低浓度SO_2烟气处理及NO_2和CO_2对其过程的影响研究
摘要
我国S02排放量高居世界各国前列,由此带来的大气污染和酸雨问题十分严重,经济损失巨大,已成为制约我国经济社会可持续发展的主要因素之一,控制S02污染已势在必行。
湿法脱硫以其脱硫效率高、适应范围广、技术成熟等优点得以广泛应用。其中,应用最广泛的是石灰石—石膏洗涤法,但该方法存在固体沉积易使装置结垢堵塞,设备腐蚀、磨损严重,运行、维护费用高,副产品的综合利用价值低等缺点。硫化钠溶液吸收-还原硫法烟气脱硫,具有操作简单,固体废料少,无废水废渣排放,脱硫效率高,产品易于储存和运输等优点,是未来二氧化硫烟气治理颇具前景的脱硫技术。
为了将硫化钠溶液吸收-还原硫法较好地应用于低浓度S02烟气的治理,本文通过热力学分析以及条件实验,对Na2S溶液吸收低浓度S02烟气以及NO2和CO2对吸收过程的影响进行了研究,并得出以下结论：
(1)通过SO2-Na2S-H2O体系的热力学分析可知,液相中主要存在S2O32-、HSO3-、H2SO3以及少量HS-。当吸收液pH值在3-8之间时,液相中基本上只存在S2032-；当吸收液pH值小于3之后,液相中只存在S2032-和HSO3-。
(2)Na2S溶液对低浓度S02烟气具有很好的吸收效果,两级总吸收率基本达到100%。吸收液组成主要受气流速度和终点pH值的影响,而且改变气流速度以及吸收液终点pH值均可控制HSO3-和S2032-合适的浓度比。
(3)烟气中的NO2不影响S02气体的吸收效果,但消耗吸收剂(Na2S),而且影响吸收液中离子的种类和浓度。NO2抑制S02吸收过程中HSO3-的生成,同时促进该过程中S2032-和SO42-的生成,从而降低HSO3-和S2032-的浓度比。
(4)烟气中的CO2也基本不影响S02气体的吸收效果,但迅速降低吸收液的pH值,并且加快溶液中S2-的消耗。CO2会使S02吸收过程中HSO3-的生成量减少,S2032-的生成量增加。
SO2 emission in China tops the forefront of the world. The resulting air pollution and acid rain problems are very serious and the economic loss is very huge, which has become one of the main factors to restrict the economic and social sustainable development. Therefore, it is imperative to control SO2 pollution.
Wet FGD is of high desulphurization efficiency, adapts to wide range, and its technology is very mature. For these advantages, wet FGD is widely used. Among wet FGD, limestone-gypsum washing is the most widely used, but there are many disadvantages, such as easy rolling skin and blocking devices, serious corroding and abrading equipments, high cost of operation and maintenance, and less comprehensive utilization of by-products and so on. Sodium sulfide solution absorption-reduction of sulfur FGD, whose operation is simple, solid waste is less, waste water discharge is none, desulfurization efficiency is high and product is easy to store and transport, will be a promising desulfurization technology of SO2 gas in future.
In order to apply sodium sulfide solution absorption-reduction of sulfur method to SO2 gas in low concentration, sodium sulfide solution absorbing SO2 gas and the impacts of NO2 and CO2 in flue gas on the absorption process were studied in this paper by thermodynamic analysis and conditional experiments, and draw the following conclusions:
(1) The thermodynamic analysis of SO2-Na2S-H2O system shows that the liquid mainly includes S2O32-, HSO3-, H2SO3, and a small amount of HS-. When the absorption solution's pH value is from 3 to 8, the liquid is essentially only S2O32-; when the absorption solution's pH value is less than 3, the liquid phase includes only S2O32-and HSO3-.
(2) Na2S solution is of a good absorption of SO2 gas in low concentration, and the total absorption rate reaches 100%.The liquid content is mainly affected by gaseous flow rate and final pH value. So changing gaseous flow rate and final pH of absorption solution may control suitable concentration ratio between HSO3-and S2O32-.
(3) NO2 in the flue gas does not affect the absorption efficiency of SO2 gas,but it consumes absorbent(Na2S) and affects the type and concentration of ions in absorption solution. NO2 inhibites the generation of HSO3- during SO2 absorption process, while promoting the formation of S2O32-and SO42-, which decreases the concentration ratio between HSO3-and S2O32-.
(4) CO2 in the flue gas does not affect the absorption efficiency of SO2 gas either.However,it will reduce the absorption solution's pH rapidly, and speed up the consumption of S2- in the solution. CO2 will reduce the formation of HSO3- during SO2 absorption process, and increase the generation of S2O32-.
湿法脱硫以其脱硫效率高、适应范围广、技术成熟等优点得以广泛应用。其中,应用最广泛的是石灰石—石膏洗涤法,但该方法存在固体沉积易使装置结垢堵塞,设备腐蚀、磨损严重,运行、维护费用高,副产品的综合利用价值低等缺点。硫化钠溶液吸收-还原硫法烟气脱硫,具有操作简单,固体废料少,无废水废渣排放,脱硫效率高,产品易于储存和运输等优点,是未来二氧化硫烟气治理颇具前景的脱硫技术。
为了将硫化钠溶液吸收-还原硫法较好地应用于低浓度S02烟气的治理,本文通过热力学分析以及条件实验,对Na2S溶液吸收低浓度S02烟气以及NO2和CO2对吸收过程的影响进行了研究,并得出以下结论：
(1)通过SO2-Na2S-H2O体系的热力学分析可知,液相中主要存在S2O32-、HSO3-、H2SO3以及少量HS-。当吸收液pH值在3-8之间时,液相中基本上只存在S2032-；当吸收液pH值小于3之后,液相中只存在S2032-和HSO3-。
(2)Na2S溶液对低浓度S02烟气具有很好的吸收效果,两级总吸收率基本达到100%。吸收液组成主要受气流速度和终点pH值的影响,而且改变气流速度以及吸收液终点pH值均可控制HSO3-和S2032-合适的浓度比。
(3)烟气中的NO2不影响S02气体的吸收效果,但消耗吸收剂(Na2S),而且影响吸收液中离子的种类和浓度。NO2抑制S02吸收过程中HSO3-的生成,同时促进该过程中S2032-和SO42-的生成,从而降低HSO3-和S2032-的浓度比。
(4)烟气中的CO2也基本不影响S02气体的吸收效果,但迅速降低吸收液的pH值,并且加快溶液中S2-的消耗。CO2会使S02吸收过程中HSO3-的生成量减少,S2032-的生成量增加。
SO2 emission in China tops the forefront of the world. The resulting air pollution and acid rain problems are very serious and the economic loss is very huge, which has become one of the main factors to restrict the economic and social sustainable development. Therefore, it is imperative to control SO2 pollution.
Wet FGD is of high desulphurization efficiency, adapts to wide range, and its technology is very mature. For these advantages, wet FGD is widely used. Among wet FGD, limestone-gypsum washing is the most widely used, but there are many disadvantages, such as easy rolling skin and blocking devices, serious corroding and abrading equipments, high cost of operation and maintenance, and less comprehensive utilization of by-products and so on. Sodium sulfide solution absorption-reduction of sulfur FGD, whose operation is simple, solid waste is less, waste water discharge is none, desulfurization efficiency is high and product is easy to store and transport, will be a promising desulfurization technology of SO2 gas in future.
In order to apply sodium sulfide solution absorption-reduction of sulfur method to SO2 gas in low concentration, sodium sulfide solution absorbing SO2 gas and the impacts of NO2 and CO2 in flue gas on the absorption process were studied in this paper by thermodynamic analysis and conditional experiments, and draw the following conclusions:
(1) The thermodynamic analysis of SO2-Na2S-H2O system shows that the liquid mainly includes S2O32-, HSO3-, H2SO3, and a small amount of HS-. When the absorption solution's pH value is from 3 to 8, the liquid is essentially only S2O32-; when the absorption solution's pH value is less than 3, the liquid phase includes only S2O32-and HSO3-.
(2) Na2S solution is of a good absorption of SO2 gas in low concentration, and the total absorption rate reaches 100%.The liquid content is mainly affected by gaseous flow rate and final pH value. So changing gaseous flow rate and final pH of absorption solution may control suitable concentration ratio between HSO3-and S2O32-.
(3) NO2 in the flue gas does not affect the absorption efficiency of SO2 gas,but it consumes absorbent(Na2S) and affects the type and concentration of ions in absorption solution. NO2 inhibites the generation of HSO3- during SO2 absorption process, while promoting the formation of S2O32-and SO42-, which decreases the concentration ratio between HSO3-and S2O32-.
(4) CO2 in the flue gas does not affect the absorption efficiency of SO2 gas either.However,it will reduce the absorption solution's pH rapidly, and speed up the consumption of S2- in the solution. CO2 will reduce the formation of HSO3- during SO2 absorption process, and increase the generation of S2O32-.
引文
[1]童志权主编.工业废气净化与利用.北京：化学工业出版社,2001,380-392
[2]王腊姣.吸附法脱除烟气中二氧化硫的研究.武汉：武汉理工大学资源与环境工程学院,2002,1-3
[3]黄佩丽,田荷珍编.基础元素化学.北京：北京师范大学出版社,1994,84-96,198-204
[4]Э.П.罗津克诺普著.从工业气体中回收二氧化硫(南京化工研究院译).北京：化学工业出版社,1966,1-16
[5]南京化学工业公司研究院《硫酸工业》编辑部.低浓度二氧化硫烟气脱硫.上海：上海科学技术出版社,1981,1-256
[6]沈伯雄主编.大气污染控制工程.北京：化学工业出版社,2007,128-140
[7]郝吉明,马广大.大气污染控制工程(第二版).北京：高等教育出版社,2002,306-309
[8]孙克勤,钟秦编.火电厂烟气脱硫系统设计、建造及运行.北京：化学工业出版社,2005,2-10
[9]蒋文举主编.烟气脱硫脱硝技术手册.北京：化学工业出版社,2007,159-382
[10]王乐亮.水泥立窑的烟气特点及治理方法.山东建材,1996,4：16-19
[11]赵由才,牛冬杰.湿法冶金污染控制技术.北京：冶金工业出版社,2008,69-70,81
[12]World bank group.Sulfur oxides.pollution prevention and control.Pollution Prevention and Abatement Handbook,1998,258-260
[13]Robert E.,Sommerlad,Cranford,N.J..Method for removing sulfur dioxide from flue gases. USP4666690,1987
[14]黄震,石莹.国外烟气脱硫技术.节能与环保,2001,18-21
[15]孙胜奇,陈荣永,王平.我国二氧化硫烟气脱硫技术现状及进展.中国铝业,2005,29(1)：44-47
[16]Taha Ramzi.Environmental and engineering properties of flue gas desulfurization gypsum. Research Record,1993,(1424):14-19
[17]Guilin Hu,Kim Dam Johansen,Stig Wedel,Jens Peter Hansen.Review of the direct sulfation reaction of limestone.Progress in Energy and Combustion Science, 2006,32:386-407
[18]Paolo Davini.Investigation of the SO2 adsorption properties of Ca(OH)2-fly ash systems.Fuel,1996,75(6):713-716
[19]Kuroda iroshi.Limestone-gypsum flue gas desulfurization process.USP4487784, 1984
[20]黄隆焜,刘勇,王大伟.石灰石—石膏脱硫与海水脱硫的应用比较.科技创新报,2007,(31)：36
[21]孙光铭.火电厂石灰石-石膏法与海水法烟气脱硫的比较.能源工程,2009,(2)：45-47
[22]李喜,李俊.烟气脱硫技术研究进展.化学工业与工程,2006,23(4)：351-354
[23]karlsson H.T,Klingspor T. Absorption of hydrochlorid acid of solid slakd lime for flue gas clean up.Air pollute control assoc,1981,18(5):239
[24]吕慧,兰凤春.海水法烟气脱硫工艺在国内火电厂的应用研究.吉林电力,2007,35(4)：23-30
[25]Tandon N,Ramalingam P,Malik A.Q.Dispersion of Flue Gases form Power Plants in Brunei Darussalam.Appl.Geophys,2003,160:405-418
[26]陈东,林继发.湿法烟气脱硫技术简述.陕西环境,2003,10(5)：32-34
[27]周玉昆.威尔曼-劳德烟气脱硫工艺及其发展前景.环境科学动态,989,(8)：6-11
[28]曹霞,陈秀萍.浅谈氢氧化镁法脱硫技术.有色冶金设计与研究,2000,21(1)：47-51
[29]涂瑞.浅谈钙法、镁法脱硫方案的技术分析.有色冶金设计与研究,2008,29(3)：7-8
[30]徐长香,傅国光.氨法烟气脱硫技术综述.电力环境保护,2005,21(2)：17-20
[31]崔莲溪.磷铵肥法(PAFP)烟气脱硫技术.硫酸工业,1992,(4)：3-10
[32]徐正中.磷铵肥法烟气脱硫中试研究.热力发电,1993,(2)：14-19
[33]何涛.柠檬酸钠法制液体二氧化硫.内蒙古石油化工,2007,(3)：23-25
[34]袁孝竞,沙勇,郭卫东.柠檬酸-柠檬酸钠缓冲溶液在烟气脱硫中的应用.石油化工设计,1998,15(4)：35-39
[35]李卫昌.柠檬酸钠法治理冶炼厂低浓度S02.有色金属(冶炼部分),2002,(6)：20-22
[36]赵新宏,符新科,沈明科.柠檬酸盐法处理低浓度SO2烟气的试验研究.中国钼业,2004,28(1)：22-25
[37]Bauer B,Gerner F J,Strathmann H.Development of bipolar membranes. Desalination,1988,(68):279-292
[38]Olusola Sunday Ogundiran.Application of Membranes in Chemically Reactive Systems:[A thesis for the degree of Doctor].America:University of Toledo,1991
[39]Frank N W,Kawamura K,Miller G A.SO2/NOx a natural resource should not go up in smoke.Chem Eng Prog,1985,81(6):30-36
[40]李喜,李俊.烟气脱硫技术研究进展.化学工业与工程,2006,23(4)：351-354
[41]邱炜,周刚,付英杰.干法烟气脱硫综述.电站系统工程,2005,21(3)：19-20
[42]张大欣,徐光,罗经宇.电子束半干法烟气净化技术.环境污染治理技术与设备,2001,2(3)：69-72.
[43]贾利军,刘炳光.我国烟气脱硫技术综述.盐业与化工,2006,35(5)：35-39
[44]于庆波,王新华,秦勤等.我国烟气脱硫技术的发展及应用现状.冶金能源,2000,(6)
[45]Nijdam J.J.Guo.An Experimental Investigation of Agglomeration with One and Two Nozzle Atomization.Drying,2002,Volume A:653
[46]范经涛.工业化烟气脱硫技术综述.山东环境,2003,(3)：40-41
[47]陈亚非.烟气脱硫技术综述(待续).制冷空调与电力机械,2001,22(1)：17-38
[48]陈亚非.烟气脱硫技术综述(续完).制冷空调与电力机械,2001,22(1)：28-30
[49]贺亮,张少峰.半干法烟气脱硫技术研究现状及进展.天津化工,2007,21(2)：18-20
[50]王永慧译.用还原硫法脱除高浓度二氧化硫.有色冶炼,1993,4：37-41
[5l]石林,古国榜,邹智毅.硫化碱溶液脱除工业烟气中的二氧化硫.中山大学学报论丛,1997,(5)：189-192
[52]舒余德,李红剑,尹玉麟.二氧化硫冶炼烟气制硫粉的研究-二氧化硫的吸收.有色金属：冶炼部分,1997,(12)：5-8
[53]I.M.柯尔蜀夫,R.贝尔学等著.容量分析(卷三)(梁树权译).北京：科学出版社,1963,265-276
[54]李红剑,舒余德,饶凌.联立方程组法分别测定多价硫的研究.湖南有色金属,1996,12(1)：62-64
[55]张龙.气体脱硫过程分析方法.北京：化学工业出版社,2006,46-49,74-76,80-83
[56]张深林,斯公敏.硫化钠脱硫制碱.环境污染与防治,1995,17(3)：1-2
[57]Tung Siu.Kinetic and Mechanistic Study Aqueous Slufide-Sulfite-Thiosulfate System:[A thesis for the degree of Master].Canada:University of Toronto,1999
[58]Miller,Ralph.Production of hydrogen sulfide from sulfur dioxide obtained from flue gas.EP0000251(Al),1979
[59]Miller,Ralph.Production of sulfur from sulfur dioxide obtained from flue gas.EP0246403(Al),1987
[60]夏士朋.多硫化钠的制取.四川化工,1994,(2)：14-16
[61]林平娣.无机化学热力学.北京：北京师范大学出版社,1986,136-144
[62]姜涛,许时.硫代硫酸盐提金理论研究-浸金的化学及热力系原理.黄金,1992,13(2)：31-34
[63]Robert C.West.CRC Handbook Chemistry and Physics.Boca Raton,FL:CRC Press,69ed,1988-1989,D-87
[64]张平民.工科大学化学.湖南：湖南教育出版社,2002,294-336
[65]张立红.碱溶液烟气脱硫的热力学计算.殷都学刊(自然科学版),1997,(1)：41-44
[66]Young Sun Mok.Absorption-reduction technique assisted by ozone injection and sodium sulfide for NOx removal from exhaust gas.Chemical Engineering Journal,2006,118:63-67
[67]国家环境保护总局,水和废水监测分析方法编委会编.水和废水监测分析方法.北京：中国环境科学出版社,2002,164-165,266-268,271-274
[68]Yamamoto T.,OkuboM.,Nakao T.,Hayakawa K.,IEEE Trans.Ind.Appl.2002,38: 1168-1173.
[69]Siddiqi M.A.,Petersen J..A Study of the Effect of Nitrogen Dioxide on the Absorption of Sulfur Dioxide in Wet Flue Gas Cleaning Processes.Ind.Eng. Chem.Res,2001,40(9):2116-2127
[70]王珲,宋蔷,杨小勇.氮氧化物在湿法烟气脱硫过程中的作用.煤炭转化,2005,28(3)：43-46
[71]Takeuchi H.,Ando M.,Kizawa N.Absorption of Nitrogen Oxides in Aqueous Sodium Sulfite and Bisulfite Solutions.Ind.Eng.Chem.Process Des.Dev,1977, 16:303-308.
[72]Sato T.,Matani S.,Okabe T.The Oxidation of Sodium Sulfite with Nitrogen Dioxide.With Special Reference to Analytical Methods for Nitrogen-Sulfur Compounds Produced in the Reaction System.Nippon Kaguku Kaishi,1979,7: 869-878.
[73]Lee Y.N.,Schwartz S.E.Kinetics of Oxidation of Aqueous Sulfur(IV) by Nitrogen Dioxide.Fourth International Conference on Precipitation Scavenging,Dry Deposition,and Resuspension,St.Monica,CA,1982;Elsevier:New York,1982.
[74]Little john D.,Wang Y.,Chang S.GOxidation of Aqueous Sulfite Ion by Nitrogen Dioxide.Environ.Sci.Technol,1993,27:2162-2167.
[75]Chang S.G,Littlejohn D.,Lin N.H.Kinetics of Reactions in a Wet Flue Gas Simultaneous Desulfurization and Denitrification System.ACS Symp.Ser,1982, 188:127-152.
[76]陆少红,宫葵.硫氮液相反应研究进展.沈阳航空工业学院学报,2004,21(2)：76-79
[77]傅军,肖博文,涂晋林.NOX、S02液相反应研究进展——一种同时脱硫脱氮的新思路.化工进展,1999,(1)：26-28
[78]吴晓琴,童仕唐,吴高明.CO2对Na2S脱除S02同时制取H2S过程的影响.武汉科技大学学报(自然科学版),2005,28(3)：249-251
[2]王腊姣.吸附法脱除烟气中二氧化硫的研究.武汉：武汉理工大学资源与环境工程学院,2002,1-3
[3]黄佩丽,田荷珍编.基础元素化学.北京：北京师范大学出版社,1994,84-96,198-204
[4]Э.П.罗津克诺普著.从工业气体中回收二氧化硫(南京化工研究院译).北京：化学工业出版社,1966,1-16
[5]南京化学工业公司研究院《硫酸工业》编辑部.低浓度二氧化硫烟气脱硫.上海：上海科学技术出版社,1981,1-256
[6]沈伯雄主编.大气污染控制工程.北京：化学工业出版社,2007,128-140
[7]郝吉明,马广大.大气污染控制工程(第二版).北京：高等教育出版社,2002,306-309
[8]孙克勤,钟秦编.火电厂烟气脱硫系统设计、建造及运行.北京：化学工业出版社,2005,2-10
[9]蒋文举主编.烟气脱硫脱硝技术手册.北京：化学工业出版社,2007,159-382
[10]王乐亮.水泥立窑的烟气特点及治理方法.山东建材,1996,4：16-19
[11]赵由才,牛冬杰.湿法冶金污染控制技术.北京：冶金工业出版社,2008,69-70,81
[12]World bank group.Sulfur oxides.pollution prevention and control.Pollution Prevention and Abatement Handbook,1998,258-260
[13]Robert E.,Sommerlad,Cranford,N.J..Method for removing sulfur dioxide from flue gases. USP4666690,1987
[14]黄震,石莹.国外烟气脱硫技术.节能与环保,2001,18-21
[15]孙胜奇,陈荣永,王平.我国二氧化硫烟气脱硫技术现状及进展.中国铝业,2005,29(1)：44-47
[16]Taha Ramzi.Environmental and engineering properties of flue gas desulfurization gypsum. Research Record,1993,(1424):14-19
[17]Guilin Hu,Kim Dam Johansen,Stig Wedel,Jens Peter Hansen.Review of the direct sulfation reaction of limestone.Progress in Energy and Combustion Science, 2006,32:386-407
[18]Paolo Davini.Investigation of the SO2 adsorption properties of Ca(OH)2-fly ash systems.Fuel,1996,75(6):713-716
[19]Kuroda iroshi.Limestone-gypsum flue gas desulfurization process.USP4487784, 1984
[20]黄隆焜,刘勇,王大伟.石灰石—石膏脱硫与海水脱硫的应用比较.科技创新报,2007,(31)：36
[21]孙光铭.火电厂石灰石-石膏法与海水法烟气脱硫的比较.能源工程,2009,(2)：45-47
[22]李喜,李俊.烟气脱硫技术研究进展.化学工业与工程,2006,23(4)：351-354
[23]karlsson H.T,Klingspor T. Absorption of hydrochlorid acid of solid slakd lime for flue gas clean up.Air pollute control assoc,1981,18(5):239
[24]吕慧,兰凤春.海水法烟气脱硫工艺在国内火电厂的应用研究.吉林电力,2007,35(4)：23-30
[25]Tandon N,Ramalingam P,Malik A.Q.Dispersion of Flue Gases form Power Plants in Brunei Darussalam.Appl.Geophys,2003,160:405-418
[26]陈东,林继发.湿法烟气脱硫技术简述.陕西环境,2003,10(5)：32-34
[27]周玉昆.威尔曼-劳德烟气脱硫工艺及其发展前景.环境科学动态,989,(8)：6-11
[28]曹霞,陈秀萍.浅谈氢氧化镁法脱硫技术.有色冶金设计与研究,2000,21(1)：47-51
[29]涂瑞.浅谈钙法、镁法脱硫方案的技术分析.有色冶金设计与研究,2008,29(3)：7-8
[30]徐长香,傅国光.氨法烟气脱硫技术综述.电力环境保护,2005,21(2)：17-20
[31]崔莲溪.磷铵肥法(PAFP)烟气脱硫技术.硫酸工业,1992,(4)：3-10
[32]徐正中.磷铵肥法烟气脱硫中试研究.热力发电,1993,(2)：14-19
[33]何涛.柠檬酸钠法制液体二氧化硫.内蒙古石油化工,2007,(3)：23-25
[34]袁孝竞,沙勇,郭卫东.柠檬酸-柠檬酸钠缓冲溶液在烟气脱硫中的应用.石油化工设计,1998,15(4)：35-39
[35]李卫昌.柠檬酸钠法治理冶炼厂低浓度S02.有色金属(冶炼部分),2002,(6)：20-22
[36]赵新宏,符新科,沈明科.柠檬酸盐法处理低浓度SO2烟气的试验研究.中国钼业,2004,28(1)：22-25
[37]Bauer B,Gerner F J,Strathmann H.Development of bipolar membranes. Desalination,1988,(68):279-292
[38]Olusola Sunday Ogundiran.Application of Membranes in Chemically Reactive Systems:[A thesis for the degree of Doctor].America:University of Toledo,1991
[39]Frank N W,Kawamura K,Miller G A.SO2/NOx a natural resource should not go up in smoke.Chem Eng Prog,1985,81(6):30-36
[40]李喜,李俊.烟气脱硫技术研究进展.化学工业与工程,2006,23(4)：351-354
[41]邱炜,周刚,付英杰.干法烟气脱硫综述.电站系统工程,2005,21(3)：19-20
[42]张大欣,徐光,罗经宇.电子束半干法烟气净化技术.环境污染治理技术与设备,2001,2(3)：69-72.
[43]贾利军,刘炳光.我国烟气脱硫技术综述.盐业与化工,2006,35(5)：35-39
[44]于庆波,王新华,秦勤等.我国烟气脱硫技术的发展及应用现状.冶金能源,2000,(6)
[45]Nijdam J.J.Guo.An Experimental Investigation of Agglomeration with One and Two Nozzle Atomization.Drying,2002,Volume A:653
[46]范经涛.工业化烟气脱硫技术综述.山东环境,2003,(3)：40-41
[47]陈亚非.烟气脱硫技术综述(待续).制冷空调与电力机械,2001,22(1)：17-38
[48]陈亚非.烟气脱硫技术综述(续完).制冷空调与电力机械,2001,22(1)：28-30
[49]贺亮,张少峰.半干法烟气脱硫技术研究现状及进展.天津化工,2007,21(2)：18-20
[50]王永慧译.用还原硫法脱除高浓度二氧化硫.有色冶炼,1993,4：37-41
[5l]石林,古国榜,邹智毅.硫化碱溶液脱除工业烟气中的二氧化硫.中山大学学报论丛,1997,(5)：189-192
[52]舒余德,李红剑,尹玉麟.二氧化硫冶炼烟气制硫粉的研究-二氧化硫的吸收.有色金属：冶炼部分,1997,(12)：5-8
[53]I.M.柯尔蜀夫,R.贝尔学等著.容量分析(卷三)(梁树权译).北京：科学出版社,1963,265-276
[54]李红剑,舒余德,饶凌.联立方程组法分别测定多价硫的研究.湖南有色金属,1996,12(1)：62-64
[55]张龙.气体脱硫过程分析方法.北京：化学工业出版社,2006,46-49,74-76,80-83
[56]张深林,斯公敏.硫化钠脱硫制碱.环境污染与防治,1995,17(3)：1-2
[57]Tung Siu.Kinetic and Mechanistic Study Aqueous Slufide-Sulfite-Thiosulfate System:[A thesis for the degree of Master].Canada:University of Toronto,1999
[58]Miller,Ralph.Production of hydrogen sulfide from sulfur dioxide obtained from flue gas.EP0000251(Al),1979
[59]Miller,Ralph.Production of sulfur from sulfur dioxide obtained from flue gas.EP0246403(Al),1987
[60]夏士朋.多硫化钠的制取.四川化工,1994,(2)：14-16
[61]林平娣.无机化学热力学.北京：北京师范大学出版社,1986,136-144
[62]姜涛,许时.硫代硫酸盐提金理论研究-浸金的化学及热力系原理.黄金,1992,13(2)：31-34
[63]Robert C.West.CRC Handbook Chemistry and Physics.Boca Raton,FL:CRC Press,69ed,1988-1989,D-87
[64]张平民.工科大学化学.湖南：湖南教育出版社,2002,294-336
[65]张立红.碱溶液烟气脱硫的热力学计算.殷都学刊(自然科学版),1997,(1)：41-44
[66]Young Sun Mok.Absorption-reduction technique assisted by ozone injection and sodium sulfide for NOx removal from exhaust gas.Chemical Engineering Journal,2006,118:63-67
[67]国家环境保护总局,水和废水监测分析方法编委会编.水和废水监测分析方法.北京：中国环境科学出版社,2002,164-165,266-268,271-274
[68]Yamamoto T.,OkuboM.,Nakao T.,Hayakawa K.,IEEE Trans.Ind.Appl.2002,38: 1168-1173.
[69]Siddiqi M.A.,Petersen J..A Study of the Effect of Nitrogen Dioxide on the Absorption of Sulfur Dioxide in Wet Flue Gas Cleaning Processes.Ind.Eng. Chem.Res,2001,40(9):2116-2127
[70]王珲,宋蔷,杨小勇.氮氧化物在湿法烟气脱硫过程中的作用.煤炭转化,2005,28(3)：43-46
[71]Takeuchi H.,Ando M.,Kizawa N.Absorption of Nitrogen Oxides in Aqueous Sodium Sulfite and Bisulfite Solutions.Ind.Eng.Chem.Process Des.Dev,1977, 16:303-308.
[72]Sato T.,Matani S.,Okabe T.The Oxidation of Sodium Sulfite with Nitrogen Dioxide.With Special Reference to Analytical Methods for Nitrogen-Sulfur Compounds Produced in the Reaction System.Nippon Kaguku Kaishi,1979,7: 869-878.
[73]Lee Y.N.,Schwartz S.E.Kinetics of Oxidation of Aqueous Sulfur(IV) by Nitrogen Dioxide.Fourth International Conference on Precipitation Scavenging,Dry Deposition,and Resuspension,St.Monica,CA,1982;Elsevier:New York,1982.
[74]Little john D.,Wang Y.,Chang S.GOxidation of Aqueous Sulfite Ion by Nitrogen Dioxide.Environ.Sci.Technol,1993,27:2162-2167.
[75]Chang S.G,Littlejohn D.,Lin N.H.Kinetics of Reactions in a Wet Flue Gas Simultaneous Desulfurization and Denitrification System.ACS Symp.Ser,1982, 188:127-152.
[76]陆少红,宫葵.硫氮液相反应研究进展.沈阳航空工业学院学报,2004,21(2)：76-79
[77]傅军,肖博文,涂晋林.NOX、S02液相反应研究进展——一种同时脱硫脱氮的新思路.化工进展,1999,(1)：26-28
[78]吴晓琴,童仕唐,吴高明.CO2对Na2S脱除S02同时制取H2S过程的影响.武汉科技大学学报(自然科学版),2005,28(3)：249-251