• 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 method of preparing ω -lactams, in particular caprolactam, comprising: a step of premixing cycloaliphatic acids having the formula where n = 3 - 13, with a dehydrating agent; the first step of reaction with a nitrosating agent; the second step of reaction with the addition of a very small amount of water corresponding to a molar ratio U = H2O/SO3 within the 0.1 to 0.9 range; and the step of reclaiming the unreacted cycloaliphatic acid. The method affords improved output from the lactamization reaction and reduced byproducts.
    公开号:SU1588278A3
    申请号:SU864027185
    申请日:1986-03-26
    公开日:1990-08-23
    发明作者:Сенни Паоло；Цульяни Леандро；Феррудзи Серджо
    申请人:Кимика Дель Фриули С.П.А. (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to a process for the preparation of caprolactam (CL) obtained by the nitrosation of cyclohexanecarboxylic acid (CCGC), and can be used in chemical industry.
    The aim of the invention is to increase the output of CL.
    FIG. 1 shows a diagram of a semi-continuous laboratory setup; in fig. 2 is a diagram of an industrial continuous installation.
    Examples 1-10. Nitrosylsulfuric acid is continuously fed to the laboratory setup (Fig. 1), and the remaining reagents are fed periodically.
    The proposed method is carried out in four stages.
    At the first stage, par gvKGK is obtained in oleum. This stage is carried out in a glass-lined reactor A, having a volume of 700 ml, with an internal condenser, in which cooled water circulates to maintain a pre-mix temperature of 20 ° C. First, load the CCGC solution and its by-products in n-hexane through line 1, and then dropwise with vigorous stirring in order to maintain the temperature, oleum of the desired concentration is added along line 2. The mixture is then transferred.
    sd
    00 00
    Yu "
    00
    s
    but line 3 to separatory funnel B, in which the n-hexane phase is separated from sulfate via line 4, which is withdrawn through line 5,
    In the second stage, the first part of lactamization is carried out. This operation is carried out in a 2000 ml glass reactor B equipped with an internal heat exchanger adapted to be connected to a hot water thermostat (temperature 90 ° C) and / or a cold water source (temperature) and a mechanical turbine agitator .. Chloride sulfuric acid-15 is loaded into the reactor; P 5 and add a certain amount of solvent (n-hexane) through line 6. Then the mixture is stirred while hot water is circulating (90 ° C) through the heat exchanger and the temperature of the mixture is raised from 20 to 71 - 72 ° s After that, the reactor through line 7 is loaded with a solution of nitrosyl-sulfuric acid in oleum with a dosing pump for 12 min. 25
    In the third stage, the second part of lactamization is carried out. At the completion of the nitrosylsulfuric acid addition stage, the reaction mass is left at a predetermined temperature for 3 minutes and water is then added along line 8 to the reactor to cool some SOj, and the mixture is stirred at a constant temperature for 10 minutes. The mass is cooled by circulating cold water (with a temperature of about 15 ° C) through a heat exchanger.
    At the fourth stage, the regeneration of unreacted CCGC is carried out. At that time, as the temperature of the reaction mass: 1 ° C to 20 ° C, hydrolytic water starts to be added through line 9, maintaining a temperature of about 20 ° C, as a result of which unreacted
    stage. At the first stage, a solution of CCCC in oleum is obtained. This operation is carried out in a lined reactor D, through the jacket of which cooled water circulates to maintain the pre-mixing temperature (). To the reactor D, the CCGC solution, its by-products and n-hexane are fed through line 14, and then dropwise with vigorous stirring for In order to maintain the temperature at 20 ° C, oleum is added through line 15 with a given concentration. The mixture then flows into a sump E, from which the n-hexane phase is withdrawn via line 17, separated from the sulfate phase, which is withdrawn along line 1B.
    In the second stage, the first part of lactamization is carried out. This operation is carried out in reactor G. The reactor contains seven separation walls arranged in a cascade, and the reaction mixture, the flow from one section to the next, goes through a series of successive reaction stages. The reactor W serves the sulfate phase through line 18 and added a certain amount of n-hexane. A solution of the nitrosating mixture in oleum is then added through line 19.
    In the third stage, the second part of lactamization is carried out. Upon completion of the addition of the nitrosating mixture, the reaction mass in the last two stages 7 and 8 of the reactor W is maintained at a predetermined temperature, after which the reaction mixture flows through line 20 to reactor 3, where water is added line 23 to cool some SOj, and the mixture is stirred at constant temperature.
    At the fourth stage, the regeCGKK is transferred from the CL solution into a time-45 eraction of unreacted CCGC. Slawed fillet, acid. The two-phase DUKty reaction precedes the stage, the mixture through line 11 is poured into separating funnel D, the reactor is washed with n-hexane through line 10, and the n-hexane phase is withdrawn, along line 12 containing CGCH, and the sulfuric acid phase output of line 13, which contains CL, by-products of lactamyzapium and, in small quantities, CGCC.
    Examples 11 and 12. The experiments were carried out on continuous projectile systems: Fig. 2. The preferred method is the implementation of Gvppyut in even-yrs
    50
    55
    flow through pipe 22 into hydrolyzate I, to which hydrolytic water is added via line 23, maintaining a low temperature (about 20 ° C) in order to separate the unreacted CCGC and the CL solution in dilute sulfuric acid. The biphasic mixture through line 24 then flows into decanter K, in which the mixture separates into the n-hexane phase, which is drawn through line 25, containing CCGC, and the sulfate, which is output via line 26, which will contain CL, by-products of the laxadium. At the first stage, a solution of CCCC in oleum is obtained. This operation is carried out in a lined reactor D, through the jacket of which cooled water circulates to maintain the pre-mixing temperature (). To the reactor D, the CCGC solution, its by-products and n-hexane are fed through line 14, and then dropwise with vigorous stirring for In order to maintain the temperature at 20 ° C, oleum is added through line 15 with a given concentration. The mixture then flows into a sump E, from which the n-hexane phase is withdrawn via line 17, separated from the sulfate phase, which is withdrawn along line 1B.
    In the second stage, the first part of lactamization is carried out. This operation is carried out in reactor G. The reactor contains seven separation walls arranged in a cascade, and the reaction mixture, flowing from one section to the next, goes through a series of successive reaction stages. The reactor W is fed with a sulfate phase through line 18 and added a certain amount of n-hexane. A solution of the nitrosating mixture in oleum is then added through line 19.
    In the third stage, the second part of lactamization is carried out. Upon completion of the addition of the nitrosating mixture, the reaction mass in the last two stages 7 and 8 of the reactor W is maintained at a predetermined temperature, after which the reaction mixture flows through line 20 to reactor 3, where water is added line 23 to cool some SOj, and the mixture is stirred at constant temperature.
    In the fourth stage, the recalculation of the unreacted CCGC is carried out. Pro-DUKty reaction foreshadowed stage
    flow through pipe 22 into hydrolyzate I, to which hydrolytic water is added via line 23, maintaining a low temperature (about 20 ° C) in order to separate the unreacted CCGC and the CL solution in dilute sulfuric acid. The biphasic mixture through line 24 then flows into decanter K, in which the mixture separates into the n-hexane phase, which is drawn through line 25, containing CGCC, and the acid sulfate, which is output through line 26, which.-Contains CL, by-products varnish 1588278 6
    tamisation and, in a small amount, followed by exposure at the same
    cgkk
    The results of the experiments in examples 1-12 are presented in table. 1 - 12 respectively.
    As a result of water supply to the lactamization and hydrolysis stage, the CL yield is increased from 87–91 to 95%.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    The method of obtaining caprolactam by mixing cyclohexanecarboxylic acid with oleum with a concentration of 36-50% by reacting the mixture with nitrosylsulfuric acid in n-hexane at 60 - at the molar ratio of dehydrating agent
    ...-- G ,, -. - .l ... .aIclJIbHOrO K
    SOj) To nitrosating (o, 7 - 1, 1): 1 to 20 hydrolysis.
    temperature for the completion of lactamization and the supply of water for hydrolysis at J 60 - 80 ° C, regeneration of unreacted cyclohexanecarboxylic acids by neutralizing the reaction mixture with recovery and recycling of cyclohexane carboxylic acid, separation and
    to purify caprolactam, wherein the lactamization and hydrolysis step is carried out n discontinuously, characterized in that, in order to increase the yield of caprolactam, the cell membrane completes 15 and lactamization are fed with a portion of water at a molar ratio of H, 0: SOi (0.50 - 0.59): 1, preferably (0.55 - 0.59): 1, with the supply of the remaining amount of water per stage
    IclJIbHOrO K
    hydrolysis.
    temperature for the completion of lactamization and the supply of water for hydrolysis at 60–80 ° C, the regeneration of unreacted cyclohexanecarboxylic acid by neutralizing the reaction mass with isolation and recycling of cyclohexanecarboxylic acid, separation and
    purification of caprolactam, the lactamization and hydrolysis stages being carried out continuously, characterized in that, in order to increase the yield of caprolactam, the control of the lactamization termination stage is carried out with the supply of a part of water at a molar ratio of H, 0: SOi (0.50-0.59) : 1, preferably (0.55 - 0.59): 1, with the supply of the remaining amount of water to the stage
    With
    mecha and „. e.“ -J -. -o. „„. e „„ „: SO / NO -, 10, H- O / SOj 0.55. Code Code 95,12.
    Spreadsheets
    lElZIll EIIlll-iXEZti:
    148.2 136.2 12.0
    12.0
    3.4
    8.6
    200.0 352.4 352.4
    pTM h n. e. Molar ratios: SOj / NO 0.96; 3.51 ;, CGCC / NO
     2.16. CL output 91.02.
    Table 3
    Note. Molar ratios: SOj / NO 0.97; S, / m. - 3.20; CGKK / NO
     2.20; H o / SOj 0.59. Vkod KL 95.0%.
    Take an and o; Molar correspondences: S0, 0.97; S, f / N0 - 3.20; CGKK / NO
     2.20. Exit KJI 90, YA.
    EZti:
    8 Continued
    ten
    336.7 336.7
    148.0 103.1 14.8 148.0 103.1 14.8
    Table 4
    I 1
    1583278
    2.20. Output KP 87,7%.
    Note. Molar ratios: SOj / NO 0.95; S / NO 4.46; CGKK / NO
     2.19; HjO / SO.j 0.58. The output of KL is 91.0%.
    12 Continue1 {Table 7
    Table 9
    13
    285, A
    20.1
    97.4
    Examples h and e. Molar ratios: 0.95; S j / NO 4.46; CGKK / NO
     2.19. Y1 yield 87.0%.
    Note. Molar ratios: SO, / t 1.00; S. Y / NO 3.54; CGKK / NO
     2.43; H o / SOj 0.58. The output CL is 95.0%.
    I / j
    t a b l and c a About
    Table 11
    Table
    15
    1588278
    : li;:; tz: i: i :::: T: Liz :: ii: ni :: T: L :: i
    one
    7 2706
    t4Q2 3906
    3906 3716 190
    203 2A4
    244
    63
    181
    4029 4029
    4029 4029
    220 1639
    1593
    em no. e. Molar ratios: SOj / NO 1.00; / NO 3.54; Cgcc / no 2.43. The output of CL is 91%.
      SHS /
     Itltht
    lzhi /
    .ETC
    I I I I I /
    ms 3
    sixteen
    Continued table 12
    : ni :: T: L :: i
    7 2706
    ten

    3466 3108
    3108
    2196 2196 2196 2196
    160 280 280 280
    Itltht
    Shzhi /
    .ETC
    I I I I I / "
    ms 3-j.
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    同族专利:
    公开号 | 公开日
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    MX165249B|1992-11-04|
    BR8601349A|1986-12-02|
    ES553304A0|1987-05-16|
    AR241134A2|1991-11-29|
    IT8520089D0|1985-03-27|
    EP0197408A2|1986-10-15|
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    ES8705859A1|1987-05-16|
    IN167050B|1990-08-25|
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    引用文献:
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    US3022291A|1962-02-20|cuhno |
    GB1050547A|1963-03-06|
    IT723201A|1964-05-15|
    IT1125603B|1979-11-02|1986-05-14|Snia Viscosa|PROCEDURE FOR THE PREPARATION OF OMEGA-LACTAMS, IN PARTICULAR CAPROLATTAME|
    US4349437A|1980-07-24|1982-09-14|Rickett David A|Automatic and continuous chemical feed system|US4775527A|1986-06-27|1988-10-04|Gaf Corporation|Compositions used in permanent alteration of hair color|
    US4793994A|1986-06-27|1988-12-27|Gaf Corporation|Compositions used in permanent structure altering of hair|
    US5153307A|1991-07-31|1992-10-06|International Business Machines Corporation|Stabilization of polyamide alkyl ester solutions|
    US5284357A|1991-11-01|1994-02-08|Tinkler Michael R|Apparatus and method for damping deflections and vibrations in skis|
    CN100374418C|2006-03-01|2008-03-12|湘潭大学|Synthesis of caprolactam and its oligomer|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    IT2008985A|IT1187655B|1985-03-27|1985-03-27|PROCEDURE FOR THE PREPARATION OF W-LATTAMI, IN PARTICULAR CAPROLATTAME|
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