TWI337995B - Anthracene and other polycyclic aromatics as activators in the oxidation of aromatic hydrocarbons - Google Patents

Description

IX. Invention Description: This application is for the US Provisional Application No. 60/530,759 (Application on December 18, 2003) and US Provisional Application No. 60/530,752 (Application for December 18, 2003) Benefits, etc. are hereby incorporated by reference in their entirety. TECHNICAL FIELD OF THE INVENTION 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 onions or another polycyclic aromatic compound, to produce aromatic carboxylic acids. acid. The present invention comprises liquid phase oxidation of pseudocumene (PSC) (1,2,4-trimethylbenzene) in the presence of a catalyst comprising a multivalent catalyst, a bromine source and a polycyclic aromatic hydrocarbon to produce trimellitic acid ( TMLA). The present invention relates to the liquid phase oxidation of PSC to produce TMLA in the presence of a catalyst comprising a polyvalent metal oxidation catalyst, a bromine source, and a polycyclic aromatic hydrocarbon selected from the group consisting of onion, naphthalene, naphthacene, and the like. Trimellitic acid can be dehydrated to produce trimellitic anhydride (TMA). TMA and TMLA are commercially valuable as raw materials for the manufacture of polyester materials. The stupid triester is used as a plasticizer for polyethylene gas, especially for the insulation of high-performance wires and cables, and therefore has the main characteristics of temperature stability and low volatility. Trimellitic acid needles are used in the manufacture of resins for electrodeposition and powder coatings, and as binders for glass fibers 'sand and other aggregates. The stupid tri-anhydride is used as an embossing agent for vinyl flooring' and as a curing agent for epoxy resins. It is also used as a synthetic surface coating chemical, adhesive polymer, dye printing ink, pharmaceutical and soil chemicals. C Prior Art 3 Background of the Invention Aromatic carboxylic acid such as stupid dicarboxylic acid and naphthalene dicarboxylate is of commercial value as a raw material for the manufacture of polyester materials for the production of fibers, films, resins and many other stone compounds. U.S. Patent No. 2,833,816, the disclosure of which is incorporated herein by reference in its entirety in its entirety in the the the the the the the the the the the The oxidation of the dimethylnaphthalene liquid phase to naphthalenedicarboxylic acid can also be accomplished in the presence of bromine and a catalyst having a cobalt and manganese component, as described in U.S. Patent No. 5,103,933, the disclosure of which is incorporated herein by reference. Typically, the aromatic carboxylic acid is purified in a subsequent process, for example, in 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 the aromatic hydrocarbon to the aromatic carboxylic acid is carried out using a reaction mixture comprising an aromatic hydrocarbon and a solvent. Typically, a Cl_C8 monocarboxylic acid is included, for example, acetic acid, benzoic acid, or a mixture thereof with water. As used herein, "aromatic hydrocarbon, preferably means a molecule consisting essentially of carbon atoms and hydrogen atoms and having one or more aromatic rings, especially dimethylbenzene, trimethyl stupid, and Methylnaphthalene. Aromatic fumes suitable for liquid phase oxidation to produce a group of tracing acids generally comprise aromatic cigarettes having at least a substituent which can be oxidized to a tickic acid group. In this case, 'aromatic acid' Preferably, it is meant an aromatic hydrocarbon having at least one carboxyl group. A bromine promoter and a catalyst are added to the reaction mixture, which is reacted in the presence of an oxidant gas. Typically, the catalyst comprises at least one suitable heavy metal component. Suitable heavy metals comprise heavy metals having an atomic weight ranging from about 23 to about 78. Examples include cobalt, manganese, vanadium, molybdenum, nickel, zirconium, titanium, hafnium or lanthanide metals such as ruthenium. Suitable forms of such metals include, for example, B 1337995 acid salts, hydroxides, and carbonates. The conversion of the aromatic carboxylic acid-modified reactant is carried out by liquid phase oxidation using a desert. USSR Patent No. 239936 (Ι. ν. Zakhar〇v) discloses an alkyl group in the presence of a catalyst-cobalt salt and a dibromo onion in the presence of a catalyst at a temperature of 5 〇 11 11 〇 1 A method of liquid phase oxidation of an aromatic hydrocarbon with molecular oxygen, wherein, to enhance the process, a manganese salt addition of 1-3% of the cobalt salt concentration is introduced into the reaction mixture. The amount of aromatic carboxylic acid is generally determined by the concentration of the intermediate product found as an impurity in the aromatic carboxylic acid product. The type and concentration of such impurities will vary depending upon the type and concentration of the catalyst and promoter used and the particular aromatic carboxylic acid product desired. The presence of such impurities can be disturbed by the use of the carboxylic acid product and makes it less desirable for some purposes. For example, when terephthalic acid is used in the direct condensation process for the manufacture of polyesters, impurities in terephthalic acid can cause unwanted coloration of the polymer and act as chain terminators. 15 It has been found that onions and other polycyclic aromatic hydrocarbon-activated daunyl aromatic compounds are oxidized to aromatic carboxylic acids, even when added in very small amounts. This activation is reflected by increased oxygen uptake, temperature increase, lower intermediates and shorter reaction times, and higher product yields. The oxidation of onions, naphthalenes and other polycyclic aromatic hydrocarbons to alkyl aromatic compounds (~, xylene, trimethylbenzene and dimethylnaphthalene) causes a significant activation of the unpredictable 20^ period. It can promote the growth of aromatic acids such as terephthalic acid (TA), iso-g-acid (IPA), trimellitic acid (TMLA), and naphthalene dicarboxylic acid (NDA). The higher activity of these oxidations (catalyzed by Co, Μ and Br) results in lower catalyst costs for the lower intermediates and by-products and a reduction in corrosion and emissions by Br of 7 1337995. Very small amounts of onions and other polycyclic aromatic hydrocarbons are necessary for this activation. The use of hydrazine or another polycyclic aromatic hydrocarbon as the activator can reduce the catalyst cost by allowing it to be converted to the desired aromatic carboxylic acid with less catalyst metal to obtain the desired aromatic carboxylic acid. For example, the use of less cobalt can produce significant savings in this process. Oxidation of aromatic hydrocarbons to aromatic carboxylic acids with polycyclic aromatic compounds (such as onions) can result in a significant reduction in catalyst concentration, which can significantly reduce catalyst costs, especially if cobalt (which is the most expensive component of the catalyst package) When the content can be lowered. The ability to use less catalyst is an unpredictable advantage that provides cost savings and a more economical approach. This method of recycling or recycling of expensive catalyst components such as cobalt provides a particularly cost saving. Furthermore, the use of onion to activate the oxidation of an aromatic hydrocarbon to an aromatic carboxylic acid allows the oxidation process to be carried out at a lower temperature. This means that less energy is used in the process. This 15 also provides cost savings, and in addition, the use of less energy is desirable from an environmental point of view. Another difficulty encountered in the liquid phase oxidation of aromatic hydrocarbons to form aromatic carboxy hydrazines is the combustion of solvents and aromatic hydrocarbons. The liquid phase oxidation reaction typically results in the combustion of at least 2 hydrazine/hydrazine solvent and more than 2% aromatic hydrocarbons. We have found that the use of polycyclic aromatic hydrocarbons as a 20 promoter increases the yield of the product aromatic carboxylic acid without adversely increasing the combustion of the solvent and hydrocarbons. SUMMARY OF THE INVENTION The present invention relates to the oxidation of a c1 hydrocarbon to a source of molecular oxygen in the presence of a catalyst system comprising at least one suitable 8 heavy metal, a bromine source and at least one polycyclic aromatic hydrocarbon in liquid phase conditions. The method. The present invention comprises a method of liquid phase oxidation of pseudocumene to trimellitic acid, the method comprising oxidizing pseudo-purine in the presence of a catalyst comprising at least one suitable heavy metal, a source of bromine, and at least one polycyclic aromatic hydrocarbon. The present invention is also directed to 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) Acyclic aromatic hydrocarbons. The invention is also directed to a process for the liquid phase oxidation of pseudodecene to trimellitic acid wherein the catalyst comprises at least one suitable heavy metal, bromine source, and onion. The invention further relates to a method for liquid phase oxidation of pseudocumene to trimellitic acid in a catalyst system at a temperature in the range of from about 4 to about 250 ° C. The catalyst system comprises at least one suitable heavy metal, bromine source, And at least one polycyclic aromatic hydrocarbon preferably selected from the group consisting of onions, naphthalenes, tetras, and the like. In the catalyst system of the present invention, the polycyclic aromatic hydrocarbons may be onions, naphthalenes, naphthacenes, and A mixture of such polycyclic aromatic hydrocarbons may be a heavier by-product stream derived from petroleum refining containing a polycyclic aromatic hydrocarbon. The heavy metal comprises cobalt and one or more selected from the group consisting of manganese, cerium, zirconium, and titanium. And minor metals present in an amount ranging from about 100 ppmw to about 6,000 ppmw. Typically, the atomic ratio of elemental bromine to heavy metal is from about 0.1:1 to about 4:1; for example, 'about 〇·2: 1 to about 2:1; for example, about 3:1 to about 1:1. Polycyclic 1339995 aromatic hydrocarbons include onions, naphthalenes, or tetras, alone or in mixtures. One embodiment of the invention is In a reaction solvent comprising a crc8 monocarboxylic acid, in a liquid phase, at a temperature of from about 120 ° C to about 250 ° C a method of oxidizing pseudocumene by an oxidant gas, the method comprising oxidizing pseudo-lysate in the presence of a catalyst comprising at least one suitable heavy metal, a bromine source, and one or more polycyclic aromatic hydrocarbons. One or more bromine compounds selected from the group consisting of Br2 'HBr, NaBr, KBr, NH4Br, benzyl bromide, bromoacetic acid, dibromoacetic acid, tetrabromodecane, dibromoethane and bromoethyl bromide. All of the bromine may be derived from a single bromine source, for example, an ionic bromine source (HBr, NaBr, ΝΗ4Β γ, etc.) or a mixed form derived from bromine, for example, an organic bromide such as benzoyl bromide, tetrabromodecane, etc. Preferably, the polycyclic aromatic hydrocarbon comprises onion, coix, or naphthacene, or a mixture thereof, and the onion is more preferred. 15 Description of the Preferred Embodiments The present invention relates to the use of onions or another Polycyclic aromatic hydrocarbons act as catalyst activators in a process utilizing cobalt-catalyzed oxidation of alkyl aromatic compounds. In particular, p-xylene (ΡΧ) becomes terephthalic acid (ΤΑ), and then 20 purification is purified. Terephthalic acid ), m-nonylbenzene (MX) becomes isodecanoic acid (IPA), pseudocumene (1,2,4-trimercaptobenzene) becomes trimellitic acid (TMLA), and 2,6-dimethylnaphthalene (2,6-DMN) becomes 2,6-naphthalenedicarboxylic acid (NDA). The increase in activity provided by onions and similar compounds can be utilized in different ways depending on the product line. 10 The present invention comprises a liquid phase condition. Next, in the presence of a catalyst system comprising a heavy metal oxidation catalyst, a bromine source, and a polycyclic aromatic hydrocarbon activator, a method of oxidizing pseudocumene (PSC) with molecular oxygen to trimellitic acid (TMLA). When used in a catalyst system, the addition of onions or other polycyclic aromatic hydrocarbons to the starting catalyst or continuously (ie, 'tailout') can convert pseudocumene to trimellitic acid with low levels. Undesired by-product of methyl diacid. The activation of the onion is more pronounced when the catalyst is continuously added to the finishing catalyst. In one embodiment, the catalyst system comprises a cobalt-manganese-ruthenium bromine catalyst and onions. In another embodiment, the catalyst system comprises a ruthenium titanium-cobalt-manganese-bromo catalyst and onions. In another embodiment, the catalyst system comprises a erbium-cobalt manganese-bromine catalyst and ruthenium. The invention also provides seeding in a reaction solvent comprising CrC8 monoacid, in the liquid phase, in the range of from about 50 to about 25 Torr (eg, from about 丨〇〇 to about 250 ° C, for example, about UHTC to Approximately 20 (TC, for example, from about 12 〇t to about 25 (TC, such as 'about 丨 thief to about 21 (). The temperature of 〇, oxidizing an aromatic hydrocarbon with an oxidant gas to form an aromatic (four) method. Using onions or another The multi-ring smoke month b is gasified at a lower temperature (if necessary). The method is included in the Weihe in the towel oxygen (four) heavy metal containing at least - suitable heavy metals, indifferent to one or more polycyclic aromatic hydrocarbons Including a knot and one or more secondary metals selected from the group consisting of m and a weight. The weight is preferably present in an amount from about loo ppmw to about 6000 ppmws, for example, from about 500 ppmw to about 3 ppmw. 1337995 Oxidation system The pressure is in the range of from about 1 to about 40 kg/cm2 (about 15 psig to about 569 psig), for example, from about 9 〇pSig to about 450 psig, for example, from about 90 psig to about 400 psig. The oxidation of DMN to the NDA system Preferably, the pressure is from about 350 to about 450 psig at a pressure of from about 300 to about 450 psig. The 5 aromatic hydrocarbon preferably comprises dimethyl benzene. Methyl xylene 'pseudoene, and dimethyl naphthalene. The polycyclic aromatic hydrocarbon preferably comprises onion, naphthalene, naphthacene, and mixtures thereof, and the onion is more preferred. In some embodiments, The ruthenium as the activator can have a maximum Rj of about 75 /ί> reducing the catalyst demand, so that less heavy metals can be used in the catalyst. 10 The present invention provides a method for use at about 5 (TC to about 250. (: range (for example, From about 100 ° C to about 250 ° C, for example, from about 150 ° C to about 2 Torr. For example, from about 120 ° C to about 220 ° C, for example, from about 17 Torr to about 210. (:, for example a catalyst system for the liquid phase oxidation of an aromatic hydrocarbon to form an aromatic carboxylic acid at a temperature of from about 170 C to about 200 C. 15 In one embodiment of the invention, wherein the pseudocumene is oxidized to form a stupitriic acid, the temperature At the beginning of the oxidation, about 17 〇〇c, and the reaction temperature increased to about 210-220 ° C. The oxidation of pseudo-cumene is typically between about 9 psig to about 4 psig. Performing 'for example, about 9 psig to about 3 〇〇 pSig, for example, about 1 〇〇 psig 20 to about 29 〇 ps, for example, about 105 psig to 280 psig. The amount of polycyclic compound used in the catalyst system can range from about 5 ppm to about 10,000 ppm, for example, from about 5 ppm to about 5 Torr, for example, from about 5 ppm to about 1000 ppm, for example, about 5 ppm to Approximately 200 ppm. The catalyst system contains at least one suitable heavy metal, bromine source, and one or more than 12 fragrant shots! . Preferably, the 'heavy metal and ruthenium or other polycyclic aromatics are present in a solution comprising Ci_c8 mono Wei and: or a plurality selected from the group consisting of from 4 100 ppmw to about 6, 〇〇〇 ppmw. Preferably, the atomic ratio of the 5 element to the heavy metal ranges from about 0.1:1 to about 4: more preferably from about 0.3:1 to about 1:1. The polycyclic aromatic hydrocarbon preferably comprises onion naphthalene, naphthacene, or an exhibit thereof. Another source of polycyclic aromatic hydrocarbons may be a by-product stream from petroleum refined polycyclic aromatic hydrocarbons. The oxidation of the aromatic hydrocarbon to the aromatic carboxylic acid in the present month is carried out at a pressure ranging from about 1 to about 10 4 kg/cm2, for example, from about 5 to about 40 kg/cm2, for example, from about 14 to about 32. The kg/cm2 is metered, for example, from about 22 to about 29 kg/cni2. The aromatic hydrocarbon contains an alkyl aromatic hydrocarbon, preferably one to four methyl groups such as p-xylene, m-xylene, pseudo-lysate, and dimethylnaphthalene, but is not limited thereto. Another source of polycyclic aromatic hydrocarbons selected from the group consisting of H, naphthacene and 15 polycyclic aromatic hydrocarbons may be a by-product stream from petroleum refined polycyclic aromatic hydrocarbons. The present invention relates to a compound which oxidizes an aromatic hydrazine with molecular oxygen in the presence of a catalyst activated by onion under liquid phase conditions. In a preferred embodiment, the catalyst is also supported by a rhodium-activated cobalt-manganese bromine catalyst which also contains an additional 20 metal additives. The present invention also provides a catalyst system for the formation of an aromatic carboxylic acid in the liquid phase oxidation of an aromatic hydrocarbon at a temperature in the range of from about 1 Torr to about 25 (the TC range). The catalyst system comprises at least one suitable heavy metal, bromine source, And one or more of the plurality of rings. The bromine source is preferably selected from the group consisting of Br2, HBr, NaBr, KBr, NH4Br, 13 stupid methyl bromide, bromoacetic acid, dibromoacetic acid, tetrabromodecane, dibromodiethyl a bromine compound of alkane and bromoethyl bromide. Preferably, a heavy metal, a bromine source, and a polycyclic aromatic hydrocarbon are present in a solvent comprising a carboxylic acid. The heavy metal preferably comprises cobalt and one or more selected from the group consisting of manganese. The minor 5 metals of cerium, zirconium, titanium and hafnium, and preferably in an amount ranging from about 100 PPmw to about 6000 ppmw. Preferably, the atomic ratio of elemental bromine to heavy metal is about 丨1•丨 to Approximately 4:1 'e.g., from about 0,2:1 to about 2: for example, from about 3:1 to about 1:1. The polycyclic aromatic hydrocarbon comprises onions, naphthalenes, and tetras, or a mixture thereof. An embodiment of the present invention, wherein the pseudocumene is oxidized to a stupid tri-10 acid, the catalyst comprising one or more heavy metal oxidation catalysts, Including cerium, zirconium, lanthanum and lanthanum, and wherein the cerium content is from about 9 to about 3% by weight, the error content is from about 2 to about 5% by weight, the manganese content is from 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 a percentage by weight of all metals present; wherein the bromine source is added to provide about 30 to about 1 Torr of the total metal catalyst in the presence of bromine plus bromine 15 a total molar ratio of 〇%; and wherein polycyclic aromatic hydrocarbons are added to provide from about 5 ppm to about 1 〇〇〇〇 ppm of polycyclic aromatic cigarettes', for example, from about 5 ppm to about 5,000 ppm Polycyclic aromatic hydrocarbons, such as from about 5 ppm to about 1 ppm of polycyclic aromatic hydrocarbons, for example, from about 5 pprn to about 200 ppm of polycyclic aromatic hydrocarbons. 20 Use of multivalent catalysts and bromine promoters The method of oxidizing a liquid phase of a pseudo-cumene to a TMLA is described in U.S. Patent No. 4,755,622 and U.S. Patent No. 4,992,579, the entire disclosure of which is incorporated herein by reference. Liquid phase oxidation of pseudo-cumene in the presence of a source-promoted multivalent catalyst, wherein oxidation With the system 14 1337995, the total amount of the added amount is added to the first stage, and the residue is added to the second stage. The US Patent No. 4,992,579 reveals the false The dilute (psc) liquid phase oxygen enthalpy is used in the semi-continuous or batch mode after the semi-continuous or batch mode is followed by the batch tail (four) row, the towel, the bulking agent and the positive trivalent state. The lanthanum is added at the batch finishing stage, thus reducing the contact time of the poly-part with the H- or erroneous catalyst, and improving the yield of the stupid triacid (TMLA) from the psc. 10 15 - The embodiment of the invention relates to a method for converting pseudo-lean to trimellitic acid, comprising liquid phase conditions, containing a source of bromine and polycyclic aromatic hydrocarbons In the presence or absence of a catalyst of the source, at about the temperature of the 25th generation (4) of the UKTC, and the catalytic oxidation of the source containing the pseudo-lysate and the source of the molecular oxygen in two stages, wherein the first stage is in batch or Semi-continuous operation and the second stage is carried out in batch mode, wherein the addition of the desert component is carried out to add about 1 to about 35% by weight of the total bromine in the first stage, and the remainder is in the first stage. Two stages of addition, of which the second stage

The temperature is about 175 ° C to about 250 ° C, and the temperature of the first stage is between about 165 ° C; and about 165 ° C, wherein the second phase of the bromine component is added to the molecular oxygen is introduced to the feed At the same time.

20 Another embodiment of the present invention relates to a catalyst comprising - or a plurality of heavy metal oxidation catalysts comprising a positive trivalent ruthenium, rhodium, cobalt and manganese to provide about 3 per gram of mole cumene under liquid phase conditions. a method for oxidizing pseudocumene and molecular oxygen at a temperature ranging from about 10 ° C to about 275 ° C in the presence of about 1 〇 milligram of total metal, bromine source, and polycyclic aromatic hydrocarbons. 15 One stage adds the phase component of the desert component 'where the total bromine amount is from 0 to about 350/0 is added in the first stage' and the remainder is added in the final stage, and wherein all the nectarines are added in the final stage. And wherein the temperature of the last stage is raised from about 175 C to about 275 ° C, and the temperature of the previous stage is between about 125 ° C and 5 about 165 ° C. The liquid phase oxidation of aromatic fumes produces aromatic carboxylic acids which can be carried out in a batch process, a continuous process or a semi-continuous process. The oxidation reaction can be carried out in one or more reactors. 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. The reaction mixture component is preferably mixed in a mixing vessel before the introduction to the oxidation reactor in a continuous 10 or semi-continuous process, but the reaction mixture can be formed in the oxidation reactor. The aromatic carboxylic acid suitable for the present invention comprises a mono- and polycarboxylated species having one or more aromatic rings, and which can be obtained by reacting a gaseous or liquid 15 reactant by a liquid phase system, in particular It is the vapor phase in which the solid reaction product is prepared and/or the liquid component of the reaction mixture enters the liquid phase of the reactor. Examples of the aromatic carboxylic acid to which the present invention is particularly suitable include trimesic acid, iso-acid, terephthalic acid, benzoic acid, and naphthalene dicarboxylic acid. Suitable aromatic hydrocarbon feeds generally comprise an aromatic hydrocarbon having at least - a group which can be oxidized to the acid 20 group. The oxidizable substituent may be an alkyl group such as a methyl group, an ethyl group or an isopropyl group. It may also be a group which already contains oxygen, such as a carbyl group, a decyl group or a ketone group. The substituents may be the same or different. The aromatic moiety of the feed compound can be a stupid core, or it can be a bi or polycyclic ring, such as a naphthalene nucleus. The number of oxidizable substituents on the aromatic moiety of the feed compound may be equal to the number of positions available on the 16 parts of the aromatic moiety, but - such as from > to about 4, and more preferably must be Examples of feed compounds containing toluene, ethylbenzene, and o-dimethyl phenyl groups are as follows: toluene, m-xylene, benzylidene benzene, i-methyl methyl group Benzene, 12,4 • tridecyl benzene, ^methyl fluorenyl from dimercapto, U, 4, 5, fluorenyl benzoyl-, fluorenyl- and fluorenyl-substituted naphthalene τ ', For example, 2,6- and 2 7--methylnaphthalene, 2-bristylnaphthalene, 2,cartofuran 7 ethylnaphthalene, and 2,6-diethylnaphthalene. Methyl·6· Manufacture of aromatic acid for the oxidation of ruthenium oxide, such as the production of isodecanoic acid from m-disubstituted benzene, from the case of 15 20 formic acid 'made from 1,2,4_tri-ruthenium This is a pair of stupid thieves, preferably _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ , or higher feed. The wt%, and more preferably the aromatic hydrocarbon feed comprises p-nonylbenzene. It is preferred to use the raw material for the stupa dicarboxylic acid. The best supply package for the heart (f) is used to make 2,6·naphthalene, and the material is included in the material. A preferred feed for the manufacture of stupid formate. #'2'6' Dimethyl Cai. A stupidity is in the present invention - the actual _, ^ - liquid phase Dunhua material in the batch method 'fake (four). The oxidation reaction method, or the semi-continuous method, is carried out by a mixed false _#_ 5 ^ ^ chemist. The reaction mixture is a hydrocarbon promoter, a solvent, a catalyst 1 promoter, and a polycyclic aromatic component, preferably a semi-continuous branch, and the reaction mixture is placed in the mixing vessel before the gas is introduced into the gasification reactor. Medium mixing, but 17 1337995 is that the reaction mixture can be formed in the oxidation reactor. A solvent comprising an aqueous carboxylic acid (especially a lower alkyl (e.g., CrC8) monorexic acid, such as acetic acid or benzoic acid) is preferred because it is less preferred under the typical oxidation reaction conditions used to make the aromatic acid. It is easy to oxidize and can promote the catalytic effect on oxidation 5 . Examples of such carboxylic acids include acetic acid, propionic acid, butyric acid, benzoic acid, and mixtures thereof. Oxidized into a single rebellious ethanol and its ruthenium under the conditions of aromatic acid oxidation; the granule material can also be used or mixed with a slow acid, and has good results. For the overall process efficiency and minimization of separation, it is preferred that when a solvent comprising a mixture of a monocarboxylic acid and the cosolvent is used, the cosolvent is required to oxidize the monoacid used. The catalyst used in accordance with the present invention comprises a material which is capable of effectively catalyzing the oxidation of an aromatic hydrocarbon feed to an aromatic carboxylic acid. Preferably, the catalyst is soluble in the liquid oxidation reaction to promote contact between the catalyst, oxygen and liquid feed; however, a heterogeneous catalyst or catalyst component can also be used. Typically, the 15 catalyst system comprises at least one suitable heavy metal component, such as a metal having an atomic weight ranging from about 23 to about 178. Examples of suitable heavy metals include cobalt, fierce, hunger, key, road, iron, recorded, knotted, titanium, tantalum, or rotten metals, such as, for example. Suitable forms of such metals include, for example, acetates, hydroxides, and carbonates. The catalyst of the present invention preferably comprises a cobalt component, the 20 of which is alone or in combination with one of a compound, a ruthenium compound, a wrong compound, a titanium compound, or a compound. The bromine promoter is used to promote the oxidizing activity of the catalyst metal, preferably without producing an undesired form or amount of by-products' and preferably in a form soluble in the liquid reaction mixture. Traditional bromine promoters contain 2, HBr, 18 1337995

NaBr, KBr, NH, and organic desertification. We have found that onions and other polycyclic compounds (such as naphthalene and naphthacene (2,3-Bist and Onion)) are effective as a living agent for the oxidation of the liquid phase of the tobacco to produce an aromatic acid. Liquid phase oxidation of the aromatic hydrocarbon to form the aromatic acid can be accomplished in the presence of a promoter comprising onion, naphthalene or a compound and a metal catalyst, preferably comprising a diamond and a diamond or other metal additive. The addition of ruthenium, naphthalene and/or other polycyclic aromatic hydrocarbons to alkylaromatic compounds such as 'monophenylene and dinonylnaphthalenes' homogenized oxides causes unpredictable and significant effects which promote aromatic acids (such as , for the production of stearic acid (TA), 1 SS S too acid (IPA), trimellitic acid / liver (10) L Α / ΤΜ A) and Cai Di texic acid (NDA). The higher activity of these oxidations Catalyzed by Co, Μ, and Br) results in reduced intermediates and by-products, and lower catalyst costs. A very small amount of polycyclic aromatic hydrocarbons is required to cause this activation. Depending on the particular reaction, onions or otherwise Polycyclic aromatic hydrocarbons can be added to the batch oxidation at the beginning of I5, continuously in the continuous oxidation of the tailing catalyst in batch oxidation or batch and finishing modes. Other polycyclic aromatics can be used in the activation. The hydrocarbon activation concentration and mode of addition vary for some reason 'Using onions as catalyst activators can use lower reaction temperatures & or can reduce the amount of catalyst metal (especially Ming). For some reasons, If the catalyst system is operating in its optimum state, then There is no further increase in catalyst activity; however, in such systems, onions will exhibit activation at lower than preferred conditions (such as at lower temperatures or less catalytic metals). This has reduced operation of the process. Advantages of the cost The oxidation reaction is carried out in an oxidation reactor. The oxidation reactor may contain 19 reactor capacities H. The tonicizer gas is also introduced into the oxidation reactor. The oxidant gas used in accordance with the invention contains molecular oxygen. , 丨,: also, is the source of molecular oxygen. Oxygen-enriched air, pure oxygen and other gaseous mixtures containing up to 5.8% molecular oxygen can also be used. Containing at least about 1% - human § oxygen source is beneficial As will be appreciated, as the molecular & amount of this source increases, the compressor requirements and inert gas treatment of the reactor off-gas are reduced. 10 15 20 The ratio of feed, catalyst, oxygen and solvent is not critical to the invention, ^ Not only does it change with the supply and the desired product, but also the choice of the secret treatment equipment and the operating factors. The appropriate proportion of the weight ratio of the dissolved feed is about 〇:1. Typically, it is used at least stoichiometrically (on a feed basis), but not so large that unreacted oxygen escapes from the liquid to the overhead gas phase to form a flammable mixture with the other components of the gas phase. Suitable for use at a catalyst concentration greater than about 1 〇〇 ppmw (based on the aromatic hydrocarbon feed and solvent), preferably greater than about 500 ppmw, and less than about 10,000 ppmw' preferably less than about 6,000 ppmw, More preferably less than about 3000 ppmw. The bromine promoter is preferably such that the atomic ratio of bromine to catalyst metal is suitably greater than about 0.1:1, preferably greater than about 0.2:1, and more preferably greater than about 0:3:1. And suitably less than about 4··1, preferably less than about 3:1. The accelerator comprises one or more polycyclic aromatic hydrocarbons in combination with a conventional filler. The atomic ratio of bromine to catalyst metal is preferably in the range of about 0.25:1 to about 2·1. The pressure in the reaction vessel is at least as high as maintaining a substantial liquid phase containing the solvent in the vessel. Generally, a pressure of about 5 to about 40 kg/cm2 is suitable, and the preferred pressure for a particular method varies with the feed and solvent composition, the degree of the dish, and other factors. The residence time in the reaction vessel can be appropriately changed depending on the specific production conditions and conditions, and the pressure range is generally about 2 Torr to about 15 Torr. As is well known to those skilled in the art of aromatic acids, the preferred conditions and operating parameters vary with different products and methods and can vary within the above specific ranges or beyond. The aromatic carboxylic acid product recovered from the liquid may be used or stored by itself or may be subjected to purification or other processing. Purification is advantageous for removing by-products and impurities which may be present in the recovered aromatic carboxylic acid. For aromatic carboxylic acids such as terephthalic acid and isodecanoic acid, the purification is preferably carried out at elevated temperatures and pressures, including metals having hydrogenation catalytic activity such as ruthenium, rhodium, platinum or palladium. a catalyst, which is typically supported on carbon, titanium oxide or other suitable chemically resistant support or support for the catalyst metal, in the presence of hydrogen which is typically soluble in water or other aqueous solvent. 15 effect. The purification method is known, for example, from U.S. Patent No. 3,584,039, U.S. Patent No. 4,782,181, U.S. Patent No. 4,626,598, and U.S. Patent No. 4,892,972. If the purification is carried out using water as a solvent, washing with water to remove residual oxidizing solvent from the solid aromatic carboxylic acid can be accomplished by additional drying. This cleaning can be accomplished using a suitable solvent exchange device, such as the 20 filter, as disclosed in U.S. Patent No. 5,679,846, U.S. Patent No. 5,175,355, and U.S. Patent No. 5,2,557. Typically, the mother liquor is separated from the aromatic carboxylic acid product by separation techniques known in the art, for example, by filtration, centrifugation, or a combination of known methods. Preferably, at least a portion of the mother liquor is recycled, and the commercial operation is typically 21 1337995. It has been found that when 2,6-naphthalene dicarboxylic acid (NDA) is prepared by MC-oxidation of 2,6-dimethylnaphthalene (DMN) under certain conditions, onion addition increases NDA yield by about 2 weight%. The increase of 2% by weight is significant in the commercial operation system. 5 It appears that the addition of onions can be carried out under mild conditions (which are not feasible under other conditions) and the benefit is a higher NDA yield. The advantage of lower cost can be achieved under milder conditions. The ability to reduce cobalt in the catalyst is particularly helpful in the oxidation of DMN to the NDA system. Since oxidation of DMN to NDA is more difficult than oxidation of pX to TA, a significantly higher content of expensive oxidation catalyst metal is used to produce NDA. The use of onions or other polycyclic aromatic hydrocarbons as DNM to form an activator of NDA can be carried out under milder conditions by using less catalyst metal' and/or by reducing DMN and acetic acid combustion. Has the advantage of reducing costs. 15 It has also been found that when 2,6-naphthalene dicarboxylic acid (NDA) is produced by oxidation of MC of 2,6-dimethylnaphthalene (Dmn), the NDA yield is optimal, and adding onion does not increase NDA. Yield. The oxidation reaction can be operated with its optimal activity and selectivity under selected conditions' and is not further stimulated by the addition of green onions. In the case where DMN is oxidized to produce NDA, the activation of onion is seen when 20 Torr is continuously added, but it is not seen when added to the starting reaction mixture. In the manufacture of trimellitic acid from pseudocumene, lower catalyst costs can be achieved due to the ability to use lower cobalt in the catalyst. The lower acetic acid solvent and the combustion of the pseudo-cumene feed occur due to the enthalpy, which also provides cost savings. 22 1337995 The use of onions or another suitable polycyclic aromatic hydrocarbon as an activator to increase the rate of oxidation and to allow the pseudo-cumene oxidation reaction to operate at lower temperatures, which means lowering the acetic acid's 'better color' and better choice for the product Sex. The preferred color product can be achieved at lower temperatures and lower temperatures. 5 蒽 and other polycyclic compounds (such as onion and naphthacene (2,3-Bist and Onion)) are effectively used as an activator of trimellitic acid in the liquid phase oxidation of pseudocumene. Oxidation of the pseudo-baked liquid phase to form trimellitic acid may be an activator or a metal catalyst comprising a polycyclic compound (preferably selected from the group consisting of onion, naphthalene, tetracene, or the like), preferably containing cobalt. And manganese, antimony or both) and bromine source are present in the presence. 10 When onion or another polycyclic compound is used as a promoter, the cobalt content of the catalyst can be reduced to one to two times lower than the initial content of the catalyst system without the polycyclic activator compound, resulting in the use of tradition. The yield of the reaction is obtained by comparison with the yield of the conversion agent. In one embodiment, the method of the present invention comprises the use of a zirconium 15 cobalt-manganese-niobium-bromo catalyst or a cobalt-manganese-ruthenium-bromo catalyst and an onion as a catalyst activator in liquid phase conditions to make pseudocumene The molecule is deuterated into trimellitic acid. When pseudocumene is deuterated in the presence of an acetic acid solvent, each of Zr, Μ, and Co can be conveniently used as its acetate. For commercial reasons, hydrazine can be obtained from a ZrO 2 solution in acetic acid, and therefore, it is desirable to use liquid phase oxidation using 20 acetic acid as a reaction solvent. When one component of the lanthanide catalyst is used, ruthenium is preferably added to the finishing reaction. The appropriate ruthenium compound having a positive trivalent needs to be soluble in the finishing reaction, and may include cesium carbonate and cesium acetate. The molecular oxygen used for promoting oxidation in the present invention is derived from the cerium 2 content which can be varied from air to oxygen gas. For 120. (: and the temperature of up to 275 ° C to carry out 23 1337995, air is a preferred source of molecular oxygen, for oxidation by molecular oxygen, the preferred temperature system is 100. (: to 2 〇〇 £) The range of such oxidations is such that the 7G-8G% of the reaction medium (net pseudo-cumene, or pseudo-alkenes and 70-80% acetic acid) is maintained at a substantially liquid pressure. 5 When using an acetic acid solvent, the appropriate range is from 1 part by weight per cumene oxime to the basis of weight. The pseudo-cumene and/or acetic acid which is evaporated in the liquid phase due to the heat of reaction is advantageously Condensation, 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 also acts by evaporating the lower boiling point. The product water 10 is completed. When it is desired to take back the benefits of acetic acid and water from the liquid phase oxidation, the condensate does not return to oxidation. The molecular oxygen used to promote oxidation is derived from air. Change to oxygen gas. For 120 ° C and up to 275 ° C Oxidation of the degree 'Air is a preferred molecular source of oxygen. For the oxidation of 15 by molecular oxygen, the temperature is preferably in the range of 100 ° C to 20 (the range of TC. The minimum pressure of such oxidation can make the reaction medium 70-80% of (net pseudo-cumene (PSC), or PSC and 70-80% acetic acid) is maintained at a substantially liquid pressure. When using an acetic acid solvent, the content is M0 parts per part of PSC ( Based on the weight basis, the non-liquid phase PSC and/or acetic acid evaporated due to the heat of reaction is advantageously condensed, and the condensate is returned to oxidation by removing heat, thereby controlling the exothermic oxidation reaction by temperature. This evaporation of the PSC reactant and/or the acetic acid solvent is also accomplished by evaporating the lower boiling by-product water. When it is desired to utilize the benefits of acetic acid and water from the liquid phase deuteration to recover the reaction, as follows It will be shown that the condensate does not return to oxidation. 24 The ratio of catalyst, oxygen and solvent is not critical to the invention, not only with the choice of feed and desired product, but also with the choice of processing equipment and # factor. Change. Solvent vs. feed The appropriate range of weight ratios is from 1 to about 1 : 1. The oxidant gas is typically used at least stoichiometrically (based on the feed), but not so large that unreacted oxygen escapes from the liquid to the column. The top gas phase forms a flammable mixture with the other components of the gas phase. The catalyst is suitably used at a catalyst metal concentration of greater than about 1 〇〇 ppmw (based on the aromatic tobacco feedstock and solvent), preferably greater than about 5 00 ppmw, and less than about 1 〇, 〇〇〇ppmw, preferably less than about 6 〇〇〇ppmw, more preferably less than about 3000 PPmw. Using onion as an activator can reduce cobalt demand up to About 75%, it uses less cobalt in the catalyst metal and less catalyst metal as a whole. Preferably, the bromine promoter is such that the atomic ratio of bromine to catalyst metal is suitably greater than about 0.1:1, preferably greater than about 〇3:1, and suitably less than about 15:1, preferably less. At about 1: the amount of 丨 exists. In accordance with the present invention, the bromine source is present in an amount such that the atomic ratio of bromine to catalyst metal ranges from about 3:1 to about 1:1. Acetic acid or aqueous acetic acid is a preferred solvent, and the ratio of solvent to feed is from about 1:1 to about 5:1 'e.g., from about 1.8:1 to about 4:1, for example, from about 15:1 to about 20; :1. Preferably, the catalytic sword comprises a mixture of smashing, returning, erroneous titanium, or any mixture thereof. The edge source is preferably used as a promoter. The catalyst is present in an amount to provide from about 600 ppmw to about 2500 ppmw of catalyst metal based on the weight of the aromatic hydrocarbon and solvent. Preferably, the bromine promoter is such that the atomic ratio of bromine to the catalyst metal ranges from about 0:3:1 to about 1:1 by 25 1337995. The stupitritic acid product recovered from the liquid can be used or stored by itself, or can be subjected to purification or other processing. Purification is advantageous for the removal of by-products and impurities which may be present in the recovered aromatic acid. A typical 5' mother liquor is separated from the aromatic carboxylic acid product by separation techniques known in the art, for example, by filtration, centrifugation, or a combination of known methods. The following examples illustrate the invention in more detail. The following examples are presented to illustrate certain specific embodiments of the invention disclosed herein. However, the examples are not to be construed as limiting the scope of the novel inventions disclosed herein, as many modifications may be made without departing from the spirit of the invention. Example 1-5 Oxidation of dimethyl-formaldehyde to isophthalic acid: Experimental enthalpy and crucible The experiment was carried out in a 300 ml titanium parr mini reactor. The initial 15 reactor was charged with the 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 vol% 02 in N2. After the reactor was saturated at 8% 02 (determined by the 02 content in the outlet gas), 25 to 30 ml of MX was pumped at a 60 minute oxidation time. At the same time, another 20 25 ml of HOAc was continuously added at the same time. The onion is added to the initial reactor charge (referred to as batch addition) or continuously added to the solution in HOAc during oxidation (6 minutes). After 60 minutes, 8% 〇2 was switched to nitrogen, the reactor was cooled to room temperature, and the contents of the reactor were removed and subjected to HPLC analysis. The gas exiting was continuously analyzed for 〇2, c〇2, co during oxidation. The outlet 26 1337995 gas was also sampled two or three times during each experiment and the volatile organic compounds were analyzed using a laboratory GC. In all of the examples, the catalyst in the initial charge consisted of Co(OAc)2. 4H2O = 0.264 g; Mn(OAc)2. 4Η20 = 〇·278 g; 48% HBr = 0.240 g. In Examples 2 5 to 4, hydrazine (AC) was added in a saturated solution of 95/5 wt% H0Ac/H20 (0.12-0.14 wt% octagonal. In Example 5, AC (0.300 g) was added to Start reactor injection. The effect of onion is to use a typical Co-Mn-Br oxidation catalyst at 180 ° (: and 195 ° C two different temperatures and two kinds of strontium addition mode (continuous and batch) to explore 1 〇 The results are shown in Table 1. Table 1 Example Opinion VC Mox Yield % Cox/MX (combustion) MeBr, Ppm 1PA 3-CBA-M-formic acid 1 Control group no 蒽180 73 0.70 2.5 0.21 3 2 蒽Continuous 92 1.7 5.6 0.21 4 3 Onion batch type 80 0.6 2.2 0.23 4 4 Control group without onion 195 91 0.30 1.0 0.58 19 5 Onion continuous 89 0.25 0.8 0.60 23 Experimental results Beam leeks (AC) hang TPA connection rate The effect of continuously adding onion to MX oxidation resulted in an improvement in the yield of the product. The comparative examples and 2 showed that the continuous addition of AC caused the IPA yield 攸73 to increase to 92 mol%. The increase in IPA yield did not cause combustion. Increased, this is an additional unpredictable beneficial effect. The effect of onion addition on IPA yield Changed to 27 1337995 with the temperature of oxidation. This effect is smaller at higher temperatures (assuming other experimental conditions are the same). Although the effect is very significant at 18 (see Tc (Examples 1 and 2), No improvement was observed at 195 ° C (see Examples 3 and 4) <· At higher temperatures, the oxidation reaction can be operated under optimal conditions. 5 _!, can be compared to lower temperature skin Huaihang gasification Control experiments at 18 ° C and 19 5 ° C (Examples 1 and 4) showed that oxidation at 180 ° C produced a lower IpA yield (73%) than oxidation at i95 ° C (91%). Therefore, in order to achieve high IPA yields, commercial oxidation is carried out at 190-200 C. However, oxidation at higher temperatures results in a higher combustion loss and a higher content of methyl bromide (MeBr). - Adjusted ozone depleted compound. As can be seen from Examples 1 and 4, the continuous oxidation of onion at i8 〇 °c resulted in an IPA that was more oxidized than 195 ° C without AC oxidation (91%). Yield (92%). At the same time, the combustion at 180 ° C is about 1/3 of the combustion at i9 ° C. Compared to 195. (:, at 18 (TC of MeBr formation system is reduced by 80%) 15 Thus, the addition of anthracene to reduce the effect of temperature oxidation, and without compromising IPA yield, to reduce burning losses and to reduce MeBr formation. Adding a batch to the work of Example 3 shows that the onion can be added in batch mode. The addition of 〇 3 g (or 〇 4 wt% in the initial shot) resulted in an IPA yield increase from 73 to 80 mol %. 2〇 _Requires a small amount of thinness Only a small amount of ruthenium is needed to improve the oxidation reaction. In Examples 2 and 5, the total amount of onions supplied in 6 minutes was 0.06 mol% of the amount of MX. In Example 3, the amount of MX of the MX supplied by the batch was 0.6 mol%. Examples 6 and 7 28 1337995 p-Dimethyl oxidized to a p-acid

The experiment was carried out in a 3 ml milliliter titanium Parr mini reactor. The initial reactor shot contained the catalyst and 100 grams of 95% HOAc. The reactor was pressurized to 400 psig under N2 and heated to 170 °C. After the desired temperature was reached, the nitrogen 5 atmosphere was switched to a continuous fluid of 8 vol% 02 in N2. After the reactor was saturated at 8% 〇 2 (determined by the 〇 2 content in the outlet gas), the feed (p-terpene) 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 reactor effluent (TRE) was removed and subjected to HPLC analysis. The gas exported is continuously analyzed 02, C02, 10 CO. The exit gas was also sampled two or three times during each experiment and the volatile organic compounds were analyzed using gas chromatography (GC) in the laboratory. In Examples 6 and 7, the catalyst in the initial charge consisted of Co(OAc)2. 4H20=0.400 g; Mn(OAc)2.4H2〇=〇, 115 g; 48% HBr=0.127 g . Example 7 'AC (0.3 g) was added to the initial reactor shot. 15 Example 2 Example Molex yield, % Cox/PX (combustion) TA 4-CBA p-toluic acid 6 Control no onion 24 5 22 0.08 7 Onion batch 44 7 29 0.08 Examples 6 and 8 It is to be explored that Examples 6 and 7 are present at the time of oxidation of p-xylene to TA. The control experiment (Example 6, no onion) showed a TA yield of 24 mol%, a burning amount of 0.08. The addition of 0.3 wt%/0 onion to the initial reactor injection yielded 20% TA yield increased to 44 mol/0, while the combustion was maintained at 〇.〇8. Thus, Examples 6 and 7 illustrate the onion-modified p-dimethyl oxidization to TA, and this improvement does not increase the unfavorable combustion of 29 1337995. Example 8-14 i 嫱 葱 葱 葱 葱 葱 2 2 2 2 2 2 2 2 2 2 2 2 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The water is added to the initial charge to adjust the water concentration to 8-10% at the end of the reaction. About 1 〇 8 ml of glacial acetic acid was also placed in the initial reactor for injection. During the run, 18 ml of acetic acid solvent and 27 g of DMN were added to the reactor during 60 minutes. The oxygen source is 8 mol% 〇2. The source of the onion solution was used for these experiments. A solution containing 10 Π 50 ppmw of onion was prepared by sacrificing glacial acetic acid with onion. Another solution containing 530 ppmw onion was prepared by 72 ° ρ (22, 2 ° (:;) with onion saturated 95/5 (wt / wt) acetic acid / water solution. This two onion source was used to control the addition The amount of onion to the oxidation reactor. Example 8 was operated as a control group, which did not add onions to the reaction mixture. In Examples 9 and 10, hydrazine was only added to the initial 15 reactor injection, while during the oxidation reaction Further, onion was added. In Examples 11 and 12, glacial acetic acid saturated with onion at 72 T was used as a solvent for the initial injection of the reactor, and also as a solvent continuously added during the oxidation reaction. In Example 13, the reactor was started. The ingots were not contained, but glacial acetic acid saturated with onion was continuously added during the oxidation reaction at 72. In Example 20, the initial injection of the reactor did not contain onions, but was saturated at 72 T with onions 95/5 The acetic acid/water mixed solvent was continuously added during the oxidation reaction. The actual amount of onion present in the different experiments is shown in Table 3. 30 13J7995 1337995 The results of Examples 8-12 show that the addition of onions can reduce the addition of the onion and a onion Continuously added and used in the catalyst system The amount of 〇 増 増 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 There will be benefits in Example 11. In the basic case of the concentration, continuous addition of onions will not produce benefits.

In Example 12, with a 30% less cobalt concentration and a continuous addition of hydrazine, the 10 2,6-NDA yield increased from 76 mole % to 82 3 mole %, which was a significant increase in the yield of the product. Thick green onion

In Examples 8, 13, and 14, all the oxidation conditions were based on the values of the basic conditions except for the onion content which was continuously added to the oxidation reactor. In all of the examples, there was no enthalpy in the initial injection of the reactor. The 2,6-NDA yield increased from 76 mol% to 86.7 mol% when added at 70 ppmw. However, the higher onion addition value of '23, ppmw' was reduced to 84.5 mol%. Obviously, the degree of agronomy in the reactor > cereals affects the 2,6-NDA yield. The optimum concentration of ruthenium seems to depend on whether it is present in the initial charge or whether it is continuously added during the operation, and it depends on the concentration, reaction concentration and reaction temperature of the reaction mixture. . In Example 11, the onion was present in the initial reactor charge at a concentration of 1392, and 230 ppmw of additional onion was continuously added during the operation. In Example 13, no onion was present in the initial reactor charge, but was added continuously during the period of 230 ppmw during the operation of 32 1337995. The 2,6-NDA yield was only 74.4 mol% in Example 11 because of the high initial onion concentration compared to 84.5 mol% of Example 13. This clearly demonstrates that the 2,6-NDA yield is reduced when the starting onion in the reactor before the oxidation reaction is still in the basic condition. 5 pseudo-cumene (PSCk liquid phase argonization name

Comparative Example A 0.87 g of cobalt acetate tetrahydrate, 1.0 g of acetic acid tetratetrahydrate, 0.29 g of hydrogen bromide solution (48%), and 86·086 g of acetic acid wrong solution (17% Zr) were injected thereto. 10 2 liters of titanium autoclave with 529 g of glacial acetic acid, 28 g of water' and 293 g of pseudocumene. The initial charge was heated to 3 20 °F (16 0 °C) under slow nitrogen purge, and then pressurized air (increased to 24.5% 〇2) was added at 54 standard cubic feet per hour for about 15 minutes. During this 15 minute period, the temperature was maintained at 330 卞 (165.6 ° (:) by maintaining the pressure at about 105 卩 81 §. After adding air for 3 minutes, the 15 tail catalyst was dissolved at 0.8 g/min and added to 40.0. The gram was added. The finishing 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 hydrazine solution, 12.39 g of HBr solution, and 2.10 g of cesium acetate. Oxidation started at 15 minutes. The pressure and temperature were linearly increased from 345 (173.9 〇 and 20 105 psig to 410 卞 (210 〇 and 280 48 48. The final temperature and pressure were achieved by oxidation in about 40 minutes. Then, the temperature and pressure were maintained here). Equivalent oxygen to the outlet quickly rises to 14%, indicating complete oxidation.

In addition to temperature and pressure rise, the air rate is increased from 54 to 60 SCFH in stages from the 15th to the 20th minute. It was maintained at 58 SCFH 33 1337995 to the 45th minute and then gradually reduced to 5 〇 SCFH during 7 minutes. The air rate is maintained at 50 SCFH until the helium is complete. The air rises in this way to maximize oxygen consumption and to avoid oxygen from the outlet rising to the flammable range. The product of this oxidation was collected and the sample was dried to a solid and separated. Table 4 has this operation and the relevant data of Examples 15 and 16. Example 15 This oxidation was carried out in the same manner as in Comparative Example A, except that 5 g of hydrazine was added to the starting reaction mixture. Example 16 0 This oxidation was carried out in the same manner as in Comparative Example A, except that the tailing catalyst was saturated at 320 ppm and was not added to the starting catalyst. Table 4, % by weight of solids Comparative Example A No onion Example 15 Starting 0.5 g of onion Example 16 320 ppm of onion stearic acid in the finishing catalyst 86.2 90.5 92.9 _ Methyl diacid 436 1.17 0.31 _ Reaction time (minutes) 58.2 56.0 58.7 Table 4 shows the activation of onion added at the beginning and added via the tailing catalyst (i.e., continuously added at low levels throughout the batch oxidation). The yield of trimellitic acid (TMLA) is higher because of the major intermediate, methyl diacid (also known as methyl dibasic acid or MDB), which is significantly reduced by higher activity. This reaction uses cobalt at a level 2-3 times lower than the usual commercial concentration, indicating that the onion has the potential to provide a substantial reduction in catalyst cost. The cobalt concentrations of Comparative Example A, Example 15, and Example 16 were 0.07% by weight based on the injected pseudocumene. In a typical commercial reaction, the cobalt concentration is 0.16% by weight. Therefore, comparing the results of Examples 15 and 16 with the results of Comparative Example 34 1337995, A, it can be seen that the addition of onions to the starting or ending catalyst can be used in the lower 3: (ie, 0.07 wt%). The pseudocumene is well converted to trimellitic acid in the catalyst system and has a low content of methyl diacid by-product. The lower content of cobalt used in the above examples exhibited a 56% cobalt reduction compared to the 16% by weight drill. The ability to reduce cobalt while maintaining acceptable activity results in significant catalyst savings. [Circular Simple Description 3 (None) [Main Component Symbol Description] (None) 35

Claims (1)

丄幻/995 ------------------ X. Patent application scope: 1. A method for oxidizing aromatic hydrocarbons with molecular oxygen source to form aromatic carboxylic acids in liquid phase conditions and in the presence of a catalyst. The method, the aromatic carboxylic acid is selected from the group consisting of isophthalic acid, p-dicarboxylic acid, trimellitic acid, and 2,6-cainic acid. The catalyst comprises: 5 a) at least one heavy metal oxidation catalyst; b) - bromine Source; and c) an unsubstituted polycyclic aromatic hydrocarbon. ^ If you apply for a patent range! The method of the present invention, wherein the unsubstituted polycyclic aromatic hydrocarbon is selected from the group consisting of onions, naphthalenes, tetras, and the like. 10 3. The method of claim 2, wherein the unsubstituted polycyclic aromatic hydrocarbon system is ruthenium. 4. The method of claim 1, wherein the bromine source comprises - or more selected from the group consisting of βΓ2, HBr, NaBr, KBr, NH4Br, benzyl desertification acetic acid, dimethoacetic acid, and tetracalcin. Bromine compounds of ErMo E and Molybdenum. 5. The method of claiming the scope of the patent, wherein the heavy metal comprises or is selected from the group consisting of ϋ, 锦, lead, 钦, sharp, key, recorded, and secondary metals. 6. The method of claim 2, wherein the heavy metal is present in an amount ranging from about 20 ppmw to about 600 〇 ppmw. 7. The method of claim 1, wherein the oxidizing is carried out at a temperature ranging from about 5 °C to about 250 Torr. Please refer to the material of the first item of the patent system, the towel, and the temperature of the Weihuaxian 120C to about 250 °C. The method of claim 1, wherein the oxidizing is carried out at a pressure in the range of from about 90 psig to about 450 psig. 10. The method of claim 1, wherein the oxidizing is carried out at a pressure in the range of from about 100 psig to about 400 psig. 5. The method of claim 1, wherein the method comprises the steps of: oxidizing p-xylene with a molecular oxygen source in the presence of a catalyst under liquid phase conditions to form terephthalic acid, the catalyst comprising: a) at least one heavy metal An oxidation catalyst; b) a source of bromine; and 10 15 20 c) an unsubstituted polycyclic aromatic hydrocarbon. 12. The method of claim 11, wherein the unsubstituted polycyclic aromatic hydrocarbon is selected from the group consisting of ruthenium, naphthalene, naphthacene, and the like. 13. The method of claim 12, wherein the unsubstituted polycyclic aromatic hydrocarbon based onion. 14. The method of claim 1, wherein the method comprises the steps of: oxidizing meta-indenylbenzene with a molecular oxygen source in the presence of a catalyst under liquid phase conditions, the catalyst comprising: a) at least one heavy metal oxide a catalyst; b) a source of bromine; and c) an unsubstituted polycyclic aromatic hydrocarbon. 15. The method of claim 14, wherein the unsubstituted polycyclic aromatic hydrocarbon is selected from the group consisting of onion, naphthalene, naphthacene, and the like. 16. The method of claim 15, wherein the unsubstituted polycyclic aromatic hydrocarbon onion is used. 37 1337995 π. The method of claim i, which is used in the presence of a catalyst to oxidize 2,6-dimethylcaxane in a molecular oxygen source in the presence of a catalyst to form "cai dicarboxylic acid, the catalyst And comprising: a) at least one heavy metal oxidation catalyst; 5 b) - a bromine source; and c) an unsubstituted polycyclic aromatic cigarette. 18. The method of claim 17, wherein the unsubstituted The polyvalent aromatic hydrocarbon is selected from the group consisting of onion, naphthalene, naphthacene, and the like. 19. The method of claim 18, wherein the unsubstituted poly 10 ring aromatic hydrocarbon system 20. The method of claim 1, wherein the method is for oxidizing pseudocumene to phthalic acid, comprising catalyzing the oxidation of pseudo-cumene by molecular oxygen source in the presence of a catalyst under liquid phase conditions. The catalyst comprises: a) at least one heavy metal oxidation catalyst; 15 b) - a bromine source; and c) an unsubstituted polycyclic aromatic hydrocarbon. 21. The method of claim 20, wherein Unsubstituted polycyclic aromatic tobacco is selected from the group consisting of onion, naphthalene, and tetracene, and the like 22. The method of claim 21, wherein the unsubstituted poly 20-ring aromatic hydrocarbon-based onion. 23. The method of claim 20, wherein the heavy metal comprises One or more selected from the group consisting of lanthanum, cerium, zirconium, titanium, and secondary metals. 24. The method of claim 20, wherein the heavy metal is present in an amount ranging from about 100 ppmw to about 6000 ppmw. 38. The method of claim 2, wherein the method is for converting pseudocumene to trimellitic acid, comprising catalytically oxidizing a pseudo-cumene with a molecular oxygen source in the presence of a catalyst under liquid phase conditions. The catalyst comprises: a) a guram-tellurium catalyst; 5 b) a bromine source; and c) an onion. 26. If the method of applying the full-time second item is applied, the sputum is converted into a stupid a triacid comprising a feedstock for catalytically oxidizing pseudodecene containing a molecular oxygen source in the presence of a catalyst under liquid phase conditions, the catalyst comprising: 10 a) a lead-cobalt-manganese-ruthenium catalyst; b) a source of bromine; c) onion. 27. The method of claim 2G, wherein the oxidation The method is carried out at a temperature ranging from about 50 ° C to about 250 ° C. The method of claim 20, wherein the oxidation is carried out at a temperature ranging from about 100 ° C to about 250 ° C. The method of claim 2, wherein the oxidation is carried out at a pressure in the range of from about 90 psig to about 300 psig. 30. A method for converting pseudo-lean to trimellitic acid, comprising The feed containing pseudocumene is catalytically oxidized by a molecular oxygen source in the presence of a catalyst under liquid phase conditions 20, the catalyst comprising: a) at least one heavy metal oxidation catalyst; b) a bromine source; and 0 is selected from M, Polycyclic aromatic hydrocarbons of unsubstituted 39 1337995; naphthalene, naphthacene, and mixtures thereof, which are at a temperature in the range of from about 100 ° C to about 250 ° C: at a pressure in the range of from about 90 psig to about 300 psig . 31. The method of claim 30, wherein the oxidizing is carried out at a temperature ranging from about 5 ° C to about 220 ° C and at a pressure in the range of from about 105 psig to about 280 pSig, and wherein The unsubstituted polycyclic aromatic hydrocarbon based onion. 32. The method of claim 30, wherein the heavy metal comprises cobalt and one or more selected from the group consisting of manganese, lanthanum, cerium, titanium, and a secondary metal 'and wherein the heavy metal is about 100 ppmw to Amounts in the range of about 6000 ppmw are now available. 33. The method of claim 1, wherein the method is for converting pseudocumene to trimellitic acid, comprising liquid phase, comprising a cobalt source, a manganese source plus a bromine source, and an unsubstituted In the presence of a polycyclic aromatic hydrocarbon catalyst, with or without a source of zirconium, catalytically oxidizing pseudo-cumene with a molecular oxygen source at a temperature of from about 10 ° C to about 25 (temperature in the range of TC and in a second order) Feed, of which, the first stage The batching is carried out in batch or semi-continuous, and the second stage is carried out in batch mode, wherein the addition of the bromine component is carried out such that about 5% of the total bromine is added to the first stage by adding And the remaining is added in the second stage, wherein the temperature of the second stage is raised from about 175 ° C to about 250 a C, and the temperature of the first stage 2 〇 is about S 2 S ° C to about 165 ° C The two-stage addition of the bromine component is simultaneously performed when the molecular oxygen source is introduced to the feed. 34. The method of claim 33, wherein the unsubstituted polycyclic aromatic hydrocarbon is selected from the group consisting of onion, naphthalene, naphthacene, and the like. 35' The method of claim 1, wherein the method comprises the use of one or more of about 3 to about 10 milligrams of total metal in the liquid phase condition 40 to provide a pseudocumene per gram of mole. The catalyst comprising a heavy metal oxidation catalyst having a positive trivalent ruthenium, zirconium, cobalt and manganese, a bromine source, and an unsubstituted polycyclic aromatic hydrocarbon in the range of from about 100 ° C to about 275 ° C, Oxidizing the pseudocumene 5 to trimellitic acid by molecular oxygen, the method comprising adding the bromine component in stages in at least two stages, wherein from 0 to about 35% by weight of the total bromine is added in the first stage, and the remaining Added in the final stage, and wherein all the lanthanum is added at the final stage, and wherein the temperature of the last stage is raised from about 175 ° C to 275 ° C, and the temperature of the previous stage is about 125 ° C Between approximately 10 165 ° C. The method of claim 35, wherein the unsubstituted polycyclic aromatic hydrocarbon is selected from the group consisting of onions, naphthalenes, tetras, and the like. 37. The method of claim 1, wherein the unsubstituted polycyclic aromatic hydrocarbon comprises a petroleum refinery by-product 15 containing an unsubstituted polycyclic aromatic hydrocarbon. 41