• 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:
    The invention relates to amines, in particular, to a process for the preparation of primary alkylamines and N, N-dimethylalkylamines C 10 -C 18 and to a catalyst for its implementation. The goal is to increase the selectivity of the process. Receiving lead by reaction in one stage of the methyl ester of the corresponding carboxylic acid with ammonia and hydrogen-containing stream in the presence of a catalyst in the following ratio, wt.%: Copper oxide 15,1-22,1 cobalt oxide 1.5-2.6 chromium oxide 1.1-20.1 titanium dioxide the rest. In the case of the preparation of N, N-dimethylalkylamines, the process is preferably carried out in the presence of methanol, and the mass content of chromium in the catalyst is 20.1%. 2 sec. and 1 z. p. f-ly.
    公开号:SU1598864A3
    申请号:SU874203486
    申请日:1987-10-08
    公开日:1990-10-07
    发明作者:Барро Жоэль；Сеффен Муги；Форки Кристиан
    申请人:Сека С.А. (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to an improved process for the preparation of primary alkylamines and H, M-dimethylalkylamines -C, j and a catalyst for its implementation.
    Pel of the invention is to increase the selectivity of the process by using a catalyst and increasing its activity and selectivity.
    Example 1 It works with a catalyst of composition: CuO / Al Oj 9.1 / 90.9 wt.%, Obtained by impregnating aluminum oxide with copper (II) nitrate. The reaction is carried out at 300 ° C with a molar ratio of ester, ammonia and hydrogen of 1: 10: 100, and a volumetric rate of the reactants of 0.33 h. As the methyl ester using 99% methyldodecanoate, BP. at 766 mm Hg
    Conversion is complete, but the selectivity of the composition of the liquid flows
    low
    the following, Dodecylamine N-Ketyldo-decylamine M, K-Dimethyl-dodecylamine Dodestil lamide Dodecyl Nitrile Other amines
    72.0 16.0
    2.5 8.0
    1.0
    0.5
    cl
    x 00
    00
    05 4
     CM
    Example 2. In the production of dimethylamine, a reagent stream containing methanol is used, the tertiary amine content is increased, but the selectivity is also reduced. The composition of the liquid flows obtained with the catalyst CuO / AljOj 17.8 / 82.2 May. % with a ratio of ester, methanol, ammonia, hydrogen 1:40:10:: 100, a bulk velocity of 0.17 h at 250 C, the following,%:
    Dodecylamine. N-Methyldodecylamine N, N-Dimethyl-dodecylamine Dodecylamide Dodecyl Nitrile
    29.20 34.7
    15.6
     9.1 11.4
    20
    PR and measure 3. The process is carried out under the conditions of example 1 with a catalyst CuO / ZnO 9/91 wt.%, The ester is converted to 90%, but the composition of the converted fraction is as follows: 25
    75.0 6.7
    1.5
    14.0
    2.5
    0.3
    The composition indicates a low yield of primary amine, mainly due to the formation of amide.
    Example 4. In the preparation of the primary amine, the process is carried out under the conditions of Example 1 with a catalyst type copper chromite of composition CuO / Cg O 40/60 May. % Work at temperatures of 300 and.
    The composition of the obtained product is the following,%, at a temperature, ° С:
    Dodecylamine N-Methyl Dodecylamine Dodecylamide
    N, N-Dimethyl-dodecylamine Dodecylnitrile Other amines
    In both cases, the selectivity is very low or very mediocre, although the conversion rate reaches respectively 95 and 100%.

    five
    0
    five
    0
    0
    five
    0
    five
    Example 5. For the preparation of dimethyldodecylamine, a CuO / CtjOj catalyst of 40/60 wt.% Under the conditions of Example 2 is used, with hydrogen and ester ratios of 100 and 400.
    Get the following composition,%, with respect to hydrogen and ester:
    100,400 N-Methyldodecylamine 7.4 28.2 N, N-Dimethyldodecylamine. 30.2 43.2 Dodecylamine 1.5 4.9 Dodecylamide 44.2 17.0 Dodecylnitrile 3.6. 2.5 Other amines 13.1 10.2 The said catalyst results in a higher yield of metalalkylamines, but. due to unacceptably high concentrations of amide and dialkylamines, and the selectivity is the lower, the higher the overall yield of methylamines.
    Example 6. The process is carried out in the presence of a catalyst obtained by impregnating the support (TiOj) with a solution of salts of the starting components, followed by calcining with and having the composition CuO / COjO / TiOj 20 (2.5) / / 77.5 wt.%. The process temperature is 250 C. All other working conditions are identical to Example 1. The following composition is obtained,%:
    Dodecylamine 86,2
    N-Methyldodecylamine 2, 1
    N, N-Dimethyldodecylamine. 0.9 Dodecylamide Not Measure Dodecyl Nitrile Dodecane1,7
    Other amines9,1.
    Example 7. The process is carried out using a mixed catalyst CuO / CrjOj / COjO / TiOj 20 / 1.5 / / 1.5 / 77 wt.%, Obtained by coprocessing titanium oxide with salts of the starting components and subsequent calcination at 350 ° C. The reaction temperature is. All other conditions are identical to example 1. Get the following composition,%:
    Dodecylamine 83,0
    K-MetIldoDecilamine .4,1
    N, N-Dimethyldodedic ilamin0, 5

    1.0 0.7 8.0
    2.7
    Example 8. The process is carried out with a CuO / Crj / TiOj catalyst of 15.1 / 1.1 / 2.6 / 81.2 wt.%, Obtained by mechanical mixing of the impregnated catalysts and CuO / Cr Oj / TiOj. The liquid stream has the following composition,%:
    Dodecylamine 74,5
    N-Methyldodecylamine 1, 0
    M, N-Dimetsh1dodecylamine1, 0
    Dodecylamide. 1.0
    Dodecylnitrile1,0
    Dodecane 16.4
    Other amines5,1
    The mixed catalyst allows almost complete conversion of the ester, with the resulting long chain alkylamine containing very few methylated homologs.
    Hydrocarbons may make up a prominent part of these reaction products; they usually do not interfere with the subsequent use of the primary amine, and can easily be released.
    Example 9. To obtain dimethylalkyamine, a catalyst based on titanium oxide and a triple mixture of CuO / Cr2Oj / Sod0, highly chromium enriched, and a stream containing methanol are used.
    The composition of the catalyst TiO / CuO / Crj 0,6 / 22,1 / 20,1 / 2.2 masl. Reaction conditions: a ratio of ester, methanol, ammonia and hydrogen is 1: 40: 10: 400, the temperature is 250 s and the space velocity is 0.33 h. In this way, almost complete conversion of the ester to dimethyldodecyl amine is obtained. The composition of the streams is the following,%:
    N-methyldode
    cylamine
    N, N-Dimethyldodecylamine Dodecylamine Dodecylamide Dodecyl Nitrile Other amines Dodecane Prim Reamer 1,
    93 1.5 0.5
    Do not measure - 11
    one
    er 10. Proceed as with the difference that instead
    ten
    15
    20
    25

    598864
    methypdodecanoate is charged with an industrial fraction during the distillation of methylated copra acids (methyl esters / of methyl) composition,%: C, 1; 5 seconds ,, 55; C, 20; C ,, 9; C „3; C, f 3. The exponent neomite -236.
    The streams have a total alkalinity of 4.13 ml-eq / g, of which 0.25 ml-eq / g of primary alkalinity and 3.80 ml-eq / g of tertiary alkalinity, with the initial distribution of chains as follows,%:
    N-Methylcopraamine6
    N, N-Dimethylcopraamine90
    Other amines and
    amides2
    Not Amines2
    Thus, the proposed method allows to increase the selectivity of the process when using a new catalyst with increased activity and selectivity.
    权利要求:
    Claims (3)
    [1]
    Invention Formula
    1 o A method of producing primary alkyl amines of iH, N-dimethylalkylamines by reacting in one step the methylester of the corresponding carboxylic acid with ammonia and hydrogen-containing stream in the presence of a catalyst based on metal oxides, including chrome oxide, characterized In order to improve the selectivity of the process, ncf use a catalyst that additionally contains as oxides of metals oxides of copper, cobalt and titanium, in the following ratio of components, May. %:
    Q
    five
    15,1-22,1
    1.5-2.6 1.1-20.1
    Rest
    about tl and h and yu0
    five
    Copper oxide cobalt oxide
    Chromium oxide
    [2]
    2. The method according to claim 1,
    y and so that in the case of the preparation of M, N-dimethylalkylamines, the process is carried out in the presence of methanol, and the mass content of chromium in the catalyst is 20.1%.
    [3]
    3. Catalyst for the production of primary alkylamines and K, L-dimethyl-. alkylamines based on metal oxides, including chromium oxide, characterized in that.
    15988648
    in order to increase activity and sentiment, May. %:
    lexivity, the catalyst is an additional - Oxford copper 1-22 1
    but contains as oxides of cobalt oxide-1 5-2 6
    tall oxides of copper, cobalt, and tita — chromium oxide G1-20 1
    on the following ratio of titanium dioxide Else
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    同族专利:
    公开号 | 公开日
    CN87106873A|1988-05-04|
    US4935546A|1990-06-19|
    EP0267081A1|1988-05-11|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2166971A|1932-09-14|1939-07-25|Ig Farbenindustrie Ag|Production of amines|
    GB421718A|1933-04-26|1934-12-27|Ig Farbenindustrie Ag|Improvements in the manufacture and production of amines and amides|
    US2223303A|1939-04-12|1940-11-26|Du Pont|Process for the catalytic hydrogenation of carboxylic acid substances to amines|
    DE1543676B1|1966-12-07|1970-07-30|Henkel & Cie Gmbh|Process for the preparation of primary amines|
    DE1643418A1|1967-12-07|1971-07-01|Henkel & Cie Gmbh|Process for the preparation of N-methyl-substituted alkylamines|
    DE1768641A1|1968-06-11|1971-10-28|Henkel & Cie Gmbh|Process for the production of amines|US6198114B1|1997-10-28|2001-03-06|Stmicroelectronics, Inc.|Field effect transistor having dielectrically isolated sources and drains and method for making same|
    WO2012158182A1|2011-05-17|2012-11-22|Bioamber S.A.S.|Processes for producing butanediol and diaminobutane from fermentation broths containing ammonium succinates|
    BR112012029447A2|2010-05-19|2017-03-07|Bioamber Sas|processes for the production of diaminobutane , succinic dinitrileand succinamide |
    US9464030B2|2011-05-18|2016-10-11|Bioamber Inc.|Processes for producing butanediol , diaminobutane , succinic dinitrileand succinamide |
    EP2571839A1|2010-05-19|2013-03-27|BioAmber S.A.S.|Processes for producing diaminobutane , succinic dinitrileand succinamide |
    WO2012170060A1|2011-06-10|2012-12-13|Bioamber S.A.S.|Processes for producing hexanediol , hexamethylenediamine , and derivatives thereof|
    EP2582657A1|2010-06-16|2013-04-24|BioAmber S.A.S.|Processes for producing hexamethylenediamine , adiponitrile , adipamideand derivatives thereof|
    EP2582653A1|2010-06-16|2013-04-24|Bioamber, S.A.S.|Processes for producing hexamethylenediamine , adiponitrile , adipamideand derivatives thereof|
    CN106748805B|2016-11-25|2019-03-19|上海科技大学|A kind of alkylation of amine|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR8614044A|FR2605002B1|1986-10-09|1986-10-09|PROCESS FOR THE SYNTHESIS OF PRIMARY AMINES FROM ESTERS|
    FR8614045A|FR2605003B1|1986-10-09|1986-10-09|PROCESS FOR THE SYNTHESIS OF DIMETHYL-ALKYLAMINES FROM ESTERS OF CARBOXYLIC ACIDS AND METHANOL|
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