Method (versions) and systems for producing isophthalic acid and terephthalic acid |
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IPC classes for russian patent Method (versions) and systems for producing isophthalic acid and terephthalic acid (RU 2496764):
  
 Method of modifying surface of polyethylene terephthalate granulate / 2495885
Present invention relates to a method of modifying the surface of a polyethylene terephthalate granulate in order to increase heat-, light-, wear- and hydrolytic resistance, as well as reduce gas permeability of polymer materials. The method involves treating the surface of a polyethylene terephthalate granulate with a modifier while heating. The modifier used is a mixture of fluorine-containing prepolymers in amount of 2 pts.wt per 100 pts.wt polyethylene terephthalate in weight ratio of 83(I):12(II+III):5(IV), represented by formulae (I)-(IV) in the claim. Said compounds are obtained in advance by reacting 4,4'-diphenylmethane diisocyante with 1,1,5-trihydroperfluoropentanol-1 in the presence of catalytic amounts of di-n-butyltin dilaurate in molar ratio of 1:1:0.005, respectively, in a medium of chlorobenzene and n-hexane in volume ratio of 8:1, at temperature of 80°C, ultrasound frequency 40 kHz for 2 hours. Modification is carried out in a medium of chlorobenzene at 150°C for 4 hours.
 Method of modifying surface of polyethylene terephthalate granulate / 2495884
Present invention relates to a method of modifying the surface of a polyethylene terephthalate granulate in order to increase heat-, light-, wear- and hydrolytic resistance, as well as reduce gas permeability of polymer materials. The method involves treating the surface of polyethylene terephthalate with a modifier while heating, wherein the modifier used is a fluorine-containing prepolymer with isocyanate groups in amount of 2 pts.wt per 100 pts.wt polyethylene terephthalate of general formula:
Polyethylene terephthalate-based modified polymer articles and methods for production thereof / 2495057
Present invention relates to a method of producing polyethylene terephthalate (PET) based modified polymer articles which can be used in textile industry, construction, as special-purpose articles, in medicine and in other industries. The method of producing PET-based modified polymer articles involves drawing a PET-based polymer article in an adsorption-active liquid medium containing at least one modifying additive and drying the article. The adsorption-active liquid medium further contains at least one component which enables the polymer matrix to hold the modifying additive. Another version of the method involves drawing a PET-based polymer article in an adsorption-active liquid medium containing at least one modifying additive and drying the article, wherein before drawing or after drawing before drying, or after drying, the polymer article is treated with a solution containing at least one component which enables the polymer matrix to hold the modifying additive.
 Mixtures of polylactic acid and thermoplastic polymers for packaging applications / 2480485
Composition contains 1-20 wt % polylactic acid with molecular weight of 50000-110000 and polyethylene terephthalate. The composition is characterised by axial Young's modulus of 1.4 Pa and radial Young's modulus of 2.8 Pa, as well as characteristic viscosity greater than 0.5 dl/g. The method of making a packaging product involves preparing a polymer mixture from polylactic acid and polyethylene terephthalate, mixing thereof, heating, extrusion and blow moulding.
 High-molecular weight polymer esters characterised by low content of acetaldehyde / 2474592
Method of obtaining solid particles involves the following steps: polycondensation of a composition of said polyester in the presence of a catalyst containing at least 5 ppm titanium compounds; adding a catalyst deactivator; curing the composition after achieving characteristic viscosity of 0.69 dl/g until solid particles are obtained, wherein the obtained particles do not contain added aldehyde acceptors; reducing the amount of residual acetaldehyde in the particles to 10 ppm or less without increasing the value of characteristic viscosity by more than 0.03 dl/g. Said catalyst deactivator is added in different conditions which are described in the claim. The method of making articles involves feeding into a processing zone solid particles in a melt and an additional catalyst deactivator containing a phosphorus compound in an amount which satisfies the ratio P:Ti which is less than 2.5:1; melting the particles and making articles.
Crystalline copolyesters with high solubility in non-halogenated solvents and use thereof / 2470039
Present invention relates to crystalline copolyester which can be granulated, used in adhesive compositions. Said copolyester consists of 20-50 mol % terephthalic acid, 20-50 mol % isophthalic and/or phthalic acid, 10-30 mol % linear aliphatic C9-C20 dicarboxylic acid, 1-20 mol % dimer of fatty acid and one or more glycols. Said copolyester can dissolve in non-halogenated and non-aromatic solvents with solid phase content of at least 30 wt %.
 System for producing polycarboxylic acid, using cooled mother solution from oxidative combustion as cleaning system charge / 2458907
Method of producing a polycarboxylic acid composition involves: (a) oxidation of a multiphase reaction medium containing an oxidisable starting aromatic compound, a solvent and water, in a primary oxidation zone to obtain a starting suspension containing crude terephthalic acid; (b) oxidative combustion of at least a portion of said starting suspension in a combustion zone to obtain a combustion product suspension having one or more of the following characteristics: (i) contains less than 9000 ppm isophthalic acid; (ii) contains less than 15000 ppm benzoic acid, (iii) contains less than 64 ppm 4,4'-dicarboxybiphenyl, (iv) contains less than 70 ppm 2,6-dicarboxyfluorenone, (v) contains less than 12 ppm 2,7-dicarboxyfluorenone, (vi) contains less than 12 ppm 9-fluorenone-2-carboxylic acid, (vii) contains less than 4 ppm 4,4'-dicarboxystilbene, (viii) contains less than 6 ppm 4,4'-dicarboxyanthraquinone; (c) cooling at least a portion of said combustion product suspension in a cooling zone to obtain a cooled suspension containing cooled liquid and solid phases; and (d) using the solvent cleaning system to remove at least one aromatic impurity containing benzoic acid, para-toluic acid, 4-carboxy-benzaldehyde and/or trimellitic acid, present in the solvent cleaning charge, fed into said solvent cleaning system, where said cooled liquid phase of said cooled suspension forms at least 20 wt % of said solvent cleaning charge.
 Polyester polymers with low rate of formation of acetaldehyde and high concentration of terminal vinyl groups / 2458074
Method of producing said polymer involves polycondensation of a polyester polymer in the presence of a polycondensation catalyst, adding a compound containing a catalyst deactivator after the polyester polymer achieves characteristic viscosity of 0.45 dl/g. Further, characteristic viscosity of the polyester polymer is increased to 0.72 dl/g to obtain a polyester polymer. The obtained polyester polymer has concentration of terminal vinyl groups equal to 0.8 microeq./g and rate of formation of acetaldehyde less than 22 ppm.
 Oxidation system having secondary reactor for side stream / 2457197
Invention relates to an improved method of producing a composition of aromatic dicarboxylic acid, involving (a) oxidation of a multiphase reaction medium in a primary oxidation reactor to obtain a first suspension; (b) further oxidation of at least a portion of said first suspension in a secondary oxidation reactor which is of the bubble column type, wherein the method further involves feeding an aromatic compound into said primary oxidation reactor, where at least about 80 wt % of said aromatic compound fed into said primary oxidation reactor is oxidised therein, wherein head gases are moved from the top of the secondary oxidation reactor into the primary oxidation reactor. Disclosed are an optimised process and equipment for more efficient and cheaper liquid-phase oxidation. Such liquid-phase oxidation is carried out in a bubble column type reactor which ensures a highly efficient reaction at relatively low temperatures. When the oxidised compound is para-xylene and the oxidation reaction product is crude terephthalic acid (TPA), such a product, TPA, can e purified and extracted using cheaper methods than when TPA is obtained using the conventional high-temperature oxidation process.
Method of producing alkyd resins / 2454438
Present invention relates to a method of producing alkyde resins and can be used to produce polymer compounds, particularly high-quality bitumen. The method of producing alkyde resins involves reaction of a mixture of organic acids with a polyatomic alcohol at 160-180°C and molar ratio of mixture of organic acids to polyatomic alcohol equal to 1:1-2 until achieving acid number 5-50 mg KOH/g in the reaction mixture. The mixture of organic acids contains 80-87 wt % terephthalic acid, 8-15 wt % p-toluic acid, up to 0.4 wt % benzoic acid, up to 0.1 wt % carboxybenzaldehyde and water - the balance.
 Simple method and system for efficient recycling of mother solution from apparatus for producing purified terephthalic acid / 2471767
Invention relates to an improved method for efficient recycling of a refinery mother solution from apparatus for producing purified terephthalic acid PTA, involving the following steps: (1) cooling the refinery mother solution using a heat exchange technique; (2) treating the cooled refinery mother solution by ultrafiltration and recycling the ultrafiltered concentrated solution for an oxidation apparatus; (3) conducting ion-exchange treatment of the filtrate obtained from ultrafiltration: selective adsorption of Co ions and Mn ions in the filtrate, recycling the desorption solution of Co and Mn as a catalyst and subsequent adsorption of metal ions such as Fe ions, Ni ions and Na ions; and (4) using the solution after ion exchange as a heat-absorbing medium at step (1) for exchanging heat with the refinery mother solution, wherein a large portion of the solution is fed into a spray tower drier, and the remaining portion after heat exchange is discarded; the solution which is sprayed in the spray tower drier is recycled in the refinery system. The invention also relates to a system for recycling a refinery mother solution from apparatus for producing purified terephthalic acid PTA, having a heat exchange system, an ultrafiltration system, an ion exchange system and a spray tower drier, wherein the heat exchange system includes a first heat exchange apparatus and a cooling device; the ion exchange system includes a first ion exchange apparatus and a second ion exchange apparatus; the outlet of the heat-dissipating medium from the first heat exchanger is connected to the inlet of the heat-dissipating medium into the cooling device; the outlet of the heat-dissipating medium from the cooling device is connected to the inlet of the ultrafiltration system; the outlet of the filtrate from the ultrafiltration system is connected to the inlet of the first ion exchange apparatus, the outlet of the first ion exchange apparatus is connected to the inlet of the second ion exchange apparatus; the outlet of the second ion exchange apparatus is connected to the inlet of the heat-absorbing medium of the first heat exchanger; and the outlet of the heat-absorbing medium of the first heat exchanger is connected to the pipe of the sprayer of the spray tower drier.
 Method of producing aromatic carboxylic acid / 2467998
Invention relates to a method of producing aromatic carboxylic acid. Said method involves an oxidative step for oxidising an alkyl aromatic compound in the presence of a bromine compound to obtain an aromatic carboxylic acid; and a step for burning exhaust gas formed at the oxidation step in an incinerator. The gas obtained after burning the exhaust gas at burning temperature ranging from 450°C to 1000°C is cooled to 250°C or lower, and the time for cooling from 450°C to 250°C in the cooling process is not more than 1 second.
 Method for ethanolysis of poly(ethylene terephthalate) (pet) with formation of diethylene terephthlate (det) / 2458946
Invention relates to a method of processing polyethylene terephthalate wastes. The method involves ethanolysis of polyethylene terephthalate (PET), in which material containing PET reacts with ethanol. Ethylene glycol and an aromatic diethyl ester, such as diethyl isophthalate and/or diethyl terephthalate, are separated. PET or a terpolymer containing a terephthalate monomer and ethylene glycol monomers react with ethanol and ethanol, diethyl terephthalate, ethylene glycol and optionally diethyl isophthalate are separated. The separated diethyl components can undergo liquid-phase oxidation to obtain an aromatic carboxylic acid. Acetic acid can also be obtained via liquid-phase oxidation of the separated diethyl components. Aromatic carboxylic acid can be used to obtain polymers. The invention also describes apparatus for processing polyethylene terephthalate wastes. The apparatus includes a reactor, a distillation column operating at atmospheric pressure and a vacuum distillation column.
System for producing polycarboxylic acid, using cooled mother solution from oxidative combustion as cleaning system charge / 2458907
Method of producing a polycarboxylic acid composition involves: (a) oxidation of a multiphase reaction medium containing an oxidisable starting aromatic compound, a solvent and water, in a primary oxidation zone to obtain a starting suspension containing crude terephthalic acid; (b) oxidative combustion of at least a portion of said starting suspension in a combustion zone to obtain a combustion product suspension having one or more of the following characteristics: (i) contains less than 9000 ppm isophthalic acid; (ii) contains less than 15000 ppm benzoic acid, (iii) contains less than 64 ppm 4,4'-dicarboxybiphenyl, (iv) contains less than 70 ppm 2,6-dicarboxyfluorenone, (v) contains less than 12 ppm 2,7-dicarboxyfluorenone, (vi) contains less than 12 ppm 9-fluorenone-2-carboxylic acid, (vii) contains less than 4 ppm 4,4'-dicarboxystilbene, (viii) contains less than 6 ppm 4,4'-dicarboxyanthraquinone; (c) cooling at least a portion of said combustion product suspension in a cooling zone to obtain a cooled suspension containing cooled liquid and solid phases; and (d) using the solvent cleaning system to remove at least one aromatic impurity containing benzoic acid, para-toluic acid, 4-carboxy-benzaldehyde and/or trimellitic acid, present in the solvent cleaning charge, fed into said solvent cleaning system, where said cooled liquid phase of said cooled suspension forms at least 20 wt % of said solvent cleaning charge.
 Method of producing crude aromatic dicarboxylic acid for hydrogenation purification / 2458038
Invention relates to an improved method of producing crude terephthalic acid for use at a hydrogenation purification step via liquid-phase oxidation with an oxygen-containing gas in an oxidation reactor fitted with a mixer, using as the starting material para-xylene in a solvent - acetic acid, in the presence of a metal-containing catalyst which contains cobalt (Co), manganese (Mn) and bromine (Br) as an oxidation promoter, where the oxidation reaction temperature is controlled such that is lies in the interval from 185 to 197°C, average dwell time of the starting mixture in the reactor for liquid-phase oxidation ranges from 0.7 to 1.5 hours, content of water in the reaction solvent is controlled such that it ranges from 8 to 15 wt %, and the composition of the catalyst in the solvent is controlled in a range defined depending on the reaction temperature such that it includes: (1) a catalytically active metal (Co+Mn) in amount of 2650 ppm or less and in amount equal to or more than a value determined by the following relationship: (Co+Mn) = -0.460(t-185)3+18.4(t-185)2-277.5(t-185)+2065, in which (Co+Mn) is the content of (Co+Mn) in ppm, t is the reaction temperature (°C) (temperature range from 185 to 200°C), (2) weight ratio Mn/Co is controlled in a range from 0.2 to 1.5, preferably from 0.2 to 1; (3) content of Br is equal to or less than 1.7, if represented by a value Br/(Co+Mn) in form of weight ratio, and in amount equal to or greater than a value given by the equation: Br/Mn = -0.00115(t-185)3+0.0362(t-185)2-0.5803(t-185)+5.18, in which Br/Mn is weight ratio Br/Mn (wt/wt), and t is reaction temperature (°C) (temperature range from 185 to 200°C), and crude terephthalic acid is obtained with content of 4-carboxybenzaldehyde in amount from 2000 to 3500 ppm as an intermediate product of liquid-phase oxidation. The method provides cheap production of crude terephthalic acid for use in hydrogenation purification and use of a controlled amount of oxidation catalyst, which does not have undesirable effect on the life of a hydrogenation purification catalyst, as well as conditions for carrying out the corresponding reaction.
Oxidation system having secondary reactor for side stream / 2457197
Invention relates to an improved method of producing a composition of aromatic dicarboxylic acid, involving (a) oxidation of a multiphase reaction medium in a primary oxidation reactor to obtain a first suspension; (b) further oxidation of at least a portion of said first suspension in a secondary oxidation reactor which is of the bubble column type, wherein the method further involves feeding an aromatic compound into said primary oxidation reactor, where at least about 80 wt % of said aromatic compound fed into said primary oxidation reactor is oxidised therein, wherein head gases are moved from the top of the secondary oxidation reactor into the primary oxidation reactor. Disclosed are an optimised process and equipment for more efficient and cheaper liquid-phase oxidation. Such liquid-phase oxidation is carried out in a bubble column type reactor which ensures a highly efficient reaction at relatively low temperatures. When the oxidised compound is para-xylene and the oxidation reaction product is crude terephthalic acid (TPA), such a product, TPA, can e purified and extracted using cheaper methods than when TPA is obtained using the conventional high-temperature oxidation process.
 Method and apparatus for producing aromatic carboxylic acids (versions) / 2449980
Invention relates to improved methods of producing aromatic carboxylic acids, involving bringing material containing at least one initial substituted aromatic hydrocarbon, where the substitutes are oxidisable to carboxylic acid groups, with oxygen gas in a liquid-phase oxidation reaction mixture containing a monocarboxylic acid as a solvent and water, in the presence of a catalyst composition containing at least one heavy metal, which is effective for catalysing oxidation of the substituted aromatic hydrocarbon to an aromatic carboxylic acid, in a reaction section at high temperature and pressure, effective for keeping the liquid-phase oxidation reaction mixture in a liquid state and forming an aromatic carboxylic acid, and impurities containing by-products of oxidation of the initial aromatic hydrocarbon, which are dissolved or suspended in the liquid-phase oxidation reaction mixture, and a high-pressure vapour phase containing a solvent - monocarboxylic acid, water and small amounts of the initial aromatic hydrocarbon and by-products; transferring the high-pressure vapour phase from the reaction section into a separation section sprinkled by a liquid reflux containing water and capable of almost completely separating the solvent - monocarboxylic acid and water in the high-pressure vapour phase to form a liquid rich in solvent - monocarboxylic acid and depleted of water, high-pressure gas containing water vapour; transferring the high-pressure gas containing water vapour from the separation section without processing to remove organic impurities into a condensation section and condensation of the high-pressure gas to form a liquid condensate containing water and exhaust gas from the condensation section under pressure, containing non-condensed high-pressure gas components, transferred into the condensation section; removal from the condensation section of a liquid condensate containing water and suitable for use without further processing as at least one liquid containing water in a method of purifying aromatic carboxylic acids; and feeding the liquid condensate containing water removed from the condensation section during purification of aromatic carboxylic acids in which at least one step includes: (a) preparing a purification reaction solution containing an aromatic carboxylic acid and impurities which are dissolved or suspended in a liquid containing water; (b) bringing the purification reaction solution containing aromatic carboxylic acid and impurities in the liquid containing water, at high temperature and pressure, into contact with hydrogen in the presence of a hydrogenation catalyst to form a liquid purification reaction mixture; (c) separating the solid purified product containing carboxylic acid from the liquid purification reaction mixture containing aromatic carboxylic acid and impurities in the liquid containing water; and (d) using at least one liquid containing water to wash the obtained purified solid aromatic carboxylic acid separated from the liquid purification reaction mixture containing aromatic carboxylic acid, impurities and the liquid containing water; such that the liquid containing water on at least one step of the purification method contains a liquid condensate containing water and which needs processing to remove organic impurities.
 Methods of drying aromatic carboxylic acid and methods of obtaining dry aromatic carboxylic acid / 2444510
Invention relates to an improved method of drying aromatic carboxylic acid, involving drying of aromatic carboxylic acid precipitate using a fluidised bed drier, where the precipitate is fed into the drier at a rate of 50 kg/h or higher, and a drying gas at temperature 80-160°C is fed into the drier with reduced speed of 0.3-1 m/s, so that content of liquid in the precipitate is equal to or less than 14 wt %; as well as to an improved method of obtaining dry aromatic carboxylic acid, involving continuous drying of aromatic carboxylic acid precipitate using a fluidised bed drier to obtain ready aromatic carboxylic acid, where the precipitate is fed into the drier at a rate of 50 kg/h or higher, and drying gas at temperature 80-160°C is fed into the drier at reduced speed of 0.3-1 m/s so that content of liquid in the precipitate is equal to or less than 14 wt %. The aim of the invention is to develop a method of drying aromatic carboxylic acid and a method of drying aromatic carboxylic acid, each method solving problems associated with use of a fluidised bed drier, such as clogging by crystals or aromatic carboxylic acid crystals sticking in the drier, and low efficiency of the drier.
 Method of recovering energy during production of aromatic carboxylic acids / 2435754
Invention relates to an improved method of recovering energy during production of aromatic carboxylic acids via liquid phase oxidation of aromatic hydrocarbons wherein vapour containing reaction solvent and water forms in the top part of the reactor, and the method comprises the following steps: a) high efficiency separation of the vapour from the top part of the reactor to form at least a high-pressure gas stream containing water and organic impurities; b) recovering heat of the high-pressure gas stream via heat exchange with a heat sink, where a condensate forms, said condensate containing approximately 20-60 wt % water, present in the high-pressure gas stream, and high-pressure exhaust gas containing approximately 40-80 wt % water present in the high-pressure gas stream, remains uncondensed and temperature or pressure of the heat sink increases; and c) expansion of the high-pressure exhaust gas which is uncondensed at step (b), containing approximately 40-80 wt % water, present in the high-pressure gas stream, in order to recover energy of the high-pressure exhaust gas in form of work; and d) directing the heat sink, whose temperature and pressure increases at step (c), to another step of the method for heating or using outside the method. The invention also relates to a method of producing aromatic carboxylic acids with energy recovery and a device for recovering energy.
 Optimised liquid-phase oxidation / 2435753
Invention relates to an improved continuous method of producing terephthalic acid, involving (a) feeding para-xylene into an oxidation reactor; (b) oxidation of at least a portion of said para-xylene in the liquid phase of a multi-phase reaction medium contained in said oxidation reactor until crude terephthalic acid is obtained, where said oxidation results in production of carbon dioxide, carbon monoxide and/or methyl acetate; and maintaining, during said oxidation, the molar ratio of obtained carbon oxides to said para-xylene in the range from 0.02:1 to 0.24:1. The invention also relates to a continuous method of producing terephthalic acid, involving (a) feeding para-xylene into an oxidation reactor; (b) oxidation of at least a portion of said para-xylene in the liquid phase of a multi-phase reaction medium, contained in said oxidation reactor, until crude terephthalic acid is obtained; and (c) maintaining, during said oxidation, molar ratio of persistence of said para-xylene in the range from 99.0 to 99.7%.
 Method of producing isophthalic acid and formic acid by oxidation of m-diisopropylbenzene and m-ethyl-isopropylbenzene / 2485091
Invention relates to the technology of organic and petrochemical synthesis, specifically to the technology of producing isophthalic acid and a by-product - formic acid by liquid-phase oxidation with O2 gas in the medium of acetic acid in the presence of a Co and Mn salt catalyst at high temperature and pressure, followed by extraction of isophthalic acid and purification thereof by recrystallisation in a water-acetic solvent, extracting formic acid by distillation from the anhydrous acetic acid condensate formed when cooling the vapour-gas mixture removed from the reaction zone with spent air, where there is oxidation of m-diisopropylbenzene or m-ethyl-isopropylbenzene in three steps while raising temperature in steps in the range of (°C) 130-150; 140-160; 165-185°C, pressure (MPa) 0.3-0.6; 0.6-0.8; 0.9-1.2, overall concentration of the Co-Mn-Ni catalyst (ppm) 800 - 1060; 1000 - 1435; 1250 - 1744; and during air flow through the oxidation zone, concentration of CO/CO2 in the spent gas after each step is kept in the following ranges (vol. %): 0.16, 0.17, 0.18-0.25, 0.26 / 0.24, 0.25, 0.9-1.12, 1.19, 1.20, 1.21; 0.18, 0.2-0.3 / 0.9, 1.1-1.42; 0.2, 0.23-0.42 / 1.15, 1.2-1.6,1.8; 93.2-98.8% content of isophthalic acid in oxidation products extracted from the cooled oxidation product of step 3 is achieved, after which process isophthalic acid is purified by successive recrystallisation in CH3COOH while heating the suspension to 180-200°C, and then in H2O while heating the suspension to 200-230°C to obtain highly pure isophthalic acid, and formic acid formed during the oxidation process is extracted from the vapour-gas mixture from the oxidation reactor by cooling the vapour-gas mixture to 30-40°C, separating the formed condensate and treatment thereof with n-butyl acetate in ratio of acid to n-butyl acetate of 1:0.17; further, reaction water in form of its azeotropic mixture with n-butyl acetate and then formic acid and acetic acid are successively extracted from the obtained mixture by fractionation.
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FIELD: chemistry. SUBSTANCE: invention relates to an improved method of converting a raw material stream containing at least one C8 aromatic compound, ortho-xylene, meta-xylene, para-xylene and ethylbenzene, into at least one product stream containing isophthalic acid and terephthalic acid (IPA/TA), which comprises the following steps: a) removing ethylbenzene from said raw material stream to form a raw material stream poor in ethylbenzene; b) removing ortho-xylene from said ethylbenzene-poor raw material stream to form a raw material stream poor in ortho-xylene, containing meta-xylene and para-xylene; c) oxidising said ortho-xylene-poor raw material stream to form a product stream containing IPA/TA in ratio of 0.5% to 99.5% IPA and 0.5% to 99.5% TA; d) drying said product stream in a drier to remove residual solvent and water; e) removing the substantially purified IPA/TA product stream; f) dissolving said product stream; and g) separating said IPA and said TA from said dissolved product stream. EFFECT: method enables to obtain optimum amounts of IPA and TA from a raw material stream containing at least one C8 aromatic compound, in order to optimise output of IPA and TA. 7 cl, 4 dwg
The level of technology Meta-xylene and para-xylene are valuable intermediate products in the production of purified or crude isophthalic and terephthalic acid (IPA/TA or (CIPA/CTA), which is used in the manufacture of resins. Currently there is a great need in the resins used in the manufacture of bottles. It is expected that this market in the coming years will grow. Meta-xylene can be obtained from mixtures of aromatic hydrocarbons, C8allocated from oil sources of raw materials, especially from the products of reforming, of which the xylenes are usually obtained by fractional distillation or selective solvent extraction. The composition of the aromatic hydrocarbon, C8in such mixtures and their properties are: 866.3
There are various sources of mixtures of aromatic hydrocarbon, C8. One such source is the product of the catalytic reforming of crude oil and distillates, pyrolysis products. Other sources include, but are not limited to, the products of alkylation, dealkylation or transfer alkyl groups, such as the products of the disproportionation of toluene (TDP), alkylation of toluene, parallelomania and/or the like. The fraction of aromatic hydrocarbons, C8from crude oil and distillates, pyrolysis products vary greatly in composition and usually contain 10-32 wt.% ethylbenzene (EB), and a mixture of xylenes, which are composed of about 50 wt.% meta-xylene and 25 wt.% para-xylene and ortho-xylene. The boiling point of ethylbenzene is very close to the boiling point of para-xylene and meta-xylene. Complete removal of ethylbenzene from raw materials by conventional methods, for example, by distillation, usually not carried out for reasons of economy. Ethylbenzene can be removed in other ways, such as selective adsorption, for example, by the method described in US 4021499; US 4079094; US 4108415 and US 4497972. Usually ethylbenzene is subjected to catalytic conversion in the circulation of reastauraatorile-separation. In many ways isomerization of xylene unable to implement the conversion of ethylbenzene, since at least part of xylenes is also converted into other substances. So, although the catalytic removal of ethylbenzene in principle possible, the operating conditions must be chosen so as to compensate for the disadvantages associated with the loss of xylene by dealkylation or parallelomania simultaneously with the conversion of ethylbenzene, which reduces the number of meta-xlola or para-xylene, is available for the production of the corresponding isophthalic and/or terephthalic acid (IPA and/or TA(STA)). There is therefore a need in balanced systems and methods of transformation of raw materials containing at least one aromatic compound C8in the flow of products containing isophthalic and terephthalic acid (IPA/TA). The INVENTION Different variants of the present invention include systems and methods of transformation of raw materials containing at least one aromatic compound C8in the flow of products containing isophthalic and terephthalic acid (IPA/TA). One variant of the method according to the present invention reveals the transformation of the flow of raw materials containing at least meta-xylene, para-xylene, ethylbenzene and optional ortho-xylene, at least one product stream, sod is rasih isophthalic and terephthalic acid (IPA/TA), moreover, the method involves the following stages: a) removal of ethylbenzene from the stream of raw material with the formation of ethylbenzene depleted stream of raw materials; b) removal of ortho-xylene from ethylbenzene depleted stream of raw materials with the formation of depleted ortho-xylene stream of raw materials; c) oxidation of the flow of raw materials, depleted ortho-xylene, with the formation of the product stream containing IPA/TA ratio of about 0.5 to 99.5% IPA and about 0.5 to 99.5% TA. Other variants of the present invention disclose a way of turning raw materials containing at least meta-xylene and para-xylene, at least one product stream containing isophthalic and terephthalic acid (IPA/TA), and the method comprises the stage of: oxidation of the flow of raw materials, depleted ortho-xylene, with the formation of a product stream containing IPA/TA ratio of about 0.5 to 99.5% IPA and about 0.5 to 99.5% TA. This invention also provides a system for receiving a stream of products containing isophthalic and terephthalic acid (IPA/TA), from the stream of raw materials containing at least meta-xylene and para-xylene, and the system includes: a) the removal area of ortho-xylene; b) the zone of oxidation, moreover, in the zone of removal of ortho-xylene may remove high-boiling components more than meta-xylene, with the formation of a stream depleted in ortho-xylene, and in the joint area of the Oka is of possible oxidation as meta-xylene, and para-xylene in the crude isophthalic and terephthalic acid (IPA/C-TA). BRIEF DESCRIPTION of FIGURES In order to show the above and other advantages and objects of the present invention, briefly described above, the invention further discussed in the attached drawings more specifically with reference to specific illustrated options. Understanding that these drawings only describe the typical variants of the invention and therefore may not be considered as limiting its scope, the invention will be described in more specific detail with the help of the accompanying drawings, on which: The figure 1 shows a block diagram of one variant of the method according to this invention. The figure 2 shows the block diagram of the system of the prior art to obtain terephthalic acid from p-xylene) or isophthalic acid (raw material containing p-xylene, substituted raw materials containing m-xylene). The figure 3 shows an alternative system according to the present invention. The figure 4 shows an alternative system according to the present invention. DETAILED description of the INVENTION In the description taken with the following definitions and explanations, which then can be adjusted in any phrases until they are explicitly modified in the following description or until the use of these those who Minov will not deny phrase meaning completely or partially. When the phrase with any term will lose its meaning completely or partially, the definition should be taken from the Webster's Dictionary, 3rd edition. You should not use definition and/or interpretation of other patent applications, patents, or publications related to this or not, as long as it is not mentioned explicitly in the description or must enter to save the meaning. For example, non-limiting variants and/or describe the way in which isophthalic acid and purified terephthalic acid include, but are not limited to, patents 7285684; 7271286; 6562997; 6187569; 6461840; 5739384; 5068406; 4978741; 4855492 and 4046782, the contents of which are incorporated herein by reference and are presented here in its entirety. Used herein, the term "liquid" means a continuous, amorphous substance whose molecules move freely, one after the other and which can take the form of a vessel, for example, liquid or gas. Used here, the term "membrane apparatus" means and refers to flat membranes, spiral sheet membranes, tubular bars, tubular membranes, the membranes of the hollow fibers and/or other membranes, commonly used in industry. Used here, the term "mixed xylene or mixed xylenes" means the flow of aromatic hydrocarbons containing about 20-80 m is SS.% meta-xylene, about 10-60 wt.% para-xylene, it is not necessarily about 10-60 wt.% ortho-xylene, and optionally about 0.1-30 wt.% ethylbenzene. In addition to working examples, or where otherwise indicated, all numbers reflect the number of components, it should be understood in all cases as containing the term "about". Terephthalic acid or especially isophthalic acid usually get the same or very similar ways in the presence of the system shown in figure 2. Usually feedstock with a para-xylene obtain terephthalic acid, and from raw material with meta-xylene get isophthalic acid. In a variant of the prior art in the presence of a system for obtaining terephthalic or isophthalic acids, as shown in figure 2, the flow of xylene 5 serves in apparatus for the oxidation of 10. Gas for oxidation, usually air or pure oxygen, is fed into the apparatus for the oxidation of 10, in which the catalyst and the solvent. Then separate thread 15 of the apparatus for the oxidation of 10 in the form of acid in the form of flow 5, for example, by means of the filter 20, and the catalyst and/or solvent can be returned to process or delete/atdot. After separation of the stream 35, containing the crude acid formed from xylene in the stream 5, is fed into the apparatus for dissolving, usually containing water or other solvent, when polysensitization to accelerate dissolution. Optional stream 35 can be kept in memory products 40 to use in the way or if necessary in other reactions. Usually the products of this stage are crude terephthalic acid (CTA) or the crude isophthalic acid (C-IPA). Thread 55 is then applied to the system 60 of the hydrogenation reactor to remove impurities. Usually present in stream 55 impurities react with hydrogen and the resulting products can be separated from the acid, for example, by using a filter, screens, centrifuges, cyclone separators and/or the like Thread 65 allocated from the system 60, then cooled and subjected to crystallization, for example, crystallization 70. Impurities can be removed by using at least one separation system 80. Separation system 80, if present, can contain multiple centrifuges or filters in the washing systems and/or the like, the resulting product stream 95 is then dried in the dryer 90. Optional content of the product stream 95 can be kept in memory products 100. Usually the products of this stage are either purified terephthalic acid (PTA), or pure isophthalic acid (IPA). However, the MOUTH and the IPA does not receive the same product stream. Accordingly, in General, different variants of the present invention include a method and/or system for transforming a flow of raw materials containing m is Nisha least meta-xylene, para-xylene and ethylbenzene, and optionally ortho-xylene in at least one product stream containing isophthalic and genetalia acid (IPA/TA), which involves the following stages: a) removal of ethylbenzene from the stream of raw material with the formation of the flow of raw materials, ethylbenzene depleted; b) removal of ortho-xylene from the stream of raw materials, ethylbenzene depleted, with the formation of the flow of raw materials, depleted ortho-xylene; c) oxidation of the flow of raw materials, depleted ortho-xylene, with the formation of a product stream containing IPA/TA ratio of about 0.5 to 99.5% IPA and about 0.5 to 99.5% TA. Alternatively, get a product stream containing IPA/TA ratio of 0.2-10.0% IPA and about 90-99 .8% TA. In another alternative embodiment, receive the flow of products containing IPA/TA ratio of about 0.1-25.0% IPA and about 75-99 .9% TA. In yet another alternative embodiment, receive the flow of products containing IPA/TA ratio of 0.1-99.9% IPA and about 1.0-99.9% TA. In General variant of the method according to the present invention can be modified to obtain IPA/TA in any desired ratio. In General, the flow of raw material contains about 1-40 wt.% ethylbenzene, about 20-80 wt.% meta-xylene, about 5-30 wt.% ortho-xylene and about 0.5-40 wt.% para-xylene. An alternative stream of hydrocarbon feedstock contains about 1-20 wt.% ethylbenzene, about 50-65 wt.% mega-xylene, note the RNO 20-30 wt.% ortho-xylene and about 0.5-5 wt.% para-xylene. In another alternative embodiment, the flow of the hydrocarbon feedstock contains about 0.1-50 wt.% ethylbenzene, about 0.1-99.9 wt.% meta-xylene, about 0.1-99.9 wt.% ortho-xylene and about 0.1-99.9 wt.% para-xylene. In yet another alternative embodiment, the flow of raw material contains a mixture of xylenes comprising from about 20% ethylbenzene, about 20% ortho-xylene, about 40% of meta-xylene and about 20% para-xylene. The resulting IPA and/or THAT find wide application. Very common is the production of polymers and resins based on IPA and TA. A widely known example is the receipt of polymers on the basis of the IPA and the PTA for the manufacture of polyester bottles. The figure 1 shows the basic block diagram describing the stage generalized method. In General, different variants of the present invention depending on the flow of the raw material stage include: receiving stream 115 mixture of xylenes 110, for example, mixed xylenes; remove ethylbenzene 120 from a stream of a mixture of xylenes 115 education stream 125, ethylbenzene depleted; the removal of ortho-xylene 130 or more high-boiling component from a mixture of xylenes 115 education stream 135, containing meta-xylene and para-xylene; the optional addition of an excess of para-xylene and/or meta-xylene (not shown); joint oxidation 150 stream containing meta-xilo and para-xylene 145, wherein the received stream 155 contains acid, formed from meta-xylene and para-xylene; separation/drying 160 received stream 155; optional cleaning 170 received stream 165 to form product stream 172 containing isophthalic and terephthalic acid (IPA/TA); optional dissolution 180 thread 175, wherein IPA and TA into solution; optional removal of 190 flow 185 education stream 192 containing TA and/or stream 195 containing IPA. There are many other work options, obvious to the person skilled in the art, such as, but not limited to, the location of the zone of removal of ortho-xylene from the zone of removal of ethylbenzene or use the same zone for the removal of ortho-xylene and ethylbenzene. To oxidation of the flow of raw materials containing para-xylene and meta-xylene, in various embodiments of the present invention is expected to set the ratio IP/TA by adding excessive amounts of para-xylene or meta-xylene to the flow of raw materials, depleted ortho-xylene. An excess of para-xylene and/or meta-xylene allows you to set the process conditions, and as a result, the oxidation leads to more or IPA, or TA, which determines important for a manufacturer of polymers, the ratio of these acids. Usually in various embodiments, the crust is asego of the invention it is possible to use any solvent, significantly for professionals in this field. A non-limiting list of solvents used in the oxidation, includes acetic acid, water, other acids and/or the like, Similarly, in various embodiments of the present invention it is possible to use all catalysts oxidation. A non-limiting list of catalysts include cobalt, manganese, bromine, fluorine and/or etc. After oxidation the flow of meta-xylene and para-xylene contains the catalyst and the solvent, which should be removed, for example, on the filter and in the drying apparatus. The catalyst separated from the product stream and returned to the process or discarded. The collected solvent is returned to the process or sent to waste water. For separating and/or drying, you can use different drying apparatus and/or filters. At this point, the product stream contains raw, or untreated, C-TA, C-IPA. C-TA, C-IPA can then be processed to obtain the product stream containing purified TA and IPA. In one embodiment, the crude IPA/TA is again dissolved in the solvent, share and/or dried, yielding the purified stream containing IPA/TA, or pure IPA/PTA. In other embodiments, purified IPA and MOUTH if necessary, can be divided into separate products. Also here disclosed system to receive the stream of products containing isophthalic and therephtale the th acid (IPA/TA), from the stream of raw materials containing at least meta-xylene and para-xylene, optionally ethylbenzene and ortho-xylene, including: a) the removal area of ortho-xylene; b) the zone of oxidation, and in the zone of removal of ortho-xylene can be removed more high-boiling components than meta-xylene and para-xylene, and to receive a stream depleted in ortho-xylene, and in the area of co oxidation to oxidize as meta-xylene and para-xylene in the crude isophthalic and terephthalic acids (C-IPA/C-TA). Other options include the removal area ethylbenzene removal of ethylbenzene. Other options include cleaning area, where you can remove impurities from the C-IPA/C-TA and get cleaned IPA and TA. The structure and operating conditions of the zone of removal of ethylbenzene, the zone of removal of ortho-xylene, zone co oxidation, cleaning zones, etc. can be any that are used in this area/for example, this can be the rectification column or separation, drying machine, drums, they can contain partitions, the catalyst layers, the device for varying the pressure and temperature of the adsorption layers, molds and/or the like In various embodiments of the present invention can be obtained acid that can be converted into a polymer, for example, a polyester polymer. Polyester polymers used in the manufacture of various products, that is, but not limited to, bottles, films, fibers or articles obtained by moulding under pressure. In yet another variant discovered a way to turn the flow of raw materials containing at least meta-xylene and para-xylene, at least one product stream containing isophthalic and terephthalic acid (IPA/TA), which involves the following stages: a) removal of ortho-xylene from the stream of raw material with the formation of the flow of raw materials, depleted ortho-xylene and b) oxidation of the flow of raw materials, depleted ortho-xylene, with the formation of a product stream containing IPA/TA ratio from 0.5% to about 99.5% IPA and about 0.5 to 99.5% TA. The present invention can be implemented in other embodiments not departing from its spirit or essential characteristics. Describes the options should be considered in all respects only as illustrative and non-limiting. Therefore, the scope of this invention defined by the attached formula, not only the above-mentioned description. All changes to the formula in the scope of its meaning and scope of equivalence to include in its scope. In addition, all of these published documents, patents and applications incorporated herein by reference and is presented in its entirety. Examples: Raw materials In General, in the method according to the present invention can be used as raw material of any mixture of aromatic compounds C 8containing ethylbenzene and xylene. Usually the flow of raw material contains about 1-25 wt.% ethylbenzene, about 20-80 wt.% meta-xylene, about 5-30 wt.% ortho-xylene and about 0.5-20 wt.% para-xylene. In an alternative embodiment, the flow of the hydrocarbon feedstock contains about 1-20 wt.% ethylbenzene, about 50-65 wt.% meta-xylene, about 20-30 wt.% ortho-xylene and about 0.5-5 wt.% para-xylene. Alternatively, the flow of raw material contains a mixture of xylenes containing about 20% ethylbenzene, about 20% ortho-xylene, about 40% of meta-xylene and about 20% para-xylene. Way The figure 3 shows a variant of a system for implementing the method according to the present invention. Usually the flow of raw material 201 containing raw materials of meta-xylene and para-xylene, served in apparatus for the oxidation of 200. In this exemplary embodiment, it is assumed that the benzene plus toluene and more high-boiling components, such as ortho-xylene, have been removed and/or their contents is minimized. In the apparatus for oxidation of 200 is at least one solvent and catalyst, and gas for oxidation or air serves as stream 202. Raw material remains in the apparatus for oxidation of 200 per period of time sufficient for the oxidation of xylenes to the corresponding acid, i.e. para-xylene is oxidized in TA and meta-xylene in IPA. The upper straps or off-gas from the top is part of the oxidation apparatus 200 can take the form of a stream 202, which can be treated flowing through the condenser 208 and/or other setting in order to reduce the amount or eliminate the flow of environmentally dangerous waste gas. After oxidation divert the stream 205 containing stream is oxidized raw material 201, the catalyst and the solvent. To remove from the stream 205 of the catalyst and/or solvent used machine division, such as the filter 210, the Separated catalyst is collected in installing 220 and return flow 221 in apparatus for the oxidation of 200. Then the stream 215 is subjected to drying in the drying apparatus 230 to remove residual moisture and/or solvent. The dried crude TA and IPA (crude product) then take away in the form of a stream 235 and sent to the storage tank 240. If desired purified TA and IPA, the crude product is put up in the form of a stream 245 and served in the apparatus for dissolving 250 in which to dissolve the crude product can be traditionally used various solvents, heat and/or pressure. The crude acid is served in the form of a stream 255 in the hydrogenation reactor 260, where the impurity is introduced into reaction with hydrogen and the resulting products are separated from the acid. Then the stream 265 is crystallized in consecutive crystallizers 270 and serves as a stream 275 in apparatus for separating 280. Then the stream 285 dried in a drying apparatus 290, from which he removed have a mixture of pure terephthalic and isophthalic acids in the form of a stream 295. The method of the present invention is designed to turn the flow of raw materials from a mixture of xylenes containing about 20% ethylbenzene, about 20% ortho-xylene, about 40% of meta-xylene and about 20% para-xylene, isophthalic and terephthalic acid in a ratio of about 2:1. In other embodiments, the flow of raw material contains xylene in a ratio of from about 0.1 to about 10.0: from about 0.5 to about 10.0. In an alternative embodiment, the flow of the raw material contains xylene in a ratio of from about 1.0 to about 5.0: from about 1.0 to about 5.0. Method of removing crude mixture of TA and IPA is illustrated in figure 4. Usually a mixture of one HUNDRED and C-IPA from the storage tank or storage device 300 serves as a stream 305 in the apparatus for dissolving 310, which are acid and/or other solvents, which dissolve one HUNDRED and C-IPA. Stream 315, abstracted from the apparatus for dissolving, served in the removal area 320, where the substance is selectively crystallized, filtered, centrifuged and/or the like, and a HUNDRED separate in the form of a stream 325, which is dried in the drying apparatus 340, and receives as a product of 350 or subjected to further purification. Stream 322 contains a C-IPA and the solvent. For easier removal of the solvent from the C-IPA use solvent replacement 360, such as a column 370. Stream 372 containing the selected solvent, return to the device DL is dissolving 310 and receive the product C-IPA (380), you can clean on. Process conditions According to the present invention, the above-described raw materials can be brought into contact with a catalytic system in the necessary conversion for carrying out the hydrogenation. Examples of such conditions include a temperature of about 200-550°C, pressure from 0 psi to about 1000 psi, space velocity WHSV of about 0.1-200 h-1and the molar ratio of H2/HC of about 0.2-10. Alternative conditions may include a temperature of about 325-475°C, a pressure of about 50-400 pounds/square inch, a WHSV of about 3-50 h-1and the molar ratio of H2/HC of about 1-5. The WHSV value determined based on the weight of the catalytic composition, i.e. on the total weight of active catalyst and carrier, if any. Oxidation In various embodiments, the oxidation of xylenes to a HUNDRED and C-IPA carried out in a reactor with stirring, in which the air supplied through the nozzle. In the reactor serves a mixture of xylenes, solvent type acetic acid and the catalyst. The blower speed adjust depending on the content of O2in the exhaust gas from the reactor, which monitor and record the use of gas analyzers. The reaction temperature is about 200°C and a pressure of about 1.6 MPa. Generated in the oxidation reactor dissipate heat by evaporation of the solvent and water react in the re. Catalyst The shape and size of the catalyst particles is not critical in this invention and can be varied depending on, for example, on the type of reaction system. Non-limiting examples of catalysts of this invention include beads, pellets, spheres, extrudates, corrugated blocks, cell blocks, microspheres, tablets or catalysts in the form of petals, shamrocks, chetyrehlistnik, round tablets, pellets, honeycombs, powders, granules, etc. manufactured by conventional methods such as extrusion or spray drying. In General, the catalyst can be dissolved in the reaction medium containing the solvent and precursors of aromatic carboxylic acids, or, alternatively, it is possible to use a heterogeneous catalyst. Homogeneous or heterogeneous catalyst usually contains one or more compounds of heavy metals, for example, compounds of cobalt and/or manganese, and optionally may contain a hydrogenation promoter. In one embodiment, the catalyst is palladium. The heterogeneous catalyst can be placed in the reaction zone to provide contact between the continuously moving the reaction medium and catalyst. In this case, to ensure such contact, the catalyst can be applied to the substrate and/or to limit the reaction zone without reducing the cross with the treatment stream. For example, the heterogeneous catalyst can be placed or applied or embedded in the fixed part of the reactor (for example, areas with open structure) inside the reaction zone, through which flows the reaction medium. Such a fixed part of the reactor used for additional mixing of the reactants passing through the reaction zone. Alternatively, the catalyst can be in the form of mobile tablets, particles, melkorazdroblennyh particles, metal sponge or the like, together with devices that help to keep the catalyst in the reaction zone, so that when the tablets of the catalyst was suspended or embedded in a reaction medium flowing through the reaction zone. The use of heterogeneous catalyst in any of these ways creates the advantage that it limits the catalytic effect of a clearly defined area, and as a result, when the passage of the reaction medium through the zone further hydrogenation proceeds at a reduced speed or markedly suppressed. The carrier for the catalytic hydrogenation may be less catalytically active or even inert in the hydrogenation. The media can be porous and usually have a surface including the surface of pores, at least 15-500 m2/g, for example, 50-200 m2/g, preferably about 80-150 m2/, Carriers for the catalyst to what must be almost resistant to corrosion and oxidation under typical conditions. The carrier of the oxidation catalyst can be a single component or a composite material, the latter is used, for example, to obtain a catalyst of the desired chemical or physical properties. In one embodiment, the carrier for catalyst comprises zirconium dioxide. In an alternative embodiment, the carrier is carbon. In General, in various embodiments of the present invention will work with any catalyst. 1. The method of converting the flow of raw materials containing at least one C8-aromatic compound, ortho-xylene, meta-xylene, para-xylene and ethylbenzene at least one product stream containing isophthalic acid and terephthalic acid (IPA/TA), which involves the following stages: 2. The method according to claim 1, further comprising adding one or para-xylene or meta-xylene, to a specified flow of raw materials, depleted ethylbenzene and ortho-xylene. 3. The method according to claim 1, in which stage the removal of ethylbenzene from the specified stream of raw materials is carried out by selective adsorption on the material type molecular sieves or by using a distillation apparatus. 4. The method according to claim 1, in which the flow of raw material contains a stream of mixed xylenes, containing 20% ethylbenzene, 20% ortho-xylene, 40% meta-xylene and 20% para-xylene. 5. The method according to claim 4, in which the flow of raw material enters at least one of the following: installing or catalytic reforming process, installation or process of cracking with steam, installation or process of coking, installation or process of pyrolysis oil, installation or process of alkylation or parallelomania aromatic hydrocarbons. 6. The method according to claim 1, wherein the product stream contains IPA/TA ratio of 2.0% IPA and 98% TA. 7. The method according to claim 1, in which the flow of raw material contains 1-25 wt.% ethylbenzene, 20-80 wt.% meta-xylene, 5-30 wt.% ortho-xylene and 0.5-20 wt.% para-xylene.
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