• 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 preparing carboxylic acids (eg acetic acid) from alcohols (eg methanol) by carbonylation is provided. The process employs a catalyst comprising rhodium and nickel supported upon a carbon, preferably a high surface area carbon. The process described is carried out in the presence of hydrogen and a halide promoter leading to high yields of the carboxylic acid under very mild conditions (1 to 50 atmospheres, 150-300°C).
    公开号:SU1715203A3
    申请号:SU894613760
    申请日:1989-03-24
    公开日:1992-02-23
    发明作者:Пимблетт Джилльян
    申请人:Бп Кемикалз Лимитед (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to the production of carboxylic acids, in particular, to an improved process for the production of acetic acid, which is widely used in basic organic synthesis.
    A known method of producing acetic acid by carbonylation of methanol in an aqueous phase at 185 ° C and 35 bar in the presence of a nickel catalyst promoted with molybdenum and tungsten, and trivalent organophosphorus or organo-nitrogen, and iodide. Hydrogen does not delay the reaction and can stabilize the catalyst.,
    However, for a number of reasons, including the yfr4eHbuieHMe separation of the catalyst and the problem of recycling, preference is given to conducting the reaction in the gas phase using a heterogeneous catalyst.
    A number of nickel-supported catalysts are known in dp reaction in the gas phase.
    High conversions of meta-acryl to acetyls on activated carbon are reported at 202-345 ° C m
    pressure of 14 kg / cm.
    However, the use of large amounts of hydrogen in the raw materials is undesirable.
    A known method for the carbonylation of methanol in the presence of nickel on activated carbon with promoters such as palladium or palladium with copper at 280-310 ° C.
    The closest to the technical essence and the achieved result to the proposed is a method of obtaining acetic acid by the interaction of methanol with carbon monoxide in the gas phase in the presence of a catalyst on a carbon carrier containing rhodium and metal or compound, metal I, III, lY - Yl or group of the periodic table items.
    in the presence of a halide promoter at 50-500 ° C. a pressure of 1-50 these.
    However, the selectivity of this method is not high enough.
    The aim of the invention is to increase the selectivity of the process.
    A method of producing acetic acid by reacting methanol with a gaseous mixture of carbon monoxide and hydrogen at 150-300 ° C and 1-50 atm in the presence of methyl iodide and a catalyst containing rhodium and a metal of group Y1II of the Periodic Table of the Elements on a carbon carrier YII1 group nickel at a mass ratio of nickel and a rod of 0.32, 5: 1. Preferably, the catalyst contains 0.3-2.5 wt.% Nickel and 1 wt.% Rhodium. Preferably, the molar ratio of carbon monoxide and hydrogen in the gas mixture is in the range of 4: 1 to 1: 2.
    Getting a catalyst. The activated carbon used as a carrier in the preparation of the catalyst is highly porous carbon {ex Suteliffe Speakman, AC 610). It has a surface area of 1600-1800, a micropore count of 0.74 cm g and a total number of pores of 0.82 cm g.
    The catalyst containing nickel / rhodium / activated carbon is obtained by saturating the carbon with an aqueous solution of nickel nitrate and drying at 110 ° C for 24 hours in an air thermostat. Then the catalyst is activated at 400 ° C for 3 h under the influence of a stream of hydrogen, then cooled and passivated with nitrogen containing impurities of oxygen and water. Rhodium in the form of a solution of rhodium nitrate is saturated on the resulting substance and the catalyst is dried at 110 ° C for 24 hours in an air thermostat. Before use, the catalyst is activated at 280 ° C for 1 h under the influence of hydrogen at atmospheric pressure.
    In a catalyst containing nickel on activated carbon, the stage of rod saturation can be eliminated.
    In a catalyst containing rhodium on activated carbon, the stage of saturation of nickel can be excluded.
    At m in p 1. Use a reactor with a fixed catalyst bed at elevated pressure. Methanol and methylyrdide are mixed, loaded using a pump, subjointV, in a mode with incoming gas in a preheater furnace, and the mixed vapors are directed through a bed of 2 ml of catalyst into the reactor furnace. Then the substances are fed through a pressure-reducing valve to the chromatograph.
    The catalyst 2.5 wt.% Ni / lMac.% Rh (2 ml, 0,836 g) is placed in the tube of the reactor.
    Before being used in the reaction, the catalyst is activated in situ at 280 ° C in a stream of hydrogen (average hourly gas flow of 2.400 h) for 1 h. The reactor tube is cooled to 180 ° C and the reactants are added.
    Table 1 shows the conversion of methanol to acetic acid on various catalysts.
    Listed in table. 1 conversion is obtained at a ratio of CO: H2 1: 2, in total
    a pressure of 9 bar, an average hourly supply of fluid equal to 1, a gas supply ratio: methanol: methyl iodide 100: 19: 1 and a temperature of about 188 ° C.
    EXAMPLE 2. Example 1 is repeated for
    except that a catalyst containing 2.5% N1 on activated carbon is used instead of a catalyst containing 2.5% Ni / 1% Rh / activated carbon (Table 1).
    Example 6 p. 3. Example 1 is repeated.
    except that a catalyst containing 1% Rh / activated carbon is used instead of a catalyst containing 2.5% Ni / 1% Rh / activated carbon.
    Example 1. 2 and 3 do not correspond to the proposed method, since there is no significant component.
    The results are shown in Table. 1, show that a catalyst containing
    lMi / Rh / activated carbon is very active under mild carbonylation of methanol to acetic acid. In addition, there is a synergistic effect between rhodium and nickel, since the activity
    The bimetallic catalyst does not match the combined activities of the individual catalysts. Synergy lowers methane production and increases selectivity to acetic acid relative to
    the combined activities of individual metal catalysts.
    Examples 4 and 5. Example 1 is repeated, but the proportion of hydrogen in the gas supply is changed.
    Example 6. Example 1 is repeated, but the supply of hydrogen is excluded.
    In tab. 2 shows the conversion of methanol and the dependence on the ratio of CO: H2. . . ,,: /
    From tab. Figure 2 shows that hydrogen activates a rhodium-containing catalyst when acetic acid is obtained without a significant change in the selectivity to methane. Examples7 and 8. Example 3 is repeated, using different proportions of hydrogen for gas supply. PRI me R 9. Hydrogen supply is eliminated. 3 shows the conversion of methanol depending on the ratio of CO: H2. From tab. 3 shows that hydrogen activates a catalyst containing a rhodium / carbon carrier, but not to the same extent as a catalyst containing a nickel / rhodium / activated carbon, and, in particular, with a less satisfactory result with CO: H2 1: 2. Examples 10 -13. Example 1 is reproduced, except that the nickel content (May.%) In the catalyst is changed. The reaction is carried out at 200 ° C and the catalyst consists of 0.9 ml of Asbestos carbon and 1.1 ml of catalyst. The results are presented in Table. 4, which shows the conversion of methanol depending on the N1 content of the catalyst. The results are shown in Table. 4 shows that reducing the nickel content of the catalyst reduces the selectivity to methane without significantly altering the conversion to acetyl derivatives. Fo rumula and 3 o bre n i 1. Method for the production of acetic acid by the interaction of methanol with a gaseous mixture of carbon monoxide and hydrogen at 150-300 ° C 1-50 atm in the presence of methyl iodide and a catalyst containing rhodium and a metal of group III of the periodic table of elements on a carbon carrier, characterized in that, in order to increase the selectivity of the process, a catalyst is used which contains as; The metal of the YII1 metal of the nickel group at a mass ratio of nickel and a rod of 0.32, 5: 1. 2. The method according to claim 1, which is tl and h and y and the fact that the catalyst contains 0.3-2.5 wt.% Nickel, 3. The method according to claims. 1 and 2, distinguishing-V with the fact that the catalyst contains 1 wt.% Rhodium. 4. Method according to paragraphs. T-3, characterized in that the molar ratio of carbon monoxide and hydrogen in the gas mixture is in the range of 4: 1-1 :. Table
    Table 2
    Table 3
    T a & l and c a 4
    权利要求:
    Claims (4)
    [1]
    Claim
    1. The method of producing acetic acid by the interaction of methanol with a gaseous mixture of carbon monoxide and hydrogen at 150-300 ° C and 1-50 atm in the presence of methyl iodide and a catalyst containing rhodium and metal of group YIII of the periodic table of elements on a carbon carrier, characterized in that , in order to increase the selectivity of the process, a catalyst is used containing nickel as the metal of group YIII at a mass ratio of nickel and rhodium of 0.32.5: 1.
    [2]
    2. The method according to claim 1, characterized in that the catalyst contains 0.3-2.5 wt.% Nickel.
    [3]
    3. The method according to PP. 1 and 2, characterized in that the catalyst contains 1% by weight of rhodium.
    [4]
    4. The way popp. 1-3, characterized in that the molar ratio of carbon monoxide and hydrogen in the gas mixture lies in the range 4: 1-1: 2.
    Table!
    Example Catalyst CO: Ng, molar ratio 1 2.5% N1 / 1% Rh /activated 1: 2 2 carbon2.5% Nl / assetcarbonated 1: 2 s Lerod1% Rh / activ-carbon 1: 2
    The conversion of methanol,%, in
    MeOAc
    Ason
    MegSO
    2.4
    Total
    92.8
    11.7
    54,4
    7 1715203 8
    Table 2
    Example CO: H 2 . molar ratio The conversion of methanol,%, in CH4 Mego MeOAc Ason MegSO Total 6 1-0 0.3 2.0 30.7 28.8 0.5 62,4 4 4: 1 3,7 0 6.4 76.9 2.9 89.9 5 2: 1 4.4 0 3.4 79.3 4.2 91.3 1 1: 2 7.5 0 3.2 79.7 I :; 2,4 I 92.8
    Ta bl and ca 3
    CO: H 2 . The methanol conversion,%,  in' ' · Example molar ratio SND Me 2 OMeOAc Ason MegSO Total nie 9 1-0 4.8 033,4 7.9 1.3 47.4 7 4: 1 7.1 034.1 19.2 1.6 62.1 8 2: 1 6.4 1.636.5 10.7 0.6 55.3 3 1: 2 10.5 2.033.7 8.2 0 54,4
    Ta 6l tsa 4
    Example NI, May. % The conversion of methanol,% CH4 Ason MeOAc Total 10 0.3 2.2 55,4 13.3 70.9 eleven 0.6 9.6 65.9 9,4 84.9 12 1.25 8.9 66.9 9.1 84.9 thirteen 2,5 17.7 72.0 1.9 91.6
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    同族专利:
    公开号 | 公开日
    CN1036947A|1989-11-08|
    KR0132673B1|1998-04-13|
    EP0335625A3|1990-02-07|
    DE68907247D1|1993-07-29|
    AT90931T|1993-07-15|
    JP2868528B2|1999-03-10|
    MY110253A|1998-03-31|
    NO891230D0|1989-03-21|
    EP0335625B1|1993-06-23|
    US5258549A|1993-11-02|
    EP0335625A2|1989-10-04|
    GB8807284D0|1988-04-27|
    NO891230L|1989-09-27|
    KR890014432A|1989-10-23|
    JPH01299248A|1989-12-04|
    AU3164189A|1989-09-28|
    NO169889B|1992-05-11|
    AU612804B2|1991-07-18|
    NO169889C|1992-08-19|
    DE68907247T2|1993-10-21|
    CN1024001C|1994-03-16|
    NZ228449A|1992-01-29|
    引用文献:
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    US5916840A|1994-07-01|1999-06-29|Monsanto Company|Process for preparing carboxylic acid salts and catalysts useful in such process|
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    CN1295551A|1998-03-31|2001-05-16|哈尔多·托普森公司|Process for production of acetic acid|
    US6160163A|1999-02-16|2000-12-12|Eastman Chemical Company|Method for the vapor-phase carbonylation of lower aliphatic alcohols using a supported platinum catalyst and halide promoter|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    GB888807284A|GB8807284D0|1988-03-26|1988-03-26|Chemical process|
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