针对现有季铵盐N263合成工艺毒性大、转型步骤冗长和设备要求高等问题，以三辛基甲基溴化铵为催化剂、碳酸二甲酯(DMC)为季铵化试剂替代传统的氯甲烷与N235在高压反应釜中合成甲基碳酸酯季铵盐，考察反应物摩尔比、反应温度、溶剂、催化剂和反应时间等主要因素对叔胺转化率的影响。结果表明：在最适宜的条件下，当N235与碳酸二甲酯的摩尔比为1：5.6、甲醇与N235的体积比为1：2、三辛基甲基溴化铵催化剂为反应体系总质量的5%、反应温度为110℃、反应时间为8 h时，叔胺转化率可达99.39%；该甲基碳酸酯季铵盐用3 mol/L H 2 SO 42-4SO酸洗、0.6 mol/L NaOH碱洗，转型为季铵盐；用转型后的2-4SO 季铵盐按以下比例配成有机相：50%转型后的2-4SO 季铵盐+30%仲辛醇+20%磺化煤油(体积分数)，在25℃下用该有机相萃取钨矿苏打浸出模拟料液(105.7 g/L WO 3，100 g/L Na 2 CO 3)，相比O/A=2：1，萃取时间为5 min时，单级萃钨率可达80.88%，有机相饱和萃钨量(以WO 3计)为83.92 g/L。
The synthesis of methyl carbonate quaternary ammonium salt in high pressure reactor was investigated by using dimethyl carbonate (DMC) substituting for traditional methylene chloride as alkylating agent, tri-n-octylmethylammonium bromine as catalyst and N235 as tertiary amine material to solve the problems in the existing quaternary ammonium salt extractant N263, such as toxic synthesis process, long transformation step, and high equipment requirements. The influences of molar ratio of reactants, reaction temperature, solvent, catalyst and reaction time on the conversion rate of tertiary amine were inspected. The results show that under the optimal conditions of molar ratio of dimethyl carbonate to N235 5.6, volume ratio of methanol to N235 1:2, catalyst 5% (mass fraction for reaction system), temperature 110 ℃, reaction time 8 h, the highest conversion of tertiary amine can reach 99.39%. The product was totally transformed to quaternary ammonium salt after the treatment of 3 mol/L H2SO4 - 24 SO and 0.6 mol/L NaOH. Under conditions of extraction temperature 25 ℃, phase ratio (O/A) 2:1, extraction time 5 min, with 50% quaternary ammonium salt in 30% sec-octyl alcohols and 20% sulphonated kerosene as extractant (volume fraction), the single-stage extraction rate of tungsten from autoclave-soda leach solution of scheelite which contains 105.7 g /L WO3 and 100 g/L Na2CO3 is 80.88%, and the saturated loading capacity(for WO3) of organic reaches 83.92 g/L.
参考文献
| [1] | 袁承业;邹震中;陈耀焕;夏家治 周莉影 涂通源 严金英 林芳乐 .季铵型萃取剂 N263 的合成研究[J].化学试剂,1984,6(01):1-7. |
| [2] | 朱茂电,刘绍英,贾树勇,王公应.碳酸二甲酯甲基化反应催化剂和反应机理研究进展[J].化学试剂,2012(07):615-619. |
| [3] | 姜获秋,周淑晶.碳酸二甲酯作甲基化试剂合成取代苯甲醚的研究进展[J].化学工程与装备,2012(08):151-154. |
| [4] | 郑园,田军,吴立霞,谭美珊,刘小平,杨乐敏,倪春林.溴化苄基取代吡啶类季铵盐的制备和抗菌性能[J].化学研究与应用,2010(03):370-373. |
| [5] | 赵丽娟,韩相恩,钱露露.甲基化试剂碳酸二甲酯的应用研究[J].化工中间体,2011(12):44-46. |
| [6] | 李波,宋淑群,汪志国.碳酸二甲酯发展现状及前景[J].精细石油化工进展,2011(06):38-41. |
| [7] | 舒婷,李光兴.碳酸二甲酯作甲基化试剂的研究进展[J].化工中间体,2008(01):20-23. |
| [8] | 董燕敏,尹振燕,程琦,陈兴权,赵天生.碳酸二甲酯作甲基化试剂合成2,6-二氯苯甲醚[J].精细化工,2010(07):667-671. |
| [9] | 谢建刚,吴承尧,李树白,权静,郑妍,朱利民.碳酸二甲酯作甲基化试剂催化合成2-甲硫基苯并噻唑[J].化学试剂,2010(09):779-782. |
| [10] | 耿涛,李秋小,於水新,姜亚洁,王伟.甲基碳酸酯季铵盐及其衍生物的研究进展[J].日用化学工业,2010(01):44-47. |
| [11] | 李秋小;李运玲;张明慧;李明 候素珍 李永胜 .一种脂肪叔胺季铵盐衍生物的合成方法[P].中国,CN 1939889A,2008-04-23. |
| [12] | Bao-cai Xu;Fu Han;Jin-huan Shui .Synthesis and Characterization of Lauryl Trimethyl Ammonium Surfactants with New Counteranion Types[J].Journal of Surfactants and Detergents,2009(4):351-354. |
| [13] | 耿涛,李秋小,姜亚洁,王伟.甲基碳酸酯季铵盐的合成与表征[J].精细化工,2010(06):537-541. |
| [14] | Hongqin Liu;Fei Li;Baocai Xu .Synthesis, Characterization and Properties of New Lauryl Amidopropyl Trimethyl Ammoniums[J].Journal of Surfactants and Detergents,2012(6):709-713. |
| [15] | Yajie Jiang;Tao Geng;Qiuxiao Li .Synthesis of Quaternary Ammonium Salts with Novel Counterions[J].Journal of Surfactants and Detergents,2012(1):67-71. |
| [16] | 卢涌泉;邓振华.实用红外光谱解析[M].北京:电子工业出版社,1989:176-178. |
| [17] | 邬震中;严金英;蔡起秀;周莉影 潘柏熙 陈耀焕 .季铵型N263的基本性能[J].化学试剂,1984,6(01):8-11. |
| [18] | 陈耀焕;盛怀禹 .季铵盐萃取剂N263的纯化、转型和分析研究[J].化学试剂,1984,6(01):12-15. |
| [19] | 关文娟,张贵清.用季铵盐从模拟钨矿苏打浸出液中直接萃取钨[J].中国有色金属学报,2011(07):1756-1762. |
| [20] | 张贵清 .从碱性介质中萃取钨制取纯钨酸铵溶液的研究[D].中南工业大学,1994. |
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