• 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:
    Process for the manufacture of 1,1,1,2-tetrafluoroethane by the vapor phase hydrodehalogenation of 1,1,1,2-tetrafluorochloroethane in the presence of a catalyst consisting essentially of palladium on an aluminum fluoride or fluorinated alumina support.
    公开号:SU1757457A3
    申请号:SU894614023
    申请日:1989-05-19
    公开日:1992-08-23
    发明作者:Стефен Келлнер Карл；Нотт Маликарджуна Рао Веллиюр
    申请人:Е.И.Дюпон Де Немур Энд Компани (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to a process for the preparation of 1,1,1,2-tetrafluoroethane, which finds use as a refrigerant.
    A known method for producing tetrafluoroethanes of the formula CHF2CHF2 and CP3CH2 consists in that haloethane having four or five fluorine atoms of formula CF2XCFYZ reacts with hydrogen at elevated temperature in the presence of a hydrogenation catalyst.
    The known method includes treating 1,1,1,2-tetrafluorochloroethane with hydrogen to obtain 1,1.1,2-tetrafluoroethane using palladium on carbon as a catalyst. The selectivity to 1,1,1,2-tetrafluoroethane at a temperature in the range of 280-420 ° C ranges from 85.8 to 97.3%.
    It is also known to obtain 1,1,1,2-tetrafluoroethane from isometric mixtures.
    dichlorotetrafluoroethanes through selective hydrogenolysis of CPsSS P, canalized palladium coal.
    In addition to this, along with the target product, СРзСНз is also formed, which leads to the formation of HF in the stream flowing from the reactor; the removal of HF from the reaction mass is required.
    The purpose of the invention is to increase the selectivity of the formation of the target product.
    Example A. Getting media.
    The reactor (0.5 inch diameter, 12 inch length Inconel tube) is filled with 20 g of alumina and placed in a sand bath. The bath is gradually heated to 400 ° C, while simultaneously passing dry nitrogen through the reactor at a rate of 50 ml / min to remove traces of water. Then the temperature is lowered to 200 ° C and a mixture of HF and nitrogen (1: 4 mol.) Is passed through the reactor. Nitrogen flow with time
    Xi
    4 SL VI

    WITH
    It is reduced until pure HF passes through the reactor. At this time, the temperature is raised to 450 ° C and maintained for 300 minutes. Then the action of nitrogen is cooled to room temperature. The ratio of fluorine to aluminum in the carrier is at least 2.4: 1, which corresponds to at least 54.3% of fluorine.
    Example B. Preparation of 5% PdPd Supported Catalyst.
    Palladium acetate 570 ml is dissolved in 4.4 g of CH2CI2 and 5 g of the support obtained in Example A is added. The solid is then dried and reduced with hydrogen at 300 ° C before starting the reaction.
    Example C. Preparation of a 2% Pd catalyst on a carrier.
    This catalyst was prepared according to Example B, using 230 mg of Pc) (OOCN3) 2
    Examples 1-10 The goal is achieved in that, according to the method for producing 1,1,1,2-tetrafluoroethane, that 1,1,1,2-tetrafluorochloroethane is treated with hydrogen gas in the gas phase at a temperature of 200-300 ° C in the presence of a catalyst — palladium on a carrier, which is aluminum fluoride or fluorinated alumina, obtained by treating the alumina with hydrogen fluoride at a temperature of 200-450 ° C until the fluorine concentration in the used catalyst carrier is at least 54, 3 wt.%, And the process of ve when the concentration of palladium on the support is 0.1–5 wt.%, when the amount of hydrogen used in the process is 0.5–5 moles per mole of 1,1,1,2-tetrafluorochloroethane.
    The process can be carried out in any suitable reactor, including fixed bed or fluidized bed reactors. The reaction vessel should consist of materials not subject to corrosion by the action of hydrogen halide, for example Hastelloy or InconeP.
    Pressure does not matter. Atmospheric pressure and atmospheric pressure are most suitable and, accordingly, preferable. 1,1,1,2-Tetrafluorochloroethane which has not been reacted can be returned to the reactor to further produce 1,1,1,2-tetrafluoroethane. The present method has the advantage that the target product 1,1,1,2-tetrafluoroethane is obtained with sufficient quantitative selectivity (selectivity). Sequence of hydrodehalogenation.
    For examples 1-10, the amount of palladium on the carrier (20x30 mesh) indicated in Table 1 is placed in a tubular reactor (1/4 inch diameter Inconet). Reactor
    support at the temperature specified in the table. 1, using a fluidized sand bath and at the specified table. 1 using a back pressure regulator. The SRSCHS F is fed to the reactor, which is pre-evaporated and hydrogen is passed at the rate indicated in Table 1. The products leaving the reactor are analyzed using gas chromatography.
    Listed in table. 1, the results of the analysis show a high selectivity (selectivity) in the order of 99-100% in comparison with the prototype 85-97%.
    Example D. Getting 5% Pd on A1Rz.
    Palladium acetate (570 mg) is dissolved in CH2Cl2 and added to A1P3 (5 g). The solid is then dried and reduced in situ with hydrogen at 300 ° C before starting the reaction.
    PRI me R E. Obtaining 0.1% Pd on AIF3.
    Palladium acetate (11.4 mg) is dissolved in CH2CI2 and added to (5 g). The solid is then dried and, before starting
    the reaction is reduced at 300 ° C with hydrogen in situ.
    Examples 11-15, Hydro-dehalogenation procedure.
    Used methods of examples 110. In tab. 2 shows the results obtained under different conditions using 5% Pd / AIFs or 0.1% Pd / AIFs obtained in Examples D and E.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    The method of obtaining 1,1,1,2-tetrafluoroethane by treating 1,1,1,2-tetrafluorochloroethane with hydrogen in the gas phase at elevated temperature in the presence of a catalyst — palladium on a carrier, characterized in that, in order to increase the selectivity of the process, catalyst carrier using aluminum fluoride or fluorinated alumina obtained by treating the alumina with hydrogen fluoride at 200-450 ° C until the concentration of fluorine in the used catalyst carrier is at least 54.3 wt.% and the process is 200-300 ° C, at a concentration of palladium on a carrier of 0.1-5 wt.% And the amount of hydrogen used in the process of 0.5-5 moles per mole of 1,1,1,2-tetraftorhlore- tana.
    Fluorine content using A1F is 67.9%. with. 5% Pd / AlFs with. 0.1% Pd / AlFf e. 124 - CF3CHC1F
    类似技术:
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    同族专利:
    公开号 | 公开日
    BR8902297A|1990-01-09|
    AU3488989A|1989-11-23|
    DE68907808T2|1994-01-27|
    KR890017212A|1989-12-15|
    JPH0267235A|1990-03-07|
    EP0349115A1|1990-01-03|
    KR970011700B1|1997-07-14|
    CN1038634A|1990-01-10|
    MX165549B|1992-11-19|
    AR246503A1|1994-08-31|
    AT92020T|1993-08-15|
    US4873381A|1989-10-10|
    ZA893775B|1991-01-30|
    AU613296B2|1991-07-25|
    DE68907808D1|1993-09-02|
    EP0349115B1|1993-07-28|
    IN172056B|1993-03-27|
    ES2058523T3|1994-11-01|
    CN1016418B|1992-04-29|
    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
    US07/199,811|US4873381A|1988-05-20|1988-05-20|Hydrodehalogenation of CF3 CHClF in the presence of supported Pd|
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