含硫烟气生产二甲基硫醚流程模拟及优化
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摘要
工业废气中的SO_2是导致雾霾问题的一个重要因素。文章通过大量工艺论证提出了含硫烟气生产高附加值二甲基硫醚的工艺流程及工艺条件,工艺流程包含硫磺工段、硫化氢工段、二甲基硫醚工段。各工段反应转化率均能达到90%以上,反应副产物少,分离过程较简单。最后运用Aspen Plus软件对整个流程进行模拟,分别应用了Rstoic模块、Radfrac模块、flash 2模块等。在二甲基硫醚工段,通过对各塔进料位置、回流比、理论板数等操作参数的优化,确定最佳工艺条件。模拟结果表明:二甲基硫醚年产量为1.2万t,纯度为99.02%,具有良好的经济效益与环境效益,可为含硫烟气资源化处理生产提供理论指导。
SO_2 in flue gas is an important factor causing fog and haze problem. So it is urgent to treat waste gas resource fulization. This paper put forward the process of dimethyl sulfide which had high added value from SO_2 in flue gas. The process included three sections: sulfur section, hydrogen sulfide section, dimethyl sulfide section. The conversion rate of each reaction can reach more than 90%. The separation process is simple with few reaction by-products, simulated by Rstoic, Radfrac and flash 2 blocks, etc of Aspen Plus. In the dimethyl sulfide section, the operation parameters such as the feed temperature, the reflux ratio and the theoretical plate number have been optimized by using sensibility block to determine the best process conditions. The simulation results show that the annual production of dimethyl sulfide is 12000 t with the purity of 99.02 %, it has good economic benefit and nice environmental benefit, and it can provide some advice for the disposal of SO_2 in flue gas resource fulization.
SO_2 in flue gas is an important factor causing fog and haze problem. So it is urgent to treat waste gas resource fulization. This paper put forward the process of dimethyl sulfide which had high added value from SO_2 in flue gas. The process included three sections: sulfur section, hydrogen sulfide section, dimethyl sulfide section. The conversion rate of each reaction can reach more than 90%. The separation process is simple with few reaction by-products, simulated by Rstoic, Radfrac and flash 2 blocks, etc of Aspen Plus. In the dimethyl sulfide section, the operation parameters such as the feed temperature, the reflux ratio and the theoretical plate number have been optimized by using sensibility block to determine the best process conditions. The simulation results show that the annual production of dimethyl sulfide is 12000 t with the purity of 99.02 %, it has good economic benefit and nice environmental benefit, and it can provide some advice for the disposal of SO_2 in flue gas resource fulization.
引文
[1] 成铭.工业含硫废气的脱硫技术与回收净化[J].化工管理,2017(9):115.
[2] 沈春红,夏道宏.国内外脱硫技术进展[J].石化技术,1999,6(1):44-47
[3] 韩伟明, 李建锡, 段正洋,等. 对钙法和有机胺法烟气脱硫技术的研究探讨[J]. 硅酸盐通报, 2016, 35(1):154-159.
[4] MA X, KANEKO T, TASHIMO T. Use of limestone for SO2 removal from flue gas in the semidry FGD process with a powder-particle spouted bed[J]. Chemical Engineering Science, 2000, 55(20):4643-4652.
[5] BOKOTKO R P, HUPKA J, MILLER J D. Flue gas treatment for SO2 removal with air-sparged hydrocyclone technology[J]. Environmental Science & Technology, 2005, 39(4):1184.
[6] 邓庚凤, 曹霞, 廖春发,等. 烟气中SO2催化还原制取硫磺[J]. 材料导报, 2010, 24(s1):421-424.
[7] 徐文渊. 天然气中硫资源的利用——硫磺混凝土和硫磺沥青[J]. 石油与天然气化工, 2004, 33(5):329-332.
[8] 张航. 火电厂烟气脱硫石膏和粉煤灰综合利用可行性分析[J]. 大科技, 2017(18):86.
[9] PARK H H, DESHWAL B R, KIM I W, et al.Absorption of SO2, from flue gas using PVDF hollow fiber membranes in a gas-liquid contactor[J]. Journal of Membrane Science, 2008, 319(1/2):29-37.
[10] MAJUMDAR S, SENGUPTA A, Cha J S, et al. Simultaneous SO2/NO separation from flue gas in a contained liquid membrane permeator[J]. Ind Eng Chem Res, 1994, 33(3):667-675.
[11] KIM Y S, PAEK M S, YOO J S, et al. Development of demonstration plant using non-thermal plasma process to remove SO2 and NOx from flue gas[J]. Journal of Advanced Oxidation Technologies, 2016, 6(1):35-40.
[12] LI Wen,GAO Guanjun,LIU Ying, et al. Using Ionic liquid mixtures to Improve the SO2 absorption performance in flue gas[J]. Energy & Fuels, 2017, 31(2).
[13] 关莉莉,汪颖,慕旭宏,等.一种二甲基硫醚的制备方法:中国, 201410129629.6[P].2014-04-01.
[14] 杨义谟. 二甲基硫醚的合成[J]. 辽宁化工, 1998(4):223-225.
[15] 李海城, 卞贺, 张士国,等. 甲硫醇、二甲硫醚、噻吩与过氧乙酸气相反应机理的理论研究[J]. 计算机与应用化学, 2014, 31(12):1547-1551.
[16] 孟菊英, 吴昊, 王彦,等. 用甲基硫酸钠废渣制备二甲基硫醚[J]. 化工环保, 2006, 26(4):315-317.
[17] 赵均瑞,徐红喜,师明中,等.一种从烟气回收二氧化硫的方法:中国,201710801366.2[P].2017-09-07.
[18] 茆卫兵, 纪罗军. 二氧化硫制硫磺技术研究及进展[J]. 硫酸工业, 2015(4):1-6.
[19] 李天文,刘坤,尚念刚,等.一种硫化氢的制备方法:中国, 201110343178.2[P].2011-11-03.
[20] 潘兴朋, 吴相英, 杜君,等. 碱处理Beta分子筛吸附脱硫动力学[J]. 化工学报, 2016, 67(9):3747-3754.
[2] 沈春红,夏道宏.国内外脱硫技术进展[J].石化技术,1999,6(1):44-47
[3] 韩伟明, 李建锡, 段正洋,等. 对钙法和有机胺法烟气脱硫技术的研究探讨[J]. 硅酸盐通报, 2016, 35(1):154-159.
[4] MA X, KANEKO T, TASHIMO T. Use of limestone for SO2 removal from flue gas in the semidry FGD process with a powder-particle spouted bed[J]. Chemical Engineering Science, 2000, 55(20):4643-4652.
[5] BOKOTKO R P, HUPKA J, MILLER J D. Flue gas treatment for SO2 removal with air-sparged hydrocyclone technology[J]. Environmental Science & Technology, 2005, 39(4):1184.
[6] 邓庚凤, 曹霞, 廖春发,等. 烟气中SO2催化还原制取硫磺[J]. 材料导报, 2010, 24(s1):421-424.
[7] 徐文渊. 天然气中硫资源的利用——硫磺混凝土和硫磺沥青[J]. 石油与天然气化工, 2004, 33(5):329-332.
[8] 张航. 火电厂烟气脱硫石膏和粉煤灰综合利用可行性分析[J]. 大科技, 2017(18):86.
[9] PARK H H, DESHWAL B R, KIM I W, et al.Absorption of SO2, from flue gas using PVDF hollow fiber membranes in a gas-liquid contactor[J]. Journal of Membrane Science, 2008, 319(1/2):29-37.
[10] MAJUMDAR S, SENGUPTA A, Cha J S, et al. Simultaneous SO2/NO separation from flue gas in a contained liquid membrane permeator[J]. Ind Eng Chem Res, 1994, 33(3):667-675.
[11] KIM Y S, PAEK M S, YOO J S, et al. Development of demonstration plant using non-thermal plasma process to remove SO2 and NOx from flue gas[J]. Journal of Advanced Oxidation Technologies, 2016, 6(1):35-40.
[12] LI Wen,GAO Guanjun,LIU Ying, et al. Using Ionic liquid mixtures to Improve the SO2 absorption performance in flue gas[J]. Energy & Fuels, 2017, 31(2).
[13] 关莉莉,汪颖,慕旭宏,等.一种二甲基硫醚的制备方法:中国, 201410129629.6[P].2014-04-01.
[14] 杨义谟. 二甲基硫醚的合成[J]. 辽宁化工, 1998(4):223-225.
[15] 李海城, 卞贺, 张士国,等. 甲硫醇、二甲硫醚、噻吩与过氧乙酸气相反应机理的理论研究[J]. 计算机与应用化学, 2014, 31(12):1547-1551.
[16] 孟菊英, 吴昊, 王彦,等. 用甲基硫酸钠废渣制备二甲基硫醚[J]. 化工环保, 2006, 26(4):315-317.
[17] 赵均瑞,徐红喜,师明中,等.一种从烟气回收二氧化硫的方法:中国,201710801366.2[P].2017-09-07.
[18] 茆卫兵, 纪罗军. 二氧化硫制硫磺技术研究及进展[J]. 硫酸工业, 2015(4):1-6.
[19] 李天文,刘坤,尚念刚,等.一种硫化氢的制备方法:中国, 201110343178.2[P].2011-11-03.
[20] 潘兴朋, 吴相英, 杜君,等. 碱处理Beta分子筛吸附脱硫动力学[J]. 化工学报, 2016, 67(9):3747-3754.