TW200526568A - Anthracene and other polycyclic aromatics as activators in the oxidation of aromatic hydrocarbons - Google Patents

Abstract

The present invention relates to the liquid phase oxidation of aromatic hydrocarbons in the presence of at least one heavy metal oxidation catalyst and bromine, which is activated by at least one of anthracene or another polycyclic aromatic compound to produce aromatic carboxylic acid.

Description

200526568 IX. Description of the Invention: This application is requesting US Provisional Application No. 60 / 530,759 (filed on December 18, 2003) and US Provisional Application No. 60 / 530,752 (filed on December 18, 2003) The benefits are fully incorporated here for reference 5 purposes. [Yun ^ Ming Hu Jin's ^ control ^ Xuanyuan member domain ^] The present invention relates to the presence of at least one heavy metal oxidation catalyst and bromine (which is activated by onion or another polycyclic aromatic compound) Aromatic hydrocarbons are oxidized in the liquid phase to produce aromatic carboxylic acids. The present invention includes pseudocumene (PSC) (1,2,4-trimethylbenzene) liquid phase oxidation in the presence of a catalyst comprising a polyvalent catalyst, a bromine source, and a polycyclic aromatic hydrocarbon to produce a trimellitate . The present invention relates to the liquid-phase oxidation of PSC to produce TMLA in the presence of a polyvalent metal oxidation catalyst, a molybdenum, and a polycyclic aromatic smoke catalyst selected from the group consisting of anthracene, naphthalene, tetracene, and the like. Trimellitic acid can be dehydrated to produce 1S trimellitic acid (TMA). TMA and TMLA are commercially valuable as raw materials for the manufacture of polyacetic acid materials. Trimellitic acid brewing system is used as a plasticizer for polyethylene gas, especially for the insulation of high-performance electric wires and coils. Therefore, it has the main characteristics of temperature stability and low volatility. Trimellitic acid is a resin used for deposition and powder coatings, and as a binder for glass fibers, sand, and other materials. Trimellitic anhydride is used as a curing agent for vinyl flooring and as a curing agent for epoxy resins. Also used as a synthetic surface coating chemical, adhesive polymer, dye printing inks, pharmaceuticals and soil chemistry intermediates. Zikoukou L 3 Prior Art 3 200526568 BACKGROUND OF THE INVENTION Aromatic carboxylic acids such as benzene dicarboxylic acid and naphthalenedicarboxylic acid are of commercial value as a polyester material used in the manufacture of fibers, films, resins, and many other petrochemical compounds. raw material. U.S. Patent No. 2,833,816 (incorporated herein by 5 for McCaw) discloses the use of a catalyst with cobalt and manganese components to oxidize xylene in the liquid phase to the corresponding benzenedicarboxylic acid in the presence of bromine. As described in U.S. Patent No. 5,103,933 (herein incorporated by reference in its entirety), the liquid phase oxidation of difluorenylnaphthalene to naphthalenedicarboxylic acid can also occur in the presence of bromine and catalysts with cobalt and manganese components carry out. Typically, aromatic carboxylic acids are purified in subsequent processes, for example, as described in 10 U.S. Patent No. 3,584,039, U.S. Patent No. 4,892,972, and U.S. Patent No. 5,362,908. The liquid-phase oxidation of aromatic hydrocarbons to aromatic carboxylic acids is performed using a reaction mixture containing aromatic hydrocarbons and a solvent. Ci-c8 monocarboxylic acids, such as acetic acid, benzoic acid, or a mixture with water are typically included. As used herein, "aromatic hydrocarbons, preferably 15" means molecules consisting mainly of carbon and hydrogen atoms and having one or more aromatic rings, especially dimethylbenzene, trimethylbenzyl, and Dimethylnaphthalene. Aromatic hydrocarbons suitable for liquid phase oxidation to produce aromatic carboxylic acids generally include aromatic hydrocarbons having at least one substituent that can be oxidized to a carboxylic acid group. As used herein, "aromatic carboxylic acid" Preferably, it means an aromatic hydrocarbon having at least one carboxyl group. 20 A bromine promoter and a catalyst are added to the reaction mixture, which reacts in the presence of a gasifier gas. Typically, the catalyst contains at least one suitable heavy metal group. Suitable heavy metals include heavy metals having an atomic weight in the range of about 23 to about 178. Examples include cobalt, manganese, vanadium, molybdenum, nickel, zirconium, hafnium, hafnium, or lanthanide metals such as hafnium. Suitable types of these metals include For example, ethyl 200526568 acid salts, hydroxides, and carbonates. Using bromine to improve the conversion of aromatic carboxylic acids by liquid-phase oxidation. USSR Patent No. 239936 (I. V. Zakharov) discloses a In acetic acid solution, Catalyst-cobalt salt and dibromide onion, in the presence of 90 ° 11 (rc < 5 temperature, a method of alkyl-aromatic hydrocarbons and molecular oxygen liquid phase oxidation, wherein, in order to strengthen this method, 1- The addition of a manganese salt at a concentration of 3% of the cobalt salt concentration is introduced into the reaction mixture. The amount of aromatic ferulic acid is generally determined by the concentration of intermediate products found in the aromatic ferulic acid product as impurities. These impurities The type and concentration are changed according to the type and concentration of the catalyst and promoter used and the specific aromatic carboxylic acid product desired. The presence of these impurities will be disturbed by the use of tritium products and make them Some purposes are less desirable. For example, when terephthalic acid is used in a direct condensation process for the manufacture of polyesters, impurities in terephthalic acid can cause unwanted coloration of the polymer and act as a chain terminator. 15 & Discovery and others? Oxidation of ring silk fibrillation compounds to aromatic weuric acid, even when added in very small amounts. This activation is to increase oxygen absorption, increase temperature, lower intermediates and shorter Reflected by reaction time and higher yields of major products Adding en, naphthalene, and other polycyclic aromatic hydrocarbons to the aromatic aromatic compounds (such as toluene_methylbenzene and dimethyl) caused unpredictable oxidation "and ,,,, and page activation '# Promote the production of aromatic acids such as p-dicarboxylic acid (τα), isophthalic acid 1 (IPA), p-biphenyl gt (TMLA), and naphthalenedicarboxylic acid (Nda). Higher oxidation activity (Catalyzed by Co, Mn and Br) Intermediates and by-products that will cause low P content, lower catalyst cost, and reduce the corrosion and emission caused by Br by 200526568. Minimal amount of shallots and others * Group hydrocarbons are necessary for this activation. Use onion or another polycyclic aromatic: as an activator, it can be converted into the desired aromatic wei acid by making it obtain the starting aromatic smoke with less catalyst metal. Reduce catalyst costs. For example, the use of less cobalt can result in significant cost savings in this method. Polycyclic aromatic compounds m such as, 'i) Activated aromatic hydrocarbons to be oxidized to aromatic acetic acid will cause a significant reduction in catalyst concentration, which will significantly reduce the use of catalysts, especially Ruogu (the most expensive catalyst in its catalyst package). When the content of component) can be reduced. The ability to use fewer catalysts is an unexpected advantage, which can provide a cost saving and more economical method. This method in which the recovery and recycling of expensive catalyst components (such as ' cobalt) is difficult or impossible provides special cost savings. / Dioxidant oxidation to aromatic carboxylic acid allows the oxidation method to be carried out at a lower temperature, which means that less energy is used for this method. This 15 can also be mentioned, the cost is saved, and in addition, using less energy is desirable from an environmental point of view. The liquid phase oxidation of / aromatic hydrocarbons forms another difficulty encountered by aromatic reduction and aromatic combustion. The liquid-phase oxidation reaction typically causes at least 1% and 2% aromatic hydrocarbons to burn. We found that the use of polycyclic aromatic cigarettes as a 20 promotes the production of aromatic slow acids in muscle addition products without adversely increasing the combustion of solvents and hydrocarbons. [韵 ^ 明 内容 ^] Summary of the Invention _ A method for oxidizing aromatic hydrocarbons from a source of molecular oxygen in the presence of a catalyst system containing at least one suitable 200526568 heavy metal, desert source, and at least-polycyclic aromatic hydrocarbons under liquid phase conditions. The present invention includes a pseudo-alkene A method for liquid-phase oxidation to trimellitic acid, the method comprising oxidizing 5 pseudocumene in the presence of a catalyst comprising at least one suitable heavy metal, bromine source, and at least-polycyclic aromatic hydrocarbons. -A catalyst system for producing aromatic rhenium by liquid-phase oxidation of aromatic hydrocarbons, the catalyst system comprising: a) at least one heavy metal oxidation catalyst; b) a bromine source; and 10 c) a polycyclic aromatic hydrocarbon. The present invention also relates to a method for liquid-phase oxidation of pseudocumene to trimellitic acid, wherein the catalyst contains at least one suitable heavy metal, bromine source, and stilbene. The present invention further relates to a method of about 5 (rc to About 2 Method for oxidizing pseudocumene liquid phase to trimellitic acid in a catalyst system at a temperature in the range of 50 ° C to 15 'This catalyst system comprises at least one suitable heavy metal, a bromine source, and at least one preferably selected from the group consisting of onion, naphthalene, and Polycyclic aromatic hydrocarbons of tetrabenzene and mixtures thereof. In the catalyst system of the present invention, the polycyclic aromatic hydrocarbons may be onions, naphthalenes, and tetrabenzyl 'and their mixtures. Others of polycyclic aromatic hydrocarbons One source may be a heavier byproduct stream derived from petroleum refining containing 20 polycyclic aromatic hydrocarbons. Heavy metals include cobalt and one or more metals selected from the group consisting of manganese, hafnium, zirconium, titanium, and metals, and are It is present in an amount ranging from about 100 ppmw to about 6,000 ppniw. Typically, the atomic ratio of elemental bromine to heavy metals ranges from about 0.1: 1 to about 4: 1 · ', for example, about 0.2 ·· 1 to about 2 : 1; for example, from about 0.3: 1 to about 1: 1. Polycyclic 200526568 aromatic hydrocarbons include onion, naphthalene, or tetracene, alone or mixtures thereof. One embodiment of the present invention relates to a compound containing C! -In the reaction solvent of C 8 monocarboxylic acid, under the condition of liquid phase, at a temperature ranging from about 120 ° c to about 250 ° c, using an oxidant gas A method for oxidizing pseudocumene, the method comprising oxidizing pseudocumene in the presence of a catalyst comprising at least one suitable heavy metal, bromine source, and one or more polycyclic aromatic smoke. The desert source may include one or more selected from Br2, HBr, NaBr, KBr, NH4Br, benzyl bromide, bromoacetic acid, dibromoacetic acid, tetrabromomethane, dibromoethane, and bromoethenyl bromide. 10 All the bromine added can come from a single desert source, For example, ionic desert sources (HBr, NaBr, NH4Br, etc.) or mixed types derived from bromine, for example, organic bromides, such as benzyl bromide, tetrabromomethane, etc. Polycyclic aromatic hydrocarbons preferably include onions , Naphthalene, or tetracene, or mixtures thereof, and allium is more preferred. 15 [Embodiment] Description of the preferred embodiment The present invention relates to the use of onion or another polycyclic aromatic hydrocarbon as a catalyst activator in a method for oxidizing an alkyl aromatic compound using cobalt. In particular, paraxylene (PX) is changed to terephthalic acid (TA), and then purified to produce purified terephthalic acid (PTA), m-xylene (MX) is changed to isophthalic acid (IPA), and false Cumene (1,2,4-trimethylbenzene) becomes trimellitic acid (TMLA), and 2,6-dimethylnaphthalene (2,6-DMN) becomes 2,6-naphthalenedicarboxylic acid (NDA) ) 〇 The active booster provided by onion and similar compounds can be used in different ways depending on the product line. 10 200526568 The present invention includes the oxidation of pseudocumene (PSC) with molecular oxygen to trimellitic acid in the presence of a catalyst system containing a heavy metal oxidation catalyst, a bromine source, and a polycyclic aromatic hydrocarbon activator under liquid phase conditions. TMLA). When lower levels of cobalt are used in the catalyst system, adding onion or another polycyclic aromatic hydrocarbon to the starting catalyst 5 or continuously (ie, to the tailout catalyst) can convert pseudocumene to trimellitene Acid with low levels of undesired methyl diacid by-products. The activation of onion is more significant when the catalyst is continuously added to the finishing catalyst. In one embodiment, the ' catalyst system includes an initiating-fierce-titanium-catalyst and 10 shallots. In another embodiment, the catalyst system includes a decoration catalyst, and an onion catalyst. In another embodiment, the catalyst system includes a fault-recording clock and a catalyst. The present invention also provides a reaction solvent 15 containing crcs monofluoric acid under a liquid phase condition in a range of about 50 to about 250 ° C (for example, about 100 to about 250 ° C, for example, about 100t: To about 200. (:, for example, about 1200c to about 250 ° C, for example, a method of oxidizing aromatic smoke with an oxidant gas to form aromatic weilk acid at a temperature of about 12 ° C to about 21.0 ° C. The use of shallots or other polycyclic furnaces enables oxidation at lower temperatures, if desired. 20 The method comprises the oxidation of aromatics in the presence of a catalyst comprising at least one suitable heavy metal, bromine and one or more polycyclic aromatic hydrocarbons. Family. Heavy metals may include one or more secondary metals selected from the group consisting of fibrous, hafnium, tungsten, titanium, and metals. The heavy metals are preferably present in an amount ranging from about 100 ppmw to about 6000 ppmw, for example, from about 500 ppmw to About 3000 ppmw. 200526568 Oxidation is performed at a pressure ranging from about 1 to about 40 kg / cm2 (about 15 psig to about 569 psig), for example, about 90 pSig to about 450 psig, for example, about 90 psig to about 400 psig. Oxidation of DMN to NDA is performed at a pressure of about 300 to about 450 psig. It is about 350 to about 400 psig. 5 Aromatic hydrocarbons preferably include p-xylene, fluorenyl-xylene, pseudocumene, and dimethylnaphthalene. Polycyclic aromatic hydrocarbons preferably include onion, naphthalene, Pentacene, and mixtures thereof, and onions are better. In some embodiments, the use of onions as an activator can reduce catalyst requirements by up to about 75%, so that less heavy metals can be used in the catalyst. 10 The invention provides One for use in a range of about 50 ° C to about 250 ° C (eg, about 100 ° C to about 250 ° C, for example, about 150 ° C to about 200 ° C, for example, about 120 ° C to about 220 ° C For example, a catalyst system for oxidizing aromatic hydrocarbons in the liquid phase to form aromatic weiric acid at a temperature of about 170 ° C to about 210 ° C, for example, about 170 ° C to about 200 ° C. 15 In one embodiment of the present invention, Among them, pseudocumene is oxidized to form trimellitic acid, and the temperature is about 170 ° c at the beginning of oxidation, and the reaction temperature is increased to about 210-220 C. The oxidation of pseudocumene is typically based on A pressure of about 90 psig to about 400 psig, for example, about 90 psig to about 300 psig, for example, about 100 pSig 20 to about 29 0 psig, for example, about 105 psig to about 280 psig. The amount of polycyclic compound used in the catalyst system can be about 5 ppm to about 10,000 ppm, for example, about 5 ppm to about 5,000, for example, about 5 ppm to about 1000 ppm, for example, about 5 ppm to about 200 ppm. The catalyst system contains at least one suitable heavy metal, bromine source, and one or more polycyclic aromatic hydrocarbons. Preferably, heavy metals and shallots or other polycyclic aromatic hydrocarbons are present in a solvent containing ^-(: 8 monocarboxylic acid. The heavy metals preferably include cobalt and one or more selected from manganese, hafnium, zirconium, titanium and Rhenium is a minor metal, and is preferably present in an amount ranging from about 100 ppmw to about 6,000 ppmw. Preferably, the atomic ratio of 5-element bromine to heavy metal ranges from about 0.1: 1 to about 4: 1, more preferably about 0.3: 1 to about 1: 1. Polycyclic aromatic hydrocarbons preferably include shallot, naphthalene, tetracene, or mixtures thereof. Another source of polycyclic aromatic hydrocarbons may be polycyclic aromatic hydrocarbons from petroleum refining. The by-product stream of smoke. In the present invention, the oxidation of aromatic hydrocarbons to aromatic carboxylic acids is performed at a pressure in the range of about 1 to about 10 gW, for example, about 5 to about 40 kg / cm2, 2 for example, about 14 to about 32 kgW, for example, 'about 22 to about μ kg / cm2. Aromatic hydrocarbons include alkyl aromatic hydrocarbons', preferably one to four methyl groups, such as' para-xylene, m-xylene, Cumin, and dimethyl naphthalene, but not limited to this. Polycyclic aromatic hydrocarbons are selected from the group consisting of onion, Qin, tetracene, and mixtures of 15. Polycyclic aromatic hydrocarbons are another It can be a by-product stream containing polycyclic aromatic hydrocarbons from petroleum refining. The present invention relates to a method for oxidizing aromatic amidine molecules in the presence of a catalyst activated by green onion under liquid phase conditions. The example catalyzes rhenium is a cobalt-manganese-bromine catalyst activated by En, which also contains another 20 metal additives. This month also provides a liquid phase for aromatic liquids at a temperature of about 1Q Goc to about A catalyst system for oxidizing to form an aromatic acid. This system contains at least one suitable heavy metal, bromine source, and one or more sulphur compounds.> The odor source is preferably selected from Bf2, HBr, NaBr, KBr, NH4Br , 13 200526568 benzyl bromide, bromoacetic acid, dibromoacetic acid, tetrabromomethane, dibromoethane and ethenyl desert compounds. Preferably, heavy metals, odorous sources and polycyclic aromatic hydrocarbons Is present in a solvent containing (^ -0: 8 monocarboxylic acid. Preferably, the heavy metal comprises a metal and one or more metals selected from the group consisting of titanium, metal, titanium, titanium and a secondary metal, and is preferably Rhenium is present in the range of 100 ppmw to about 6000 ppmw. Preferably, elemental bromine The atomic ratio to heavy metals ranges from about 0.1: 1 to about 4: 1, for example, about 0.2: 1 to about 2: 1, for example, about 0.3: 1 to about 1: 1. Polycyclic aromatic hydrocarbons Contains onion, naphthalene, tetracene, or a mixture thereof. In one embodiment of the present invention, pseudocumene is oxidized to trimellitic acid, and the catalyst includes one or more heavy metal oxidation catalysts including hafnium, zirconium, and cobalt. And manganese, and wherein the hafnium content is about 9 to about 30% by weight, the zirconium content is about 2 to about 5% by weight, the manganese content is about 25 to about 40% by weight, and the cobalt content is about 30 to 70% by weight. %, The amount of each metal present is expressed as the weight percentage of all metals present; wherein a bromine source is added to provide a total mole ratio of about 30 to about 100% of the total metal catalyst present in the bromine plus bromine series 15 And wherein the 'polycyclic aromatic fe' is added to provide about 5 ppm to about 10,000 ppm of polycyclic aromatic hydrocarbons, for example, about 5 ppm to about 5,000 ppm of polycyclic aromatic hydrocarbons, for example, about 5 to about 10,000 ppm of polycyclic aromatic hydrocarbons, for example, about 5 to about 200 ppm of polycyclic aromatic hydrocarbons. 20 A method for liquid-phase oxidation of pseudocumene to TMLA using a polyvalent catalyst and a bromine accelerator is described in U.S. Patent No. 4,755,622 and U.S. Patent No. 4,992,579, all of which are incorporated herein by reference in their entirety. U.S. Patent No. 4,755,622 discloses the liquid-phase oxidation of pseudocumene in the presence of a multivalent catalyst promoted by a bromine source. The oxidation system 14 200526568 is performed in two steps. Thus, the bromine content added in the first stage is About 10 to about 35% of the total bromine is added, and the remainder is added in the second stage. U.S. Patent No. 4,992,579 discloses the liquid-phase oxidation of pseudocumene (psc), in which the initial part of the reaction is carried out in semi-continuous or batch mode, and then it is carried out in batch after five, of which most The bromine accelerator and the trivalent tritium are added at the end of the batch. Therefore, the contact time between the polycarboxylic acid part and the cobalt-manganese-bromine or zirconium-cobalt-manganese-bromine catalyst is reduced, and the production from PSC is improved. Production of trimellitic acid (TMLA). An embodiment of the present invention relates to a method for converting pseudocumene to cumene 101, which includes a liquid source, a cobalt source, a manganese source plus a molybdenum source, and a yin-fang smoke ( In the presence of a catalyst with or without the wrong source), at a temperature ranging from about 100C to about 250 ° C, the pseudocumene-containing feed and molecular oxygen source are catalytically oxidized in two stages. Batch or semi-continuous, and the second stage is performed in a batch, where the addition of bromine component 15 is performed so that about 10 to about 35% by weight of the total bromine is 'added' in the first stage and The remainder is added in the second stage, where the temperature in the second stage is about 175. (: To about 250 ° C, and the temperature of the first stage is about 25t: to about 165 ° C, wherein the two-stage addition of the bromine component is performed simultaneously when molecular oxygen is introduced to the feed. Another embodiment of the invention relates to a solution containing one or more heavy metal oxidation catalysts (including brocade, zirconium, cobalt, and trivalent trivalent valerum) in a liquid phase condition to provide about 3 to about A method for oxidizing pseudocumene with molecular oxygen at a temperature in the range of about 10 (rc to about 275 ° C.) in the presence of 10 mg of atomic total metal, bromine source, and polycyclic aromatic hydrocarbons. This method includes less than 15 200526568 The two stages make the bromine component be added in stages, wherein 0 to about 35% of the total bromine content is added in the first stage and the remainder is added in the final stage, and wherein all of the amidines are added in the final stage, and where The temperature in the final stage increased from about 175 ° C to about 275 ° C, and the temperature in the previous stage was between about 125 ° C and 5 about 165 ° C. Liquid-phase oxidation of aromatic smoke to produce aromatic weird acid can Batch method, continuous method, or semi-continuous method. The oxidation reaction can be performed at The reaction mixture is formed by mixing an aromatic hydrocarbon feed, a solvent, a heavy metal oxidation catalyst, a bromine source, and a polycyclic aromatic hydrocarbon activator. In a continuous 10 or semi-continuous method, the reaction mixture is formed. The components are preferably mixed in a mixing container prior to inducing the oxidation reaction, however, the reaction mixture may be formed in an oxidation reactor. 15 20 The aromatic carboxylic acid suitable for the present invention comprises one or more aromatic Mono- and multi-weilerated species of the ring, which can be produced by reacting gaseous or liquid reactants due to the liquid phase system, especially during which the solid reaction products are prepared and / or the liquid components of the reaction mixture enter The vapor phase on the liquid phase of the reactor. Examples of aromatic carboxylic acids that are particularly suitable for the present invention include trimellitic acid, isophthalic acid, terephthalic acid, benzoic acid, and naphthalenedicarboxylic acid. Suitable ^ aromatic hydrocarbons The feed typically contains an aromatic hydrocarbon having at least a base that can be oxidized to a neoyl group. The oxidizable substituent can be a alkynyl group such as methyl, ethyl, or isopropyl. It can also be a group that already contains oxygen , Such as base Or keto. The substituents may be fluorene or different. The aromatic portion of the feed compound may be a benzene nucleus, or it may be bicyclic or polycyclic, such as a naphthalene core. The aromatic moiety of the feed compound The number of oxidizable substituents may be equal to the number of positions available on the aromatic moiety 16 200526568, but-generally less than all of these positions, and better than the 1-,-,-, 4 'and 仏 series. Useful for Examples of feed compounds include toluene, ethylbenzene, o-dibenzyl, p-xylene, m-xylbenzyl, methyl 5 10 15 methyl-4-methylbenzene, 1 minus methyl + methylbenzene , 1,2,4 · trimethylbenzene, 1-methyldonyl · 2,4-dimethylbenzene, ^, tetramethylbenzene, alkyl, hydroxymethanyl-, formamyl- and Fluorenyl · substituted naphthalene compounds such as 2,6 and = dimethylnaphthalene, 2 · fluorenyl-6-methylnaphthalene, 2-methylfluorenyl-6-methylnaphthalene, 2-methyl · 6_ethyl Naphthalene, and 2,6-diethylnaphthalene. For the production of aromatic acids by oxidizing the corresponding aromatic hydrocarbon precursors, for example, from iso-mono-substituted benzene to iso-iso-peroxo-acid, from p-di-substituted benzene to p-xylylenediamine, from 1,2,4 · Dimethylbenzene is used to make trimellitic acid and disubstituted naphthalene is used to make Caidi_. It is better to use relatively pure feedstock, and more preferably the content of the precursor corresponding to the desired acid is at least about 95% by weight, and more preferably J 98 reset%, or higher. A preferred feed for the production of terephthalic acid includes para-xylene. The preferred feedstock for the manufacture of neutonic acid contains m-xylene. A preferred feedstock for making trimellitic acid includes pseudo-dry welding. The preferred feedstock for the production of 2,6-naphthalenedicarboxylic acid is 2,6-dimethylnaphthalene. Methylbenzyl is a better feed for making benzyl formic acid. In the embodiments of the present invention, the liquid phase oxidation of pseudo-dry roasting for the production of trimellitic acid can be performed by a hybrid method, a continuous method or a semi-continuous method. The oxidation reaction can be carried out-or in multiple oxidizers. The reaction mixture is obtained by mixing pseudocumene feed, solvent, catalyst, packing promoter, and polycyclic aromatic hydrocarbon promoter. In a continuous or semi-continuous method, the components of the reaction mixture are preferably mixed in a mixing vessel before being introduced into the oxidation reactor, but 17 200526568 is that the reaction mixture can be formed in the oxidation reactor. Solvents containing aqueous chloric acid (especially lower calcining group (e.g., C) -c8) monotarctic acid, e.g., acetic acid or benzoic acid) are preferred because of the typical oxidation reaction conditions used to make aromatic hydrazones The lower system is less susceptible to oxidation and can promote catalytic effect on oxidation 5. Examples of these acids include acetic acid, propionic acid, butanoic acid, and mixtures thereof. 1 Aromatic acid oxidation to ethanol and other co-solvent materials under the oxidation reaction conditions of aromatic acids and other co-solvent materials can also be used or mixed with acid. . Use tools (good results. For overall method efficiency and minimization of separation, it is preferred that when using a solvent containing 10 mixtures of monocob and this co-solvent, the co-solvent needs to be able to oxidize the monocarboxylic acid used. Basis The catalyst used in the present invention includes a catalyst capable of effectively catalyzing the oxidation of an aromatic hydrocarbon feedstock to an aromatic carboxylic acid. Preferably, the catalyst system is soluble in a liquid oxidation reaction body to promote the catalyst, oxygen, and liquid feedstock. Contact; however, heterogeneous catalysts or catalyst components can also be used. Typically, 15 catalyst systems contain at least one suitable heavy metal component, such as a metal having an atomic weight ranging from 23 to about 178. Examples of suitable heavy metals include In particular, manganese vanadium 4 mesh, chromium, iron, nickel, copper, titanium, trim, or steel-based metals, such as' 铪. Suitable forms of these metals include, for example, acetates, hydroxides, and carbonates. The catalyst of the present invention preferably contains a cobalt component, 20 of which is alone or mixed with one or more of a fibrous compound, a rhenium compound, an erbium compound, an ammonium compound, or a erbium compound. The bromine promoter is To promote the oxidation activity of the catalyst metal, it is preferred that it does not produce undesired by-products or content by-products, and is preferably used in a form that is soluble in the liquid reaction mixture. Traditional bromine accelerators include Bh, HBr, 18 200526568

NaBr, KBr, NH4Br, and organic bromide. We have discovered that shallots and other polycyclic compounds such as naphthalene and tetracene (2,3-benzo shallots) are effective activators for the liquid-phase oxidation of hydrocarbons to aromatic carboxylic acids. The liquid-phase oxidation of aromatic hydrocarbons to form aromatic carboxylic acids can be accomplished in the presence of an onion, naphthalene, or fluorinated accelerator and a metal catalyst (preferably including starting and fibrous, rhenium, or other metal additives). The addition of onion, naphthalene, and / or other polycyclic aromatic hydrocarbons to the homogeneous oxidation of alkyl aromatic compounds (such as xylene and difluorenylnaphthalene) results in unexpected and significant activation, which can promote aromatic acids ( Such as the production of terephthalic acid (TA), 10 isophthalic acid (IPA), trimellitic acid / anhydride (TMLA / TMA) and naphthalenedicarboxylic acid (NDA)). The higher activity of these oxidations (catalyzed by co, Mn & Br) will result in reduced intermediates and by-products, and lower catalyst costs. A very small amount of polycyclic aromatic hydrocarbons is required for this activation. Depending on the specific reaction, shallot or other polycyclic aromatic hydrocarbons may be batch-oxidized at the beginning of 15 and continuously oxidized continuously, at the finishing catalyst, at the batch-oxidation or batch-and-finish mode Add to. The activation effect can be changed according to the concentration and addition mode of other polycyclic aromatic hydrocarbon activators and for some reasons. 'Using onion as a catalyst activator can use a lower reaction temperature or can make the catalyst metal (especially The amount of correction is reduced. For some reasons, if the catalyst system is already operating in its optimal state, f will not further increase the catalytic performance; however, in this system, g will react less than optimally. It can be used as a catalyst (such as a catalytic metal with a low temperature) to exhibit activation. This has the advantage of reducing the cost of this method. The oxidation reaction is carried out in an oxidation reactor. The oxidation reactor may contain 19 200526568 one or more reactions Vessel. The oxidant gas is also introduced into the oxidation reactor. The oxidant gas used in accordance with the present invention contains molecular oxygen. Air is conveniently used as a source of molecular oxygen. Oxygen-enriched air, pure oxygen and others contain at least about 5% molecular oxygen Gaseous mixtures can also be used. Such oxygen-rich sources containing at least about 10% 5 molecular oxygen are advantageous. As is understood, as the molecular oxygen content of this source increases, the pressure The requirements of the shrinking machine and the inert gas treatment of the reactor exhaust gas are reduced. The ratio of feed, catalyst, oxygen and solvent is not important to the present invention, and it varies not only with the choice of feed and desired product, but also with the processing equipment and 10 operating factors The choice ranges from about 1: 1 to about 10: 1 by weight of the solvent to the feed. The oxidant gas is typically used at least stoichiometrically (based on the feed), but not too large The unreacted oxygen escapes from the liquid to the i-top gas phase and forms a flammable mixture with the other components of the gas phase. The catalyst is based on a catalyst concentration greater than about 100 ppmw (based on the aromatic hydrocarbon feed and 15 solvents) Appropriately used, preferably greater than about 500 Ppmw, and less than about 10,000 ppmw, preferably less than about 6,000 ppmw, and more preferably less than about 3000 ppmw. The bromine accelerator is preferably used to make bromine react with the catalyst The atomic ratio of the metal is suitably greater than about 1: 1, preferably greater than about 0.2: 1, preferably greater than about 0.3: 1 and suitably less than about 4: 1, preferably less than about Amount of 3: ι is present. 20 According to the present invention, the accelerator pack Containing one or more polycyclic aromatic cigarettes mixed with traditional desert promoters, the content is such that the optimal range of atomic ratio to catalyst metal is about 0.25 ·· 1 to about 2:] [. The pressure is at least as high as the container maintains a substantially liquid phase containing the feed and the solvent.-Generally, the pressure measured from about 5 to about 40 kg / cm2 is 20 200526568, which is suitable for special method temperatures and other factors. The preferred pressure is to change the residence time in the reaction vessel appropriately depending on the composition of the feed and solvent, and the production conditions and conditions, and about 20 to 150 minutes is generally appropriate for the range of pressure. For example, 孰 羽 _ A ▲ …, Baifang's acid-free manufacturers understand that the better conditions and operating parameters vary with different yields and methods of N products, and can be changed within or outside the specified range. The aromatic polyacid product recovered from the liquid may be used or stored as such, or may be subjected to purification or other processing. Purification is advantageous for removing by-products and impurities in the recovered aromatic acids. For aromatic compounds such as terephthalic acid and isoammonioic acid, the purification effect is preferably included at elevated temperatures and pressures, and includes hydrogenated catalytically active metals (such as ruthenium, money, sulphur or sulphur) Catalysts (typically supported on carbon, titanium oxide or other suitable chemically resistant supports or supports for catalyst metals) Chlorine 15 in the presence of oxidation products typically dissolved in water or other aqueous solvents化 Effect. Purification methods are known, for example, U.S. Patent No. 3,584,039, U.S. Patent Nos. 4,782,181, 4,626,598, and U.S. Patent No. 4,892,972. If the purification is carried out with water as the solvent, washing with water to remove the residual oxidizing solvent from the solid aromatic carboxylic acid can be accomplished by alternative drying. This cleaning can be done using a suitable solvent exchange device, such as a 20 filter, as disclosed in US Patent No. 5,679,846, US Patent No. 5,175 355, and US Patent No. 5,200,557. Typically, the mother liquor is separated from the aromatic carboxylic acid product by separation techniques known in the art, such as filtration, centrifugation, or a combination of known methods. It is preferred that at least a portion of the mother liquor is circulated, and commercial operations are typical. 21 200526568 Most of the mother liquor is circulated. It has been found that the addition of t-caine (NDA) increases the yield by about 2% by weight when t is added due to MC-oxidation of% dimethylnaphthalene_N) under certain conditions. The increase of 2% by weight is significant in commercial operations. Adding 1 can perform the oxidation process under mild conditions (which are not feasible under other conditions), and the benefit is a higher NDA yield. Performing at milder conditions may have the advantage of lower costs. The ability to reduce the cobalt in the catalyst is particularly helpful in the oxidation of DMN to NDA. Because DMN oxidation to NDA is more difficult than ρχ oxidation to Dingba, a significantly higher content of expensive oxidation catalyst metals is used to produce NDA. The use of en or another polycyclic aromatic hydrocarbon as an activator for the oxidation of DNM to NDA can be performed by using less catalyst metal, allowing the reaction to proceed under milder conditions, and / or by reducing the combustion of DMN and acetic acid. Has the advantage of reducing costs. 15 It was also found that when 2,6-naphthalene dicarboxylic acid (NDA) is produced by MC oxidation of 2,6-dimethylnaphthalene (DMN), the NDA yield is optimal, and adding onion does not increase NDA Yield. The oxidation reaction can be performed with its optimal activity and selective operation under selected conditions, and is not further stimulated by the addition of onions. In the case of NDA oxidized by DMN, the activation of onion was seen when 20 onions were added continuously, but not when anthracene was added to the initial reaction mixture. In the production of trimellitic acid from pseudocumene, lower catalyst costs can be achieved due to the ability to use lower cobalt in the catalyst. Combustion of the lower acetic acid solvent and pseudocumene feed occurred due to anthracene, which also provided cost savings. 22 200526568 Use en or another appropriate polycyclic aromatic hydrocarbon as an activator to increase the oxidation rate and enable the oxidation reaction of pseudocumene to operate at lower temperatures, which means reducing the combustion of acetic acid, a better color, and a better choice for the product Sex. Better color products can be achieved with lower temperatures and lower cobalt. 5 Allium and other polycyclic compounds (such as onion and tetracene (2,3-benzolion)) are effective as activators of liquid phase oxidation of pseudocumene to produce trimellitic acid. Liquid phase oxidation of pseudocumene to form trimellitic acid can include polycyclic compounds (preferably selected from the group consisting of onion, naphthalene, tetracene, or a mixture thereof), metal catalysts (preferably containing cobalt And manganese, thorium or both) and bromine sources. 10 When onion or other polycyclic compounds are used as promoters, the cobalt content in the catalyst can be reduced to two to three times lower than the cobalt content in the catalyst system when no polycyclic activator compounds are used. Comparable yields and converters obtained using conventional cobalt content reactions. In the examples, the method of the present invention comprises pseudo-cumene in the presence of a 鍅 _15 cobalt-manganese-rhenium-bromine catalyst or a cobalt-manganese-rhenium-bromine catalyst and a catalyst activator under liquid phase conditions. Oxidation to trimellitic acid with molecular oxygen. When pseudocumene is oxidized in the presence of an acetic acid solvent, Zr, Mn and each of them can be conveniently used as their acetate. For commercial reasons, thallium can be obtained in a ZK 2 solution in acetic acid, and therefore, it is ideally suited for liquid-phase oxidation using 20 acetic acid as a reaction solvent. When the rhenium-based catalyst is a component, rhenium is preferably added in the finishing reaction. A suitable trimming compound having a positive trivalent value needs to be soluble in the finishing reaction 'and may include carbonic acid trimming and acetate bromide. The molecular oxygen used in the present invention to promote oxidation is derived from 02 and the content can vary from air to oxygen gas. For 120t and up to 275. Oxygen at a temperature of 23 ° C is the preferred source of molecular oxygen. For oxidation with molecular oxygen, the preferred temperature is in the range of 100 ° C to 2000 ° C. The minimum pressure for these oxidations is to maintain 70-80% of the reaction medium (net pseudocumene, or pseudo-granene and 70-80% acetic acid) at a substantially liquid pressure. When using 5 acetic acid> cereals, the appropriate range is from 1 to 10 parts per serving of pseudocumenoid (based on weight). The pseudocumene and / or acetic acid which is not in the liquid phase and evaporated due to the heat of reaction is advantageously cold-chilled, and the condensate is returned to oxidation by removing heat, whereby the temperature controls the exothermic oxidation reaction. This evaporation of the pseudocumene reactant and / or the acetic acid solvent is also accomplished by evaporating the lower-boiling by-product water 10. When the benefits of acetic acid and water from the reaction are recovered by liquid-phase oxidation, the condensate does not return to oxidation. The source of molecular oxygen used to promote oxidation can be varied from air to oxygen gas content. For oxidation at temperatures of 120 ° C and up to 275 ° C, air is the preferred source of molecular oxygen. For oxidation with molecular oxygen at 15, the preferred temperature is in the range of 100 ° C to 200 ° C. . The minimum pressure for these oxidations is to maintain the pressure of 70-80% of the reaction medium (net pseudocumene (PSC), or PSC and 70-80% acetic acid) to a substantially liquid pressure. When using an acetic acid solvent, the content is M0 parts per part of PSC (based on weight). The non-liquid phase PSC and / or acetic acid that is evaporated due to the heat of reaction is favorably condensed, and the condensate is returned to oxidation by removing heat, thereby controlling the temperature of the exothermic oxidation reaction. This evaporation of the PSC reactants and / or the acetic acid solvent is also accomplished by evaporating the lower-boiling by-product water. When it is desired to take advantage of the reaction of acetic acid and water from liquid-phase oxidation, as will later be demonstrated, the condensate does not return to oxidation. 24 200526568 The ratio of feed, catalyst, oxygen and solvent is not important to the present invention, and it changes not only with the choice of feed and desired product, but also with the choice of processing equipment and operating factors. A suitable range of the weight ratio of the solvent to the feed is about 1: 1 to about 10: 1. The oxidant gas is typically used at least stoichiometrically (based on 5 feeds), but is not large enough to allow unreacted oxygen to escape from the liquid to the i-top gas phase and form flammable with other components of the gas phase Sexual mixture. The catalyst is suitably used at a catalyst metal concentration of more than about 100 ppmw (based on aromatic hydrocarbon feed and solvent), preferably more than about 500 ppmw, and less than about 10,000 ppmw, preferably less than About 600 ppmw, more preferably Line 10 is less than about 3000 PPmw. The use of spring onion as an activator can reduce the demand by up to about 75%, making it possible to use less cobalt in the catalyst metal and less catalyst metal as a whole. The desert promoter is preferably such that the atomic ratio of bromine to the catalyst metal is suitably greater than about 0.1 · 1, preferably greater than about 0.3: 1, and suitably less than about 15 4: 1. The good line exists in an amount of less than about 1: 1. According to the present invention, Hanyuan is present in an amount such that the range of the atomic ratio of bromine to catalyst metal is optimally from about 03: 1 to about 1β1. Acetic acid or aqueous acetic acid is a preferred solvent, and the ratio of solvent to feed is about 1: 1 to about 5: 1, for example, about 1.8: 1 to about 4: 1, such as ^ ~ such as' about 1.5: 1 to 20 About 3: 1. The catalyst preferably comprises cobalt mixed with any mixture of manganese, rhenium, rhenium, titanium, yuge, and the like. The bromine source is preferably used as a promoter. Catalytic leaching is present in an amount that provides about 600 ppmw to about 2500 ppmw of catalyst metal (based on the weight of the aromatic smoke and solvent). The best performance promoter > The atomic ratio of odor to catalyst metal ranges from about 0.3: 1 to about ^ 25 200526568. The trimellitic acid product recovered from the liquid may be used or stored as such, or may be subjected to purification or other processing. Purification is advantageous for removing by-products and impurities that may be present with the recovered aromatic carboxylic acid. Typically, the mother liquor is separated from the aromatic carboxylic acid product by separation techniques known in the art, such as filtration, centrifugation, or a combination of known methods. The following examples illustrate the invention in more detail. The following examples are intended to illustrate some specific embodiments of the invention disclosed herein. However, these examples should not be construed as limiting the scope of the novel inventions contained herein, as many variations may be made without departing from the spirit of the disclosed invention, as known to those skilled in the art. Examples 1-5: Dioxidation to isoS macro acid: experimental procedure; experiments were performed in a 300 ml titanium parr mini-reactor. The initial 15 reactant injection content catalyst and 76 grams of 95% acetic acid (HOAc). The reactor was pressurized to 400 psig under N2 and heated to the desired temperature. After reaching the desired temperature, the nitrogen atmosphere was switched to a continuous fluid of 8% by volume in N2. After the reactor was saturated with 8% 02 (determined by the content of a in the outlet gas), 25 to 30 ml of MX was pumped at an oxidation time of 60 minutes. At the same time, another 20 25 ml of HOAck was added continuously over the same period. The onion system was added to the initial reaction shot (known as batch addition) or continuously in solution during the oxidation (60 minutes). After 60 minutes, 8% of 02 was switched to nitrogen, the reactor was cooled to room temperature, the contents of the reactor were removed and subjected to 111 ^ (:: analysis. The gas at the outlet was continuously analyzed during the oxidation period 02, c. 2.c0. Outlet 26 200526568 The gas was also sampled two or three times during each experimental period, and the volatile organic compounds were analyzed by GC in the laboratory. In all examples, the catalyst in the initial injection was composed of the following : Co (OAc) 2. 4Η20Ο = 0.264g; Mn (OAc) 2 · 4Η20Ο = 0.278g; 48% HBr = 0.240g. In Examples 2 to 4, the onion (AC) was 95 A saturated solution (0 · 12_0 · 14% by weight AC) in / 5 wt% HOAc / H20 was added. In Example 5, AC (0.300 g) was added to the starting reactor injection. The effect of anthracene was using a typical Co -Mn-Br oxidation catalyst was tested at 180 ° C and 195 C at two different temperatures and in two onion addition modes (continuous and batch). The results are shown in Table 1. Table 1

The effect of i (AC) on the yield of IPA ^ The oxidative conversion of continuous addition of MMX resulted in an unacceptable improvement in the product ιρΑ yield. Comparative Examples and 4 without continuous addition of AC caused the IPA yield to increase from 73 to 92 mole%. The IPA yield of 9 plus did not cause an increase in combustion, which is an additional unexpected advantage. The effect of En addition on the yield of IPA can be changed with the temperature of oxidation 27 200526568. This effect is less at higher temperatures (assuming other experimental conditions are the same). Although extremely significant effects were seen at 180 ° C (Examples 1 and 2), no improvement was seen at 195 ° C (see Examples 3 and 4). The oxidation reaction at higher temperatures can be operated under optimal conditions. 5 Comparison of hydrogenation at a lower temperature of 18 0 ° C and 19 5 ° C. The control group experiments (Examples 1 and 4) showed that the oxidation at 180 ° C produced an oxidation that was greater than 195 ° C (91%). ) Lower IPA yield (73%). Therefore, to achieve high IPA yields, commercial oxidation is performed at 190-200 ° C. However, oxidation at higher temperatures results in significantly higher combustion losses and high levels of bromide (MeBi:)-regulated ozone depleted compounds. It can be seen from Examples 1 and 4 that the continuous addition of scallion oxidation at i80 ° C resulted in a higher IPA yield (92%) than 195 ° C without AC oxidation (91%). At the same time, the combustion system at 180 ° C is about 1/3 of TC combustion. Compared to 195 ° C, the MeBr formation system at 180 ° C is reduced by 80%. 15 Therefore, the addition of onion can reduce the temperature of oxidation And it will not damage the yield of IPA, reduce the combustion loss and reduce the formation of MeBr. The effect of adding scallion Example 3 shows that spring onions can be added in batch mode. Add 0.33 grams of green onions (or in the initial injection 〇 · 4% by weight) resulting in an increase in IPA yield from 73 to 80 mole%. 20! For small I anise, only a small amount of onion is needed to improve the oxidation reaction. The amount of onion supplied in Examples 2 and 5, 60 minutes The total amount is 0.66 mol% of the MX amount. In Example 3, 0.6 mol% of the MX supplied by the onion series was batch-loaded. Examples 6 and 7 28 200526568 Pair-Dimethyl molybdenum paired The experiment was carried out in a 300 ml titanium Parr mini reactor. The initial reactor charge contained a catalyst and 100 g of 95% HOAc. The reactor was pressurized to 400 psig under heating and heated to 170 ° C. After the desired temperature is reached, the nitrogen 5 atmosphere is switched to a continuous fluid of 8% by volume 02 in N2. After the reactor is saturated with 8% 02 (by (The content of O2 in the mouth gas), the feed (p-xylene) was pumped at 0.5 ml / min for 60 minutes. After 60 minutes, 8% 02 was switched to nitrogen, the reactor was cooled to room temperature, and all reactions The effluent from the reactor (TRE) was removed and subjected to HPLC analysis. The gas at the outlet was continuously analyzed 〇2, C02, ίο co. The outlet gas was also sampled two or three times during each experiment, and the laboratory gas chromatography was used. (GC) analysis of volatile organic compounds. In Examples 6 and 7, the catalyst in the initial charge consisted of the following: c0 (〇Ac) 2 · 4Η20 = 0 · 400g; Mn (OAc) 2 · 4Η20 = 0 · ΐΐ5 g; 48% ΗΒγ = 0.127 g. In Example 7, AC (0.3 g) was added to the starting reactor charge. 15 Table 2 Example Example Molar Yield,% Cox / PX (combustion) Τα 4-CBA terephthalic acid 6 Control group without onion 24 5 22 0.08-7 Enquiries 44 7 29 0.08 Discussion of Examples 6 and 8 Examples 6 and 7 are presented at 170 ° C At the same time, p-dioxobenzene was oxidized to TA. The control group experiment (Example 6, no green onion) showed that the TA yield was 24 mol%, 0.08 burned. Batch added 0.3% by weight The onion to the initial reactor injection was made to 20% but the yield was increased to 44 mole%, and the combustion was maintained at 0.008. Therefore, Examples 6 and 7 illustrate the improvement of onion oxidation of p-dioxobenzene to TA, and This improvement did not increase the combustion of 29 200526568. Examples 8-14 Continuous addition of onion and 2,6-difluorenylfluorene (DMN) gasification to produce 2,6-fluorenedicarboxylic acid (NDA) The reactor was injected with Desired amounts of cobalt acetate, manganese acetate and HBr. Water was added to the initial charge to adjust the water concentration to SdO% at the end of the reaction. Approximately 108 milliliters of glacial acetic acid was also placed in the initial reactor charge. During the run, 18 ml of acetic acid solvent and 27 g of DMN were added to the reactor over a period of 60 minutes. 10 15 20 Milk source 8 mol% 02. A source of dill onion solution was used in these experiments. A solution containing 1750 PPmw shallots was made by 72Ίρ (22) with onion saturated glacial acetic acid. Another solution containing 530 ppmw green onion was prepared by 72 卞 (22 2.0) saturated onion with 95/5 (wt / wt) acetic acid / water solution. This dimer was used to control the addition to the oxidation reaction itm. Example 8 is a control group operation, which does not add onions to the reaction mixture. In the implementation of w and i G, ㈣ is added to the initial reactor injection, and shoots are transferred to the seedlings during the oxidation reaction. In Examples 11 and 12 'at 72. The onion saturated acetic acid glacial acetic acid is used as the solvent for the initial injection of the reactor, and it is also used as the solvent continuously added during the oxidation reaction. In the implementation of the ship, the anti-fresh injection does not contain f, but Slightly saturated onion glacial acetic acid was used in the oxidation reaction for continuous addition. In Example M, the reaction start injection did not contain f, and the bamboo was added with anthracene-saturated acetic acid / water mixed solvent to the oxidation reaction. The actual amount of onions present in different experiments is shown in Table 3. 30 200526568 Description of the basic conditions of Example 8 & (control group;) Implementation 9 Based on the initial injection tool Onion Table 3 Example 10 Basic conditions at the beginning Injection with onion, but 20% less Co anthracene reactor solvent in injection Concentration of onion, ppmw solvent ratio (g / g), starter, acetic acid (g), acetic acid (g), 48% HBr (g) water (g), acetic acid (g) »it (g) reaction conditions Total DMN (g) 3.9753 T〇8.7Cf 27.00, ^ 9749 ^ ~ 〇50〇Γ

Total HOAc injected (g) Concentration of supply gas oi (volume_%) Response time (minutes) In volume (g) Ping] sentence temperature one (° F) average pressure _ (Psii average inlet air flow (scfh) blessed 4 stream (scih) net yield (Mole-TMLA ~~ FNA Tna 2-Me-6-Na 2,6-NDA 18.00 7.96 407〇F (2083t) ~ 35Γ 4〇〇〇〇2083t) " 350 ~ U9_ 0.71 " αοΓ ~ 15Μ ~ 4.1452 'ToSr ^ 5〇〇Γ 4〇7〇F i208 £ C) 350 丨 Example Ί1 Basic situation, and continuous addition of green onions " " " Basic situation, with continuous addition of green onions , But 30% less Co _ ~ tmnT true; ST and the basic situation of continuous addition of green onions, and continuous addition of new onions + indium in the starting material + continuous addition of 7 ^ ----- new system, and less 30% cobalt + green onion in the initial injection + continuous addition of new system + continuous addition of new system + continuous addition of green onion T --- ------Yes No No 1622 -------- -Γ622 230 70 4? 7 4.7 4.7 4.7 " ^ 3743 ^ -0.9618 1.3739 1.3741 " ^ 04506 ~ 04506 0.4506 0.4506 ^ 0 ^ 6197 ^ " -0.6198 0.6202 0.6198 ^^ 9752 3.9480 3.9751 3.975 j〇 ^^ + + 08.70 108.7 108.7 — 27.00 27.00 27.00 18Ό0 ______ ~ " Γ8.00 18.00 18.00 8Ό0 ^ ------- ~ 8 ^ 00 8.00 8.00 60 ^ 60 60 60 152.50 157.40 155.5 156.2 (208.3¾) ~ 407T (208.3 ° 〇407〇F ( 208.3 ° 〇407T (208.3 ° 〇 " ^ 350 ^ —'350 351 351 ~ * 10: 75 10.17 10.17 ~ · 10.28 9.81 9.80 —1.91. 2.69 2.57 ΙΙ〇49 ^ — ^ 0.43 0.48 0.62 IliC: " ~ " 046 1.12 1.16 ~ " αιο 0.14 0.25 ~ 82.35 84.46 86.71

31 200526568 The results of Examples 8-12 show that the addition of onion can reduce the addition of cobalt, and the NDA yield is also increased when the onion is continuously added and a smaller amount of cobalt is used in the catalyst system. In Examples 8 and 9, the onion in the initial shot did not produce benefits. 5 In Example 10, the lower cobalt and shallot mixture in the initial shot did not produce a benefit. Stomach In Example 11, at the cobalt concentration of the basic case, continuous addition of anthracene did not produce a benefit. In Example 12, with a cobalt concentration of less than 30% and continuous addition of anthracene, the yield of 10 2,6-NDA increased from 76 mol% to 82.3 mol%, which is due to the significant increase in product yield. The function of 7 degrees is used in Examples 8, 13, and 14. All the conditions for oxidation are based on the values of the basic case except for the tritium content continuously added to the oxidation reactor. In all 15 examples, there was no onion in the initial injection of the reactor. When 70 ppmw green onions were added, the yield of 2,6-NDA increased from 76 mol% to 86.7 mol%. However, at a higher addition value of 23 ppmw, the yield of 2,6_ndA was reduced to 84.5 mole%. Obviously, the concentration of onion in the reactor solvent affects the 2,6-NDA yield. The optimal onion concentration appears to depend on whether it is present in the starting charge or continuously added during operation 20, and it also depends on the concentrations of cobalt, manganese, and bromine in the reaction mixture and the reaction temperature. . In Example U, the shallot was present in the initial reactor charge at a concentration and 230 ppmw of additional shallot was continuously added during operation. In Example 13 ', no onion was present in the initial reactor charge, but anthracene of 23.0% was continuously added during operation. Due to the high initial onion concentration, the yield of 2,6-NDA was only 74.4 mole% in Example 11 compared to 84.5 mole% in Example 13. This clearly demonstrates that the high starting onions in the reactor before the oxidation reaction reduced the 2,6-NDA yield under the basic conditions. Examples of Liquid Phase Oxidation of Pseudophyllene (PSC)

Comparative Example A 0.87 grams of acetic acid tetrahydrate, 1/74 grams of acetic acid tetrahydrate, 0.29 grams of hydrogen bromide solution (48%), and 0.086 grams of rhenium acetate solution (17% Zr) were injected to have 529 grams of ice A 102-liter titanium autoclave with acetic acid, 28 grams of water, and 293 grams of pseudocumene. The initial shot was heated to 320 ° F (160 ° C) under a slow nitrogen purge, and then pressurized air (increase to 24.5% of 02) was added at 54 standard cubic feet per hour for approximately 15 minutes. During this 15 minute period, the temperature was maintained at 33 ° F (165.6 ° C) by maintaining the pressure at approximately 105 psig. Three minutes after the air was added, 15 tails of the catalyst were dissolved and added at 0.8 g / min until 40.0 g was added. The closing solution was supplemented by mixing 328 g of acetic acid, 60 g of water, 1.31 g of manganese acetate tetrahydrate, 0.91 g of osmium solution, 12.39 g of HBr solution, and 2.10 g of osmium acetate. Oxidation started at 15 minutes, and the pressure and temperature increased linearly from 345 ° F (173.9 ° C) and 20 105 Psig individually to 41 ° F (21 (TC) and 280 psig. The final temperature and pressure were oxidized in about 40 minutes Achieved. Then, the temperature and pressure were maintained at these values until the oxygen at the outlet rose rapidly to 14%, indicating complete oxidation.

Except for temperature and pressure rises, the air rate gradually increased from 54 to 60 SCFH from 15 to 20 minutes. It was kept at 58 SCFH 33 200526568 to the 5th minute, and then gradually reduced to $ 0 s c f η over a period of 7 minutes. The air rate was maintained at 50 SCFH until the oxidation was complete. Air rising in this way maximizes the consumption of oxygen and prevents the oxygen at the outlet from rising to the flammable range. The products of this oxidation are collected and the sample is dried to a solid and analyzed. Table 4 has data for this operation and Examples 15 and 16. Example 15 This oxidation was performed in the same manner as in Comparative Example A, but 0.5 g of shallot was added to the starting reaction mixture. Example 16 0 This oxidation was performed in the same manner as in Comparative Example A, except that the finishing catalyst was saturated with 320 ppm of onion and was not added to the starting catalyst. Table 4 Components,% solids by weight Comparative Example A Onion-free Example 15 Starting 0.5 grams of onion Example 16 320 ppm of onion trimellitic acid in the finishing catalyst 86.2 90.5 92.9 Amidinic acid 4.36 1.17 0.31 Reaction time (Minutes) 58.2 56.0 58.7 Table 4 shows the activation effect of shallots when added at the beginning and via the finishing catalyst (ie, 'continuously added at low levels throughout the batch oxidation). The yield of trimellitic acid (TMLA) is higher because the main intermediate, methyldicarboxylic acid (also known as methyl dibasic acid or MDB), is significantly reduced due to higher activity. The beginning of this reaction using a content that is 2-3 times lower than the usual commercial concentration 'indicates that onion has the potential to provide a significant reduction in catalyst costs. 20 The cobalt concentration of Comparative Example A, Example 15, and Example 16 was 0.07% by weight, which is based on the injected pseudocumene. In a typical commercial reaction, the initial concentration is 0.16% by weight. Therefore, comparing the results of Examples 15 and 16 with the results of 34 200526568 Example A. It can be seen that the addition of onion at the beginning or the end of the catalyst can be used at the beginning of the lower content (ie, 7% by weight) for the catalyst system. When obtained, pseudocumene is well converted to trimellitic acid, and has a low content of methyl diacid by-product. Compared with the typical cobalt content of 0.16% by weight, the low content of cobalt used by the vehicle driver in the above embodiment exhibits a cobalt reduction rate of 56%. The ability to reduce cobalt while maintaining acceptable activity can result in significant catalyst cost savings. [Schematic description] (None) [Description of main component symbols] (None) 35

Claims (1)

200526568 10. Scope of patent application: 1. A method for oxidizing aromatic hydrocarbons with molecular oxygen sources to form aromatic carboxylic acids in liquid phase conditions and in the presence of a catalyst, the catalyst comprising: a) at least one heavy metal oxidation catalyst; 5 b ) —A source of bromine; and c) a polycyclic aromatic hydrocarbon. 2. The method of claim 1 in which the polycyclic aromatic hydrocarbon is selected from the group consisting of onion, naphthalene, tetracene, and mixtures thereof. 3. The method according to item 2 of the patent application, wherein the polycyclic aromatic hydrocarbon is spring onion. 10 4. The method according to item 1 of the application, wherein the bromine source comprises one or more selected from the group consisting of Br2, HBr, NaBr, KBr, NH4Br, benzyl bromide, bromoacetic acid, dibromoacetic acid, tetrabromomethane, Desert compound of dibromoethane and bromoacetamidine bromide. 5. The method according to item 1 of the patent application scope, wherein the heavy metal comprises cobalt and 15 one or more selected from the group consisting of manganese, trim, titanium, titanium, hafnium, nickel, and secondary metals. 6. The method of claim 1 in which the heavy metal is present in an amount ranging from about 100 ppmw to about 6000 ppmw. 7. The method according to item 1 of the patent application range, wherein the oxidation is performed at a temperature ranging from about 20 to 50 ° C to about 250 ° C. 8. The method according to item 1 of the patent application range, wherein the oxidation is performed at a temperature ranging from about 12 CTC to about 250 ° C. 9. The method of claim 1, wherein the oxidation is performed at a pressure ranging from about 90 psig to about 450 psig. 36 200526568 10. The method of claim 1 in which the oxidation is performed at a pressure in the range of about 100 psig to about 400 psig. 11. The method of claim 1, wherein the aromatic carboxylic acid is selected from the group consisting of isophthalic acid, terephthalic acid, trimellitic acid, and 2,6-naphthalenedicarboxylic acid. 5 12. A catalyst system for producing an aromatic carboxylic acid by liquid-phase oxidation of an aromatic hydrocarbon, the catalyst system comprising: a) at least one heavy metal oxidation catalyst; b) a bromine source; and c) one Cyclic aromatic hydrocarbons. 10 13. The catalyst system according to claim 12 in which the polycyclic aromatic hydrocarbon is selected from the group consisting of onion, naphthalene, tetracene, and mixtures thereof. 14. The catalyst system according to claim 12 in which the polycyclic aromatic hydrocarbon is onion. 15. The catalyst system according to claim 12, wherein the bromine source package 15 contains one or more selected from the group consisting of Br2, HBr, NaBr, KBr, NH4Br, benzyl bromide, bromoacetic acid, dibromoacetic acid, Bromine compounds of methyl bromide, dibromoethane and bromoethenyl desert. 16. The catalyst system according to item 12 of the patent application, wherein the heavy metal comprises one or more secondary metals selected from the group consisting of manganese, rhenium, tungsten, titanium, titanium, nickel, and 20 rhenium. 17. The catalyst system of claim 12 in which the heavy metal is present in an amount ranging from about 100 ppmw to about 6000 ppmw. 18. The catalyst system of claim 12 in which the oxidation is effected at a temperature in the range of about 50 ° C to about 250 ° C. 37 200526568 The oxidation 19. The catalyst system according to item 12 of the patent application range, wherein the oxidation is performed at a temperature ranging from about 120 ° C to about 250 ° C. 'The oxidation is performed'The oxidation is performed'The aromatic carboxylic naphthalenedicarboxylic acid. 20. The catalyst system according to item 12 of the patent application, wherein the pressure is in the range of about 90 psig to about 450 psig. 21. The catalyst system according to item 12 of the application, wherein the pressure is in the range of about 300 psig to about 400 psig. 22. · The catalyst system of item 12 in the scope of patent application, wherein the acid system is selected from isophthalic acid, terephthalic acid, trimellitic acid, and 2,6,23 · The scope of patent application! The method of the present invention is used to form terephthalic acid by oxidizing p-dioxin with a molecular oxygen source in the presence of a catalyst under liquid phase conditions. The catalyst comprises: a) at least one heavy metal oxidation catalyst; b) bromine Source; and c) a polycyclic aromatic hydrocarbon. 15 24. The method of claim 23, wherein the polycyclic aromatic hydrocarbon is selected from the group consisting of onion, naphthalene, tetracene, and mixtures thereof. 25. The method according to item 24 of the patent application, wherein the polycyclic aromatic hydrocarbons are seedlings. 26. The method according to item 1 of the patent application, which is used in the presence of a catalyst under liquid phase conditions. The isophthalic acid is formed by oxidizing m-dimethylbenzyl with a molecular oxygen source. The catalyst comprises: a) at least one heavy metal oxidation catalyst; b) a bromine source; and c) a polycyclic aromatic hydrocarbon. 38 200526568 27. The method according to claim 26, wherein the polycyclic aromatic hydrocarbon is selected from the group consisting of onion, naphthalene, tetracene, and mixtures thereof. 28. The method according to claim 27 in the scope of patent application, wherein the polycyclic aromatic hydrocarbon system is used. 29. The method according to claim 1 in the scope of patent application, which is used for the presence of a catalyst in the presence of a catalyst under liquid phase conditions. A molecular oxygen source oxidizes 2,6-dimethylnaphthalene to form 2,6-naphthalene dicarboxylic acid. The catalyst comprises: a) at least one heavy metal oxidation catalyst; b) a bromine source; and 10 c) a polycyclic aromatic hydrocarbon. 30. The method of claim 29, wherein the polycyclic aromatic hydrocarbon is selected from the group consisting of onion, naphthalene, tetracene, and mixtures thereof. 31. The method according to item 30 of the patent application, wherein the polycyclic aromatic hydrocarbons are seedlings. 15 32. The method according to item 1 of the patent application, which is used to oxidize pseudocumene to trimellitic acid, Including the supply of catalytically oxidized pseudocumene with a molecular oxygen source in the presence of a catalyst under liquid phase conditions, the catalyst comprising: a) at least one heavy metal oxidation catalyst; b) a bromine source; and 20 c) a polycyclic aromatic compound Group of hydrocarbons. 33. The method of claim 32, wherein the polycyclic aromatic hydrocarbon is selected from the group consisting of onion, naphthalene, tetracene, and mixtures thereof. 34. The method according to item 33 of the patent application, wherein the polycyclic aromatic hydrocarbons are seedlings. 39200526568 35. The method according to item 32 of the patent application, wherein the heavy metal comprises a surface and one or more selected from the group consisting of , Hafnium, zirconium, titanium, and hafnium secondary metals. 36. The method of claim 32, wherein the heavy metal is present in an amount ranging from about 100 ppmw to about 6000 ppmw. 5 10 37. The method according to item 32 of the scope of patent application, which is used to convert pseudocumen to metaboric acid 'includes the catalytic oxidation of pseudocumene containing molecular gas source in the presence of a catalyst in the presence of liquid phase conditions Material, the catalyst comprises: 3 ·) Ming- 纟 Meng-Decorative catalyst; b) a bromine source; and c) shallot. 38. The method according to item 32 of the scope of patent application, which is used to convert pseudocumene to trimellitic acid, and comprises the supply of catalytically oxidized pseudocumene-containing feedstock in the presence of a catalyst in a liquid phase under a molecular oxygen source, The catalyst comprises: a) a rhenium-cobalt-manganese-rhenium catalyst; 15 b) a source of bromine; and c) onion. 39. The method of claim 32, wherein the oxidation is performed at a temperature ranging from about 50 ° C to about 250 ° C. 40. The method of claim 32, wherein the oxidation is performed at a temperature ranging from about 20 ° C to about 250 ° C. 4 !. The method of claim 32, wherein the oxidation is performed at a pressure ranging from about 90 psig to about 300 psig. 42 · -A method for converting pseudocumenite into trimellitic acid, comprising catalyzing the oxidation of feedstock containing pseudolean with molecular oxygen source in the presence of a catalyst under liquid phase conditions, 40 200526568 The catalyst comprises: a) at least one Heavy metal oxidation catalyst; b) a bromine source; and c) a polycyclic aromatic 5-hydrocarbon selected from the group consisting of anthracene, naphthalene, tetracene, and mixtures thereof; it is in the range of about 13 (TC to about 22 (rc) Pressure in the range of about 90 ° to about 300 psig. 43. The method of claim 42 in the patent application, wherein the oxidation is at a temperature in the range of about 170 ° C to about 220 °. And at a pressure ranging from about 105 psig to about 280 psig 10, and wherein the polycyclic aromatic tobacco is spring onion. 44. The method according to item 42 of the patent application, wherein the heavy metal includes a name and one or more options. Secondary metals from manganese, hafnium, zirconium, titanium, and hafnium, and the hafnium heavy metals are present in an amount ranging from about 100 ppmw to about 600,000 hali. 15 45. As in the first patent application Method, which is used to convert pseudocumene to trimellitic acid and is contained in the liquid phase strip. Next, in the presence of a catalyst containing a cobalt source, a manganese source plus a bromine source, and a polycyclic aromatic hydrocarbon, with or without a thallium source, at a temperature in the range of about 100C to about 250 ° C, and in two stages by a molecule The oxygen source catalyzes the oxidation of the feed containing pseudocumene, wherein the first stage is carried out continuously in batch or half-20, and the second stage is carried out in batch. The addition of the bromine component is performed so that About 10 to about 35% by weight of total bromine is added in the first stage and the balance is added in the second stage, wherein the temperature of the second stage is increased from about 1751 to about 250t, and the temperature of the first stage is The temperature is between about 125 ° C and about 165 ° C, wherein the two-stage addition of the bromine component 41 200526568 is performed at the same time when the molecular oxygen source is introduced to the feed material. 46. If the scope of patent application The method according to item 45, wherein the polycyclic aromatic hydrocarbon is selected from the group consisting of onion, naphthalene, tetracene, and mixtures thereof. 47. The method according to item 1 in the scope of patent application, which is used in the liquid phase Under Condition 5 'is about 3 to about 10 milligrams of atomic total inclusive of the pseudo-depleted to provide the mother gram mole. In the presence of one or more metals including a catalyst for the oxidation of heavy metals with hafnium, zirconium, cobalt, and manganese with a trivalent value, a source of bromine, and a polycyclic aromatic hydrocarbon, at a temperature ranging from about 100 t to about 275, the false withering Oxene is oxidized with molecular oxygen to trimellitic acid. The method includes adding the 10 component bromine in stages in at least two stages, wherein 0 to about 35% by weight of the total bromine is added in the first stage and the remainder is The last stage is added, and all of them are added in the last whitening stage, and the temperature of the last stage is from about 175. (: rises to 275C, and the temperature of the previous stage is about 125. 〇 and about 165 between it. 48. The method of claim 47, wherein the polycyclic aromatic tobacco system 15 is selected from the group consisting of onion, naphthalene, tetracene, and mixtures thereof. 49. The method of claim 1, wherein the polycyclic aromatic hydrocarbon comprises a petroleum refining by-product stream containing the polycyclic aromatic hydrocarbon. 50. The method of claim 1, wherein the polycyclic aromatic hydrocarbon comprises a petroleum refining by-product stream containing the polycyclic aromatic hydrocarbon. 205. The method of claim 12 in the scope of patent application, wherein each of the polycyclic aromatic hydrocarbon packets has a petroleum refining by-product stream with polycyclic hydrocarbons. 42 200526568 VII. Designated Representative Map: (1) The designated representative map in this case is: (). (None) (II) Brief description of the component symbols in this representative figure: (None) 8. If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: (None) 4