Abstract: The oxidation regeneration process in wet desulfurization process is studied via experiments.The effects of temperature,oxygen/sulfur ratio,pH,and phthalocyanine cobalt sulfonate (PDS) concentration on the regeneration efficiency are studied through a single-factor test.Based on the results of the single-factor test,an orthogonal experiment with four factors and three levels is designed.Temperature is found to be the most important factor affecting the oxidation process,followed by oxygen/sulfur ratio and pH,while PDS concentration has the least impact on the process.The optimal conditions are as follows:1.25 mmol/mmol of oxygen/sulfur,60 mg·L-1 of PDS,pH=8.68 and at 18℃.Under the optimal conditions,the regeneration efficiency can reach 83.8%.A mechanism for the oxidation regeneration of hydrogen bisulfide (HS-) is proposed that polysulfide ion seems to be the main factor governing the formation of byproduct salts.An actual industrial desulfurization oxidation process is analyzed,and its desulfurization efficiency is found to be only 55%.The lower efficiency is possibly due to that the temperature and the oxygen/sulfur ratio in the process are very different from the experiment's optimal conditions.
[1] 上官炬,常丽萍,苗茂谦.气体净化分离技术[M].北京:化学工业出版社,2012. [2] 王祥光.脱硫副反应及副盐回收技术研究[J].化肥设计,2008,(4):37-41. [3] 朱红,王彩云,赵虎,等.HPF脱硫废液的处理方法[J].燃料与化工,2014,45(3):45-47. [4] 王芳.焦炉煤气脱硫废液资源化处理研究[D].长春:东北师范大学,2012. [5] 时秋颖.湿式氧化法脱硫废液的处理[J].燃料与化工,2009,40(6):54. [6] 段素兰,马兴敏,刘君红.焦炉煤气HPF脱硫废液无害化处理技术[J].冶金动力,2013,(9):15-17. [7] 杨树卿,赵福荣,刘勤.液相螯合物催化氧化法脱硫的研究(Ⅱ)[J].东北师大学报(自然科学版),1981,(3):73-79. [8] Steudel R.Mechanism for the formation of elemental sulfur from aqueous sulfide in chemical and microbiological desulfurization processes[J].Industrial & Engineering Chemistry Research,1996,35(4):1417-1423. [9] Pl V D B,van Beusekom O C,Buisman C J,et al. Sulfide oxidation at halo-alkaline conditions in a fed-batch bioreactor[J].Biotechnology & Bioengineering,2010,97(5):1053-10/63. [10] Bosch P L F V,Sorokin D Y,Buisman C J N,et al.The effect of pH on thiosulfate formation in a biotechnological process for the removal of hydrogen sulfide from gas streams[J].Environmental Science & Technology,2008,42(7):2637-2642. [11] Roosta A,Jahanmiri A,Mowla D,et al.Mathematical modeling of biological sulfide removal in a fed batch bioreactor[J].Biochemical Engineering Journal,2011,58(12):50-56. [12] 文娟.煤层气脱硫氧化再生槽的设计[J].矿业安全与环保,2013,40(6):26-28. [13] 侯凤博.PDS脱硫液氧化再生试验研究[D].青岛:青岛科技大学,2018. [14] 程华农,李灿,郑世清.酞菁钴磺酸盐脱硫液中硫氢根离子的测定方法[J].能源化工,2016,37(1):88-92. [15] 骆元章,曹殿芳.离子色谱法测定水溶液样品中的SO32-,SO42-和S2O32-阴离[J].化工冶金,1989,(1):52-55. [16] 李灿,程华农,侯凤博,等.PDS脱硫液中多硫化物的测定方法[J].青岛科技大学学报(自然科学版),2017,38(S1):69-72. [17] 卫都管,张建中,黄苏河,等.ADA法向PDS法过渡中脱硫塔堵塞问题的探讨与对策[J].中氮肥,1996,(4):17-20. [18] Fischer H,Wöhrle D.Oxidation of aqueous sulfide solutions by dioxygen Part Ⅰ:Autoxidation reaction[J].Chemical Engineering & Technology,1997,20(7):462-468. [19] Kleinjan W E,De K A,Janssen A J.Kinetics of the chemical oxidation of polysulfide anions in aqueous solution[J].Water Research,2005,39(17):4093-4100.