• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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  • 优先权
    • 专利摘要:
    1. METHOD OF OBTAINING META OF SULFOHLORIDE by reacting dime thyl disulfide with chlorine in the presence of a concentrated solution of hydrochloric acid in a homogeneous medium at natural temperature, separating the target product by decantation and recycling the hydrochloric acid solution, characterized in that, in order to improve the performance of the process, the interaction lead by emulsifying dimethyl disulfide in a concentrated hydrochloric acid solution to form an emulsion with droplets with a diameter of 1–20 µm through which chlorine is passed. The reaction mixture was continuously recirculated from 2/3 to 5/6 of its volume between the reaction zone and the decantation zone, the mixture was not allowed to pass through the cooling system at such a rate, and phase separation did not occur. 36 /,
    公开号:SU1176835A3
    申请号:SU813290049
    申请日:1981-05-14
    公开日:1985-08-30
    发明作者:Гонгора Анри；Турнье-Лассерв Жак
    申请人:Сосьете Насьональ Елф Акитэн (Продюксьон) (Фирма)；
    IPC主号:
    专利说明:

    2. The POP.1 method is different from the fact that the process is carried out in the presence of a surfactant such as tert-dodecyl polyethylene glycol thioether.
    3. The method according to claims 1 and 2, about tl and that decantation is carried out in two vessels, of which the second is under reduced pressure.
    The invention relates to an improved method for the preparation of methanesulfonyl chloride, which is used as an intermediate product in various organic syntheses.
    The aim of the invention is to increase the productivity of the process.
    The drawing is a process flow diagram.
    The housing 1 of the emulsifier, equipped with a stirrer 2, may be, for example, a turbo-mixer. The starting materials are injected continuously into the emulsifier, the disulfide via line 3, the hydrochloric acid solution or water through line 4, and they are mixed vigorously with the aid of a mixer 2 in order to obtain a highly dispersed emulsion. To complete the formation of the emulsion, the pump 5 continuously pumps out the liquid from the bottom of the apparatus and returns it via conduit 6 to the upper part of the emulsifier.
    The pump 7 delivers the emulsion with a certain continuous flow through the pipe 8 to the upper part of the reactor 9, from which chlorine also flows through the pipeline 10. The reactor 9 is equipped with a double cooling jacket 11 and a stirrer 12,
    At least a large part of the reaction takes place in the reactor 9, its contents are maintained at one level and are continuously removed through conduit 13 by means of a pump 14, and then pass through conduit 15 of the heat exchanger 16, designed for rapid circulation, preventing separation of the resulting sulfonyl and favorable heat transfer. When the temperature reaches the desired value and the reaction ends in the exchanger 16, the fluid moves through conduit 17 to the first
    decanter 18, the bottom of which is connected via conduit 19 with receiver 20 for the sulfonyl obtained.
    In order to keep the reaction medium in a state of homogeneous emulsion, which does not tend to split into two layers in the exchanger 16, there is an excessive recirculation through tap 21 before entering the first decanter 18. Thus, a relatively small part of the liquid entering through conduit 17, is introduced into decanter 18; most, or from 5/6 to 2/3 of the volume, is directed along the outlet 21: To the line 13 or to the reactor 9 for re-passage under the action of the pump 14 of the heat exchanger 16.
    From the top of the decanter 18, the overhead liquid phase rises to the second decanter 22, where it completes with the separation of the sulfonyl; from the bottom of the decanter 22, product 23 enters the collection tank 20. The second decanter 22 is under vacuum in order to degass the sky in the aqueous solution and reduce its concentration as an acid; the vacuum is 10-500 mbar; the concentration of the solution after degassing the HCC is about 25-35%. :
    The gases and vapors released in this way from the decanter 22 are directed through conduit 24 to the upper part of the washer ejector (scrubber 25, into which the absorption water playing the role of the working fluid is pumped through conduit 26; the ejector 25, passes through the pipeline 28 and collects in the receiving tank 27, while a part can be directed through the pipeline 29 to the evaporator 30 to clean it, from where the cleaned HC 6 collects in the tank 3. The aqueous phase with a low sky, outgoing and the decanter 22, is poured through conduit 32 for recirculation partially into the recirculation ring 21-13-14-15-16-17 through conduit 33 with suction by pump 14 and / or introduced into reactor 9; the rest of the liquid passes through conduit 34 to the device 36 for purification and neutralization. In the case where methanesulfonic acid is expected to be recovered, a drain is carried out to a pipeline 34 for the overflow of the solution, which is then introduced into the device for the hydrolysis of methane sulfon chloride for production. Position 36 denotes a device for neutralizing all gaseous and liquid effluents emanating from different parts of the installation. PRI me D 1. Continuous receipt of methanesulfonyl chloride. In the emulsifier 1 of stainless steel with a capacity of 60 liters, the CH 3 CH disulfide with a constant flow rate of 2.5 kg / h, or 26.5 mol / h is introduced through the pipeline 3, and a 25% solution of HC6 with a flow rate of 5% is applied through the pipeline 4. 5.7 kg / h of water, i.e. 317 mole The proportion of water in relation to disulfide, therefore, is 3 times more than in stoichiometry. The process is carried out at room temperature. Pump 5 delivers 1000 l / h, resulting in intensive mixing of the liquid mixture, and the contents of the emulsifier are recycled 17 times (1000: 60 16.66. Thus, a stable highly dispersed emulsion is obtained, 80% of droplets of which have diameters of 1-20 microns. In addition to NSB, the emulsion contains, wt%: CH-% CH j 3, 5%; BUT 68.5. Reactor 9, made of steel, covered inside with glass, has a capacity of 100 L. Pump 7 delivers to the reactor 9, 8, 25 kg of the emulsion per hour; at the same time, a flow rate of 9.4–9.7 kg / h of chlorine gas is directly supplied to the liquid through pipeline 10, equipped with the first of these numbers corresponds to the stoichiometric ratio, the second to the excess of 3%. The mixer 2 with three blades rotates at a speed of 150 rpm. "The temperature of the reaction mixture in the reactor 9 is maintained within 7-10 ° C due to the circulation of the liquid, which enters with temperature, into the double jacket 11. The absolute pressure of 1.5 bar is maintained in the reactor 9. The tubular exchanger 16 of glass-lined steel has a useful capacity of 60 liters; using pump 14 from the reactor 9 with a flow rate of 6–8 m / h, it receives a reaction mixture whose temperature is 5–10 s. The fraction 1–2 m, or 1 / 6–1 / 3 of this flow rate, passes into decanter 18, the rest is the ret circulating mass of mixing along the contour 21–13–14–15–16–17, and this mass partially reaches the lower part and partially the upper part of the reactor 9. The mixture is then subjected to separation in two successively located decanters 18 and 22, of which the resulting sulfonyl is poured over 5.655, 80 kg / h, which corresponds to a yield of 92.5-95%. The hydrochloric acid recovered from the aqueous phase of the decanter 22, purified in the evaporator 30 and collected in the tank 37, is recycled partially into the emulsifier 1 through conduit 35. This produces an aqueous hydrochloric acid solution for preparing the described emulsion. 2-3 kg / h of aqueous liquid from decanter 22 is removed through conduit 24-34-35, with the remainder being recycled to the reaction cycle. The conversion of the original disulfide is almost complete. The resulting crude product has the following composition: Methanesulfonyl chloride 98-98, 5 NSB1-1.5 Methanesulfonic acid 0, 5 Dimethyl disulfide Traces After distillation, 99.8% methanesulfonyl chloride is obtained containing not more than 0.18% HC8 and 100 ppm disulfide. The method also includes the recovery of methanesulfonic acid, which is obtained as a by-product, in the aqueous hydrochloric acid phase.
    Example 2. The operations are the same as in example I, but the acidic solution coming through pipeline 4 contains 0.1% as a surfactant: thioether tert-dodecyl polyethylene glycol (known as NONIOPIK 218) is used as surfactant.
    The solution of disulfide CHjSQCHj with a solution of hydrochloric acid consists of droplets, 80% of which have a diameter of 0.2-5 μm, which provides a faster reaction and easier
    Thus, the proposed method allows to obtain a constant temperature and purity of the obtained product.40 Indeed, whereas in the known method the temperature drops reach 19 ° C and the content of impurities is cooled, allowing 2.75 kg of disulfide per hour instead of 2.5 kg.
    5 Example. 3. Use the same starting materials a as in Example 1, repeating operations with a strong turbulent flow in a manner known per se. The process lasts 72 hours in parallel with the process of Example 1. The temperature at the outlet of the reactor is periodically measured and the product is analyzed for the percentage of impurities. The results obtained are presented in the table.
    It is 0.6-1.4%, the proposed method allows to maintain a stable temperature with an accuracy of 3 ° C and an impurity of 0.4-0.55%, the total yield of methanesulfonyl chloride after 72 hours of operation is 96%, and by a known method - 88%.
    权利要求:
    Claims (3)
    [1]
    1. METHOD FOR PRODUCING METHANESULFOCHLORIDE by reacting dimethyl disulfide with chlorine in the presence of a concentrated solution of hydrochloric acid in a homogeneous environment at room temperature, separating the target product by decantation and recycling a solution of hydrochloric acid, characterized in that, in order to increase the productivity of the process, the interaction is carried out by emulsification of dimethyl sulfide dimethyl sulfide in a concentrated solution of hydrochloric acid to form an emulsion with droplets with a diameter of 1-20 μm, through which chlorine is passed., pr and the reaction mixture is subjected to continuous recirculation from 2/3 to 5/6 of its volume between the reaction zone and the decantation zone, passing the mixture through the cooling system at such a rate that phase separation does not occur.
    X
    SU-, 1176835>
    [2]
    2. The method of Pop. 1, characterized in that the process is carried out in the presence of a β-surfactant, such as tert-dodecylpolyethylene glycol thioether.
    [3]
    3. The method according to PP. 1 and 2, ’characterized in that the decantation is carried out in two vessels, of which the second is under reduced pressure. ·
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    同族专利:
    公开号 | 公开日
    DK215681A|1981-11-17|
    US4699736A|1987-10-13|
    DK166019C|1993-07-12|
    DK166019B|1993-03-01|
    EP0040560A1|1981-11-25|
    EP0040560B1|1983-06-08|
    CA1161063A|1984-01-24|
    BR8103042A|1982-02-09|
    IE811080L|1981-11-16|
    DD158547A5|1983-01-19|
    DE3160413D1|1983-07-14|
    AR228057A1|1983-01-14|
    FR2482591B1|1984-02-17|
    JPS6111944B2|1986-04-05|
    IE51446B1|1986-12-24|
    FR2482591A1|1981-11-20|
    JPS5716857A|1982-01-28|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2277325A|1938-05-05|1942-03-24|Unichem Chemikalien Handels A|Sulphonyl halides|
    US2465952A|1946-06-07|1949-03-29|Allied Chem & Dye Corp|Manufacture of para-nitrobenzene sulfonyl chloride|
    US3248423A|1962-11-30|1966-04-26|Hooker Chemical Corp|Process for preparing alkyl sulfonyl chlorides|
    US3993692A|1966-01-03|1976-11-23|Stauffer Chemical Company|Methane sulfonyl chloride and process of preparation|
    US3626004A|1967-12-07|1971-12-07|Pennwalt Corp|Method of preparing alkyl sulfonyl chloride|
    DE2845918A1|1978-10-21|1980-05-22|Merck Patent Gmbh|METHOD FOR PRODUCING ALKANESULPHONIC ACID CHLORIDES|US4956494A|1987-10-26|1990-09-11|Pennwalt Corporation|Oxidation of thiols, disulfides and thiolsulfonates|
    DE3741309A1|1987-12-05|1989-06-15|Bayer Ag|METHOD FOR PRODUCING TRIFLUORMETHANESULPHONIC ACID CHLORIDE|
    US5035777A|1988-03-07|1991-07-30|Atochem North America, Inc.|Preparation of alkanesulfonyl halides and alkanesulfonic acids|
    US5093029A|1989-08-11|1992-03-03|Atochem North America, Inc.|Breaking emulsions of alkanesulfonyl chlorides in aqueous hydrochloric acid|
    US5583253A|1991-03-27|1996-12-10|Henderson; Phyllis A.|Method of preparing purified alkanesulfonic acid|
    US6066760A|1994-03-31|2000-05-23|Elf Atochem North America, Inc.|Process for the preparation of alkane sulfonic acid and alkane sulfonyl chloride|
    CA2145325A1|1994-03-31|1995-10-01|Steven G. Schon|Pressurized production of alkanesulfonyl chloride and alkanesulfonic acid|
    DE10021865C2|2000-05-05|2002-08-01|Infineon Technologies Ag|Electronic component with a semiconductor chip and electronic component with a test structure on a semiconductor chip and method for their production|
    US6441229B1|2000-06-23|2002-08-27|Phillips Petroleum Company|Process for the preparation of higher-alkane sulfonyl halides|
    CN101863803B|2010-06-10|2013-04-24|湖北星火化工有限公司|Purification method of byproduct hydrochloric acid|
    CN101863804B|2010-06-10|2013-08-14|湖北星火化工有限公司|Preparation method of high-purity methylsulfonyl chloride|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR8010993A|FR2482591B1|1980-05-16|1980-05-16|
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