CN104011005A - Process for producing terephthalic acid - Google Patents
Process for producing terephthalic acid Download PDFInfo
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- CN104011005A CN104011005A CN201280064613.0A CN201280064613A CN104011005A CN 104011005 A CN104011005 A CN 104011005A CN 201280064613 A CN201280064613 A CN 201280064613A CN 104011005 A CN104011005 A CN 104011005A
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
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- B01J2204/00—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices
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Abstract
Methods and apparatus for producing terephthalic acid using a p-xylene stream enriched with p-toluic acid are described. The apparatus includes first and second reactor zones. The reactor zones can be in the same reactor or in different reactors.
Description
Prioity claim
The application requires the U. S. application the 13/340th of submitting on December 29th, 2011, the right of priority of 132 and 13/340, No. 122.
Invention field
The present invention relates to terephthalic acid composition and prepared the method for terephthalic acid by the raw material that comprises p-Xylol.More particularly, the present invention relates to the p-Xylol stream oxidation of enrichment p-methylbenzoic acid to prepare the method and apparatus of terephthalic acid.
Background of invention
Alkylaromatics as the oxidation of toluene and dimethylbenzene be important business method.Can obtain various oxidation productss, comprise that aromatic carboxylic acid is as terephthalic acid (Isosorbide-5-Nitrae-phthalic acid and m-phthalic acid (1,3-phthalic acid)), it is for for example polymer industry.
Known oxidation products is as aromatic alcohol, aromatic aldehyde, aromatic ketone and aromatic carboxylic acid curable or crystallization under oxidizing condition and/or in the time that reaction mixture is cooling.Therefore, can prepare the mixture of oxidation products, it needs further to process the purity of expecting product to increase.For example, in the preparation of terephthalic acid, oxidation products is commonly referred to thick terephthalic acid, and this is because it contains impurity, includes colour solid and intermediate oxidation products, especially 4-carboxyl benzaldehyde (4-CBA).For obtaining grade polymer or purified terephthalic acid, various purification step known in the art, it comprises: make the thick terephthalic acid of water and/or solvent wash, additionally oxidation or crystallisation step and (generally include the catalyzer that contains palladium and carbon) under hydrogenation conditions to make solution and the H-H reaction of dissolved thick terephthalic acid.Conventionally use several purification steps.
US 2,833,816 discloses the method that aromatic substance is oxidized to corresponding aromatic carboxylic acid.Under acid exists, the method for liquid-phase oxidation Alkylaromatics is used molecular oxygen, metal or metal ion and bromine or bromide anion.Metal can comprise cobalt and/or manganese.Exemplary acid is more rudimentary carbocyclic aliphatic family monocarboxylic acid, the especially acetic acid that contains 1 to 8 carbon atom.
US 6,355,835 discloses the method for preparing benzene dicarboxylic acid by the liquid-phase oxidation of xylene isomer, and it is undertaken by being oxidized under existing as catalyzer and initiator as solvent, cobalt salt at acetic acid with oxygen or air.At oxidation step post-flush reaction mixture to remove volatile matter and cooling and filtering material, thereby obtain crude benzol diacid as solid product and filtrate.Recrystallization crude benzol diacid is also disclosed to obtain at least 99% purity and to reclaim filtrate.
US 7,094,925 discloses the method for preparing Alkylaromatics.The method is included in ionic liquid and has lower blending oxidizing agent or sulphur compound.Can use other oxide compounds of air, dioxygen, superoxide, super-oxide or arbitrary other forms of active oxygen, nitrite, nitrate and nitric acid or nitrogen or oxyhalogenide (hydration or anhydrous) as oxygenant.Conventionally under Bronstead acidic conditions, carry out the method.Preferably be oxidized in as the ionic liquid of methylsulfonic acid containing sour promotor.Midbody compound when product is preferably carboxylic acid or ketone or oxidation is as aldehyde or alcohol.
US 7,985,875 described by liquid-phase oxidation two-or trisubstituted benzene or naphthalene compound prepare aromatic multi-carboxy acid's method.The method comprises makes aromatic substance in reaction zone, contact under the existence of carboxylic acid solvent, metal catalyst and promotor with oxygenant.The ionic liquid that promotor being comprises organic cation and bromide or iodide anion.Promotor is with 10-50, and the concentration range of 000ppm (based on solvent) is used, and wherein preferable range is 10-1,000ppm.In the method without using other promotor as bromine-containing compound.The method makes the thick terephthalic acid (CTA) with 1.4-2.2%4-CBA.Need purifying CTA to obtain purified terephthalic acid (PTA).
US 2010/0174111 has described purifying aryl carboxylic acid as the method for terephthalic acid.Impure acid is dissolved or dispersed in ionic liquid.To adding non-solvent (be defined as ion solvent there is therein high-dissolvability and aryl carboxylic acid have therein less or there is no the molecular solvent of solubleness) in solution so that purified Acid precipitation.
US 7,692,036, US2007/0155985, US 2007/0208193 and US 2010/0200804 disclose the method and apparatus that carries out the liquid-phase oxidation of oxidizable compounds.This liquid-phase oxidation is to carry out in bubble column reactor, and this reactor can provide highly effective reaction under relatively lower temp.In the time that oxygenated compound is p-Xylol, the product that carrys out automatic oxidation reaction is the CTA of necessary purifying.For conventional high-temperature method, it is believed that purifying is comparatively easy.
Summary of the invention
The invention provides the method that p xylene oxidation is become to terephthalic acid.Find, the amount that the present invention can be used for preparing pollutent is different from the terephthalic acid composition of the amount of pollutant of observing in traditional method.In some embodiments, the terephthalic acid composition making by present method has low impurity content and therefore its purifying is comparatively cheap.In some embodiments, the present invention prepares grade polymer terephthalic acid or purified terephthalic acid in the situation that not using catalytic hydrogenation.
One aspect of the present invention is the method for preparing terephthalic acid.In one embodiment, present method comprises provides the p-Xylol of enrichment p-methylbenzoic acid stream; The solvent, bromine source, the catalyzer that flow with the p-Xylol that makes enrichment p-methylbenzoic acid, comprise ionic liquid contact to prepare the product that comprises terephthalic acid with oxygenant.In one aspect, provide the p-Xylol stream of enrichment p-methylbenzoic acid to comprise that the first solvent, the first bromine source, the first catalyzer that make p-Xylol, comprise carboxylic acid contact to prepare p-Xylol stream in the first reaction zone with the first oxygenant.
Another aspect of the present invention comprises the device for oxidizing alkylaromatic compounds.In one embodiment, this device comprises the first reaction zone, and it has at least one entrance and at least one outlet; Second reaction zone, it has at least one entrance and at least one outlet, and at least one second reaction zone entrance is communicated with at least one first reaction zone outlet fluid; And zone purification, it has at least one entrance and at least one outlet, at least one zone purification entrance is communicated with at least one second reaction zone outlet fluid, and at least one zone purification exports with at least one first reaction zone entrance or at least one second reaction zone inlet fluid is communicated with or at least one zone purification outlet is communicated with at least one first reaction zone entrance and the two equal fluid of at least one second reaction zone entrance.
In another embodiment, present method comprises provides the p-Xylol stream that comprises p-methylbenzoic acid, and wherein the method for content of at least 5 % by weight by p-methylbenzoic acid being maintained to the p-Xylol stream being made by it is prepared p-Xylol stream; The solvent that makes to comprise ionic liquid, bromine source, catalyzer, described in provide the p-Xylol stream of step to contact to prepare the product that comprises terephthalic acid with oxygenant.
In another embodiment, present method comprises the p-Xylol stream that makes p-Xylol, the first solvent, the first bromine source, the first catalyzer contact to prepare enrichment p-methylbenzoic acid with the first oxygenant; P-methylbenzoic acid is maintained to the content of at least 5 % by weight of the p-Xylol stream of enrichment p-methylbenzoic acid; The second solvent, the second bromine source, the second catalyzer, the second oxygenant that flow with the p-Xylol that makes enrichment p-methylbenzoic acid, comprise ionic liquid contact to prepare the product that comprises terephthalic acid.
Brief description of the drawings
Fig. 1 is the response diagram of oxidation of p-xylene.
Fig. 2 is the general technology schema of an embodiment of the method for the purified oxidizing alkylaromatic compounds of preparation.
Fig. 3 is the general technology schema of another embodiment of the method for the purified oxidizing alkylaromatic compounds of preparation.
Fig. 4 is the process flow sheet with the embodiment of single reaction vessel.
Demonstrating of an embodiment of Tu5Shi bis-district's continuous stirred tank reactors.
Demonstrating of an embodiment of Tu6Shi bis-district's piston flow bubbling style reactors.
Fig. 7 is the figure that shows the impact of raw material on foreign matter content.
Detailed Description Of The Invention
Generally speaking, the present invention relates to terephthalic acid composition and the method that p xylene oxidation is become to terephthalic acid.Wide speech, the present invention is the method for being prepared terephthalic acid by the p-Xylol stream of enrichment p-methylbenzoic acid.
As discussed below, if find, parent material is p-methylbenzoic acid but not p-Xylol, and the output of 4-CBA is significantly lower.Therefore, after measured, expect to be started by the p-Xylol incoming flow of enrichment p-methylbenzoic acid.
In addition the general response diagram of, preparing terephthalic acid by the liquid-phase oxidation of p-Xylol is shown in Fig. 1.In these reaction train, in acetic acid, can prepare p-methylbenzoic acid by p-Xylol quickly compared with in ionic liquid.But, following reaction compared with in independent acetic acid in ionic liquid/acetate mixture more quick with have more selectivity.
Can any suitable way (including but not limited to oxidation, alkylation and like that) obtain the p-Xylol stream of enrichment p-methylbenzoic acid.For example, as described below, the material stream with required p-methylbenzoic acid content can product stream form produce in oil or chemical treatment title complex.If initial product stream does not have required purity, can use currently known methods to be purified to expecting content.
The p-Xylol stream of enrichment p-methylbenzoic acid contains at least 5% and be less than the p-methylbenzoic acid of 90 % by weight.It contains at least 10 % by weight or at least 15 % by weight or at least 20 % by weight or at least 25 % by weight or at least 30 % by weight or at least 35 % by weight or at least 40 % by weight or at least 45 % by weight or at least 50 % by weight or at least 55 % by weight or at least 60 % by weight or at least 65 % by weight or at least 70 % by weight or at least 75 % by weight conventionally.It can contain and is less than 85 % by weight or is less than 80 % by weight or is less than 75 % by weight or is less than 70 % by weight or is less than 65 % by weight or is less than 60 % by weight or is less than 55 % by weight or is less than 50 % by weight or is less than 45 % by weight or is less than 40 % by weight.
Maintain the p-methylbenzoic acid content in solution (being colloid or slurries form).
The basic step of the method comprises makes the p-Xylol stream (no matter obtaining in which way) of enrichment p-methylbenzoic acid, solvent, bromine source, the catalyzer that comprises ionic liquid contact to prepare the product that comprises terephthalic acid with oxygenant.
Contact procedure can be put into practice via full scale commercial operation in laboratory scale experiment.The method can be in batches, the operation of continuous or semicontinuous pattern.Contact procedure can be carried out in every way.The order of addition of component (p-Xylol stream, solvent, bromine source, catalyzer and the oxygenant of for example enrichment p-methylbenzoic acid) is unimportant.For example, can individually add each component, or can or mix two or more components in combination with other combination of components or before mixing.
Fig. 2 is the general technology schema of the embodiment of the method for the purified oxidizing alkylaromatic compounds of preparation.
Charging 200 is introduced in oxidation zone 210 together with oxygenant 215.Evaporator overhead condenser 225 is removed heat to control reaction zone temperature from reflux stream, and the useless G&W from reaction zone is removed in uptake zone 230 and drying zone 235.
The effluent liquid 240 in autoxidation district 210 is delivered in crystallizing field 300 to complete crystallisation process in the future.Crystallizing field 300 can comprise one or more rear reaction zones and/or one or more crystallizer.If desired after, reaction zone further increases conversion, needs excess oxygen agent.Rear reaction zone can operate to contribute to crystallization under lower pressure and lesser temps.Use one or more crystallizers to complete at a lower temperature product as the crystallization of terephthalic acid.Should note making impurity cocrystallization.The solvent that comprises ionic liquid provides impurity and/or intermediate to remain in the medium that in solvent or is further oxidized to terephthalic acid, reduces in fact thus the impurity of cocrystallization.
In disengaging zone 305, make crystallized product and separated from solvent.As known in the art, disengaging zone 305 can comprise one or more strainers, sedimentator and moisture eliminator.
Use solvent 310 to wash the product crystal in disengaging zone 305.Be dried purified product 315 and be stored in product warehouse.Can need additional separation device before storing, to meet product specification to guarantee product.
To be delivered in separated from solvent district 325 through washing mother liquor 320.As known to the person skilled in the art, separated from solvent can comprise vaporizer, distillation and/or separation column, membrane separation apparatus and like that in one or more.Ionic liquid 260 recirculation are returned in oxidation zone 210.Can optionally add and supplement ionic liquid 265.
Carry catalyzer 330 for catalyst recovery.
In drying zone 340, carboxylic acid solvent 335 is dewatered.Carboxylic acid solvent's 205 recirculation can be returned in oxidation zone 210.Can optionally add and supplement carboxylic acid solvent 220.Remove waste water 345.
Fig. 3 is the general technology schema with the embodiment of two reaction zones.
In some embodiments, can in the first reaction zone, use the method for any type.For example, if expect, can use above or the patent that quotes in other places in any commercially available method discussed.
In other embodiments, use the method for oxidation of setting forth.
The charging 200 that comprises p-Xylol, carboxylic acid solvent, catalyzer, bromine source and oxygenant 215 (if existence) enters in the first reaction zone 210.Evaporator overhead condenser 225 is removed heat to control reaction zone temperature from reflux stream, and the useless G&W from reaction zone is removed in uptake zone 230 and drying zone 235.
Use product (it is the p-Xylol stream of the enrichment p-methylbenzoic acid) conduct from the first reaction zone to be used for the charging 240 of the second oxidation reaction zone 245.Charging can comprise carboxylic acid solvent, ion liquid solvent, catalyzer and bromine source.The charging of the second oxidation reaction zone 245 also comprises the ionic liquid stream 260 of oxygenant 250 and recirculation.Ion liquid solvent stream 260 can comprise the ionic liquid that supplements ionic liquid 265 and reclaim.
Solvent in the second oxidation reaction zone 245 can comprise carboxylic acid solvent and ionic liquid.Compared with traditional method, using ionic liquid when avoiding excessive solvent volume, can reduce carboxylic acid solvent's amount.
Evaporator overhead condenser 270 is removed heat to control temperature of reactor from the reflux stream of the second oxidation reaction zone 245, and the useless G&W from reaction zone is removed in uptake zone 275 and drying zone 280.
The second oxidation reaction zone 245 can comprise that the material that flows to heat exchanger 290 and then return in the second oxidation reaction zone 245 flows 285.Depend on design of reaction area, colder recirculation flow can return to the appropriate location in vapor space (upper area) or the plug-flow reaction district of reaction zone.
To be delivered in crystallizing field 300 to complete crystallisation process from the effluent mixture 295 of the second oxidation reaction zone 245.Crystallizing field 300 can comprise one or more rear reaction zones and/or one or more crystallizer.If desired after, reaction zone further increases conversion, will need excess oxygen agent.Rear reaction zone can operate to contribute to crystallization under lower pressure and lesser temps.Use one or more crystallizers to complete at a lower temperature the crystallization of terephthalic acid.
In disengaging zone 305, make crystallized product and separated from solvent.As known in the art, disengaging zone 305 can comprise one or more strainers, sedimentator and moisture eliminator.
Use solvent 310 to wash the product crystal in disengaging zone 305.Be dried purified product 315 and be stored in product warehouse.Can need additional separation device before storing, to meet product specification to guarantee product.
Washing mother liquor 320 is delivered in separated from solvent district 325.Ionic liquid 260 recirculation are returned in the second oxidation reaction zone 245 and optional the first oxidation reaction zone (depending on the method using in the first reactor).Can optionally add and supplement ionic liquid 265.
Carry catalyzer 330 for catalyst recovery.
In drying zone 340, carboxylic acid solvent 335 is dewatered.Carboxylic acid solvent's 205 recirculation can be returned in the first oxidation reaction zone 210.Can optionally add and supplement carboxylic acid solvent 220.Remove waste water 345.
If expect, the first and second reaction zones can be arranged in different reactor.But increasing by the second titanium reactor can remarkable increase method cost.In addition, may be not easy to increase the second reactor in existing installation.
Therefore,, if expect, the first and second reaction zones can be arranged in single reaction vessel.As demonstrated in Fig. 4, two reaction zone 210' and 245' are positioned at single reaction vessel 350 Zhong Liangge districts.By suitably designing Liang Ge district, can obtain identical result.
Fig. 5 has demonstrated the embodiment of the continuous stirred tank reactor (CSTR) 400 with the design of Liang Ge district.Charging 405 enters the first reaction zone 410 as in annular space.Charging 405 comprises Alkylaromatics and catalyzer and carboxylic acid solvent.Optionally, oxygenant 415 enters in the first reaction zone 410 via gas distribution ring 420., overflow and enter in second reaction zone 430 from reactant and the product 425 of the first reaction zone 410 as after being less than 10min. to 40min. at short residence time(SRT).If use p-Xylol as parent material, should be p-methylbenzoic acid from the primary product of the first reaction zone 410, p-methylbenzoic acid further reacts to generate terephthalic acid in second reaction zone 430.Top carboxylic acid and water will be in condenser 435 condensation and returning in 440 first reaction zones 410.Condenser 435 is positioned at reactor 400 tops and carries to minimize solid.Reaction times in second reaction zone than the first reaction head of district, for example, is greater than 10min conventionally.Reaction conditions in the first and second reaction zones with hereinafter discuss those are similar.
Second reaction zone 430 is under content control.Exist the second distribution rings 445 so that oxygenant 450 is introduced in second reaction zone 430.Make steam bubbling from second reaction zone 430 by the first reaction zone 410 to be provided for the suitable mixing of the first reaction zone 410.Mother liquor and ion liquid solvent 455 enter and mix with the charging 425 from the first reaction zone 410 near 430 bottoms, second reaction zone.The product 460 of second reaction zone 430 leaves via inner or outside degasifier 465.In order to control the ratio of ionic liquid and carboxylic acid, can optionally return in 470 second reaction zone 430 together with supplementary carboxylic acid 475 from the carboxylic acid of a certain amount of condenser 420.
CSTR reactor comprises that the impeller 480 with baffle plate 485 is to mix the content of second reaction zone 430.
Fig. 6 has shown and has comprised the first reaction zone 505 and second reaction zone 510 bis-district's piston flow bubbling reactors 500.Charging 515 (comprising Alkylaromatics, carboxylic acid solvent and catalyzer) enters in the first reaction zone 505.Oxygenant is added in the first reaction zone 505.The first reaction zone 505 is positioned 510 tops, second reaction zone.Flow through 505 tops, the first reaction zone and entering in second reaction zone 510 of reactant and product 520.Near 510 tops, second reaction zone, introduce the charging 525 (comprising ion liquid solvent and mother liquor) for second reaction zone 510.The condensation and returning in 535 first reaction zones 505 in condenser 530 of acetic acid overhead and water.
Exist distribution rings 550 so that oxygenant 555 is introduced in second reaction zone 510.Make steam bubbling from second reaction zone 510 by the first reaction zone 505 to be provided for the suitable mixing of the first reaction zone 505.The product 560 of second reaction zone 510 leaves via inside or the outside degasifier 565 at 510 middle parts, the second reactor zone.For controlling the ratio of ionic liquid and carboxylic acid, can optionally return in second reaction zone 510 together with supplementary carboxylic acid 545 from the carboxylic acid 540 of condenser 530.
Method for product recovery and equipment and above set forth for two reactor assemblies similar.
Solvent comprises at least one ionic liquid.If expect, can use two or more ionic liquids.
Conventionally the anhydrous organic salt that ionic liquid is made up of ion, wherein positive ion and negative ion electric charge balance.These materials have low melting point (conventionally below 100 DEG C), undetectable vapour pressure and good chemistry and thermostability.The cationic charge of salt concentrates on heteroatoms, and negatively charged ion can be any inorganic, organic or organo-metallic material.
Most of ionic liquid is to be formed by the positively charged ion that does not contain acid proton.The synthetic of ionic liquid can be divided into two parts conventionally: form and expect positively charged ion, and carry out anionresin and expect product to form.In cationic the synthesizing of ionic liquid, the quaternized of amine or phosphine is for example initial step.If can not directly form and expect negatively charged ion by quaterisation, need another step.
According to estimates, exist hundreds of thousands of kind simple ion to combine in order to prepare ionic liquid, and have almost infinite (10
18) the potential ionic liquid mixture of quantity.This means that the ionic liquid that should have desirable properties by selection negatively charged ion, positively charged ion and mixture concentration design is to adapt to application-specific.Adjustable or fine setting ionic liquid is to be provided for the specific fusing point, viscosity, density, hydrophobicity, compatibility etc. of application-specific.The thermokinetics of institute's implementation method in ionic liquid and reaction kinetics are different from those in traditional sucrose.This produces the new chance for catalyzed reaction, separation, composite reaction/sepn process, hot transfer agent, hydraulic fluid, paint additive, electrochemical applications and many other application.Ionic liquid does not distribute volatile organic compounds (VOC), thereby is provided for clean basis of manufacturing as " Green Chemistry ".
Organic cation can comprise linearity, branching or the ring-type alkyl unit of mixing.Term " assorted alkyl " refers to comprise and one or morely can form the cationic heteroatomic positively charged ion that is selected from nitrogen, oxygen, sulphur, boron, arsenic, boron, antimony, aluminium or phosphorus.Heteroatoms can be a part for the ring (for example, pyridyl, tetrahydroglyoxaline basic ring) of one or more other heteroatomss formation of use, and it can be attached with the linearity or the branched-alkyl unit that are substituted or are unsubstituted.In addition, positively charged ion can be single heteroatoms, thereby wherein the linearity that is substituted or is unsubstituted of sufficient amount or branched-alkyl unit are attached to this heteroatoms and form positively charged ion.
Can alkylation with form the heterocycle of positively charged ion unit and the limiting examples of heteroaryl unit comprise imidazoles, pyrazoles, thiazole, isothiazole, azepine thiazole, oxo thiazole,
piperazine,
azoles quinoline, oxa-azepine boron heterocyclic pentylene (oxazaborole), dithiazole, triazole, selenazoles (selenozole), oxa-phosphurane (oxaphosphole), pyrroles, boron heterocyclic pentylene, furans, thiophene, phosphurane, pentazole, indoles, indoline,
azoles, isothiazole (isothirazole), tetrazolium, cumarone, diphenylene-oxide, thionaphthene, dibenzothiophene, thiadiazoles, pyridine, pyrimidine, pyrazine, clatter piperazine, piperazine, piperidines, morpholine, pyrans, Arnold's quinoline (annoline), phthalazines (phthalazine), quinazoline and quinoxaline.
The anionicsite of ionic liquid can comprise inorganic, organic or organo-metallic structure division.The limiting examples of negatively charged ion comprises inorganic anion: halogen (for example, F, Cl, Br and I); Boron ion, BX
4(wherein X represents halogen, (for example, BF
4, BCl
4)) and like that; Phosphate radical (V), PX
6; PF
6with like that; Arsenate (V), AsX
6; AsF
6with like that; Metaantimmonic acid root (V) (antimony), SbX
6; SbF
6with like that; CO
3 2-; NO
2 1-, NO
3 1-, SO
4 2-, PO
4 3-, (CF
3) SO
3 1-with their derivative.
Other limiting examples of ionic liquid negatively charged ion comprise and are substituted azoles negatively charged ion (azolate), in position 1 and 3 (imidazole anion), 1,2 and 3 (1,2,3-triazole negatively charged ion) or 1,2,4 (1,2,4-triazole negatively charged ion) in there are 5 element heterocycle aromatic rings of nitrogen-atoms.Ring replaces and betides the position (these positions are carbon locations) that is not positioned at nitrogen position and locate and comprise the CN (cyano group-), the NO that are connected to heterocycle azoles negatively charged ion core
2(nitro-) and NH
2(amino).
Other limiting examples of negatively charged ion comprise the boron ion that is substituted or is unsubstituted: B (R)
4; The sulfate radical that is substituted or is unsubstituted: (RO) S (=O)
2o; The acyl group unit R CO that is substituted or is unsubstituted
2, for example acetate moiety CH
3cO
2, propionate CH
3cH
2cO
2, butyric acid root CH
3cH
2cH
2cO
2with benzoate anion C
6h
5cO
2; The phosphate radical that is substituted or is unsubstituted: (RO)
2p (=O) O; The carboxylate radical that is substituted or is unsubstituted: (RO) C (=O) O; The azoles negatively charged ion that is substituted or is unsubstituted, wherein azoles negatively charged ion can replace through being selected from cyano group, nitro and amino unit on carbon atom.R can be organic and inorganic or organometallic group.The limiting examples of R comprises hydrogen; The linearity, branching and the cyclic alkyl that are substituted or are unsubstituted; The linearity, branching and the cyclic alkoxy that are substituted or are unsubstituted; The aryl that is substituted or is unsubstituted; The aryloxy that is substituted or is unsubstituted; The heterocycle that is substituted or is unsubstituted; The heteroaryl that is substituted or is unsubstituted; Acyl group; Silyl; Boryl; Phosphino-; Amino; Sulfenyl; And seleno.
In one embodiment, the ionic liquid that is suitable for using includes but not limited to lower one or more: imidazoles
ionic liquid, pyridine
ionic liquid, tetraalkyl ammonium ion liquid and
ionic liquid.Can use more than one ionic liquids.Imidazoles
pyridine
there is with ammonium ion liquid the positively charged ion that comprises at least one nitrogen-atoms.
ionic liquid has the positively charged ion that comprises at least one phosphorus atom.In one embodiment, ionic liquid comprises and is selected from alkyl imidazole
dialkylimidazolium
and the positively charged ion of combination.In another embodiment, ionic liquid comprises the negatively charged ion that is selected from halogen ion, acetate moiety, carboxylate radical and combination thereof.Ionic liquid can comprise at least one in following: acetic acid 1-butyl 3-Methylimidazole
(BMImOAc), bromination 1-butyl 3-Methylimidazole
(BMImBr), acetic acid 1-hexyl 3-Methylimidazole
with bromination 1-hexyl 3-Methylimidazole
Can provide ionic liquid, or it can generate by suitable precursor original position, or these two kinds of modes are all used.If original position generates, the precursor that solvent comprises one or more ionic liquids.Ionic liquid precursor comprises that cation precursor is if alkyl imidazole, alkyl pyridine, alkylamine, alkylphosphines and like that and negatively charged ion precursor are as alkyl or aryl halogenide or acetate.In one embodiment, precursor is Methylimidazole and butyl bromide.
The introducing pattern of ionic liquid precursor can be depending on the character of institute's oxidizing alkylaromatic compounds and the character of expectation product and purity and changes to some extent.In one interpolation pattern, by cation precursor and negatively charged ion precursor (under room temperature and constant pressure normally liquid) for example, with carboxylic acid (, acetic acid) solvent and introduce in oxidation reactor.In another interpolation pattern, ionic liquid precursor can be mixed and introduces in oxidation reactor with alkyl aromatic charging.In another interpolation pattern, positively charged ion and anionic ion Liquid precursor component can be introduced in the bottom of reactor, and not with any other oxidation reactor component (for example charging, carboxylic acid solvent and catalyzer bag (catalyst package)) pre-mixing.
Solvent also can comprise carboxylic acid.Use carboxylic acid in solvent time, the amount of carboxylic acid lower than traditional method to avoid solvent volume excessive.Expect that carboxylic acid has 1 to 7 carbon atom.In one embodiment, carboxylic acid comprises acetic acid.Solvent can contain more than one carboxylic acids.For example, solvent can further comprise phenylformic acid.In another embodiment, the carboxylic acid of solvent is acetic acid.
In one embodiment, in solvent the ratio of carboxylic acid and ionic liquid in following scope: 1:16 to 16:1 (by weight) or 1:9 to 9:1 (by weight) or 3:17 to 17:3 (by weight) or 1:4 to 4:1 (by weight) or 1:3 to 3:1 (by weight) or 3:7 to 7:3 (by weight) or 7:13 to 13:7 (by weight) or 2:3 to 3:2 (by weight) or 9:11 to 11:9 (by weight) or 1:1 (by weight).In one embodiment, solvent contains and is greater than the ionic liquid of 5 % by weight or the ionic liquid of the ionic liquid of at least 6 % by weight or at least 10 % by weight or the ionic liquid of the ionic liquid of at least 15 % by weight or at least 20 % by weight or the ionic liquid of the ionic liquid of at least 25 % by weight or at least 30 % by weight or the ionic liquid of the ionic liquid of at least 35 % by weight or at least 40 % by weight or the ionic liquid of at least 45 % by weight.A certain amount of ionic liquid comprises ionic liquid precursor (if existence).The optional ion solid below discussed or can form in solution in the amount of the ionic liquid that the material (if exist) of ion salt is included in.
Optionally, can in mixture, add ion solid, for example ammonium acetate (NH
4and/or brometo de amonio (NH OAc)
4br).Another is chosen as, and can add the material that can form ion salt in solution.This material can by with solution in the ion population that exists to form ion salt in solution.For example, for example, for example, in the solution that contains bromide anion (being the form of HBr) or acetate ion (being the form of acetic acid), ammonia can combine to form brometo de amonio or ammonium acetate with bromide anion or acetate ion.The material that uses one or more ion solids or can form ion salt in solution can further reduce the content of impurity.
In one embodiment, ion solid and the amount of material that can form ion salt in solution are between (with respect to the weight of solvent) between 5 % by weight to 45 % by weight or between 10 % by weight to 45 % by weight (with respect to the weight of solvent).Solvent comprises carboxylic acid, ionic liquid and/or ionic liquid precursor, optional ion solid or can in solution, form material and the optional water of ion salt.
Optionally, solvent can further comprise water.Water can be added in mixture or in mixture, generate during oxidising process.In one embodiment, with respect to the weight of carboxylic acid, the amount of water is between 0.01 % by weight to 5 % by weight.With respect to the weight of carboxylic acid, the amount of water can be between 0.1 % by weight to 2 % by weight.
In one embodiment, the ratio of the p-Xylol of the solvent in mixture and enrichment p-methylbenzoic acid stream is between following value: 1:1 to 10:1 (by weight) or 1.5:1 to 6:1 (by weight) or 2:1 to 4:1 (by weight).Solvent comprises carboxylic acid, ionic liquid and/or ionic liquid precursor, optional ion solid or can in solution, form material and the optional water of ion salt.
Catalyzer comprises at least one in following: cobalt, manganese, titanium, chromium, copper, Ni-V-Fe, molybdenum, tin, cerium and zirconium.In one embodiment, catalyzer comprises cobalt and manganese.Metal can be inorganic or organic salt form.For example, metal catalyst can be carboxylate salt (for example, metal acetate) and its hydrate forms.Exemplary catalyzer individually or in combination comprises four hydration cobaltous acetates (II) and manganous acetate (II).In one embodiment, the amount of manganous acetate (II) is less than the amount of four hydration cobaltous acetates (II) by weight.
The amount of used catalyst of the present invention can extensively change.For example, with respect to the weight of solvent, the amount of cobalt can be between 0.001 % by weight to 2 % by weight.In one embodiment, with respect to the weight of solvent, the amount of cobalt is between 0.05 % by weight to 2 % by weight.With respect to the weight of solvent, the amount of manganese can be between 0.001 % by weight to 2 % by weight.In one embodiment, with respect to the weight of solvent, the amount of manganese is between 0.05 % by weight to 2 % by weight.In another embodiment, the ratio of cobalt and manganese with metal element weighing scale between between 3:1 to 1:2.
This area conventionally bromine source is considered as to catalyst promoting agent and it comprises bromine; Ion bromine, for example HBr, NaBr, KBr, NH
4br; And/or the known organic bromide that bromide anion is provided under oxidizing condition, for example, bromotoluene, list-and dibromoacetic acid, bromoacetyl bromide, tetrabromoethane, sym-dibromoethane.In one embodiment, bromine source comprise hydrogen bromide consisting essentially of or consisting of.With respect to the weight of solvent, the amount of hydrogen bromide can be between 0.01 % by weight to 5 % by weight.In another embodiment, with respect to the weight of solvent, the amount of hydrogen bromide is between 0.05 % by weight to 2 % by weight.Solvent comprises carboxylic acid, ionic liquid, optional ion solid or can in solution, form material and the optional water of ion salt.
The oxygenant that is applicable to the method provides Sauerstoffatom to originate with oxidation of p-xylene and/or p-methylbenzoic acid under adopted oxidizing condition and/or another intermediate oxidation products.The nitrogen compound that the example of oxygenant comprises superoxide, super-oxide and contains aerobic is as nitric acid.In one embodiment, oxygenant is bag oxygen containing gas, for example air, carbonic acid gas and molecular oxygen.This gas can be gaseous mixture.In the method, the amount of oxygen used preferably exceedes the required stoichiometry of expectation method for oxidation.In one embodiment, and the amount of the oxygen that contacts of this mixture between 1.2 times of stoichiometry to 100 times stoichiometry.Optionally, and the amount of the oxygen that contacts of this mixture can be between 2 times of stoichiometry to 30 times stoichiometry.
At least a portion of these components provides liquid phase, but during the method one or more in these component of mixture any or may not dissolve completely sometime.Can form liquid phase by mix each component under envrionment conditions.In another embodiment, in the time that being increased to oxidizing temperature, the temperature of mixture forms liquid phase.Can with oxidation step in before oxidation step, form the mixture of each component in the identical or different vessel of vessel used.In another embodiment, the mixture of each component is to form in oxidation reactor, for example, each component stream individually and/or is in combination added in continuous or semicontinuous oxidation reactor.Combination partner and/or each component stream can heat before being blended together.
Although many traditional alkyl aromatic oxidation process are normally carried out in mixed phase, and generally include three phases (for example solid, gas and liquid), but this area is referred to as " liquid phase " method for oxidation conventionally, because maintain oxidizing condition so that at least a portion of this mixture to be provided in liquid phase.This area also known during the method the quantity of existing phase can change to some extent in time.As known in the art, the inventive method can also similar fashion be carried out in liquid phase or mixed phase.
Traditional liquid-phase oxidation reactor can be used for putting into practice the present invention as known in the art.Example comprises container and the various bubble column reactor can with one or more mechanical agitators, for example US7, those that describe in 692,036.Also known for the design of adopted oxidizing condition, operate and control this reactor and oxidizing reaction, oxidizing condition for example comprises temperature, pressure, liquids and gases volume and the corrosion property of liquid and gas optionally.For example, referring to US 7,692,036 and US 6,137,001.
If expect, can carry out contact procedure under oxidizing condition.Suitable oxidizing condition generally includes: temperature between between 125 DEG C to 275 DEG C and pressure between normal atmosphere (being 0MPa (g)) between 6MPa (g) and the residence time between 5 seconds to 2 weeks., mixture has the temperature and pressure within the scope of these and can make it within the scope of these, maintain for some time within the scope of the residence time.In another embodiment, temperature is between 175 DEG C to 225 DEG C; And temperature can be between 190 DEG C to 235 DEG C.In one embodiment, pressure between 1.2MPa (g) between 6.0MPa (g); And pressure can be between 1.5MPa (g) between 6.0MPa (g).In yet another embodiment, the residence time is between 10 minutes to 12 hours.Oxidizing temperature, pressure and the residence time can be based on many factors and change to some extent, and these factors comprise that for example reactor configuration, size and the method are in batches, continuously or semicontinuous.Oxidizing condition also can change to some extent based on other oxidizing conditions.For example, use specific range of temperatures can make it possible to use different residence time scopes.
In one embodiment, under oxidizing condition and/or in the time that mixture is cooling, the terephthalic acid of preparing by the present invention can precipitation, crystallization or curing in liquid phase mixture.Therefore, mixture of the present invention can further comprise solid terephthalic acid.Other compounds (including colour solid) and other oxidation productss can solidify or be embedded together with solid oxidation product, make thus to expect that product purity reduces.In one embodiment, this mixture comprises liquid phase.This mixture can comprise gas phase, for example, in the time that oxygenant adds with gas form.This mixture can comprise solid phase, for example, cannot in this mixture, dissolve or curing component of mixture, oxidation products or by product.In one embodiment, this mixture comprises liquid phase, solid phase and optional gas phase.In another embodiment, this mixture comprises liquid and gas.
Discuss as described above and below, found with respect in traditional method viewed those, the present invention can be used for preparation and has the oxidation productss of different amount pollutents.In addition, the invention provides new mode and control the content of various pollutents in oxidation products.In one embodiment, the inventive method further comprises that the optional oxidation products that is solid form that forms under oxidizing condition is to prepare solid oxidation product and mother liquor.Solid oxidation product can separate with mother liquor (being liquid phase), and the mother liquor of recyclable the method in contact procedure or hereinafter described reuse in other steps of method.
The inventive method can comprise one or more extra oxidation steps.In one embodiment, the second oxidation step comprises the second oxidizing temperature lower than the temperature of the first oxidation step.The inventive method can comprise extra contact procedure of the present invention as described herein, and/or the present invention can for example, combine with other oxidation steps (conventional oxidation step known in the art).Multiple contacts and/or oxidation step can continuously and/or parallel mode be carried out and can for example, combine with other processing steps (purification step as herein described).
In another embodiment, the present invention further comprises purifying oxidation products.Purifying can comprise that one or more additional steps are to separate and purifying oxidation products.The example of purification step comprises: separate, wherein by for example filtering and/or centrifugal oxidation products and mother liquor or another liquid phase separation of making; Washing, is wherein used (for example) water and/or another solvent composition washing oxidation products; Dry oxidation products; And hydrogenation process.Although useful hydrogenation process carries out purifying, its compared with other purification process because cost is former thereby more undesirable.This additional process steps has been set forth in general document and for those skilled in the art know and has can be used in various combinations with purifying oxidation products of the present invention.For example, referring to the reference of quoting in this application and the technology wherein quoted.
Purification step of the present invention can further comprise one or more solvent contact procedures.Solvent contact procedure comprises makes oxidation products (also comprise through washing or dry solid oxidation product) and the 3rd solvent (it comprises water, carboxylic acid, ionic liquid and/or ionic liquid precursor and at least one in mother liquor) contact to prepare purified oxidation products.In one embodiment, the solvent of solvent contact procedure contains ionic liquid and carboxylic acid and optional mother liquor.The composition that is used for the solvent of solvent contact procedure can be as above set forth for contact procedure.
Solvent contact can be leached impurity by solid oxidation product, and/or can make oxidation products partly or completely be dissolved in solvent.Solvent contact conditions comprises solvent Contact Temperature.Solvent Contact Temperature can be lower than oxidizing temperature.In one embodiment, solvent Contact Temperature is lower at least 20 DEG C than oxidizing temperature.In some traditional methods, solvent contact can be for example carrying out in the one or more crystallizers after oxidation reactor.Oxidation products can solidify in the solvent of solvent contact procedure, precipitation or crystallization.
The product making by present method (with initial mode or use subsequently one or more extra oxidations and/or purification step) can contain and is less than the 4-CBA of 2500ppm or is less than the 4-CBA of 2000ppm or is less than the 4-CBA of 1500ppm or is less than the 4-CBA of 1000ppm or is less than the 4-CBA of 750ppm or is less than the 4-CBA of 500ppm or is less than the 4-CBA of 250ppm or is less than the 4-CBA of 100ppm or is less than the 4-CBA of 50ppm or is less than the 4-CBA of 25ppm.
It should be noted that term " first ", " second " and " the 3rd " etc. are for component or composition or stage or district or reactor etc. are distinguished from each other.In fact, " second " stage or district may not be for example physically or in time after " first " stage or district.Depend on particular case and determine, its can before or after, as understood by those skilled in the art.
Embodiment
Present embodiment further to explain aspects more of the present invention and benefit and not to be considered as limiting the scope of the invention.
Embodiment 1: experimental arrangement: in stink cupboard, to the component for given experiment and the sealed reactor that load specified amount in Parr reactor.Parr reactor comprise gas distributor (in order to via 1.6mm opening by gas dispersion to liquid), mechanical gas entrainment formula agitator and baffle plate (in order to guarantee abundant mixing).Parr reactor is at room temperature installed in heater assembly, and gas feedthroughs is connected to reactor and condenser is connected to reactor outlet.During operation, gas via condenser, then trap, then back pressure regulator leaves reactor.Safe relief outlet and the thermopair with rupture disk are connected to reactor.Water coolant recirculator is connected to condenser and starts recirculation cooling water.At room temperature and 1.4MPa (g) (200psig) the lower nitrogen that uses Parr reactor is implemented to pressure test until do not reduce 15 minutes internal pressures.Back pressure regulator on reactor outlet is set as to experimental pressure and under nitrogen, reactor is implemented to pressure test.
Under nitrogen atmosphere, start temperature of reactor to rise to experimental temperature.Follow from start to finish all explanations about particular reactor, comprise temperature and pressure limit value.In the time that reactor reaches preferred temperature, start to add air and in test time, monitor temperature of reactor and pressure under experiment speed.At test period, the airflow in reactor can be maintained to 2500 standard cm
3/ minute, pressure is maintained to 4.1MPa (g), and agitator is maintained to 1600rpm.In the time that test finishes, close well heater, cut off air-flow and make reactor cooling.When being less than 35 DEG C, open vacuum breaker in reactor cooling, stop water coolant, and removal and emptying reactor are to obtain solid oxidation product and mother liquor.
Under vacuum, filtrated stock and product are with separate solid and liquid.Then at room temperature make solid mix with 100cc deionized water and decant.Deionized water at room temperature being mixed to also decant repeats 2 times again.Continue 30 minutes and then filter be heated to 95 DEG C containing the 4th washes of deionized water.Before analysis, at 80 DEG C by solid drying 8 to 24 hours.
Embodiment 2-3: embodiment 2-3 is the indivedual tests that use equipment given in embodiment 1 and program to carry out.Each component of mixture (gram to provide), service temperature, time and air flow quantity and result provide in table 1.
Embodiment 2: use p-Xylol as parent material under oxidizing condition.
Embodiment 3: oxidizing condition is identical with embodiment 2, just uses p-methylbenzoic acid as parent material.Product 4-CBA and the amount of methylbenzene first is significantly reduced, and phenylformic acid slightly reduces, and as shown in Figure 7.The rate of recovery and selectivity increase.
Elaborating after the present invention and by with reference to specific embodiment of the invention scheme, should be appreciated that, can modify and change, this does not deviate from the scope of the invention defined in the claims of enclosing.More specifically, preferred or especially favourable although aspects more of the present invention are defined as in this article, estimate that the present invention may not be limited to these preferred aspects of the present invention.
Table 1
| Embodiment numbering | 2 | 3 |
| Oxidizing temperature, DEG C | 215 | 215 |
| Oxidization time | 3 | 3 |
| Airflow, sccm | 2500 | 2500 |
| Cooling | Fast | Fast |
| ? | ? | ? |
| Component (g) | ? | ? |
| P-Xylol | 20 | ? |
| P-methylbenzoic acid | ? | 20 |
| Acetic acid | 44 | 44 |
| BMImOAc | 20 | 20 |
| BMImBr | 16 | 16 |
| NH 4OAc | 12 | 12 |
| HBr | 0.4 | 0.4 |
| H 2O | 0.4 | 0.4 |
| Co(OAc) 2-4H 2O | 0.8 | 0.8 |
| Mn(OAc) 2 | 0.6 | 0.6 |
| ? | ? | ? |
| Product analysis | ? | ? |
| Terephthalic acid (%) | 97.2 | 99.1 |
| 4-CBA(ppm) | 1081 | 230 |
| Phenylformic acid (ppm) | 1163 | 1143 |
| P-methylbenzoic acid (ppm) | 25,607 | 7183 |
| Range estimation product color | White | White |
| The rate of recovery (%) | 85.2 | 91.0 |
Claims (10)
1. a method of preparing terephthalic acid, it comprises:
The p-Xylol stream of enrichment p-methylbenzoic acid is provided;
The p-Xylol stream of enrichment p-methylbenzoic acid, solvent, bromine source, the catalyzer that comprises ionic liquid are contacted, to prepare the product that comprises terephthalic acid with oxygenant.
2. provide the p-Xylol of enrichment p-methylbenzoic acid stream to comprise according to the process of claim 1 wherein:
The p-Xylol stream that comprises p-methylbenzoic acid is provided, and wherein prepared by the method for content of at least 5 % by weight of p-Xylol stream by p-methylbenzoic acid being maintained to the p-Xylol stream being made by it.
3. provide the p-Xylol of enrichment p-methylbenzoic acid stream to comprise according to the process of claim 1 wherein:
P-Xylol, the first solvent, the first bromine source, the first catalyzer are contacted, to prepare the p-Xylol stream of enrichment p-methylbenzoic acid with the first oxygenant.
4. according to the method for any one in claims 1 to 3, wherein solvent further comprises carboxylic acid.
5. according to the method for claim 4, wherein solvent has the ratio of the carboxylic acid in the scope of 1:16 to 16:1 and ionic liquid by weight.
6. according to the method for any one in claims 1 to 3, wherein catalyzer comprises at least one in following: cobalt, titanium, manganese, chromium, copper, Ni-V-Fe, molybdenum, tin, cerium and zirconium.
7. according to the method for any one in claims 1 to 3, wherein ionic liquid is formed by least one ionic liquid precursor original position.
8. according to the method for any one in claims 1 to 3, wherein the positively charged ion of ion fluid is formed by following material: imidazoles, pyrazoles, thiazole, isothiazole, azepine thiazole, oxo thiazole,
piperazine,
azoles quinoline, oxa-azepine boron heterocyclic pentylene, dithiazole, triazole, selenazoles, oxa-phosphurane, pyrroles, boron heterocyclic pentylene, furans, thiophene, phosphurane, pentazole, indoles, indoline,
azoles, isothiazole, tetrazolium, cumarone, diphenylene-oxide, thionaphthene, dibenzothiophene, thiadiazoles, pyridine, pyrimidine, pyrazine, pyridazine, piperazine, piperidines, morpholine, pyrans, Arnold's quinoline, phthalazines, quinazoline and quinoxaline or its combination.
9. according to the method for any one in claims 1 to 3, wherein the negatively charged ion of ionic liquid is halogen ion, boron ion, phosphate radical, arsenate, metaantimmonic acid root, acetate moiety, carboxylate radical, azoles negatively charged ion, sulfate radical, acyl group unit, CO
3 2-, NO
2 1-, NO
3 1-, SO
4 2-, PO
4 3-, (CF
3) SO
3 1-, its derivative or its combination.
10. for a device for oxidizing alkylaromatic compounds, it is substantially by forming below:
The first reaction zone, it has at least one entrance and at least one outlet;
Second reaction zone, it has at least one entrance and at least one outlet, and at least one second reaction zone entrance is communicated with at least one first reaction zone outlet fluid; With
Zone purification, it has at least one entrance and at least one outlet, at least one zone purification entrance is communicated with at least one second reaction zone outlet fluid, and at least one zone purification outlet is communicated with at least one first reaction zone entrance or at least one second reaction zone inlet fluid, or at least one zone purification outlet is communicated with at least one first reaction zone entrance and the two equal fluid of at least one second reaction zone entrance.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13/340,132 | 2011-12-29 | ||
| US13/340,132 US9085522B2 (en) | 2011-12-29 | 2011-12-29 | Process for producing terephthalic acid |
| US13/340,122 US8697905B2 (en) | 2011-12-29 | 2011-12-29 | Process for producing terephthalic acid |
| US13/340,122 | 2011-12-29 | ||
| PCT/US2012/060704 WO2013101331A1 (en) | 2011-12-29 | 2012-10-18 | Process for producing terephthalic acid |
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| CN104011005A true CN104011005A (en) | 2014-08-27 |
Family
ID=48698498
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| CN201280064613.0A Pending CN104011005A (en) | 2011-12-29 | 2012-10-18 | Process for producing terephthalic acid |
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|---|---|
| KR (1) | KR20140102761A (en) |
| CN (1) | CN104011005A (en) |
| RU (1) | RU2014131232A (en) |
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| CN116194443A (en) * | 2020-05-15 | 2023-05-30 | 阿彻丹尼尔斯米德兰公司 | Co-production of monomers, including at least one biobased monomer |
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| US6949673B2 (en) * | 2000-01-12 | 2005-09-27 | E.I. Du Pont De Nemours And Company | Process for producing carboxylic acids |
| US7485746B2 (en) * | 2003-11-14 | 2009-02-03 | Bp Corporation North America Inc. | Staged countercurrent oxidation |
-
2012
- 2012-10-18 CN CN201280064613.0A patent/CN104011005A/en active Pending
- 2012-10-18 KR KR1020147019682A patent/KR20140102761A/en active IP Right Grant
- 2012-10-18 RU RU2014131232A patent/RU2014131232A/en not_active Application Discontinuation
- 2012-10-18 WO PCT/US2012/060704 patent/WO2013101331A1/en active Application Filing
- 2012-11-07 TW TW101141407A patent/TW201326110A/en unknown
Patent Citations (5)
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| US20010041811A1 (en) * | 2000-01-21 | 2001-11-15 | Sikkenga David L. | Production of high purity aromatic carboxylic acid by oxidation in benzoic acid and water solvent |
| US20040015009A1 (en) * | 2000-10-10 | 2004-01-22 | Earle Martyn John | Oxidation of alkly-aromatic compounds |
| US20080191170A1 (en) * | 2004-10-08 | 2008-08-14 | Cambridge University Technical Services Limited | Use of Ionic Liquids |
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| CN116194443A (en) * | 2020-05-15 | 2023-05-30 | 阿彻丹尼尔斯米德兰公司 | Co-production of monomers, including at least one biobased monomer |
| CN116194443B (en) * | 2020-05-15 | 2023-11-24 | 阿彻丹尼尔斯米德兰公司 | Co-production of monomers, including at least one biobased monomer |
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| WO2013101331A1 (en) | 2013-07-04 |
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Application publication date: 20140827 |