• 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 producing an alkyl aromatic hydroperoxide, which comprises oxidizing an alkyl aromatic compound with an oxygen-containing gas in the presence of a water soluble iron compound, wherein the concentration of the compound of iron in the reaction system is 0.0001 to 10 ppm by weight as iron metal.
    公开号:BE1019084A3
    申请号:E2007/0015
    申请日:2007-01-16
    公开日:2012-03-06
    发明作者:Tomoyuki Noritake；Masaru Ishino；Mitsuru Onuma
    申请人:Sumitomo Chemical Co；
    IPC主号:
    专利说明:

    Process for producing an aromatic alkyl hydroperoxide Field of the invention
    The present invention relates to a process for producing an alkyl aromatic hydroperoxide. For example, cumene hydroperoxide obtained by oxidation of cumene is used for the industrial production of phenol, and ethylbenzene hydroperoxide obtained by oxidation of ethylbenzene is used for the production of propylene oxide by the process. of Halcon. In addition, the hydroperoxides of diisopropyl benzene obtained by oxidation of diisopropyl benzene can be used as raw material for the production of resorcinol or hydroquinone.
    Description of the prior art
    In a process for producing an alkyl aromatic hydroperoxide by oxidation of an alkyl aromatic hydrocarbon with air, the addition of various catalysts to accelerate the rate of oxidation reaction has been investigated. For example, the addition of a metal compound such as a transition metal complex salt catalyst (e.g. JP8-245568 A patent application), a polyvalent metal and amine complex catalyst (e.g. JP2000-119247 A) or a transition metal compound catalyst attached to active carbon (eg JP8-259529 A patent application) is known. In addition, an example is also known in which a transition metal compound is used as cocatalyst together with an N-substituted cyclic imide compound catalyst (for example, JP-2003-034679 A). However, in these conventional methods, the problems are that organic compounds whose degradation due to decomposition is to be feared, appear, or that a solid catalyst difficult to handle is added, and that therefore it is difficult to say that they are excellent stability and performance methods for obtaining a high oxidation reaction rate.
    Summary of the invention
    An object of the present invention is to provide a method for producing an alkyl aromatic hydroperoxide by oxidation of an alkyl aromatic compound with an oxygen-containing gas, which provides a stable manner for the alkyl aromatic hydroperoxide to a high oxidation reaction rate, which is therefore easy to use.
    Thus, the present invention relates to a process for producing an alkyl aromatic hydroperoxide, which comprises oxidizing an alkyl aromatic compound with an oxygen-containing gas in the presence of a soluble iron compound. in water, wherein the concentration of the iron compound in the oxidation reaction system is from 0.0001 to 10 ppm by weight as the iron metal.
    Detailed description of the invention
    As the alkyl aromatic compound to be subjected to oxidation, monoalkyl benzenes and dialkylbenzenes are used. Specific examples of the alkyl aromatic compound are monoalkyl benzenes such as ethylbenzene, cumene and sec-butylbenzene, and dialkylbenzenes such as cumene, m-diisopropylbenzene and p-diisopropylbenzene. Of these, cumene, m-diisopropylbenzene and p-diisopropylbenzene are suitably used.
    As a method of oxidizing the alkyl aromatic hydrocarbon with an oxygen-containing gas to an alkyl aromatic hydroperoxide, the following methods are used.
    As the oxygen-containing gas, air can be used as such or oxygen-rich air in which the oxygen concentration has been enriched by means of membrane separation. In addition, it is also possible to use an oxygen gas diluted with an inert gas such as nitrogen, argon or helium.
    In the oxidation reaction, organic acids such as formic acid, acetic acid and the like are obtained as by-products with the reaction. When organic acids are generated as by-products, there are adverse effects such as initiation of a hydroperoxide decomposition as a target product and inhibition of the oxidation reaction caused by the products generated by the product. decomposition, and therefore it is necessary to carry out the oxidation reaction in the presence of an aqueous solution to suppress the adverse effects.
    The amount of aqueous solution is usually 0.1 to 20% by weight, preferably 1 to 10% by weight, based on the oxidation oil. Here, the oxidation oil refers to the oil portion of the oxidation reaction mixture composed of the aqueous solution portion and the oil portion.
    When the amount of aqueous solution is less than 0.1% by weight, the effect of the water becomes low; on the other hand, when it is more than 10% by weight, the productivity decreases because the ratio of the oil layer (the oxidation oil) in the reactor decreases.
    The pH of the aqueous solution is usually 6 or more, and preferably 7 to 12. At an acidic pH of less than 6, the acidolysis of the hydroperoxide can be promoted, and further, the corrosion of the equipment such as the reactor is to be feared. On the other hand, when the alkalinity is at a pH greater than 12, the alkaline degradation of the hydroperoxide can be unfavorably initiated. To maintain the pH of the aqueous solution in the above range, it is preferable to add an aqueous solution of an alkali metal compound.
    As the alkali metal compound, use is preferably made of sodium hydroxide, sodium carbonate, sodium bicarbonate or the like.
    Organic acids such as formic acid, acetic acid and the like generated as by-products in the oxidation reaction are neutralized with alkali and appear as salts of organic acids such as sodium and sodium acetate.
    The existence of these organic acid salts is effective to stably maintain the pH of the aqueous solution in the preferred range. In addition, it is advantageous to recycle to the oxidation reaction system an aqueous layer containing organic acids or their salts removed from the reaction system to reduce the amount of water discharged. As an aqueous layer containing organic acids or their salts removed from the reaction system, it is possible, for example, to use the aqueous layer obtained by subjecting the reaction mixture to an oil-water separation, or the aqueous layer recovered from the gas purge system. 'oxidation. Therefore, the concentration of organic acid salts in the aqueous oxidation reaction solution is usually from 0.01 to 50% by weight, preferably from 0.1 to 30% by weight.
    The main feature of the present invention is to carry out the oxidation reaction in the presence of a water soluble iron compound and to maintain the concentration of the iron compound in the range of 0.0001 to 10 ppm by weight. as iron metal.
    Specific examples of the water-soluble iron compound are iron formate, iron acetate, iron propionate, iron hydroxide, iron sulfate, iron nitrate, iron phosphate, iron chloride and iron bromide. Usually, since lower organic acids such as formic acid and acetic acid formed as products of the oxidation reaction are present in the oxidation reaction system, it is advantageous that the iron compound is essentially in the form of salts. In addition, since the iron salts of the lower organic acids are partially dissolved in the oxidation reaction mixture even under conditions in which there is no aqueous solution, a high oxidation reaction rate can be obtained. . Therefore, iron formate and iron acetate as iron salts of lower organic acids are advantageously used. In the context of the present invention, it is not necessary to use a special metal complex. Organic compounds such as amine ligands and imide compounds are generally unstable in the oxidation reaction system, and the addition of these compounds to the oxidation reaction system leads to an increase in quantities of exhaust gas to be treated and wastewater to be treated by the underproduction by degradation of nitrogen oxides and decomposition products, and therefore this is not advantageous.
    The concentration of iron compound in the oxidation reaction system is from 0.0001 to 10 ppm by weight, preferably from 0.001 to 1 ppm by weight as iron metal. When the concentration is less than 0.0001 ppm by weight, the effect of increasing the rate of oxidation reaction is insufficient, on the other hand, when it is less than 10 ppm by weight, this is undesirable in view of the loss of raw material and the increase of the quantity of product to be purified by an increase of the secondary reactions other than the desired oxidation reaction.
    As a method of adding the iron compound to the oxidation reaction system, it is advantageous to bring the water-soluble iron compound in the form of a homogeneous aqueous solution obtained by dissolving with water to give a stable feed of the iron compound in infinitesimal amounts. As water for dissolving the iron compound, it is advantageous in practice to use treated water such as water separated from a reaction system, condensed water from an evacuated gas, or recycled water from a process. In addition, as an advantageous method of stable dissolution of the iron compound of very low concentration with an aqueous solution, an example is a stable method of dissolving iron-containing metal in trace amounts by means of in contact with metal with water containing an organic acid such as formic acid or acetic acid and / or water containing hydroperoxide. In this case, an aqueous solution obtained by dissolving the iron-containing metal outside the reaction system can be fed to the oxidation reaction system, the iron compound also being able to be generated in the reaction system of the reaction system. oxidation by dissolving the iron-containing metal with the aqueous solution within the oxidation reaction system. In addition, as another method of adding water-soluble iron to the oxidation reaction system, a method of dissolving the iron compound or iron-containing metal with the reaction mixture can be used. oxidation as such. Usually, in addition to the alkyl aromatic hydroperoxide, a small amount of formic acid or acetic acid is also present in the oxidation reaction mixture, and therefore an advantageous method for dissolving amounts in the form of traces of the iron compound is made by contacting the iron-containing metal with the oxidation reaction mixture.
    The iron compound may be added at one time at the beginning of the reaction, added continuously during the course of the reaction, or added separately at regular time intervals.
    According to the present invention, the oxidation reaction is usually carried out at a temperature of 50 to 150 ° C under a pressure of 0.1 to 1 MPa. The reaction can be carried out by any of the discontinuous and continuous methods.
    Examples
    The present invention will be detailed by the Examples below.
    Example 1 To a 1 liter pressure-resistant glass vessel was added 500 grams of a cumene solution containing 5.2% by weight cumene hydroperoxide (CMHP) and a solution of prepared by dissolving iron acetate with 16.7 g of an aqueous solution containing sodium carbonate and sodium salts of an organic acid (containing sodium formate and sodium acetate). The iron concentration in the introduced liquid was 0.5 ppm by weight as iron metal. The reaction was carried out under a flow of air at 95 ° C and 0.7 MPa for 4 hours. The amount of air supplied was controlled so that the oxygen concentration at the outlet of the reactor was maintained at 2% by volume during the reaction. The concentration of cumene hydroperoxide in the reaction mixture after the reaction was 11.6% by weight.
    Comparative Example 1
    A reaction was carried out in the same manner as in Example 1 except that iron acetate was not added. The concentration of cumene hydroperoxide in the reaction mixture after the reaction was 10.9% by weight.
    Example 2
    In a reactor similar to that used in Example 1, 520 g of an oil containing 25% by weight of m-diisopropyl benzene, 40% by weight of m-diisopropyl benzene monohydroxide as raw materials for the reaction were added. and a solution prepared by dissolving iron acetate with 17 g of an aqueous solution containing sodium carbonate and sodium salts of an organic acid (containing sodium formate and sodium acetate). The iron concentration in the introduced liquid was 0.1 ppm by weight as iron metal. The reaction was carried out under a flow of air at 90 ° C and 0.3 MPa for 6 hours. The amount of air supplied was controlled so that the oxygen concentration at the outlet of the reactor was maintained at 5% by volume during the reaction. The increase in the concentration of m-diisopropyl benzene dihydroperoxide in the reaction mixture after the reaction was 6.2% by weight.
    Comparative Example 2
    A reaction was carried out in the same manner as in Example 2 except that iron acetate was not added. The increase in the concentration of m-diisopropyl benzene dihydroperoxide in the reaction mixture after the reaction was 5.9% by weight.
    In accordance with the present invention there is provided a method for producing an alkyl aromatic hydroperoxide by oxidizing an alkyl aromatic compound with an oxygen-containing gas which stably provides an alkyl aromatic hydroperoxide at an high oxidation reaction rate which is of excellent applicability.
    权利要求:
    Claims (5)
    [1]
    A process for producing an alkyl aromatic hydroperoxide, which comprises oxidizing an alkyl aromatic compound with an oxygen-containing gas in the presence of a water-soluble iron compound, wherein the concentration of the The iron compound in the oxidation reaction system is from 0.0001 to 10 ppm by weight as the iron metal.
    [2]
    2. The method of claim 1, wherein the oxidation is carried out in the presence of an aqueous solution of the water-soluble iron compound.
    [3]
    3. The method of claim 1, wherein the concentration of iron compound is from 0.001 to 1 ppm by weight.
    [4]
    4. The process of claim 1, wherein the alkyl aromatic compound is a monoalkyl benzene or dialkyl benzene.
    [5]
    The process of claim 1 wherein the alkyl aromatic compound is cumene or diisopropyl benzene.
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    同族专利:
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    JP2007217399A|2007-08-30|
    引用文献:
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    法律状态:
    2014-07-31| RE| Patent lapsed|Effective date: 20140131 |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2006009616|2006-01-18|
    JP2006009616|2006-01-18|
    JP2006319697A|JP2007217399A|2006-01-18|2006-11-28|Method for producing alkyl aromatic hydroperoxide|
    JP2006319697|2006-11-28|
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