• 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 method for producing an oily aldehyde by reacting propylene with carbon monoxide and hydrogen at a temperature and pressure of 50 bar in the presence of Veda and a water-soluble rhodium-phosphine complex as a catalyst in a mixed gas-liquid phase, processing the reaction mixture by separating the gas phase from the liquid phase and then separating the liquid phase to the aqueous phase containing the catalyst and to the organic phase containing the reaction product, the isolation of the reaction products by distillation in a distant column and the of the aqueous phase containing the catalyst and unreacted gaseous reagents at the reaction stage, characterized in that, in order to reduce the formation of by-products while reducing energy consumption, the process is carried out with a content of gaseous components in the liquid phase 5-30% of the mixed volume gas-liquid phase and volume ratio of the aqueous and organic phases (L 1:
    公开号:SU1187713A3
    申请号:SU833648675
    申请日:1983-09-16
    公开日:1985-10-23
    发明作者:Гиббель Иозеф；Лидер Бернхард；Мух Иоахим；Шмидт Фолькмар；Корнильс Бой；Конколь Вернер；Вибус Эрнст
    申请人:Рурхеми Аг (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to an improved process for the production of aldehyde oil by hydroformylation.
    The purpose of the invention is to reduce the formation of by-products while reducing energy consumption,
    The drawing shows schematically an installation for carrying out the proposed method.
    Catalyst dissolved in water is fed to reactor 1, then propylene and synthesis gas are introduced through reactor 2 to reactor 1 and brought to reaction with vigorous stirring. Through the immersion nozzle 3, the reaction product is withdrawn from the reactor in a mixture with an aqueous solution of the catalyst, unreacted synthesis gas and olefin. In separator 4, the gas phase, consisting mainly of synthesis gas, olefin and saturated hydrocarbon formed from propylene, is separated from the liquid products and fed back to the reactor using a compressor 5. Condensable reaction products are removed from part of the circulating gas in the refrigerator 6 and I then feeds it to the gas exhaust system. The hot liquid which had leaked in the separator 4 without pre-cooling is fed to the separator 7. Here the crude organic reaction product is very easily separated from the aqueous phase of the catalyst.
    The organic phase is not cooled before the separation of unreacted reagents, which considerably facilitates the need to recycle gaseous olefins through the distant column 8, since the solubility of gaseous olefins in the hot organic reaction product (raw aldehyde) is much less than in the cooled reaction product. The organic reaction product is fed to the stripping column 8 by means of a pump 9, and the pump 10 recycles the aqueous phase of the catalyst to the reactor 1, and in the heat exchanger 11 the heat of the exothermic reaction is used to produce steam. Together with the cooled phase of the catalyst, water is fed to the reactor 1 through line 12 to compensate for the loss of water removed by the waste gas and the crude product of oxosynthesis.
    The hot crude oxosynthesis product in column 8 is fed in a countercurrent to 80-1.00% of the original synthesis gas fed to column 8 through line 13. In this case, the synthesis gas is enriched in propylene, dissolved in the crude product of oxosynthesis, and then synthesis gas having an increased temperature, is fed to the reactor 1. Another part of the original synthesis gas is preheated in the heat exchanger 14 of the thermal reaction. Before being fed into the reactor, fresh propylene is also preheated and evaporated in heat exchanger 15 using the waste heat of distillation of the aldehyde while the crude oxosynthesis product removed from column 8 is directly fed to the distillation without pre-cooling. The container 16 is used for intermediate storage of the product in case of process disruption.
    Example 1. In reactor 1, the reaction conditions (125 ° C; 50 bar) are maintained with 50 liters of homogenized by intensive mixing of the mixed gas-liquid phase from 40.9 g of an aqueous solution of a catalyst (25% by weight of triphenylphosphine (sodium sulfonate), 500 hours. / million rhodi), 4.1 l of crude product of oxosynthesis (5% isoaldehyde
    94% aldehyde 0.5% butano-4
    la; 0.5% of high-boiling by-products) and 5 liters of gas (volume ratio of propylene, CO and H2: 1: 1: 1). To obtain the distribution of phases between the aqueous and organic phases, as well as to remove the heat of reaction, 100 liters of water are circulated hourly catalyst of a specified composition by means of a pump 10. Under the specified reaction conditions, 10 liters of a crude product of a specified composition are formed per hour from propylene, so that the ratio of aqueous and organic phases is 10: 1. The liquid phase contains 10 vol. % of gaseous components. The resulting crude product of oxosynthesis contains, per kg, 0.4 kg of propylene removed in a distant column 8, in which the hot organic phase is fed countercurrent to 100% of the initial mixture of carbon monoxide and hydrogen, and the resulting mixture of carbon monoxide and hydrogen propylene, sent to the reaction stage. Average time of stay31
    The crude oil aldehyde in the reactor is 27 minutes. The crude product of oxosynthesis contains 0.5% by weight of high boiling point by-products.
    Example 2. The example is repeated with the difference that 35 liters of the catalyst solution circulate hourly, so that a mixed gas-liquid phase is formed from a 36.0 liters of catalyst solution (25% by weight of triphenylphosphine (sodium sulfonate), 500 ppm). Rhodi), 9.0 l of crude oxosynthesis product (5% C isoaldehyde; 93% n-aldehyde C, 0.5% butanol; 1.5% high boiling point by-products) and 5 l of gas (volume ratio of propylene, CO and Hj 1: 1: 1). The volume ratio of the aqueous and organic phases is 4: 1, and the liquid phase contains 10% by volume of the gaseous components. Under the above reaction conditions, 8.8 liters of crude product of the indicated composition are formed from propylene every hour, the average residence time of the crude aldehyde in the reactor rises to 69 minutes. The crude product of oxosynthesis contains 1.5% by weight of high boiling point by-products.
    Examples 3-6. Example 1 is repeated with the difference shown in the table. In addition, in example 6, the hot organic phase is fed in a distant column 8 in countercurrent to 80% of the initial mixture of carbon and hydrogen.
    Example 7. Example 6 is repeated with the difference that the reaction is carried out at a volume ratio of aqueous and organic phases of 2: 1. At the same time, the crude product of oxosynthesis contains,%: C 5 isoaldehyde; h-aldehyde C 92,8; butanol 0.5, high boilers co-components 1.7.
    Example 8. Example 3 is repeated, with the difference that the reaction is carried out at a volume ratio of aqueous and organic phases of 6: 1 (a) and 8: 1 () For this, the crude oxosynthesis product contains,%: isoaldehyde C 5; n-aldehyde C 93.5; butanol 0.5; high boiling point by-products 1.0 () and isoaldehyde C 5; n-aldehyde C 93.7; butanol 0.5, high boiling point by-products 0.8 (5).
    Example 9 (comparison). Example 1 is repeated with the difference that the continuously removed stream containing the catalyst solution is the crude product of the oxosynthesis indicated in 134.
    at least 1 composition, excess propylene and synthesis gas are pre-cooled before processing according to a known method. Under these conditions, 4.5 kg / kg of the crude product of oxosynthesis is dissolved in the cooled raw product, which means an increase in energy consumption as compared with example 1, in which the amount of propylene separated in the stripping column 8 and recycled to the reactor 1 is only 0.4 kg / kg syrox product of oxosynthesis. The following calculation shows the higher energy consumption. The evaporation enthalpy of 1 kg of propylene is 438 kJ, i.e.; under the conditions of example 1, in which 4 kg of propylene is subject to evaporation in column 8, the amount of heat required is 1752 kJ, whereas under the conditions of the comparative example 45 kg of propylene should be evaporated, for which 19710 kJ is required.
    Example 10 (comparison). Example 6 is repeated, with the difference that the reaction is carried out at a volume ratio of 0.5: 1 aqueous and organic phases and a gaseous content of 4% of the volume of the mixed phase in the liquid phase. In this case, the residence time is up to 400 minutes and the resulting product (5 liters) has the composition,%: C 5 isoaldehyde; n-aldehyde With 85,8; butanol 0.6; high boiling point by-products 8.6.
    Thus, the yield of the target product is reduced, and the amount of by-products formed increases, if the proposed lower limits for the content of gaseous components in the liquid phase and the volume ratio of the aqueous and organic phases are not observed.
    Example 11 (comparison). Example 4 is repeated with the difference that the reaction is carried out with a gaseous component content in the liquid phase of 32% of the volume of the mixed gas-liquid phase. At this, the obtained target product has the composition,%: isoaldehyde С 5; N-aldehyde C 93.0 butanol 0.5; high boiling point by-products 1.5.
    Thus, when the proposed upper limit for the content of gaseous components in the liquid phase is exceeded, the quality of the target product deteriorates (as compared with example 4, the amount of high-boiling by-products increases by 1%).
    Example 12 (comparison). Example 4 is repeated, with the difference that the reaction is carried out at a content of gaseous components in the liquid phase of 78% of the volume of the mixed gas-liquid phase and at a volume ratio of aqueous and organic phases of 3: 1. The resulting target product has the following composition,%: isoaldehyde C 5; n-aldehyde C 89.1; butanol 0.5;
    high boiling point 5.3 components.
     Thus, when carrying out the reaction under the conditions of a known method, the amount of by-products is increased.
    The proposed method allows to significantly reduce the amount of by-products formed (up to 0.5-2.7% against 5-8% by a known method). At the same time, the energy consumption for evaporation of the initial propylene is reduced by more than 10 times (example 9).
    Mixed gas-liquid | phase, l Amount of gas, l Aqueous phase, l Organic phase, l Composition of organic phase isoaldehyde С H-aldehyde C butanol high-boiling secondary components Gas content in liquid phase, vol. % Ratio of aqueous and organic phases
    权利要求:
    Claims (1)
    [1]
    METHOD FOR PRODUCING OIL ALDEHYDE by reacting propylene with carbon monoxide and hydrogen at a temperature of 125 ** C and pressure
    50 bar in the presence of a Veda and a water-soluble rhodium-phosphine complex as a catalyst in the mixed gas-liquid phase, processing the reaction mixture by separating the gas phase from the liquid phase, followed by separation of the liquid phase into the aqueous phase containing the catalyst, and into the organic phase containing the reaction product, isolation of reaction products by distillation in a distillation column and recirculation of the aqueous phase containing the catalyst and unreacted gaseous reactants to the reaction stage, characterized in that, with c To reduce the formation of by-products while reducing energy consumption, the process is carried out with the content of gaseous components in the liquid phase 5-30% of the volume of the mixed gas-liquid phase and the volumetric <S ratio of the aqueous and organic phases 1: (1-89), and distillation in the distillation the column is carried out by supplying a hot organic phase countercurrent to 80 to 100% of the initial mixture of carbon monoxide and hydrogen to obtain a mixture of carbon monoxide and hydrogen enriched in propylene, which is sent to the reaction stage.
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    同族专利:
    公开号 | 公开日
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    ES8405353A1|1984-06-01|
    KR840006001A|1984-11-21|
    RO86693B|1985-05-02|
    DE3234701A1|1984-04-05|
    DE3369505D1|1987-03-05|
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    AU557579B2|1986-12-24|
    CS253580B2|1987-11-12|
    IE832105L|1984-03-17|
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    AU1913283A|1984-03-22|
    BR8304995A|1984-09-04|
    US4523036A|1985-06-11|
    AT25237T|1987-02-15|
    EP0103810B1|1987-01-28|
    ZA836751B|1984-05-30|
    HUT34423A|1985-03-28|
    KR870000244B1|1987-02-21|
    YU43194B|1989-04-30|
    JPS6160057B2|1986-12-19|
    RO86693A|1985-04-17|
    HU198169B|1989-08-28|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE19823234701|DE3234701A1|1982-09-18|1982-09-18|METHOD FOR PRODUCING ALDEHYDES|
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