• 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 and reuse of a heavy-metal oxidation catalyst solution from a high-boiling distillation residue having a cobalt content of 1-10 g/kg of residue is disclosed. The distillation residue is obtained in the production of dimethyl terephthalate by the oxidation of mixtures containing p-xylene and/or methyl p-toluate in the liquid phase with oxygen or an oxygen-containing gas under an elevated pressure and at an elevated temperature in the presence of dissolved heavy-metal oxidation catalyst, by subsequent esterification of the oxidation product with methanol and by a distillatory separation of the esterification product into a fraction rich in methyl p-toluate, a fraction rich in dimethyl terephthalate, and the high-boiling distillation residue. The process involves the steps of effecting extraction of the heavy-metal oxidation catalyst from the high-boiling distillation residue with aqueous low-molecular aliphatic monocarboxylic acids under heating; treating the aqueous, acidic extract, which contains the heavy-metal oxidation catalyst and has a cobalt content with a strongly acidic cation exchange resin in the alkali metal form at an elevated temperature until the exchange capacity has been reached, and washing the cation exchange resin at an elevated temperature with water and regenerating the cation exchange resin at room temperature with a solution containing Na+ or K+ acetate to displace the catalyst components and to obtain an aqueous acetic acid catalyst solution containing the catalyst components.
    公开号:SU1053735A3
    申请号:SU803247249
    申请日:1980-12-10
    公开日:1983-11-07
    发明作者:Дисель Карл-Гейнц；Модик Рудольф；Штрус Фридрих
    申请人:Динамит Нобель Аг (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to a method for isolating catalysts, in particular to a method for isolating a catalyst based on cobalt and manganese acetates from the residue of dimethyl terephthalate.
    A known method for separating a catalyst based on heavy metals from a dimethyl terephthalate production residue is that the residue obtained by distillation is extracted with water, dilute mineral acid, aqueous low molecular weight aliphatic monocarboxylic acid with 1-4 carbon atoms or alcohol when heated and before or after extraction, the residue of the distillation with methanol at 100–450 ° C, followed by the removal of methanol by evaporation, moreover, methanol is used in an amount of 0–1000 w / h, per: Tat distillation or extract 1.
    1 A disadvantage of the known method is that the treatment with methanol must be carried out in special apparatus with a stirrer, and the treatment with methanol at the indicated temperature is associated with the loss of methanol, which adversely affects the efficiency of the process.
    The closest to the invention in its technical essence and the effect achieved is a method for separating a catalyst based on cobalt and manganese acetates from the residue of dimethyl terephthalate production, which consists in extracting the residue with water when heated with sulfur-containing compound and oxygen-containing gas, the wave may contain acetic acid, cooling extract to room temperature, separating the obtained precipitate, passing the extract through a layer of cation exchanger in hydrogen form until reaching the limit e at room temperature, washing the cation exchanger with water, desorbing the aqueous hydrobromic acid at room temperature, and distilling the resulting hydroxide 2.
    The disadvantages of this method are that the extraction is carried out using a sulfur-containing compound and an oxygen-containing gas and the eluate is distilled, this complicates the process, except TorOf, the degree of release of cobalt acetates to manganese from the residue is not high enough.
    The purpose of the Invention is to simplify the process and increase the degree of fading.
    The goal is achieved in that according to the method of catalyst removal on the basis of cobalt and manganese acetates from the residue of dimethyl terephthalate production by extracting the residue with reaction water containing acetic acid, while cooling the extract to a reaction temperature, separating the resulting precipitate, passing the extract through sodium cationite. until reaching the limit of capacity when washing the cation exchanger with desalted water at 70 ° C and desorbing with sodium acetate at room temperature tez sherature
    The proposed method makes it possible to isolate the catalyst in the form of cobalt-manganese acetates by 93.8 95%.
    The residue of pefegon used in examples 1 and 2 is obtained by continuous production of dimethyl terephthalate by the liquid oxidation of a mixture of p-xylene and p-toluic acid methyl ester with oxygen of air at a temperature of 150-170 ° C and a pressure of 8 bar in the presence of a catalyst - acetic solution. cobalt and manganese in aqueous acetic acid, with a steady-state concentration of 90 hours / mill. cobalt and 10 ppm of manganese, the subsequent esterification of the oxidation product with Methanol at a pressure of 25 bar and the separation of the esterification product with two-stage vacuum distillation. The yield of dimethyl terephthalate is 89, 5-90 mol. %
    Example. 100 kg of distillation residue containing 2.3 g / kg of cobalt and 0.2 g / kg of manganese, extracted with 60 l of the reaction solution produced in dimethyl terephthalate containing 3% acetic acid, at 95c
    .2+
    up to residual ion content: s
    equal to 20, After decanting, 56 l of extract is obtained containing 3.8 g / l of Co and 0.3 g / l. The hot extract is cooled to room temperature and the precipitated organic matter is removed by filtration.
    The solution obtained after filtration is heated again and passed through a tube containing 1.1 liters of strongly acidic cation exchanger Levatite 5,100 in sodium form. The solution is fed to the cationic to reach the capacity limit. The extract consumption is 19 liters; total content MI 78 horses; 4 g. Then the cation exchanger is washed with 1 liter of completely desalted water at, after which it is desorbed with 2.2 l of 10% aqueous acetic acid solution of sodium acetate, followed by further burning out
    权利要求:
    Claims (1)
    [1]
    METHOD FOR ISOLATING THE CATALYST ON THE BASIS OF COBALT AND Manganese Acetates from the remnant of production
    Dimethylterephthalate, including extraction of the residue with reaction water containing acetic acid at elevated temperature, cooling the extract to room temperature, separating the resulting shrinkage, passing the extract through a cation exchanger layer to the limit. containers, washing the cation exchange resin with desalted water and desorption ι at room temperature, characterized in that, in order to simplify the process and increase the degree of isolation, the residue is extracted at 95 ° C, cation exchange resin in the sodium form is used as cation exchange resin, the extract is allowed to pass through cation exchange resin and washed cation exchange resin at 70 ° C ', and the desorption is carried out with an aqueous acetic acid solution of sodium acetate.
    >
    105373b
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    同族专利:
    公开号 | 公开日
    US4410449A|1983-10-18|
    ZA807808B|1982-01-27|
    IN152932B|1984-05-05|
    JPS6328659B2|1988-06-09|
    JPS56100636A|1981-08-12|
    DE2950318B1|1981-04-02|
    DE2950318C2|1982-02-25|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    ES282073A1|1961-11-09|1963-03-01|Snia Viscosa Soc Nazionale Industria Applicazioni Viscosa S P A|Catalytic recovery procedure based on cobalt |
    US3341470A|1963-02-27|1967-09-12|Standard Oil Co|Chemical process|
    US3873468A|1970-12-09|1975-03-25|Kuraray Yuka Kk|Method of removing substance harmful to oxidation reaction in the production of benzenecarboxylic acids by oxidation|
    US3780096A|1971-07-01|1973-12-18|United States Steel Corp|Process for recovering cobalt and manganese oxidation catalysts|
    GB1460941A|1973-03-30|1977-01-06|Matsuyama Petrochemicals Inc|Method of recovering cobalt and or manganese-bromine liquid- phase oxidation catalyst|
    JPS549596B2|1973-04-20|1979-04-25|
    US4096340A|1975-06-03|1978-06-20|Teijin Hercules Chemical Co., Ltd.|Process for the preparation of dimethyl terephthalate|
    JPS54133495A|1978-04-10|1979-10-17|Asahi Chem Ind Co Ltd|Recovering method for liquid phase oxidation catalyst|
    DE2923681C2|1979-06-12|1981-11-05|Dynamit Nobel Ag, 5210 Troisdorf|Process for the recovery and reuse of heavy metal oxidation catalyst from the Wittem DMT process|US4894477A|1986-10-14|1990-01-16|Hoechst Celanese Corporation|Process for regenerating a carbonylation catalyst solution to remove corrosion metals and carbonylation of methanol to acetic acid|
    US4786621A|1987-06-17|1988-11-22|Amoco Corporation|Process for recovery of cobalt and manganese for oxidation residue incinerator ash|
    US5414106A|1994-02-14|1995-05-09|Hoechst Celanese Corporation|Process for recovering dimethyl terephthalate|
    US5980750A|1998-07-06|1999-11-09|Mobile Process Technology, Co.|Process for the purification of waste wash water|
    DE10008904A1|2000-02-25|2001-09-06|Degussa|Process for the recovery of catalyst transition metals from saline reaction mixtures|
    KR100662146B1|2005-09-07|2006-12-27|한화석유화학 주식회사|Method for treating wastes from terephthalic acid process|
    CN102824919A|2011-06-14|2012-12-19|逸盛大化石化有限公司|Method for reducing oxidation catalyst in PTA production apparatus|
    EP3582891A1|2017-02-20|2019-12-25|Rohm and Haas Company|Activation energy reducers for catalytic oxidation of gaseous mixtures|
    CN110818559A|2019-11-26|2020-02-21|南通百川新材料有限公司|Method for recycling trimellitic anhydride rectification mother liquor residues|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE2950318A|DE2950318C2|1979-12-14|1979-12-14|Recovery and reuse of cobalt or cobalt and manganese compounds from the Witten DMT process|
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