草酸铁光催化协同络合铁脱硝剂再生过程
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摘要
基于Fe(C_2O_4)_3的光化学性质,研究了Fe(C_2O_4)_3光催化协同络合铁脱硝剂再生的实验过程。实验考察了在50℃和Fe(Ⅱ)EDTA浓度为0.01 mol·L~(-1)以及NO进口浓度为530 mg·m-3的模拟烟气脱硝系统中,光催化再生模式、初始p H、Fe(C_2O_4)_3浓度及组成、氧气浓度对再生过程的影响。结果表明:Fe(C_2O_4)_3分开加入和分步光照是适合于本体系的反应方式;草酸钠与硫酸亚铁的最佳浓度比为3,浓度分别为0.06和0.02 mol·L~(-1),吸收液初始p H为5.3,有氧参与条件下,实现了络合剂有效再生,再生吸收液脱硝率最高可恢复到60%左右;氧在再生过程中表现出正协同效应。通过牺牲光敏性的草酸铁配体再生脱硝络合剂,建立了一种温和的光助低温湿式氨法同步脱硫脱硝过程。
This paper researched into regeneration of denification agent aided by photocatalysis of Fe(C_2O_4)_3 based on the photochemical properties of Fe(C_2O_4)_3. The investigated factors were the mode of illumination, the addition mode of Fe(C_2O_4)_3, initial p H, Fe(C_2O_4)_3 concentration, the ratio of Na_2C_2O_4 to FeSO_4, and oxygen concentration at 50?C of system temperature and 0.01 mol·L~(-1) of Fe(Ⅱ)EDTA concentration and 530 mg·m~(-3) of the inlet NO concentration. Experimental results indicated that Na_2C_2O_4 and Fe SO4 added into NO-riched solution after NO absorption finishing was the adequate mode for this system. The optimum ratio value of Na_2C_2O_4 to Fe SO_4 was 3 with their concentrations of 0.06 and 0.02 mol·L~(-1), respectively. Meanwhile, when the initial p H of absorption solution was about 5.3, and oxygen participated in regeneration reaction, the complexing agent got the highest regenerated denification efficiency of 60%. Oxygen played a positive effect on the regeneration process. According to this research, a process of mild photocatalytic-aided wet ammonia desulfurization and denification simultaneously could be established at the expense of Fe(C_2O_4)_3.
This paper researched into regeneration of denification agent aided by photocatalysis of Fe(C_2O_4)_3 based on the photochemical properties of Fe(C_2O_4)_3. The investigated factors were the mode of illumination, the addition mode of Fe(C_2O_4)_3, initial p H, Fe(C_2O_4)_3 concentration, the ratio of Na_2C_2O_4 to FeSO_4, and oxygen concentration at 50?C of system temperature and 0.01 mol·L~(-1) of Fe(Ⅱ)EDTA concentration and 530 mg·m~(-3) of the inlet NO concentration. Experimental results indicated that Na_2C_2O_4 and Fe SO4 added into NO-riched solution after NO absorption finishing was the adequate mode for this system. The optimum ratio value of Na_2C_2O_4 to Fe SO_4 was 3 with their concentrations of 0.06 and 0.02 mol·L~(-1), respectively. Meanwhile, when the initial p H of absorption solution was about 5.3, and oxygen participated in regeneration reaction, the complexing agent got the highest regenerated denification efficiency of 60%. Oxygen played a positive effect on the regeneration process. According to this research, a process of mild photocatalytic-aided wet ammonia desulfurization and denification simultaneously could be established at the expense of Fe(C_2O_4)_3.
引文
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[21]叶小莉,吴晓琴,王淑娟.氨水/Fe(II)EDTA溶液同时脱硫脱硝实验研究[J].环境科学学报,2014,34(6):1560-1566.DOI:10.13671/j.hjkxxb.2014.0536.
[22]钱婧,李威,张银龙,等.Fenton法/草酸钠-Fenton法降解典型抗癌药5-氟尿嘧啶[J].环境化学,2014,33(7):1229-1234.
[23]吴少林,谢四才,李明俊.Fe3+草酸盐络合物/H2O2/日光体系对垃圾渗滤液的处理[J].环境科学研究,2005,18(3):29-32.
[2]XIE J K,QU Z,YAN N Q,et al.Novel regenerable sorbent based on Zr-Mn binary metal oxides for flue gas mercury retention and recovery[J].Journal of Hazardous Materials,2013,261:206-213.DOI:10.1016/j.jhazmat.2013.07.027.
[3]ZHAO Y,HAN Y H,GUO T X,et al.Simultaneous removal of SO2,NO and Hg0from flue gas by ferrate(VI)solution[J].Energy,2014,67:652-658.DOI:10.1016/j.energy.2014.01.081.
[4]ZHAO Y,HAN Y H,CHEN C.Simultaneous removal of SO2 and NO from flue gas using multicomposite active absorbent[J].Industrial and Engineering Chemistry Research,2012,51(1):480-486.
[5]FANG P,CEN C P,WANG X M,et al.Simultaneous removal of SO2,NO and Hg0by wet scrubbing using urea+KMn O4 solution[J].Fuel Processing Technology,2013,106:645-653.DOI:10.1016/j.fuproc.2012.09.060.
[6]ZHAO Y,HAN Y H,MA T Z,et al.Simultaneous desulfurization and denitrification from flue gas by ferrate(VI)[J].Environmental Science&Technology,2011,45(9):4060-4065.
[7]朱登亮,张扬,赵世永,等.烟气干法脱硫脱硝协同工艺研究[J].煤炭加工与综合利用,2017(4):45-48.
[8]杨垒.火电厂脱硝技术与应用以及脱硫脱硝一体化发展趋势[J].科技风,2014(18):46-47.
[9]钟少芬,蔡卓弟.液相络合法脱除NOx的研究进展[J].广东化工,2012,39(2):121-122.
[10]樊响,殷旭.烧结烟气脱硫脱硝一体化技术分析[J].矿冶,2013,22(S1):168-172.
[11]刘成.光助Fe(Ⅱ)EDTA-草酸钠复合吸收液脱硫脱硝的实验研究[D].武汉:武汉科技大学,2016.
[12]苑鹏,卢凤菊,梅雪,等.高级氧化法在烟气脱硫脱硝脱汞中的应用研究进展[J].化工进展,2016,35(10):3313-3322.
[13]SKALSKA K,MILLER J S,LEDAKOWICZ S.Trends in NOxabatement:A review[J].Science of the Total Environment,2010,408(19):3976-3989.DOI:10.1016/j.scitotenv.2010.06.001.
[14]PAWEL C,PRZEMYSLAW K,PIOTR M,et al.Homogeneous photocatalysis by transition metal complexes in the environment[J].Journal of Molecular Catalysis A:Chemical,2004,224(1):17-33.DOI:10.1016/j.molcata.2004.08.043.
[15]HAN Y H,ZHANG J J,ZHAO Y.Visible-light-induced photocatalytic oxidation of nitric oxide and sulfur dioxide:Discrete kinetics and mechanism[J].Energy,2016,103:725-734.DOI:10.1016/j.energy.2015.12.007.
[16]张婷,吴少林,朱振兴.Fe(III)草酸盐络合物的光化学性质及应用[J].江西化工,2008(1):26-29.
[17]谢银德,陈峰,何建军,等.Photo-Fenton反应研究进展[J].感光科学与光化学,2000,18(4):357-365.
[18]马双忱,马京香,赵毅,等.紫外/过氧化氢法同时脱硫脱硝的研究[J].热能动力工程,2009,24(6):792-795.
[19]刘杨先,张军,盛昌栋,等.UV/H2O2高级氧化工艺湿法脱除燃煤烟气中NO实验研究[J].中国科学,2010,40(11):1353-1359.
[20]丁毓怡,刘小东,方文骥.EDTA络合铁法脱硫试验研究总结[J].河南化工,1986(1):13-20.
[21]叶小莉,吴晓琴,王淑娟.氨水/Fe(II)EDTA溶液同时脱硫脱硝实验研究[J].环境科学学报,2014,34(6):1560-1566.DOI:10.13671/j.hjkxxb.2014.0536.
[22]钱婧,李威,张银龙,等.Fenton法/草酸钠-Fenton法降解典型抗癌药5-氟尿嘧啶[J].环境化学,2014,33(7):1229-1234.
[23]吴少林,谢四才,李明俊.Fe3+草酸盐络合物/H2O2/日光体系对垃圾渗滤液的处理[J].环境科学研究,2005,18(3):29-32.