• 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 continuous process for the preparation of butane-1,4-diol comprises, in a one-stage process, catalytically hydrogenating a solution of maleic anhydride in a monohydric aliphatic alcohol, in the presence of hydrogen and a copper chromite catalyst.
    公开号:SU852165A3
    申请号:SU792830726
    申请日:1979-10-15
    公开日:1981-07-30
    发明作者:Ланге Эрхард；Цур Хаузен Манфред
    申请人:Хемише Верке Хюльс Аг (Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD OF OBTAINING. BUTANDIOL-1,4
    I
    The invention relates to a process for the preparation of 1,4-butanediol, which can be used as a solvent.
    A known method for producing butanediol-1, 4 by hydrogenating maleic acid esters at 200-260 ° C and a pressure of 100-300 atm in the presence of a copper-chromium catalyst, the yield of the target product is 64.8-70%
    The disadvantage of this method is the low yield of the target product.
    The closest in technical essence to the present invention is a method of producing butanediol-1.4 by hydrogenating maleic anhydride at 210-250 ° C and pressure of 165260 atm in the presence of a catalyst of platinum group metals on a carrier in tetrahydrofuran or dioxane-1.4. . The yield of the target product 88-91% 2.
    The disadvantage of this method is not high enough yield of the target product.
    The purpose of the invention is to increase the yield of the desired product.
    The goal is achieved by the fact that in the method of producing butanediol-1, 4 by hydrogenating maleic anhydride at 200-230 ° C and a pressure of 290-300 atm in the presence of a copper-chromium catalyst in an alcohol selected from the group n-butanol, isobutanol, at a mole ratio maleic anhydride: alcohol, equal to 1: 5-6.
    Example 1. In an electrically electrified ® ® apparatus with an internal diameter of 24 mm and a length of 1200 mm, made of stainless steel of the U4A grade, 430 ml (635 g) of a catalyst containing, in wt.%: Copper oxide 37, chromium trioxide 52 and dioxide
    5 silicon 8. After washing out the soluble components with steam condensate, the catalyst is reduced with hydrogen at 20,000 and 300 bar within 2 hours. While stirring, maleic anhydride was diluted in isobutanol at 25 ° C in a weight ratio of 1: 4, corresponding to a molar ratio of 1: 5.3. The solution and hydrogen together served in the upper part of the apparatus. Hydrogen is fed in a quantity that provides an off-gas amount of 400 ml / h of hydrogen. The hydrogenation process is carried out at 300 bar.
    Initial temperature of hydration
    30 is 210®C. As the process of hydrogenation proceeds, the temperature rises to 2300s. The reaction mixture leaving the apparatus is cooled, fed into the collection and is divided into two fractions by distillation. The first fraction consists of recovered alcohol, tetrahydrofuran, n-butanol, and water formed during the hydrogenation process. The second fraction contains butanediol-1,4, insignificant amounts of butyrolactone and high-boiling components, as well as traces of complex diisobutyl zerine succinic acid. The acid number of the second fraction is Oj2. With a nearly complete conversion of maleic anhydride, the yield of 1,4-butanediol is 92.8 mol%. The by-products are tetrahydrofuran, butyrolactone, diisobutyl ester of succinic acid and high; and downstream components are formed in the amount of 4.0; 0.8; 0.1 and 2.3 mol.%, Respectively.
    Example 2. The process is carried out as in Example 1, but n-butanol with a weight ratio to maleic anhydride of 4: 1 is used as a solvent, and the catalyst is used in an amount of 400 ml. The hydrogenation process is carried out at 210-220 ° C and .290 bar, and the amount of exhaust gas is 200 ml / h of hydrogen. After separation by distillation of the reaction mixture with an acid number of 0.1, mol% is obtained: butanediol-1.4 93.6, butyrolactone 1.6, tetrahydrofuran 3.2, high-boiling components 1.6 and traces of complex di-n-butyl succinic acid ester. The conversion of maleic anhydride is almost complete.
    Example 3. The process is carried out analogously to example 1, but the solution is hydrogenated for 20 hours, maleic anhydride for 80 hours, isobutanol on the catalyst, which, in an unreduced and non-prololized state, contains, wt%: copper oxide 33 ,. chromium trioxide 38, silicon dioxide 8, barium oxide 8 and sodium oxide 3. The hydrogenation process is carried out at 210-220 ° C and 3QO bar. After separation by distillation of the reaction mixture with an acid number of 0.1, the mole mol% is obtained: butanediol-1.4G91.0, tetrahydrofuran 3.5, butyrolactone 0.6, complex diisobutyl sequin succinic acid 2.9 and high boiling components 2.0 . The conversion of maleic anhydride is almost complete.
    Using the proposed method allows to increase the yield of the target product to 91-93.6%.
    权利要求:
    Claims (2)
    [1]
    1. The UK patent number 1464263, cl. C 2 C, pub. 09.02.74.
    [2]
    2. For the FRG 2715667,
    cl. C 07 C 31/20, published 10/12/78 (prototype).
    类似技术:
    公开号 | 公开日 | 专利标题
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    US2504407A|1950-04-18|Hydrodemethanolization
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    US5371242A|1994-12-06|Preparation of products of the reduction of 4-hydroxybutyric acid derivatives
    US4080366A|1978-03-21|Conversion of esters of 1,4-butanediol to tetrahydrofuran
    JPH08217768A|1996-08-27|Production of 3-methyltetrahydrofuran
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    同族专利:
    公开号 | 公开日
    RO77557A|1982-02-01|
    DE2845905C3|1983-05-26|
    IT7950613D0|1979-10-19|
    GB2036009A|1980-06-25|
    JPS6254289B2|1987-11-13|
    DE2845905A1|1980-04-24|
    BE879536A|1980-04-21|
    JPS5557528A|1980-04-28|
    DE2845905B2|1980-10-30|
    US4268695A|1981-05-19|
    GB2036009B|1982-12-01|
    ES485204A1|1980-05-16|
    DD146586A5|1981-02-18|
    NL7907724A|1980-04-23|
    FR2439176A1|1980-05-16|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2094611A|1934-12-11|1937-10-05|Du Pont|Process for producing alcohols from hydroxy carboxylic compounds|
    US2772291A|1953-08-31|1956-11-27|Du Pont|Hydrogenation of maleic anhydride|
    GB800847A|1955-07-08|1958-09-03|Glanzstoff Ag|Process for the hydrogenation of aliphatic mono- and dicarboxylic acids|
    DE1235879B|1964-03-17|1967-03-09|Basf Ag|Process for the production of alcohols by catalytic hydrogenation of carboxylic acids|
    DE1768313B2|1968-04-27|1977-05-18|Henkel & Cie GmbH, 4000 Düsseldorf|PROCESS FOR MANUFACTURING HIGHERMOLECULAR VALUE-VALUE ALCOHOLS|
    JPS4831084B1|1970-09-04|1973-09-26|
    US3696126A|1970-11-23|1972-10-03|Hercules Inc|Azidoformates from reduced polymerized fatty acids|
    US3830830A|1972-02-29|1974-08-20|Eastman Kodak Co|Production of dialkyl esters of succinic acid|
    GB1454440A|1974-10-03|1976-11-03|Ucb Sa|Process for the production of butane-1,4-diol from but-2-ene- 1,4-dioic acid|
    DE2501499A1|1975-01-16|1976-07-22|Hoechst Ag|PROCESS FOR THE PRODUCTION OF BUTANDIOL- |
    US4032458A|1975-08-08|1977-06-28|Petro-Tex Chemical Corporation|Production of 1,4-butanediol|
    GB1587198A|1976-11-23|1981-04-01|Ucb Sa|Process for the production of butane-1,4 diol and tetrahydrofuran|DE3106819A1|1981-02-24|1982-09-09|Basf Ag, 6700 Ludwigshafen|METHOD FOR PRODUCING 1,4-BUTANDIOL|
    DE3346134A1|1983-12-21|1985-07-04|Basf Ag, 6700 Ludwigshafen|METHOD FOR CONTINUOUSLY SEPARATING MALEIC ACID ANHYDRIDE FROM GAS SHAPED REACTION MIXTURES|
    DE3423447A1|1984-06-26|1986-01-02|Basf Ag, 6700 Ludwigshafen|METHOD FOR PRODUCING 1,4-BUTANDIOL|
    US4656297A|1985-03-11|1987-04-07|Amoco Corporation|Coproduction of butanediol and tetrahydrofuran and their subsequent separation from the reaction product mixture|
    DE3528124A1|1985-08-06|1987-02-12|Huels Chemische Werke Ag|METHOD FOR REMOVING N-BUTYRALDEHYDE FROM GAS FLOWS|
    GB8717989D0|1987-07-29|1987-09-03|Davy Mckee Ltd|Catalyst|
    US4810807A|1987-10-13|1989-03-07|The Standard Oil Company|Hydrogenation of maleic anhydride to tetrahydrofuran|
    DE3803581A1|1988-02-06|1989-08-17|Basf Ag|METHOD FOR PRODUCING 1,2,4-BUTANTRIOL|
    JP2649555B2|1988-08-26|1997-09-03|広栄化学工業株式会社|Method for producing 2-n-butyl-2-ethyl-1,3-propanediol|
    JP2596604B2|1988-12-14|1997-04-02|東燃株式会社|Method for producing 1,4-butanediol and tetrahydrofuran|
    DE3843956A1|1988-12-24|1990-06-28|Huels Chemische Werke Ag|METHOD FOR PRODUCING ALIPHATIC AND CYCLOALIPHATIC DIOLS BY CATALYTIC HYDRATION OF DICARBONIC ACID ESTERS|
    DE3942064A1|1989-10-04|1991-04-11|Henkel Kgaa|PROCESS FOR PREPARING SAEFEFEST CATALYSTS FOR THE DIRECT HYDROGENATION OF CARBONIC ACIDS TO ALCOHOLS|
    JP2595358B2|1989-12-07|1997-04-02|東燃株式会社|Method for producing 1,4-butanediol and tetrahydrofuran|
    DE4009029A1|1990-03-21|1991-09-26|Basf Ag|METHOD FOR PRODUCING 1,4-BUTANDIOL|
    GB9324752D0|1993-12-02|1994-01-19|Davy Mckee London|Process|
    GB9324823D0|1993-12-02|1994-01-19|Davy Mckee London|Process|
    GB9324785D0|1993-12-02|1994-01-19|Davy Mckee London|Process|
    GB9324786D0|1993-12-02|1994-01-19|Davy Mckee London|Process|
    GB9324753D0|1993-12-02|1994-01-19|Davy Mckee London|Process|
    GB9324782D0|1993-12-02|1994-01-19|Davy Mckee London|Process|
    GB9324784D0|1993-12-02|1994-01-19|Davy Mckee London|Process|
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    WO1998000498A1|1996-06-28|1998-01-08|The Procter & Gamble Company|Liquid cleaning compositions and shampoos containing dianionic or alkoxylated dianionic surfactants|
    DE19636066A1|1996-09-05|1998-03-12|Basf Ag|Process for the dehydrogenation of 1,4-butanediol to gamma-butyrolactone|
    US6455742B1|1999-09-02|2002-09-24|Wisconsin Alumni Research Foundation|Method for catalytically reducing carboxylic acid groups to hydroxyl groups in hydroxycarboxylic acids|
    DE10225929A1|2002-06-11|2003-12-24|Basf Ag|Two-stage process for the production of butanediol with intermediate separation of succinic anhydride|
    DE10225926A1|2002-06-11|2003-12-24|Basf Ag|Process for the production of butanediol|
    DE10225927A1|2002-06-11|2003-12-24|Basf Ag|Process for the production of butanediol by combined gas phase and liquid phase synthesis|
    GB201318175D0|2013-10-14|2013-11-27|Johnson Matthey Davy Technologies Ltd|Process|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE2845905A|DE2845905C3|1978-10-21|1978-10-21|Process for the continuous production of 1,4-butanediol|
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