十六烷基二苯醚二磺酸钠生产技术研究
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摘要
经过研究,开发出了以α-十六烯烃和二苯醚为原料的烷基化新工艺。并通过核磁共振氢谱(1~H NMR)、红外光谱(IR)、液相色谱-质谱联用(LC-MS-ELSD)等方法确定了烷基化产物为单十六烷基二苯醚。通过实验研究选择出了最佳烷基化反应条件,其摩尔转化率达到60.9%。单十六烷基二苯醚经发烟硫酸磺化、中和得到十六烷基二苯醚二磺酸钠混合物,经检测活性物含量为58.44%(平均分子量按540)。通过对十六烷基二苯醚二磺酸钠进行滴定分析,平均分子量按598计算,活性物含量达到58.44%。适宜反应条件为:反应温度为90℃,以发烟硫酸为磺化剂,C16α-烯烃与二苯醚摩尔比在1.0:1.6的条件下,反应6个小时。同时研究了十六烷基二苯醚二磺酸钠与重烷基苯磺酸盐复配使用的强碱及弱碱化三元驱油体系的界面活性情况,弱碱三元驱油体系是以两种表活剂相互复配为主体方案,以寻找与重烷基苯磺酸盐可相互配伍的新型表活剂为研究方向,通过摸索最佳的复配比例、总表活剂浓度及碱的浓度等参数,使得弱碱体系的界面张力及热稳定性等各项指标满足油田的要求,最终实现三元复合驱的弱碱化。为十六烷基二苯醚二磺酸钠作为驱油用表活剂的工业化应用进行了工业化尝试。
Through research, new process was developed with 16-alpha olefins and the dephenyl ether being raw materials. Furthermore, alkylation product was identified to be sodium hexadecyl dephenyl ether disulfonate by nuclear magnetic spectrum(1H NMR), IR spectrum(IR)and liquefied chromatogram and mass spectrum (LC-MS-ELSD). Through experimental studies, the optimum parameters for the synthesis reaction were chosen. Mole yield rate reached up to 60.9%. The alkylation product was transformed to be final product (C_(16-MADS)) through sulfurization and neutralization reactions. The surface active agent content was as much as 58.44 %(molecular weight 540 on average). The optimum reaction parameters: 90℃reaction temperature, vitriol as the sulfuric agent, 1:1.6 mole ratio between 16-alpha olefins and the dephenyl ether, 6h reaction duration. The article also executed researches on the complex systems of HABS and C_(16-MADS). In detail, the complex system was designed to be weak-alkalization oriented and low concentration ASP oriented. In search of optimum complex parameters, other co surfactants were utilized to match up with HABS and C_(16-MADS). Finally after optimization, the concentration of alkali, surfactants, the ideal mole ratio between reagents and other critical parameters were identified. As a result, the performance of the complex system all conformed to the criteria of oilfield in term s of interfacial properties, heat&salt tolerance and stability. In conclusion, it helps to realize the weak-alkalization and non-alkalization of the complex system. It also promotes the industrialization of the C_(16-MADS) as surfactant for oilfield.
Through research, new process was developed with 16-alpha olefins and the dephenyl ether being raw materials. Furthermore, alkylation product was identified to be sodium hexadecyl dephenyl ether disulfonate by nuclear magnetic spectrum(1H NMR), IR spectrum(IR)and liquefied chromatogram and mass spectrum (LC-MS-ELSD). Through experimental studies, the optimum parameters for the synthesis reaction were chosen. Mole yield rate reached up to 60.9%. The alkylation product was transformed to be final product (C_(16-MADS)) through sulfurization and neutralization reactions. The surface active agent content was as much as 58.44 %(molecular weight 540 on average). The optimum reaction parameters: 90℃reaction temperature, vitriol as the sulfuric agent, 1:1.6 mole ratio between 16-alpha olefins and the dephenyl ether, 6h reaction duration. The article also executed researches on the complex systems of HABS and C_(16-MADS). In detail, the complex system was designed to be weak-alkalization oriented and low concentration ASP oriented. In search of optimum complex parameters, other co surfactants were utilized to match up with HABS and C_(16-MADS). Finally after optimization, the concentration of alkali, surfactants, the ideal mole ratio between reagents and other critical parameters were identified. As a result, the performance of the complex system all conformed to the criteria of oilfield in term s of interfacial properties, heat&salt tolerance and stability. In conclusion, it helps to realize the weak-alkalization and non-alkalization of the complex system. It also promotes the industrialization of the C_(16-MADS) as surfactant for oilfield.
引文
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[3] Ying-chech chiu, et al. Process for displacing oil using aqueous anionic surfactant systems containing aromatic ether polysulfonates[P]. US: 3945437, 1975-03-26.
[4] Dawe Rober, et al. Gas-drive petroleum recovery using alkylated diphenyl oxide-based mobility control agents and foam -forming amphother betaine and sultaine surfactants[P]. US: 5 203411, 1993-04-20.
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[14]Dawe Bob, Oswald Tom. Reduced adsorption and separation of blended surfactants on sand and clay[J]. J Can pet Techno, 1991, 30(2):133-137.
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[16]金燕.用APCI/ESILC/MS跟踪烷基二苯醚磺化反应[J].质谱学报, 2001, 22(01):3-5.
[17]王玉丰,陆建辉,李辉辉.烷基二苯醚二磺酸盐的研究进展[J].精细与专用化学品, 2007,07) :23-25.
[18]冯玉军,孙玉海,陈志,等.双子表面活性剂结构对性能的影响[J].日用化学工业,2007, (02):22-26.
[19]赵国玺,朱步瑶.表面活性剂作用原理[M] .北京:中国轻工业出版社,2003,698-710.
[20]刘杨,邸进申.Friedel-Crafts反应催化剂的研究进展[J].精细石油化工,2001,6:19-22.
[21]黄向红,曹高库,陈燕.膨润土上负载AIC13固体酸催化剂的制备[J].工业催化,2001,9(2):24-26.
[22]刘祥.固体超强酸催化合成十二烷基二苯醚磺酸盐[J].四川化工,2004,10(4):10-13.
[23]寇元,朴玲钮,付晓,等.一种合成直链烷基的方法[P].CN:1524839A.
[24]徐军,许虎君,黄辉等.十二烷基苯醚磺酸盐的合成与表面性能研究[J].日用化学品科学,2000,23(l):71-72.
[25]苏瑜,马德浮,薛仲华.十二烷基二苯醚二磺酸钠的合成[J1.精细化工,2002,19(8): 443-445.
[26]许芳萍,方银军,高慧等.烷基二苯醚双磺酸盐的合成与性能[J].江南大学学报(自然科学版),2006,5(2):216-219.
[27]梁金龙,许虎君,奚文红,等.烷基二苯醚二磺酸钠与普通离子型表面活性剂的复配研究[J] .日用化学工业,2005,35(1):l-5.
[28]许虎君,吕春绪,叶志文,等.十六烷基二苯醚双磺酸钠溶液状态的研究[J1.2004(第八届)国际表面活性剂和洗涤剂会议.
[29]杨福廷.十二烷基二苯醚二磺酸钠预处理对脱墨浆漂白的影响[J].精细化工,2005, 22(2):40-42.
[30]Huo Q. S., et al. Generalized synthesis of periodic surfactant inorganic composite ma- terials[J]. Nature, 1994, 368: 317-321.
[2] Dawe Bob, Oswald Tom. Reduced adsorption and separation of blended surfactants on sand and clay[J]. J. Can. Pet. Technol., 1991, 30(2): 133-137。
[3] Ying-chech chiu, et al. Process for displacing oil using aqueous anionic surfactant systems containing aromatic ether polysulfonates[P]. US: 3945437, 1975-03-26.
[4] Dawe Rober, et al. Gas-drive petroleum recovery using alkylated diphenyl oxide-based mobility control agents and foam -forming amphother betaine and sultaine surfactants[P]. US: 5 203411, 1993-04-20.
[5]魏文珑,等.烷基二苯醚二磺酸钠的合成[J] .日用化学工业, 2006,36 (3):196-198.
[6] ROSEN MJ, et al. Synergism in binary mixture of surfactants [J]. Journal of Colloid and Interface Science, 1993, 157 (1): 254-259。
[7]牛金平,董万田,韩向丽.烷基二苯醚双磺酸盐类表面活性剂的多功能性和应用前景[J].日用化学品科学,2002,25(3):39-41.
[8]孟明扬.不对称金属络合染料C.I.酸性棕355的合成[J].染料与染色,2004,4(1): 43-46.
[9]宋光复,等.甲苯磺化反应工艺与设备的研究[J].化学反应工程与工艺,1998,14(2):2-6.
[10]周晴中.磺化反应和技术[J].精细化工,1995,12,(3):59-63.
[11]Acobson, Stephan Ernest. Regioselective.US6384271,2002.
[12]赵剑曦.新一代表面活性剂[J].化学进展,1999,1(4):345-357.
[13]牛金平.新型表面活性剂的结构特点与物化性能[J] .日用化学品科学,2000,23 (2):1-4.
[14]Dawe Bob, Oswald Tom. Reduced adsorption and separation of blended surfactants on sand and clay[J]. J Can pet Techno, 1991, 30(2):133-137.
[15]Dawe Rober, et al. Gas-drive Petroleum recovery using alkalized diphenyl Oxide-based mobility control agents and foam forming amp other betaine and sultaine surfactants[P]. UP: 5203411, 1993-04-20.
[16]金燕.用APCI/ESILC/MS跟踪烷基二苯醚磺化反应[J].质谱学报, 2001, 22(01):3-5.
[17]王玉丰,陆建辉,李辉辉.烷基二苯醚二磺酸盐的研究进展[J].精细与专用化学品, 2007,07) :23-25.
[18]冯玉军,孙玉海,陈志,等.双子表面活性剂结构对性能的影响[J].日用化学工业,2007, (02):22-26.
[19]赵国玺,朱步瑶.表面活性剂作用原理[M] .北京:中国轻工业出版社,2003,698-710.
[20]刘杨,邸进申.Friedel-Crafts反应催化剂的研究进展[J].精细石油化工,2001,6:19-22.
[21]黄向红,曹高库,陈燕.膨润土上负载AIC13固体酸催化剂的制备[J].工业催化,2001,9(2):24-26.
[22]刘祥.固体超强酸催化合成十二烷基二苯醚磺酸盐[J].四川化工,2004,10(4):10-13.
[23]寇元,朴玲钮,付晓,等.一种合成直链烷基的方法[P].CN:1524839A.
[24]徐军,许虎君,黄辉等.十二烷基苯醚磺酸盐的合成与表面性能研究[J].日用化学品科学,2000,23(l):71-72.
[25]苏瑜,马德浮,薛仲华.十二烷基二苯醚二磺酸钠的合成[J1.精细化工,2002,19(8): 443-445.
[26]许芳萍,方银军,高慧等.烷基二苯醚双磺酸盐的合成与性能[J].江南大学学报(自然科学版),2006,5(2):216-219.
[27]梁金龙,许虎君,奚文红,等.烷基二苯醚二磺酸钠与普通离子型表面活性剂的复配研究[J] .日用化学工业,2005,35(1):l-5.
[28]许虎君,吕春绪,叶志文,等.十六烷基二苯醚双磺酸钠溶液状态的研究[J1.2004(第八届)国际表面活性剂和洗涤剂会议.
[29]杨福廷.十二烷基二苯醚二磺酸钠预处理对脱墨浆漂白的影响[J].精细化工,2005, 22(2):40-42.
[30]Huo Q. S., et al. Generalized synthesis of periodic surfactant inorganic composite ma- terials[J]. Nature, 1994, 368: 317-321.