack --- --1 order ^ ------ rolling (please read the precautions on the back before filling out this page) The Ministry of Economy's Intellectual Property is printed by the Bureau ’s Consumer Cooperatives 4 57 A8 B8 C8 D8 Printed by the Consumer Cooperative. 6. Condensate derived from the top stream of the high pressure tower. 29. The method according to item 21 of the patent application scope, wherein the purification of the crude aromatic dicarboxylic acid is performed in the presence of dihydrogen. 30. The method according to item 21 of the patent application, wherein at least most of the purified mother liquor is recycled to the high-efficiency distillation column. 3 1. A method of hydrolyzing one or more alkyl bromides present in a gas stream to hydrogen bromide and corresponding alcohols, and recovering hydrogen bromide in a liquid stream, comprising: (a) providing Catalyst. The separation device is configured to promote the hydrolysis of alkyl bromide of 1 to 5 carbon atoms to hydrogen bromide and the corresponding alcohol; (b) provide oxygen, carbon monoxide, carbon dioxide, gas flow, 2 to 6 An aliphatic monocarboxylic acid of one carbon atom, and a gas stream of one or more carbon atoms of one to five: (c) providing a liquid liquid containing water; (d) passing the liquid stream and the gas stream through a separation device in a countercurrent manner : (E) contact the gas stream with at least a part of the hydrolysis catalyst: and the alkyl bromide coexisting in the separation device is hydrolyzed or hydrogen bromide and alkanol, and hydrogen bromide and aliphatic monocarboxylic acid are separated into a liquid stream in. Μ " 5 ^ ： — 'TJ -..... (Please read the precautions of back rain before filling this page) This paper size is applicable to China National Standard (CNS) A4 (21 〇X 297 mm) )