• 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:
    Verfahren zur Gewinnung und Wiederverwendung von Schwermetalloxidationskatalysator durch Extraktion von hochsiedenden Destillationsrückständen, die nach dem Witten-DMT-Verfahren anfallen, mit Wasser oder verdünnten wäßrigen Lösungen niedermolekularer aliphatischer Monocarbonsäuren oder Alkohole und Rückführung des Extraktes, gegebenenfalls nach Einengen, in die Oxidation, wobei im Extrakt das Mengenverhältnis von Trimellitsäure plus Trimellitsäuremonomethylester zu Schwermetalloxidationskatalysator auf einen Wert von höchstens 1,8:1 eingestellt wird und in der Oxidation die in ppm ausgedrückte Katalysatorkonzentration c auf c = 44. + d mit 60 ppm ≤ d ≤ 300 ppm und dem vorbezeichneten Wert des Verhältnisses 6 eingestellt wird.
    公开号:SU1088662A3
    申请号:SU802932202
    申请日:1980-06-10
    公开日:1984-04-23
    发明作者:Бюнгер Гейнрих；Кордес Рудольф；Хоффманн Герхард
    申请人:Динамит Нобель Аг (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to organiches This synthesis, more particularly, to methods for producing dimethyl terephthalate (fljfff. Izresten process for producing liquid phase were DMT by oxidation of p-xylene (PCs and / or methyl n slooknogo -toluilovoy kislotad (YUPTK) oxygen or an oxygen containing gas at a temperature and pressure povppennoy in the presence of a catalyst of dissolved heavy metals, the esterification of the oxidation product with methanol at a temperature and pressure, the separation by distillation of the esterification product into France with raw DMT, fraction, God h-toluic acid methyl ester and high boiling residue containing catalyst, extraction with water or dilute aqueous solution of low molecular weight aliphatic monocarboxylic acids or alcohols with previous or subsequent treatment with methanol at elevated temperature and recycling containing the catalyst for oxidation to...,,; ..: The disadvantage of the method lies in the fact that the dL needs the necessary dp to activate the recycled catalyst for the treatment with methanol Special equipment to ensure close contact of the high boiling residue or extract with methane. In addition, treatment with methanol at a higher temperature leads to an increase in energy consumption and loss of: methanol,. The closest in technical essence and achievable results to the proposed is a method of obtaining DMT by liquid phase oxidation of ri-xylene and / or sloe methyl h-toluic acid ester with oxygen or oxygen-containing. , gas at an elevated temperature k in the presence of a catalyst, dissolved heavy metals, esterification of the oxidation product with methanol at elevated temperature and pressure, separation by distillation of the product of esterification into a crude J fraction, a fraction rich in toluic acid methyl ester h and a high boiling residue, containing catalyst, extraction of the catalyst with water or a dilute aqueous solution of low molecular weight aliphatic monocarboxylic acids or alcohols and recycling the extract to oxidize follows tZJ evaporation of water and volatile acids. A disadvantage of the known method is that the catalytic selectivity of the recycled extract containing the catalyst is the regenerative catalyst solution) is less by 4 mol% than the fresh catalyst solutions of the same concentration, and the selectivity is not the same, despite the same catalyst concentration. The disadvantages of this method are that the extract from the distillation residue containing the catalyst has a variable amount of trimellitic acid (TMK.). IH of trimellitic acid monomethyl ester (SHETMK / active on the minimum permissible concentration of catalyst in the oxidation product. The aim of the invention is to increase the selectivity of the process. This goal is achieved by a method of producing DMT, including the liquid phase oxidation of p-xylene and / or p-toluic acid methyl ester with oxygen or oxygen. As a gas at ISO-iyo C and a pressure of 5-7 atm in the presence of a catalyst, cobalt and manganese acetates 5 esterify the oxidation product with methanol at 250-260 ° C and a pressure of 20-30 atm, separating the esterification product by distillation into a raw DMT fraction, p-toluic acid methyl ester and a high boiling residue containing a catalyst, extracting the residue with water or a dilute aqueous solution of low molecular weight aliphatic monocarboxylic acids or alcohols and recycling the extract for oxidation, according to which ix PE circulate extract containing TECs MMETMK and the catalyst in a proportion (0,001-1,8) and oxidation is carried out at a catalyst concentration in h / million. calculated according to the formula C 44ci7b44, where a is the sum of the concentrations of the TEC and MMETMK in the catalyst solution, g / l; B is the concentration of catalyst in solution, g / l; X - 60-300,
    wherein the concentration of TMK plus MMETMK in the extract is established by ion exchange with a weakly basic anion exchanger in the acetate and / or formate form or by mixing solutions with different co2:; 5 holding TMK + MMETMK followed. if necessary, by adding soluble catalyst compounds.
    The proposed catalyst concentration is critical, i.e. 10 below 44: d 60 may interfere, and above Deal esterification columns may be clogged. The Ratio can be established, for example, by ts addition of soluble oxidation catalyst compounds. In addition, a solution of a regenerative catalyst with a high content of TMK can be mixed in an appropriate ratio with a catalyst solution containing a small amount of TMK.
    TMK and MMETMK can be removed from the aqueous solution of the regenerative catalyst with a weakly basic anion exchanger. Macro-porous anion exchangers in acetate and formate form are particularly suitable. Thus, TMK,. MUTMK and others contained in the d solution of the catalyst di- and tricar-. bokovy acids are replaced with vinegar -. formic acid and is selectively removed from the catalyst solution.
    TMK and trimellitic acid ester can be removed by extraction by treating the anion exchanger or by distillation from the extractable residue.
    In order to extract the oxidation catalyst from the distillation residues, it is desirable to use dilute aqueous solutions of acetic acid, in particular, containing waste acetic and formic acid oxidation waters, which are obtained during the oxidation of PC and UPPK.
    Example 1. 80 kg / h of p-xylene and 98 kg / h of methyl ester of p-toluic acid 50 are subjected to liquid-phase oxidation with 60 nm of air at ° C and a pressure of 6 atm in the presence of a sintered carbon catalyst. / mln.55 cobalt and 9 ppm, manganese in the form of acetates dissolved in 2% aqueous acetic acid. The resulting oxidation product is subjected to the esterification of 80 kg / h of methanol at 26 ° C / C and a pressure of .24 atm. The product of esterification is subjected to continuous fractional distillation at 260 ° C. and a pressure of 0.1 at. This gives 230 kg / s (87 mol.2 dimethyl terephthalate) with a melting point of 140.62 ° C. and 1.5 t / h of high boiling residue, which is not After 24 hours of dimethyl terephthalate production, the oxidation gas contains 0.6 vol% carbon monoxide and 1.8 vol% oxygen, and the selectivity of dimethyl terephthalate formation is 98.5%. After 5 days of production instead of fresh KaTajmizer an extract obtained from the shlung boil residue is fed to the oxidation stage as follows: 1.5 t / h of high boiling residue containing catalyst, acids and their esters, including trimellitic acid (TMK) and its monomethyl ether (SHETMK), and substituted bi- and triphenyls, extracted with 1.5 tons / h of an aqueous solution containing 2.5% by weight of acetic acid, 1.5% by weight of formic acid and 0.8% by weight of formaldehyde, by passing a residue with a temperature of 60 ° C through the column, contained Levatite MP 62 anion exchanger Bayer AG (Germany), pre-activated with a 4% aqueous solution of sodium hydroxide and treated with an aqueous solution After concentration, 0.3 t / h of extract is obtained, which contains 35 g / l of cobalt, 3.5 g / l of manganese and 0.1 g / l of IMC plus MMETMK. This is one in which the ratio of catalyst to TJ plus MMETMK is 1: 0.0025, and a five-day oxidation stage is recycled in an amount that provides a concentration of 90 s / min of cobalt and 9 ppm manganese in the reaction medium. Moreover, the specified output of dimethyl terephthalate with so pl. 140.62c and the selectivity of dimethyl terephthalate formation is not impaired.
    EXAMPLE 2 Example 1 t is repeated. The difference is that before being recycled to the oxidation stage, the extract is passed through the column once more, and then the ratio of TMK plus MJTMK and catalyst is adjusted to ° 0.001: 1 by pushing 1 g / l addition. cobalt and 0.5 g / l manganese in the form of acetates. The yield of dimethyl terephthalate and selectivity
    权利要求:
    Claims (1)
    [1]
    METHOD FOR PRODUCING DIMETHYL-. TERPHTHALATE by the liquid phase oxidation of η-xylene and / or methyl ester of η-toluic acid with oxygen or an oxygen-containing gas at 150-170 ° C and a pressure of 5-
    7 atm in the presence of a catalyst for cobalt and manganese acetates, followed by esterification of the oxidation product with methanol at 250-260 ° С and a pressure of 20-30 atm and separation of the esterification product by distillation into a fraction of crude dimethyl terephthalate, p-toluic acid methyl ester and a high-boiling residue containing a catalyst extraction of the catalyst with water or a dilute solution of low molecular weight aliphatic carboxylic acids or alcohols and recycling the extract for oxidation, characterized in that, in order to increase process selectivity an extract containing trimellitic acid is recycled for oxidation. plus trimel-, lithic acid monomethyl ether and a catalyst in a quantitative ratio (0.001 -1.8): 1 and oxidation is carried out at a concentration to the catalyst (in parts per million) calculated by the formula
    C = 44c | / b + x f where a is the sum of the concentrations of trimellitic acid and trimellitic acid monomethyl ether, g / l;
    B is the concentration of catalyst, g / l;
    X - 60-300, while the concentration of trimellitic acid and its monomethyl ether in the extract is established by ion exchange with weakly basic anion exchange resin in acetate and / or formate form or by mixing solutions with different contents of trimellitic acid and its ether, followed by, if necessary, the addition of soluble catalyst compounds.
    , SU w, 1088662
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    同族专利:
    公开号 | 公开日
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    PL125337B1|1983-04-30|
    TR21572A|1984-10-08|
    EP0020990A2|1981-01-07|
    JPS5948142B2|1984-11-24|
    CS221918B2|1983-04-29|
    IN153472B|1984-07-21|
    AT9327T|1984-09-15|
    BR8003618A|1981-01-05|
    DD151115A5|1981-10-08|
    ZA803501B|1981-08-26|
    PL224850A1|1981-04-10|
    US4372875A|1983-02-08|
    MX153999A|1987-03-19|
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    RO79997B|1983-01-30|
    YU151780A|1983-12-31|
    YU41363B|1987-02-28|
    RO79997A|1983-02-01|
    CA1145739A|1983-05-03|
    BG49164A3|1991-08-15|
    ES492320A0|1980-12-16|
    DE2923681C2|1981-11-05|
    JPS562849A|1981-01-13|
    ES8102086A1|1980-12-16|
    EP0020990A3|1981-10-14|
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    引用文献:
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE2923681A|DE2923681C2|1979-06-12|1979-06-12|Process for the recovery and reuse of heavy metal oxidation catalyst from the Wittem DMT process|
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