• 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 polysulphide is heated with a substance capable of dissolving elemental sulphur. After cooling, the polysulphide reduced to a lower numbver of S atoms is separated from the substance, which can be recovered. An important use consists in converting the polysulphide to the form of dimethyl disulphide, the solvent used for the dissolution of sulphur deposited in conduits, particularly those used for natural gas.
    公开号:SU1452478A3
    申请号:SU4027221
    申请日:1986-03-24
    公开日:1989-01-15
    发明作者:Лаба Ив；Деграншан Ги
    申请人:Сосьете Насьональ Елф Акитэн (Продюксьон) (Фирма)；
    IPC主号:
    专利说明:


    cm
    The invention relates to a process for the decomposition of dialkyl polysulfides to i sulfur with reduced sulfur content, which can be used in dissolving sulfur deposited on the walls of pipelines, i.e. in the operation of wells with g supersulphonated natural gas. The aim of the invention is to develop a method that allows solvent to dissolve sulfur deposited on the walls of pipelines, and to use it in the operation of supersulphurized natural gas wells, which is achieved by decomposing dialkyl poly sulfides with 3-8 carbon atoms by treating hydroxide, sulfide or alkali metal or ammonium sulfite or alkali metal mercaptide, or aliphatic amine at 70-C, followed by separation of the decomposed polysulfide, preferably within 1-3 hours. m in the case of using g of ammonium compound or amine is recovered by heating at 120-150 C.
     Example 1. The use of NaOH.
    Into a reactor equipped with a stirrer and a thermostat, 80 g of polysulfide j are introduced, the average value of x of which is 6.5. 120 g of an aqueous 35% sodium hydroxide solution are added thereto. Thus, 1.05 mol of NaOH per 0.34 mol of polysulfide is present.
    The whole mixture is kept at 80 ° C and with stirring for 1 hour. After cooling to room temperature, the organic phase weighing 30 g is decanted, the average composition of which is as follows: - CH, (0.3 mol) Sodium hydroxide removes 4.4 atoms sulfur, back to the condenser polysulfide in the form of a compound very close to dimethyl disulfide. This last is obtained in a yield of 0.3: 0.34 0.88 or
    88%.
    PRI mme R 2. The use of mercaptide.
    The method of operation is the same as in example 1, but sodium hydroxide is replaced with an aqueous solution of sodium methylthiolate. This solution is obtained by the absorption of methyl mercatena in a 35% solution of ri hydroxide.
    For the same amount of 80 g Crr h J-CH3 or 0.34 mol, 0.6 mol CHjSNa is used.
    After heating and decanting, 50 g of an organic phase with an average composition of 1 or 0, 51 mol, is obtained. As in the previous example, the polysulfide results in a composition very close to dimethyl disulfide, the yield
    upon receipt of the latter, it is 0.51: (0.34-1-0.60 / 2) 0.797 or 79.7%.
    Treatment with sodium methyl thiolate 5 makes it possible to predominantly obtain dimethyl disulfide under the reaction conditions, therefore, it is possible to create an additional solvent supply by using mercaptide, which leads to the formation of fresh dimethyl disulfide, by completely breaking the polysulfide.
    PRI me R 3. Use of sodium sulfite.
    5 80 g or 0.34 mol of the same mixture of polysulfides with x 6.5 as in the previous examples, are introduced into the reaction with 274 g of an aqueous 35% solution of Ka-hNW. (0.76 mol) 0 at for 2 hours
    After cooling to room temperature and decantation, 46 g of CHj-Sj-CH or 0.34 mol of polysulfide are found.
    The yield of reduced polysulfide is 100% relative to the starting polysulfide. Although in this operation, the reduction of x is only 6.5 to 3.3, it is possible to reduce its 4Q and more by using more sulfite, namely 1 mole.
    PRI me R 4. The use of ammonium sulfide.
    Under the conditions of Example 1, a mixture of 80 g of 45 of the same polysulfides with x 6.5 or 0.34 mol was reacted with an aqueous 0.3 M solution of ammonium sulfide. This solution is obtained by exposure to hydrogen sulphide f. on ammonia solution.
    After the reaction, cooling and decantation, an organic phase weighing 42 g is formed. -CH (0.295 mol). . The yield of polysulfide with S is 0.295: 0.34 0.867. Or 86.7%. It can be destroyed up to a sulfur content of about 8-2 using about 0.45 mol (NH4) .j.S on P, 34 mol of the initial polysulfide.
    35
    55
    PRI me R 5. Use ammonium sulfide at a higher temperature.
    Example A is repeated, but the temperature is also a reaction time of 1 hour.
    Obtain 33 g of the average composition of CHj - 81,7- CHj or 0.28 mol. The yield for this product is 0.28: 0. It can be seen that by adjusting the ratio of the reactants accordingly, the temperature and the duration of the heating, the polysulfide can be re-condensed to any desired degree.
    Example Ethyl Amine Use.
    In a closed reactor with stirring at 704 for 3 hours, 80 g of dimethyl polysulfide CHj-CHj or 0.34 mol are injected into the reaction with 100 ml of an aqueous solution of 0.5 mol of ethylamine. After cooling and decantation, 36 g of dimethylpolysulfide CH3 (0.25 mol) are obtained. This corresponds to a yield of 0.25: 0.34- 75%. The reverse condensation can be reduced to Sii values from 0.7 mol of ethylamine within .4 h. The amine is recovered by heating the residue, separated from the polysulfide, at 120-150 ° C.
    PRI me R 7. The use of ethylenediamine.
    The operations of Example 6 are repeated with ethylene diamine instead of ethylene. Destroyed product corresponds to the average composition
    CH ,, 8,; SDS J.
    Example8. Regeneration of polysulfide containing physically dissolved sulfur.
    3.2 g of sulfur (0.1 mol) are dissolved in 100 g of dimethyl polysulfide CHj-S-CH3 (or 0.43 mol). The resulting solution was reacted with 250 ml of an aqueous solution of ammonium sulfide, obtained by introducing hydrogen sulfide in 250 ml of 2N ammonia solution. After reaction at 80 ° C with stirring for 1 hour, - cooling and decanting, 42 g of the organic phase formed in the form of CH3-S ,, 5- CH3 (0.38 mol) are recovered. This organ of the comb phase does not contain more physically dissolved sulfur.

    1. It is 0.38: 0.43 - or 88%.
    52478
    The output of the restored full sulfide to S, 0,8
    PRI me R 9. Recycling cyclically recycled regenerated polysulfide.
    3000 g of fresh dimethyl disulphide 10 fide was introduced into a stainless steel reactor together with 2000 g of elemental
    sulfur, the whole set is heated at. stirring with for 2 hours. Then 2300 g of an aqueous solution of ammonium sulfide, 15 containing 15.7 mol of (NH4) 2S, obtained by reacting hydrogen sulfide with an aqueous solution of ammonia, are added thereto. The mixture is then heated at 90 ° C and stirred for 3 hours. After lagging and separating the aqueous layer, ammonium polysulfide, which is formed, recovered, that organic layer of dimethyl polysulfide. The latter is reused for the new 25 dissolution of sulfur, the work as indicated above, the third such cycle was subsequently carried out.
    The table below gives the results of these three successive solutions with recovery of decomposing polysulfide.
    Despite the fact that the experiments were carried out without special precautions, they gave good results as shown by
    20
    t pours With - about s.
     the degree of solvent and sulfur recovery (0.86 - 0.98).
    PRI me R 10. The organic phase obtained after the 3rd cycle ° of Example 9, i.e. mol CHjSxCHv, where X is 2.9, mixed with 1900 g of an aqueous solution containing. 13 mol (NH) .S. The mixture is heated at 90 ° C for 3 hours with stirring for 45 without the addition of sulfur. After settling, the organic phase is separated from, where h is 2.4
    Experience has shown that by decomposing 5Q shea polysulfide, it can be decomposed even more without the addition of sulfur.
    Thus, the proposed method allows it to be used in the operation of supersulphurized natural gas wells to decompose polysulfides, i.e. to the dissolution of sulfur deposited on the walls of pipelines.
    514524786
    权利要求:
    Claims (3)
    [1]
    The invention of the comic amine at 70-1 ° C with the last. , ,, blowing a branch of decomposed polyI. Decomposition Method of Dialkyl Sulfide
    lysulfides with 3-8 sulfur atoms to
    [2]
    2. Method pop. 1, distinguishing between sulfides with a reduced content and with the fact that, in the case of using for drilling wells, the formation of an ammonium compound or
    gin with hypersulfonated natural amine; they are recovered by heating with gas, characterized in that at 120-150 ° C. that decomposition is carried out by hydroxide,
    sulfide or alkali sulfite
    [3]
    3. The method according to claim 1, about tl and h and yu,., Or ammonium or mercapti-yi, and so that the process is conducted with an alkali metal or aliphatic wire for 1-3 h.
    total number of g-atoms
    sulfur142.6 131 122
    Received
    g-sulfur atoms 44.1 42.5 38.1
    g-mole NHj21.7 20.3 18.8
    Organic solution
    mole CHjS CHj27.9 27.5 26
    x3.2 3.03 2.9
    total number of g-atrms
    sulfur 133.4 126 P3,5
    The degree of regeneration of the solvent 0, 87 0,985 0,945
    Sulfur recovery rate 0.935 0.96 0.86 NH recovery rate. 0,69 0,725 0,73
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    同族专利:
    公开号 | 公开日
    DE3610066A1|1986-09-25|
    CA1265821A|1990-02-13|
    US4827040A|1989-05-02|
    DE3610066C2|1995-11-30|
    FR2579203A1|1986-09-26|
    FR2579203B1|1987-05-29|
    CN86101929A|1986-09-24|
    CN1007350B|1990-03-28|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2435732A|1944-12-18|1948-02-10|Pure Oil Co|Refining hydrocarbon liquids|
    DE1157569B|1962-04-06|1963-11-21|Gewerkschaft Elwerath|Process to prevent sulfur deposition in the riser pipes when pumping natural gases containing hydrogen sulfide that contain dissolved sulfur|
    FR1358398A|1962-11-20|1964-04-17|Aquitaine Petrole|Manufacture of organic disulfides|
    DE1296586B|1966-12-27|1969-06-04|Gewerkschaft Elwerath|Process to prevent sulfur deposits in the riser pipes of natural gas probes|
    US3474028A|1967-07-10|1969-10-21|Wintershall Ag|Process for the extraction of sulfur from a mineral oil-sulfur solution|
    US3489677A|1967-11-20|1970-01-13|Shell Oil Co|Removal of elemental sulfur contaminants from petroleum oils|
    US3531160A|1968-09-18|1970-09-29|Phillips Petroleum Co|Production of sour gas-sulfur wells employing a sulfur solvent|
    US3846311A|1971-09-07|1974-11-05|Amoco Prod Co|Method for removing elemental sulfur from wells and flowlines|
    US4033410A|1976-02-20|1977-07-05|Shell Oil Company|Monoethanolamine process for sulfur removal from circulating oil used in sour gas wells|
    US4239630A|1978-11-29|1980-12-16|Standard Oil Company |Method for dissolving sulfur deposits rapidly|
    US4379490A|1981-04-22|1983-04-12|Standard Oil Company |Method for removal of asphaltene depositions with amine-activated disulfide oil|
    US4656266A|1985-04-30|1987-04-07|The Goodyear Tire & Rubber Company|Process for preparing N-polythiodimorpholines|
    US4663455A|1986-09-04|1987-05-05|The Goodyear Tire & Rubber Company|Process for the preparation of N,N'-tetrathiodimorpholine|AU597060B2|1986-06-25|1990-05-24|Atochem North America, Inc.|Process for desulfurizing organic polysulfides|
    US5242672A|1986-06-25|1993-09-07|Elf Atochem North America, Inc.|Process for removing sulfur from organic polysulfides|
    US4804485A|1987-05-08|1989-02-14|Pennwalt Corporation|Polyalkyleneoxyamine catalysts for dialkyl disulfides and/or polysulfides used in dissolving sulfur|
    US5186848A|1988-10-11|1993-02-16|Elf Atochem North America, Inc.|Preparing sulfur solvent compositions comprising treating a sulfide and polyalkyleneoxyamine or polyalkyleneoxypolyamine mixture with an alkylamine or alkanolamine|
    US5091593A|1989-05-26|1992-02-25|Atochem North America, Inc.|Process for removing sulfur from organic sulfides|
    US5174922A|1989-11-13|1992-12-29|Ethyl Petroleum Additives, Inc.|Reducing copper corrosiveness of organic polysulfides|
    US5208382A|1992-01-29|1993-05-04|Ethyl Petroleum Additives, Inc.|Reducing copper corrosiveness of organic sulfides|
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    US5457234A|1994-06-20|1995-10-10|Phillips Petroleum Company|Process for treating organic polysulfide compounds|
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    法律状态:
    2005-10-20| REG| Reference to a code of a succession state|Ref country code: RU Ref legal event code: MM4A Effective date: 20040325 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR8504393A|FR2579203B1|1985-03-25|1985-03-25|PROCESS FOR DEGRADATION OF ALKYLIC POLYSULFIDES TO LOWER SULFUR RANK POLYSULFIDES|
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