• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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  • 引用文献
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    • 专利摘要:

    公开号:SU942589A3
    申请号:SU792743453
    申请日:1979-03-28
    公开日:1982-07-07
    发明作者:Арди Никола；Леро Люк；Валраевен Рене
    申请人:Пропилокс (Фирма)；
    IPC主号:
    专利说明:

    (54) Hurry: ABOUT SUPPROPION
    one
    The invention relates to a method for the extraction of national propionic acid, which is used as a source of active oxygen in organic synthesis, a natrimer, for the preparation of epoxy compounds from olefins.
    A known method for the preparation of national carboxylic acids by reacting the corresponding carboxylic acid with hydrogen peroxide, usually used in the form of an aqueous solution, in the presence of small amounts of a catalyst, for example sulfuric acid, with distillation of water in a vial azeotropic mixture with benzene. The yield of supropropic acid at the same time decreases 87% of G13.
    The disadvantage of this method is the high explosion hazard of the process.
    The most close to them to the proposed technical essence is a method of producing supracarboxylic acids by the interaction of aliphatic carboxylic acids with 25-95% hydrogen peroxide in the presence of an esterification acid catalyst and organic ACID.
    a solvent having a boiling point of 5 ° -13 ° C, for example chloroform ,; with azeotropic distillation of water prt 20-90 ° t and under reduced pressure mm
    5 DT.CT. and the use of separation into a military iorganic phase of the azeotroi. The yield of and dpro pionic acid is 67% T2. .
    Disadvantages of the negative weighing method
    10 are the low yield of the target product and high explosiveness caused in | the content of the resulting peracidic acid base (53.4%).
    The purpose of the invention is to reduce the explosion hazard of the process and increase the yield of the target product.
    The delivered kerb is achieved by haem, which, according to the method of tantalizing the onic acid by reacting the onioic acid with a 7O% hydrogen peroxide D in the presence of sulfuric acid and dg chlorogropane (i.e. 97-98 ° C) with aero tropic water distillation at 30 -45 0 and a lower pressure of 10O mmHg, using separation into (C1) rk and 39 organic phases of the azeogropic process, is put by continuous search of the acid and hydrogen peroxide and continuous selection of the part of the reaction mixture from which after separation of the phases I select the aqueous phase returned to the process, and the organic phase containing the target product, while the molar ratio of capital acid to hydrogen peroxide is 0.76-1.24 at the molar ratio of sulfuric acid to the sum of propionic and supropropionic acids, equal to 0.286-1.24 and the ratio of aqueous and organic phases resulting from the selection of the reaction mixture equal to O, 2794, 13. Carrying out the process by the proposed method allows to obtain a yield of supropropic acid, which is quantitative, and to reduce the explosion hazard of the process, since the resulting solution of the desired product has a concentration of 20-2%. The drawing shows schematically the apparatus for carrying out the proposed method. The method is carried out in a continuous manner as follows. Into the reactor I, over which the distillation column 2 is located, is introduced through conduit 3 concentrated (a solution of hydrogen peroxide and a catalyst obtained by stirring in. A mixer 4 of aqueous hydrogen peroxide introduced into this mixer through a pipe 5 with the catalyst introduced into the mixer through pipe 6. Pipeline 7 is injected with a carboxylic acid solution in the organic liquid obtained by mixing in the mixer 8 the carboxylic acid introduced into this mixer through pipe 9 with the organic liquid introduced into the mixer along t In the course of the reaction, an azeogropic mixture of water — an organic liquid, which is removed from the distillation ring 2 via tap 11, is condensed in condenser 12 and sent through conduit 13 to decanter 14 for removal and separation of organic and water phases. the phase is withdrawn from the top of the decanter through conduit 15, and the organic phase from the bottom of the decanter through conduit 16, and part of it in the form of reflux is directed through conduit 17 to the distillation flask 2. In iterated cases, part 11 rt-anchorage can be directedase by conduit 18 to a mixer 94 8 for use as a solvent of the carboxylic acid. Reactor I is uninterrupted. pipeline through part 19 of the reaction mixture, which is sent to decanter 20 for separating the organic and aqueous phases with a branch through the pipeline 21 of the organic phase containing the desired product. The proposed method provides continuous production of organic solutions almost free of dilute and high concentrations of propionic acid, while reducing the explosion hazard of the process due to the fact that the total concentration of peroxide compounds is kept constant and no accumulation points of peroxidation of the compounds are observed. The total content of peroxide compounds in the reaction mixture remains constant and rather low. In order to determine the process explosiveness, tests for the explosiveness of mixtures similar to those present in the reactor for carrying out the process and the mixtures obtained when a peracid was obtained by reacting the aqueous phase of hydrogen peroxide with propionic acid in the presence of sulfuric acid, but in the absence of an organic solvent, were conducted. The explosive tests were carried out in vertical DNCOUOV 825 cylindrical tubes with an internal diameter of 52 mm, a height of 750 mm and a wall thickness of 4 mm, filled with preparation 5 minutes before the test was started with the test compound (to achieve a reaction equilibrium) heated to a predetermined temperature The reaction begins to pop action submersible electric detonator. When examining the material, after blasting, there were 5 sets of 6 types of results: a) no results: the detonator was destroyed, a small part of the liquid was ejected from the cut that remains intact; b) very slow decomposition after blasting: the same observations as in the first case, in addition, boiling of the liquid with the release of gaseous blast products; c) rapid decomposition after blasting: the same observations as in the first case, but the reaction is stormy with a large release of gaseous explosion products with possible ignition;
    g / buger combustion: at the height of the tsegonator the pipe of the slegk was broken up and its bottom was ripped out;
    v) explosion: the upper part of the tube is broken and rather large pieces and the bottom are torn off;
    e) Strong vzryu: the whole tube is broken into many small parts.
    . The results are presented in Table. one
    From tab. I can see that using the mixtures obtained by the proposed method and containing the phase and organic phase (experiments 1-2 and 3-4), more peroxide can be tolerated than in mixtures obtained only in the aqueous phase (experiments 5-6) with the same amount of organic matter.
    Example I. In a reactor with a capacity of I l is placed 0.2 kg of 45% sulfuric acid. The temperature in the reactor is maintained; the pressure is 100 mm Hg.
    Through channel 5, a 7O% hydrogen peroxide aqueous solution at a rate of 0.12 kg / h is continuously introduced into the reactor, and through channel 7, a solution of cinnamic acid in 1,2-dichloropropane with a concentration of 27 wt.% At a rate of 1, O7 kg / h
    The weight ratio of aqueous and organic phases contained in the reactor is 1, O4: the molar ratio of propionic acid in hydrogen peroxide is 1.13, with the molar ratio of cephroic acid to the sum of propionic and supropropionic acids being 0.71.
    The mixing system maintains the aqueous and organic phases through the emulsion.
    From the evaporator of the distillation column, through the channel 19, part of the reaction mixture is poured to a decanter 2O to settle in decanter. The organic phase, which is the desired product, is collected and recycled to the reactor.
    Water; During the reaction with the diluent hydrogen peroxide diluent, during the azeotropic mixture with 1,2-dichloropropane, they drink in the upper part of the column through channel 11.
    The resulting mixture is condensed and set aside, settled, the collected aqueous phase is discharged through channel 15, and the organic phase, ay consisting of 1,2-dichloropropane, is again fully directed through channel 17 to the distillate.
    The concentration of the above-propionic acid obtained is equal to 2% by weight.
    Installation performance is shown in Table. 2
    From tab. 2, that the percentage of conversion of hydrogen peroxide into national propionic acid is 96.5%, while the yield of overpropionic acid relative to the converted hydrogen peroxide is close to 00% (while the loss of hydrogen peroxide is less at dosage with an accuracy of less than 1%).
    Example 2. In a reactor with a capacity of 1.5 l, 0.21 kg of 58% sulfuric acid is placed, the temperature in the reactor is maintained at 37 ° C, and the pressure is 1OO mm Hg. The conditions are the same as in Example 1. The weight ratio of the aqueous and organic phases is 0.279. MojjbHoe ratio of propionic acid to hydrogen peroxide is equal to 1.24 with a molar ratio of sulfuric acid to the sum of propionic and supropydiaic acids equal to O, 286.
    P (x) capacity of the installation is given in table. 3..
    The percentage of conversion of hydrogen peroxide to propane acid is 96.7%, the yield of the target product is about 1OO%. The concentration of the above-propionic acid in the solution is 22 wt.%.
    Example 3. OjO54 kg of 57% sulfuric acid under a pressure of 100 mm Hg is placed in the reactor. Art. The operating conditions are similar to Example 1. The total ratio of aqueous and organic phases is 4.13. The molar ratio of propionic acid to hydrogen peroxide is 0.76, with a molar ratio of sulfuric acid to the amount propi “ns oh and supropropionic acids, equal to 1.24.
    The performance of the installation is shown in Table. four.
    The percentage of conversion of hydrogen peroxide to supropionic acid is 96.7%, the yield of the target product is about 100%.
    Table 1
    37.2
    thirty
    3.1 40.5
    30 3.6 37.2
    60 3.1
    4O, 5
    6O
    3.6
    6О 27, О
    18
    20
    60 30.1
    Components, g / h
    And aapropionic acid
    Propycic acid
    Hydrogen peroxide
    Water
    Sulfuric acid
    Caro acid ()
    1,2-Dichloropropane Total: Naprothotonic acid Propionic acid 139.7 Hydrogen peroxide 59.9 Water
    45.9
    23.4
    22.5
    None
    39.8 22.9
    16.9
    Burnout combustion
    45.9 23.4
    22.5
    Very slow decomposition
    39,8
    22.9
    16.9
    Explosion
    55
    f None 25.6
    29.4
    49.9 13.6
    36.3
    Explosion
    T a b l and d a 2
    Channel
    222
    184 65 102.3
    285
    3.2 55 Footprints
    81.7 335 469 46
    1.4
    781781
    124.4 1О66 then
    81.7
    1154
    Table 3 O7.4 357.379.3 113.619.5 4.719.0 Traces .132.7
    Sulfuric acid Caro acid (H, O) 1,2-dichloropropane
    Total:
    Supropionic acid
    Propionic acid
    Peroxide
    Warts
    Sulfuric acid
    Caro acid {Ng | 5O)
    1,2-D Chlorprop en
    权利要求:
    Claims (2)
    [1]
    Total: Claims of the invention The method of obtaining national propionic acid by reacting propishic acid with 7O% hydrogen peroxide in the presence of sulfuric acid and dichloro {pan with azeotropic distillation of water at 30-4-5 ° C and reduced pressure of 100% Hg mmHg using separation to the aqueous and organic phases of the azeotrope, characterized in that, in order to reduce the explosion hazard of the process and increase the yield of the target product, the process is conducted by continuously supplying propionic acid and hydrogen peroxide and continuous selection of cation mixture, from which, after separation
    2.1 184.4133.8
    18.1 1145.7 1145.7
    199.6 1553.1 1623.5 453133.8
    Table 4
    88,7291.2 IOI, 1 28,271,6
    1.2 69.9
    Tracks 487.6 33.2
    0.5677.2 66.6 284.4 284.4
    385.5 4ОЗ1644,1 33,2 phases take the aqueous fada returned to the process and the organic phase containing the target product, the molar ratio of propionic acid to hydrogen peroxide is 0.76-1.24 at the molar ratio of sulfuric acid to the amount of propi (zhovaya and supropropic acids, equal to 0.288-1.24, and the ratio of aqueous and organic phases formed during the selection of the reaction mixture, equal to 0.2794, 13. Sources of information taken into account during the examination 1.Patent Be / Ni Ni 8O81O8, CL O7 C, Pubpik. 1974.
    [2]
    2. US patent number 2814641, cl. 26О-5О2, published, 1957 {nptxromn).
    fejT
    P
    eleven
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