• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A process for the recovery of catalysts and solvents in a method for obtaining terephthalic acid, essentially of the type comprising the oxidation of para-xylene in acetic acid solution and in the presence of a catalytic system based on manganese, cobalt and bromine , with which water is formed during oxidation, the amount of water in the liquid oxidation mixture being less than 10% by weight with respect to acetic acid, whereby solid terephthalic acid is separated from the mother liquor and with which a liquid that is obtained by condensing the vapors released during oxidation is extracted from the oxidation zone and is constituted, essentially, by acetic acid and water; characterized in that it comprises reducing the amount of suspended solids in the mother liquors to less than 0.30% and preferably less than 0.05% by weight, with respect to the mother liquors, and because successively said mother liquors are partially anhydrified, by means of a distillation to reduce the amount of water in the partially anhydrous mother liquor below, at least, 5% by weight, with respect to acetic acid, whereby a portion of the partially anhydrous liquor, containing minus 50% of the catalytic system, present in the original mother liquors, is recycled to the oxidation zone, the remaining portion of the partially anhydrified liquor being fed as a purge to the usual treatments for catalyst separation and regeneration.
    公开号:SU1217250A3
    申请号:SU782600750
    申请日:1978-04-03
    公开日:1986-03-07
    发明作者:Бортеси Пьеро；Тонти Серджо；Танкорра Раффаеле；Константини Джузеппе；Серафини Мауро；Паоли Пьетро
    申请人:Монтэдиссон С.П.А. (Фирма)；
    IPC主号:
    专利说明:

    one
    The invention relates to the field of organic synthesis, specifically to a method for processing uterine solution from a process for the production of terephthalic acid — a monomer for the production of polymers.
    The purpose of the invention is to reduce the loss of acetic acid.
    The drawing shows a scheme for the implementation of the method.
    The following substances are present in a titanium reactor equipped with a stirrer, reflux condenser, input and output lines, wt%: 1000 paraxylene, 3800 9b54% acetic acid, 1j69 cobalt acetate, tetrahydrate, 5.35 manganese acetate tetrahydrate, 1.63 hydrogen bromide. A part of the condensed liquid is removed from the reflux condenser so as to maintain a percentage of water in the reaction medium of about 10% by weight. The reaction temperature is maintained at about 220 ° C, and the flow rate, expressed in arbitrary units, is 500 kg of para-xylene per hour and in the m of non-expanded liquid phase. The combustion losses are limited to 3.38 moles of CO2 mixture (a mixture of carbon monoxide CO and carbon dioxide COj) per kg of paraxylene feed, thus forming 22.90 kg of methyl acetate per kg of raw material of paraxylene. The crude and solid terephthalic acid is isolated and then centrifugally separated from the synthesized mother liquor.
    Example 1. The mother liquor coming in (line 1) from the stage of centrifuging terephthalic acid, containing 85% by weight of acetic acid and less than 0.30% by weight of suspended solids, is fed above the third bottom of the column tray 2, the upper part of which serves a stream of 3 aqueous acetic acid concentrations of approximately
    70 of us,
    not containing catalyst, which is obtained from other stages of the process. The bottom product of column 4, containing 0.20% by weight of solid particles in suspension, consists mainly of terephthalic acid. Part of the bottom product - containing 94 wt.% Acetic acid, 56% of the catalyst fed to the column (cobalt S manganese and bromine) ,,
    7250
    3 wt.% H, 0 and oxidation intermediate products, recycled to synthesis (column 4); Another part of the specified bottom product enters, 5 into the reboiler of the same column, which is a distillation cube 5, equipped with a stirrer, a heat exchanger 6 connected in series and heated with steam. Concentrated.
    0 the product is sent (line 7) to an evaporator (not shown) with a thin
    layer, and then - in the muffle for about
    Kalivani | the remainder of the liquid coming from the distillation
    The 5 cubes are passed through the heat exchanger 6 and sent back to the still cub, where the vapors are released, before they enter the column again. Dwell time fluid
    0 at the bottom of the distillation column is about 6 minutes, during which changes occur in the organic matter in column 4, leaving the top of the column.
    5 2 pairs enter the solvent recovery column 8, from the bottom part of which is almost anhydrous acetic acid; the acid flows out (line 9) and is reused in the oxidation reactors together with recycle 4 and with the acetic acid solution (line 10) containing the regenerated and fresh catalyst. The mixture is prepared in a storage tank,
    5 where para-xylene (line 11) is fed, through line 12 leading from the tank, the mixture goes directly to the oxidation reactor. Pipeline 13 is added to the amount of azeotropic
    l l
     agent (isobutyl acetate), sufficient to compensate for the losses, in the back of the cooler, the vertical baffle plate installed in the mixer tank 14 allows
     There is no separation of the organic phase (flowing back to the top of the column) from the aqueous phase. Isobutyl acetate, methyl acetate and other organic compounds are successively separated by stripping directly in a column azeotropic distillation column 15, equipped with a partial condenser. Reservoir: 16 section et. the uncondensed vapor phase 17 ,, 55 consisting of 92% methyl acetate, from the liquid phase 18, consisting mainly of isobutyl acetate, which goes into the mixing
    g
    50
    reservoir 14. The vapor phase, consisting predominantly of methyl acetate, is condensed in an exchanger 19 and sent for storage. The water coming from the bottom of the stripping column is drained and it contains too little organic material, only 30 ppm of acetic acid and 20 ppm of isobutylacetate compared to 10,000 ppm of organic components in this product, if the distillation is carried out in the usual way. The regenerated anhydrous acetic acid flows from the bottom of the recycling column (line 10) and contains only 3% by weight of water. The yield is 94.5% (mol of terephthalic acid per 100 mol of xylene) and the properties of the resulting terephthalic acid are as follows: Carboxy.
    1450 ppm
    35 ARNA
    The amount of recycled catalyst, wt.%
    The original content of suspended solids, wt.%
    Output ,%
    4-CBA, ppm
    Chromaticity, arna
    Transparency
    Solvent Combustion
    mole terephthalic acid per 100 mole paraxylene
    light through 15% specified
    solution) 58.9%
    Thereafter, the amount of carboxybenzaldehyde is reduced by hydrogenation to less than 20 ppm; The purified terephthalic acid thus obtained has a light transmittance of more than 95% (purity suitable for producing fiber).
    Example 2. Similarly to Example 1. However, the amount of recycled catalyst is reduced to 50% instead of 56.
    EXAMPLE 3 Analogously to Example 1, but with a change in the initial percentage of solids (0.03 instead of 0.3%).
    PRI me R 4. Analogously to example 2, however, the initial content of suspended solid particles is reduced to 0.03 instead of 0.30%. Example5. As in Example 3, however, the amount of recycled catalyst is significantly increased up to 86 instead of 56%.
    The data obtained in the examples are shown in the table.
    50
    56
    50
    86
    0.30 0.030.03 0.03
    94.4 9594.9 95.1
    144014501440 1470
    30 353045
    59. 58,758.9 57.5
    Norm Norm Norm High
    / J
    / 7
    权利要求:
    Claims (1)
    [1]
    METHOD FOR PROCESSING UTERINE SOLUTION containing up to 101 water and obtained after removal of terephthalic acid from the reaction mixture upon its preparation by oxidation of c-xylene in acetic acid at a mass ratio of 1: 4 in the presence of a catalyst containing cobalt, bromine and manganese, followed by the removal and condensation of exhaust vapors and gases, characterized in that, in order to reduce the loss of acetic acid, reduce the amount of solid suspended particles in the mother liquor from 0.03 to 0.3 ma.el. followed by partial dehydration to a water content of 3% in the distillation column p the irradiated solution, which is fed over its third plate, starting from the bottom, while condensing the exhaust gases, after which part of the obtained bottoms liquid containing 5086 wt.% catalyst is recycled to the oxidation process, and the vapors removed from the distillation column are fed to the column for azeotropic distillation with isobutyl acetate, after which the stream from the head of the azeotropic distillation column is condensed and separated into two phases, the lower aqueous phase being directed to a stripping column, then the stream leaving and the stripping columns are partially condensed and fed to a separation vessel, in which the vapors, consisting mainly of methyl acetate, are separated from the liquid phase containing isobutyl acetate, which is recycled to the azeotropic distillation column, and the methyl acetate is recovered by successive condensations from the vapors leaving the head parts of the steaming column.
    1 · 12
    类似技术:
    公开号 | 公开日 | 专利标题
    SU1217250A3|1986-03-07|Method of treatment of mother solution
    US4215051A|1980-07-29|Formation, purification and recovery of phthalic anhydride
    US3683018A|1972-08-08|Integrated oxidation of isomeric xylene mixture to isomeric phthalic acid mixture and separation of mixture of isomeric phthalic acids into individual isomer products
    JP4184948B2|2008-11-19|Process for producing purified terephthalic acid
    US3240803A|1966-03-15|Preparation of benzenecarboxylic acid
    RU2337903C2|2008-11-10|Two-stage oxidation method for obtaining aromatic dicarboxylic acids
    US3839436A|1974-10-01|Integration of para-or meta-xylene oxidation to terephthalic acid or isophthalic acid and its purification by hydrogen treatment of aqueous solution
    US5705682A|1998-01-06|Process for producing highly pure terephthalic acid
    EP0255399B1|1992-03-11|Process
    SU791221A3|1980-12-23|Method of preparing terephthalic acid
    US3629321A|1971-12-21|Integration of para-xylene oxidation to terephthalic acid and its esterification to dimethyl terephthalate
    JP4017673B2|2007-12-05|Method for producing acetic acid
    JP4520637B2|2010-08-11|Acrylic acid production method
    JP2004531572A|2004-10-14|Crystallization process for the production of purified aromatic dicarboxylic acids
    US5338882A|1994-08-16|Process for the production of DMT-intermediate product of specific purity and pure terephthalic acid
    US3484458A|1969-12-16|Trimellitic acid production and recovery of intramolecular anhydride
    US4250330A|1981-02-10|Process for the recovery of the solvent and of the by-produced methylacetate in the synthesis of terephthalic acid
    US6150553A|2000-11-21|Method for recovering methyl acetate and residual acetic acid in the production acid of pure terephthalic acid
    WO2004002933A1|2004-01-08|Process for the separation of the water produced in the catalytic oxidation of aromatic hydrocarbons to polycarboxylic aromatic acids
    US4172209A|1979-10-23|Process for producing dicarboxylic acids by the oxidation of xylene
    TWI694984B|2020-06-01|Production of an aromatic dicarboxylic acid
    EP1104396B1|2002-10-09|Method for recovering methyl acetate and residual acetic acid in the production of pure terephthalic acid
    US4215056A|1980-07-29|Formation, purification and recovery of phthalic anhydride
    US4008255A|1977-02-15|Recovery of phthalic anhydride
    US4788296A|1988-11-29|Process for the production and recovery of trimellitic anhydride
    同族专利:
    公开号 | 公开日
    ES468499A1|1979-01-01|
    DE2814448A1|1978-10-12|
    FR2386511A1|1978-11-03|
    DE2814448C2|1991-05-23|
    JPS6241219B2|1987-09-02|
    GB1593117A|1981-07-15|
    NL188282C|1992-05-18|
    NL188282B|1991-12-16|
    JPS53127430A|1978-11-07|
    MX148713A|1983-06-06|
    NL7803368A|1978-10-06|
    FR2386511B1|1980-07-25|
    BR7802069A|1979-01-23|
    IN148106B|1980-10-18|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    BE670307A|1964-12-14|1900-01-01|
    US3557173A|1968-05-09|1971-01-19|Sinclair Research Inc|Process for recovering cobalt acetate|
    DE2104909A1|1971-02-03|1972-09-07|Chemische Fabrik Kalk GmbH, 5000 Köln|Terephthalic acid prodn - by para-xylene oxidn with oxygen using cobalt and bromine compound catalysts|
    US3761474A|1971-03-22|1973-09-25|Fmc Corp|Purification of crude cyanuric acid|
    JPS5328420B2|1973-04-05|1978-08-15|
    JPS5328421B2|1973-05-15|1978-08-15|
    JPS5328901B2|1973-07-28|1978-08-17|
    FR2304255A7|1975-03-13|1976-10-08|Inst Francais Du Petrole|Terephthalic acid prodn. by oxidn. of paraxylene - with removal of byproducts from conc. reactor effluent by treatment with water|IT1129759B|1980-01-23|1986-06-11|Montedison Spa|METHOD TO RECOVER IN ACTIVE FORM THE COMPONENTS OF THE CATALYTIC SYSTEM OF THE SYNTHESIS OF TEREPHTHALIC ACID|
    US4334086A|1981-03-16|1982-06-08|Labofina S.A.|Production of terephthalic acid|
    CN1070839C|1994-08-23|2001-09-12|纳幕尔杜邦公司|Dehydration of acetic acid by azeotropic distillation in the prodn. of aromatic acid|
    US6150553A|1998-08-11|2000-11-21|E. I. Du Pont De Nemours And Company|Method for recovering methyl acetate and residual acetic acid in the production acid of pure terephthalic acid|
    WO2002068083A1|2001-02-27|2002-09-06|Mitsubishi Chemical Corporation|Azeotropic distillation method|
    US7884232B2|2005-06-16|2011-02-08|Eastman Chemical Company|Optimized liquid-phase oxidation|
    US7504535B2|2004-09-02|2009-03-17|Eastman Chemical Company|Optimized liquid-phase oxidation|
    US7589231B2|2004-09-02|2009-09-15|Eastman Chemical Company|Optimized liquid-phase oxidation|
    US7361784B2|2004-09-02|2008-04-22|Eastman Chemical Company|Optimized liquid-phase oxidation|
    US7507857B2|2004-09-02|2009-03-24|Eastman Chemical Company|Optimized liquid-phase oxidation|
    US7572936B2|2004-09-02|2009-08-11|Eastman Chemical Company|Optimized liquid-phase oxidation|
    US7741515B2|2004-09-02|2010-06-22|Eastman Chemical Company|Optimized liquid-phase oxidation|
    US7910769B2|2004-09-02|2011-03-22|Eastman Chemical Company|Optimized liquid-phase oxidation|
    US7582793B2|2004-09-02|2009-09-01|Eastman Chemical Company|Optimized liquid-phase oxidation|
    US7683210B2|2004-09-02|2010-03-23|Eastman Chemical Company|Optimized liquid-phase oxidation|
    US7381836B2|2004-09-02|2008-06-03|Eastman Chemical Company|Optimized liquid-phase oxidation|
    US7568361B2|2004-09-02|2009-08-04|Eastman Chemical Company|Optimized liquid-phase oxidation|
    US7692037B2|2004-09-02|2010-04-06|Eastman Chemical Company|Optimized liquid-phase oxidation|
    US7692036B2|2004-11-29|2010-04-06|Eastman Chemical Company|Optimized liquid-phase oxidation|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    IT2205877A|IT1075688B|1977-04-04|1977-04-04|Recovery of catalyst and solvent used in terephthalic acid mfr. - by distillation of the mother liquor|
    IT22408/77A|IT1075317B|1977-04-13|1977-04-13|METHOD FOR SOLVENT ANHYDRIFICATION AND FOR THE RECOVERY OF THE BY-PRODUCT OF METHYL ACETATE IN A SYNTHESIS PROCESS OF TEREPHTHALIC ACID|
    [返回顶部]