• 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:
    p-Benzoquinone is prepared by oxidizing phenol with molecular oxygen or with a gas in which oxygen is present, in the liquid phase, in the presence of cuprous or cupric ions. The improvement resides in carrying out the reaction in the presence of a metal, in the metallic form, which is selected from the group consisting of nickel, iron, tin, cobalt, chromium, molybdenum, magnesium and copper. The resultant p-benzoquinone is useful as an industrial source of hydroquinone, which is employed in photography.
    公开号:SU743577A3
    申请号:SU782627810
    申请日:1978-06-21
    公开日:1980-06-25
    发明作者:Константини Мишель；Жуффре Мишель
    申请人:Рон Пуленк Эндюстри (Фирма)；
    IPC主号:
    专利说明:

    one
    This invention relates to an improved process for the preparation of parabenzoquinone.
    Para-benzoquinone, which will be referred to below as benzoquinone, is an intermediate product for producing hydrogenation of hydroquinone, mainly used in the photographic industry.
    A known method for producing benzoquinone by oxidizing phenol at a temperature of 40-150 ° C and an elevated pressure flj.
    The process is carried out in the liquid phase in the presence of a copper salt in the nitrile, which forms a complex compound with a copper salt.
    The method provides a fairly high degree of conversion of phenol and the output of benzoquinone. However, when working in a reaction apparatus that is not inert with respect to the reaction medium (in an apparatus made of steel or iron), its walls are quickly eroded to such an extent that it is almost impossible to envisage the industrial use of such a method.
    The closest to the invention, according to the technical essence and the achieved result, is a method of obtaining benzoquinone from phenol by oxidation with molecular oxygen or oxygen-containing gas (for example, air) in each phase in the presence of a catcher, containing copper and ligand of chlorine, bromine, iodide thiocyanate, cyanate or cyanide, in polar solvent C.
    10 Although metallic copper can be used under conditions that ensure its oxidation to copper-containing ions or to copper-containing ions,
    IS typically uses copper salts and especially halide compounds of monovalent or divalent copper, in particular copper chloride. The process is carried out at a temperature of 30-140 ° C.
    W and pressure up to 80 atm.
    The disadvantage of this method is the relatively low yield of the target product, usually not exceeding 50-60%, and the long duration of the process is up to 3 hours.
    The aim of the invention is to provide an intensification of the process.
    权利要求:
    Claims (8)
    [1]
    This is achieved by the fact that parabenzoquinone is obtained by the liquid phase oxidation of phenol with oxygen or oxygen containing gas at elevated temperature and pressure in the presence of copper compounds as catalysts in a polar solvent. A distinctive feature is carrying out the process in the presence of a metal selected from the nickel or iron group, or tin or cobalt, or chromium, or molybdenum, or magnesium, or copper, preferably the process is carried out at a temperature of 10-120 ° C and a pressure of 5100 atm. as copper compounds are usually used chlorine or copper chloride, or copper nitrate. As a rule, the process is carried out at a ratio of copper ions per 1 mol of phenol equal to 0.01-5 and at a ratio of 1 gallon of metal to 1 copper ion is 0.1-10. In general, the process is carried out in the presence of an alkali metal halide, taken in an amount of 0.15, 0 mol per 1 copper ion. Preferably, lithium chloride or fluoride is used as the alkali halide. . Usually, methanol or adetonitrile or dimethylformamide or dimethyl sulfonic foxid is used as a solvent. It has been found that if an apparatus is used that is inert to the reaction medium, for example, reactors made from metal, coated with enamel or tantalum, phenol oxidation does not occur when the reaction is carried out in the presence of copper ions (I). The form in which the use of metal: granules, powder, chips. Different copper salts can be used as a source of copper ions (t or I 1), however, predominantly copper halide compounds are used, in particular copper chloride or copper chloride, and divalent copper nitrate. It has been found that when monovalent copper derivatives such as CugCf j are used as a catalyst, the presence of any of these free metals (all other things being equal) allows higher degrees of phenol conversion to be obtained, which improves the productivity of the process. The amount of copper catalyst, expressed as the number of copper ions per mole of phenol, can vary widely. Typically, this amount is from 0.01 to 5 copper ions per 1 mole of phenol; however, it is undesirable to resort to amounts of catalysis-Thor, introducing more than 1 copper ion per 1 mole of phenol. Usually use from 0.02 to 1 copper ion per 1 mole of phenol. The amount of metal in relation to copper is usually between about 0, 1 and 10 g at. Per presence of copper ion, preferably between 0.1 and 1 gat at 1 copper ion. Among these metals, nickel, iron, and copper are preferred. The temperature at which the reaction is carried out may vary within wide limits (10-120 s). The oxidation is carried out at a partial pressure of oxygen of at least 5 bar (4.99 atm). Although there is no critical upper pressure limit, in practice, oxygen partial pressures above 100 bar (98.69 atm), preferably above 50 bar (49.34 atm), are not used. The molecular oxygen containing gas can be air or air that is poor or enriched with oxygen, or mixtures of oxygen with various inert gases. The concentration of phenol in the solvent can take on a wide variety of values. It has been established that it is particularly advantageous to carry out the process in the presence of alkali metal halides, which increase the speed of the process. Fluorides, chlorides and bromides of lithium, potassium, sodium are mainly used. The amount of these salts is usually from 0.1 to 5 mol per 1 mon of copper, preferably from 0.5 to 2. The reaction is carried out in apparatus that is resistant to pressure and is inert with respect to the reaction mass (autoclaves made of steel, enameled or encased in tantalum). Example 1. In an autoclave encased in a tantalum casing with a volume of 0.5 l mixed in jerks, 90 CNT of methanol, 0.0755 mol of phenol, 0.022 mol of CuCf and 0.022 g atomic nickel in the form of powder are sequentially charged. The autoclave is closed and air is introduced to a pressure of 100 bar (98.69 atm), then the temperature is raised to 2 hours with stirring. After cooling, the reaction mass is degassed, in which the gas phase and polar chromatography are determined by quantitative chromatography. benzoquinone and, if necessary, diphenols. The conversion of phenol is 64%, and the yield of para-benzoquinone relative to the converted phenol is 68.5%. For comparison, previous experience, work in the absence of nickel, is repeated. After 2 hours, phenol conversion was not observed. Example 2. The process is carried out as in Example 1, loading 0.00755 g-at nickel instead of 0.022. The degree of phenol conversion was 49.4% and the yield of para-beusoquinone was 59.5%. Example 3. The process is carried out as in Example 1, adding 0.02 mol of lithium fluoride to the reaction medium. The degree of phenol conversion is increased to 79.5%, and the yield of para-benzoquinone is increased to 39%. Example 4. The process of the wire as in example 1, replacing copper chloride 0,022 mol of copper nitrate and work in the presence of 0.044 m lithium chloride. The degree of conversion of phenol is increased to 83%, and the yield of para-benzoquinone is up to 47.5. Example 5. The process is conducted as in example 1, but replacing methanol with 24 cm of acetonitrile and nickel with 0.00475 gat of metallic copper. em 0,00475 mol. After 1 h of exposure at 50 ° C and air pressure of 100 bar (98.69 atm), the degree of conversion of phenol is 78%, and the yield of para-benzoquinone is 56%. For comparison, this work is repeated in the absence of metallic copper. After 1 h, the degree of conversion of phenol is 9% and no parabenzoquinone is formed. Example 6. The autoclave of Example 1 is charged with 90 cm of acetonitrile, 0.0755 mol of phenol, O, 022 mo of CuCfj and 0.022 g. Of metallic iron. After 2 hours exposure at 65 ° C and air pressure of 100 bar (98.69 atm), the degree of phenol conversion rises to 100%, and the yield of para-benzoquinone increases to 68%. Examples 7-10. The process is carried out under the conditions of Example 1 in the presence of various metals and lithium chloride (0.044 mol). The results are shown in the table. Examples 11 and 12. The process is carried out under the conditions of example 6, the substitute for iron with tin and nickel. Conversion rates are 100% in two cases and benzoquinone yields are 49 and 63%, respectively. Examples 13 and 14. In the autoclave of Example 1, 40 cm of ac tonitrile, 0.085 mol of phenol, 0.0056 mol of copper chloride and 0.0056 g of nickel are charged. After 1 h of exposure at 50 s and an air pressure of 100 bar (98.69 atm), the degree of conversion of phenol is 67% and the yield of jiapa-benzoquinone relative to the converted phenol is 52%. If all other conditions are identical in the absence of nickel, the degree of conversion of phenol is only 56.5%, and the yield of para-benzoquinone is 53.5%. Example 15. The process is carried out as in Example 6. Replace acetonitrile with 90 cm of dimethylformamide, at 70 ° C. The degree of phenol conversion is 63% and the yield of para-benzoquinone is 49%. Example 16. In a 200 cm stainless steel autoclave, 30 cm of methanol, 2g35 g of phenol, 3.35 g of CuCfj 0.28 iron and 0.282 g of LiC are loaded. The autoclave is closed, 2 liters of atmospheric oxygen are introduced and the temperature is raised to b.S. for 4 hours, under these conditions, the reaction mass is cooled to, the gas is removed from the autoclave, and the remaining phenol and benzoquinone are quantified by gas phase chromatography and polar chromatography. The degree of conversion of phenol is 97.5%, and the yield of benzoquinone in relation to the converted phenol is 26.5%. Invention 1. A method for producing para-benzoquinone by liquid-phase oxidation of phenol with oxygen or an oxygen-containing gas at elevated temperature and pressure in the presence of copper compounds as catalysts in a polar solvent, which, in order to intensify the process, is carried out in the presence of metal selected from. groups of nickel or iron, or tin, or cobalt, or chromium, or molybdenum, or magnesium, or copper.
    [2]
    2. A method according to claim 1, wherein the process is carried out at a temperature of 10-120 ° C and a pressure of 5-100 atm.
    [3]
    3. A method according to claim 1, characterized in that copper chloride or copper chloride or copper nitrate is used as copper compounds.
    [4]
    4. Method POP.1, characterized in that the process is carried out at a ratio of copper ions to 1 mole of phenol equal to 0.01-5.
    [5]
    5. A method according to claim 1, characterized in that the process is carried out at a ratio of 1 gatam of metal to 1 copper ion of 0.1-10.
    [6]
    6. Method POP1, characterized in that the process is carried out in the presence of an alkali metal hydrogene, taken as the amount of OD-5.0 mol and 1 copper ion.
    [7]
    7. A method according to claim 6, characterized in that lithium chloride or fluoride is used as the alkali metal halide.
    [8]
    8. Method POP.1, distinguished by the fact that methanol or acetonitrile, or dimethylformacene or dimethyl sulfoxide is used as a solvent.
    Sources of information taken into account in the examination
    1. US Patent 3987068, M.C. C 07 C 49/64, published 1975.
    2.Patent of France I 2245602, M.C. C 07 C 49/64, published. 1974 (prototype).
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    同族专利:
    公开号 | 公开日
    CS207628B2|1981-08-31|
    DD135482A5|1979-05-09|
    US4208339A|1980-06-17|
    AT358011B|1980-08-11|
    ATA465578A|1980-01-15|
    PL117835B1|1981-08-31|
    SE7807240L|1978-12-28|
    FR2408570A1|1979-06-08|
    JPS5412334A|1979-01-30|
    FR2408570B1|1980-04-04|
    ZA783630B|1979-06-27|
    BR7804054A|1979-01-16|
    DE2827552A1|1979-01-11|
    LU79874A1|1979-09-06|
    BE868501A|1978-12-27|
    IT1097295B|1985-08-31|
    GB1586845A|1981-03-25|
    IT7825025D0|1978-06-27|
    PL207887A1|1979-05-21|
    CA1098532A|1981-03-31|
    NL7806842A|1978-12-29|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    CS152538B1|1967-06-12|1974-02-22|
    US3935247A|1973-09-28|1976-01-27|The Goodyear Tire & Rubber Company|Oxidation of alkylated phenols to p-benzoquinones|
    US3870731A|1973-09-28|1975-03-11|Goodyear Tire & Rubber|Oxidation of phenols and alkyl substituted phenols to their corresponding para-benzoquinone|US4478752A|1981-07-20|1984-10-23|Sun Tech, Inc.|Process for oxidizing phenol to p-benzoquinone|
    GR78368B|1981-11-18|1984-09-26|Delalande Sa|
    CA1192915A|1982-04-29|1985-09-03|Chao-Yang Hsu|Production of hydroquinone|
    US4519948A|1982-09-27|1985-05-28|Sun Tech, Inc.|Process for oxidizing a phenol to a p-benzoquinone|
    US4482493A|1982-10-22|1984-11-13|Sagami Chemical Research Center|Method for preparing benzoquinones|
    US4522757A|1982-10-25|1985-06-11|Sun Tech, Inc.|Process for oxidizing a phenol to a p-benzoquinone|
    US4442036A|1983-02-28|1984-04-10|Sun Tech, Inc.|Process for oxidizing phenol to benzoquinone|
    US4828762A|1983-06-06|1989-05-09|Mitsubishi Gas Chemical Company, Inc.|Process for the production of 2,3,5-trimethylbenzoquinone|
    JPH0451536B2|1987-05-13|1992-08-19|Eisai Co Ltd|
    DE3908768A1|1989-03-17|1990-09-20|Basf Ag|PROCESS FOR THE PREPARATION OF 2,3,5-TRIMETHYL-P BENZOCHINONE|
    US5107003A|1990-03-18|1992-04-21|Eastman Kodak Company|Preparation of quinones by the ceric-catalyzed oxidation of aromatic diols|
    US5118823A|1990-12-13|1992-06-02|Eastman Kodak Company|Oxidation of dihydroxyaromatic compounds to quinones|
    US6693221B1|2003-04-04|2004-02-17|General Electric Company|Method of preparing mixtures of bromophenols and benzoquinones|
    US6815565B2|2003-04-04|2004-11-09|General Electric Company|Method for preparing hydroquinones and dihydroxybiphenyl compounds from mixtures of bromophenols and benzoquinones|
    CN101462056B|2009-01-13|2010-09-15|天津大学|Method for preparing porous nickel metal integral type catalyst|
    CN102336643B|2011-07-13|2014-06-25|北京博源恒升高科技有限公司|Process for synthesizing benzoquinones by direct oxidation of phenols|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR7720709A|FR2408570B1|1977-06-27|1977-06-27|
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