烟气循环流化床联合脱硫脱氮模型和机理研究
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摘要
本论文首先对烟气循环流化床的流场、温度场进行分析,确定了速度场和浓度场的分布,并建立了床内温度模型。然后在此基础上,根据流化床内喷水活化脱硫的特点,对未捕集水滴的新鲜干燥脱硫剂颗粒、干燥再循环颗粒和与水滴碰撞形成的含水吸收剂颗粒分别采用表面覆盖模型、气固反应模型和浆滴脱硫反应模型,从而得到了应用高活性吸收剂的烟气循环流化床总的脱硫模型。模型计算值与实验值误差在5.5%以内。此外,本文还建立了烟气循环流化床脱氮模型,计算误差在2%以内。本论文的研究工作,为开发适合我国国情的烟气脱硫脱氮装置提供了理论参考。
At the beginning of the paper the distribution of the velocity and concentration are obtained and a model about temperature is proposed. Then according to the analysis of the spraying water that can activate the sorbents a model about flue gas desulfurization by highly active absorbent is proposed. In the model, three factors are taken into account: gas-liquid reaction of slurry droplet, gas-solid reaction of dry circulating particles and surface coverage reaction of dry fresh particles. The higher accuracy of the model was exhibited with a max error of 5.5%. At last, denitrification mechanism of highly active sorbent is analyzed in detail, and a model about flue gas denitrification by highly active absorbent is achieved with a max error of 2%. Study works of the dissertation provide theoretical references for flue gas of desulfurization and denitrification that fitted the situation of our country.
At the beginning of the paper the distribution of the velocity and concentration are obtained and a model about temperature is proposed. Then according to the analysis of the spraying water that can activate the sorbents a model about flue gas desulfurization by highly active absorbent is proposed. In the model, three factors are taken into account: gas-liquid reaction of slurry droplet, gas-solid reaction of dry circulating particles and surface coverage reaction of dry fresh particles. The higher accuracy of the model was exhibited with a max error of 5.5%. At last, denitrification mechanism of highly active sorbent is analyzed in detail, and a model about flue gas denitrification by highly active absorbent is achieved with a max error of 2%. Study works of the dissertation provide theoretical references for flue gas of desulfurization and denitrification that fitted the situation of our country.
引文
[1]陈英旭.环境学.北京:中国环境科学出版社,2001.129～134
[2]郝吉明.燃煤SO_2污染控制手册.北京:化工出版社,2001.7～9
[3]钟秦.燃煤烟气脱硫脱硝技术及工程实例.北京:化学工业出版社,2002.231～234
[4]王德荣,林彦奇,赵蔚,等.利用焦炭吸附进行燃煤烟气脱硫脱氮技术的研究.环境保护科学,2002,28(2):4～6
[5]贺儒梁.电站烟气脱硫脱氮工艺-德国AMASOXI 方法.冶金环境保护, 1998,1:15～17
[6]Farber P.S.NOX and SO2 Removal in high sulfur spay dryer system. In:International Conference on Processing and Utilization of High Sulfur Coals.Cavondale, 1987.134～141
[7]陈锐.排烟循环流化床脱硫的实验和机理研究:[硕士学位论文].北京,清华大学,1996
[8]单志峰,黄友明.国外烟气同步脱硫脱氮技术现状.冶金环境保护, 1999,4:40～45
[9]Xu Guangwen.Innovative combined desulphurization/denitration process using a powder-particle fluidized bed.Process Safety and Environmental Protection : Transactions of the Instituion of Chemical Engineers, 1999,77(2):77～87
[10]Xu Guangwen.Adaptive sorbent for the combined desulfurization /denitration process using a power-particle fluidized bed. Industrial and Engineering Chemistry Research, 2000,39(7):2190～2198
[11]Xu Guangwen.Removal efficiency of the combined desulfurization /denitration process using power-particle fluidized bed.Journal of Chemical Engineering of Japan,1999,32(1):82～90
[12] Moyeda D.K., Newton G.H., Lafond J.F.Rate controlling processes and enhancement strategies in humidification for duct SO2 capture. In:EPA/600/S2-88-047,1988.278～290
[13]H.Yoon, M.R.Stouffer.Pilot process variable study of cool side desulphurization. Environ. Prog. , 1988,7(2):104～111
[14]吴忠标,谭天恩.石灰浆滴脱硫-干燥关系的模拟研究.高校化学工程学报,1993,7(2):27～31
[15]Gerald H.Newton, John Kramlich, Roy Payne. Modeling the SO2 slurry droplet reaction.AIChE Journal,1990,36(12):1865～1872
[16]James K.Neathery.Model for flue gas desulfurization in a circulating dry scrubber.AICHE Jouranl,1996,42(1):259～268
[17]Jiang M.X., Keener T.C., Khang S.J.The use of a circulating fluidized bed absorber for the control of sulfur dioxide emissions by calcium oxide sorbent via in situ hydration.Powder Technology,1995,85:115～126
[18]Liu C .F., Shih S.A surface coverage model for the reaction of Ca(OH)_2 with SO_2 at low temperatures.Journal of the Chinese Institute of Chemical Engineers,2002,33(4):407～413
[19]Claussen R.L., Martin C.E.Duct injection technology: Engineering and design for commercial applications in proceedings.Utilization and Environmental Control Contractors Conference,Pittsburgy,Pennsylvania, 1992. 177～183
[20]朱中华.循环流化床烧结烟气脱硫机理及系统模型化过程的研究:[硕士学位论文].西安: 西安建筑科技大学,1995
[21]黄震.循环流化床烟气脱硫技术的实验和应用研究:[博士学位论文].南京:东南大学,1997
[22]谭忠超.循环流化床烟气脱硫数学模型与机理实验研究:[硕士学位论文].北京:清华大学学位论文,1999
[23]吴颖海.循环流化床烟气脱硫模拟中试实验和理论研究:[博士学位论文].南京:东南大学,2000
[24]马双忱.烟气循环流化床脱硫技术实验研究:[博士学位论文].保定:华北电力大学,2002
[25]Yoon H., Withum J.A., Rosehoover W.A., et al.Sorbent improvement and computer modeling studies for coolside desulfurization.In:1986 Joint Symposium on Dry SO_2 and Simultaneous SO_2/NO_X control Technologies, EPRI CS-4966,1986.326～332
[26]Lepovitz L.R., Brown C.A., Pearson T.E., et al.10Mw Demonstration of the ADVACATE flue gas desulfurization process.In:Preceedings of the 1993 SO_2 Control Symposium,Boston,1993.278～292
[27]陈甘棠,王樟茂.流态化技术的理论和应用.北京:中国石化出版社,1996:186～210
[28]岑可法,倪明江,骆仲泱,严建华.循环流化床锅炉理论设计与运行.北京:中国电力出版社,1998,63～64
[29] 毕晓涛,金涌,俞芷青.循环流态化(Ⅰ).化学反应工程与工艺,1991,7(2):56～61
[30] Bai D., Jin Y.Flow regimes in circulating fluidized beds.Chemical Engineering and Technology,1993,6:307～313
[31]Bai D., Kato K.1995 Saturation carrying capacity of gas and flow regimes in CFB.Journal of Chemical Engineering of Japan,28:179～185
[32]白丁荣,金涌,俞芷青.循环流化床内颗粒加速作用及气固两相间的动量交换.化学反应工程与工艺,1991,7(3),260～270
[33]金涌,祝京旭,王展文.流态化工程原理.北京:清华大学出版社,2001:123～152
[34]Werther J.Fluid mechanics of large-scale units.Circulating Fluidized Bed Technology, 1994,4:1～14
[35]Tung Y., Li J.Radial voidage profiles in a fast fluidized bed fluidization: Science and Technology.北京:科学出版社,1988,139～145
[36]骆仲泱,倪明江,岑可法.循环流化床流体动力特性的试验研究.浙江大学学报,1987,27(6):84～92
[37]李佑楚,陈丙瑜,王风鸣.快速流态化的试验研究.化工冶金,1980,4:20～45
[38]谢锐生.热力学原理.北京:人民教育出版社,1980,260～262
[39]Neathery James Kyle.A fundamental study of circulating bed absorption for flue gas desulfurization:[Ph.D. dissertation]. University of Kentucky, 1993
[40]V.Dubroveky.Particle interaction in three-phase polydisperse flows. Int.J.Multiphase Flow, 1992,18(3):337～352
[41]Christopher H.Nelli, Gary T.Rochelle.Simultaneous sulfur dioxide and nitrogen dioxide removal by calcium hydroxide and calcium silicate solids.Journal of the Air and Waste Management Association,1998,48 (9):819～828
[42]王乃华.新型半干法烟气脱硫的实验及机理研究:[博士学位论文].杭州:浙江大学,2001
[43]Chiung Fang Liu, Shin Min Shih, Ren Bin Lin.Kinetics of the reaction of Ca(OH)_2/fly ash sorbent with SO_2 at low temperatures. Chemical Engineering Science,2002,57:93～104
[44]A.F. Shaban.Determination of the kinetic parameters of the reaction between SO_2 and using the thermogravimetric technique.Thermochemical Acta, 1991,180:9～21
[45]Gerea.Kinetic of flue gas desulfurization at low temperatures using Ca(OH)_2 with SO_2: Competitive reactions of sulfation and Carbonation. Chemical Engineering Science,2001,56:1387～1393
[46]Newton G.H., Kramlich J., Payne R.Modeling the SO_2-Slurry Droplet Reaction.ACIhE J., 1990,36:1865～1872
[47]Rabe A.E., Harris J.E.Vapor liquid equilibrium data for the binary system.Sulfur dioxide and Water, J.of Chem.Eng.Data, 1963, 8:133～136
[48]樊保国.循环流化床烟气脱硫技术的实验研究:[硕士学位论文].北京:清华大学,1996
[49]黄建军.烟气循环流化床脱硫脱氮技术实验研究:[硕士学位论文].保定:华北电力大学,2003
[50] Chu H., Chien T.W. Simultaneous absorption of SO_2 and NO from flue gas with KMnO4/NaOH solutions. The Science of the Total Environment, 2001,275:127～135
[51] Sada E, Kumazawa H, Hayakawa N, Kudo I, Kondo T. Absorption of NO in aqueous solution of KMnO4. Chemical Engineering Science, 1977,32:1171～1175
[52]李汝辉.传质学基础.北京:北京航空学院出版社,1987,111～112
[53]王志魁.化工原理.北京:化学工业出版社,1987: 210～212
[2]郝吉明.燃煤SO_2污染控制手册.北京:化工出版社,2001.7～9
[3]钟秦.燃煤烟气脱硫脱硝技术及工程实例.北京:化学工业出版社,2002.231～234
[4]王德荣,林彦奇,赵蔚,等.利用焦炭吸附进行燃煤烟气脱硫脱氮技术的研究.环境保护科学,2002,28(2):4～6
[5]贺儒梁.电站烟气脱硫脱氮工艺-德国AMASOXI 方法.冶金环境保护, 1998,1:15～17
[6]Farber P.S.NOX and SO2 Removal in high sulfur spay dryer system. In:International Conference on Processing and Utilization of High Sulfur Coals.Cavondale, 1987.134～141
[7]陈锐.排烟循环流化床脱硫的实验和机理研究:[硕士学位论文].北京,清华大学,1996
[8]单志峰,黄友明.国外烟气同步脱硫脱氮技术现状.冶金环境保护, 1999,4:40～45
[9]Xu Guangwen.Innovative combined desulphurization/denitration process using a powder-particle fluidized bed.Process Safety and Environmental Protection : Transactions of the Instituion of Chemical Engineers, 1999,77(2):77～87
[10]Xu Guangwen.Adaptive sorbent for the combined desulfurization /denitration process using a power-particle fluidized bed. Industrial and Engineering Chemistry Research, 2000,39(7):2190～2198
[11]Xu Guangwen.Removal efficiency of the combined desulfurization /denitration process using power-particle fluidized bed.Journal of Chemical Engineering of Japan,1999,32(1):82～90
[12] Moyeda D.K., Newton G.H., Lafond J.F.Rate controlling processes and enhancement strategies in humidification for duct SO2 capture. In:EPA/600/S2-88-047,1988.278～290
[13]H.Yoon, M.R.Stouffer.Pilot process variable study of cool side desulphurization. Environ. Prog. , 1988,7(2):104～111
[14]吴忠标,谭天恩.石灰浆滴脱硫-干燥关系的模拟研究.高校化学工程学报,1993,7(2):27～31
[15]Gerald H.Newton, John Kramlich, Roy Payne. Modeling the SO2 slurry droplet reaction.AIChE Journal,1990,36(12):1865～1872
[16]James K.Neathery.Model for flue gas desulfurization in a circulating dry scrubber.AICHE Jouranl,1996,42(1):259～268
[17]Jiang M.X., Keener T.C., Khang S.J.The use of a circulating fluidized bed absorber for the control of sulfur dioxide emissions by calcium oxide sorbent via in situ hydration.Powder Technology,1995,85:115～126
[18]Liu C .F., Shih S.A surface coverage model for the reaction of Ca(OH)_2 with SO_2 at low temperatures.Journal of the Chinese Institute of Chemical Engineers,2002,33(4):407～413
[19]Claussen R.L., Martin C.E.Duct injection technology: Engineering and design for commercial applications in proceedings.Utilization and Environmental Control Contractors Conference,Pittsburgy,Pennsylvania, 1992. 177～183
[20]朱中华.循环流化床烧结烟气脱硫机理及系统模型化过程的研究:[硕士学位论文].西安: 西安建筑科技大学,1995
[21]黄震.循环流化床烟气脱硫技术的实验和应用研究:[博士学位论文].南京:东南大学,1997
[22]谭忠超.循环流化床烟气脱硫数学模型与机理实验研究:[硕士学位论文].北京:清华大学学位论文,1999
[23]吴颖海.循环流化床烟气脱硫模拟中试实验和理论研究:[博士学位论文].南京:东南大学,2000
[24]马双忱.烟气循环流化床脱硫技术实验研究:[博士学位论文].保定:华北电力大学,2002
[25]Yoon H., Withum J.A., Rosehoover W.A., et al.Sorbent improvement and computer modeling studies for coolside desulfurization.In:1986 Joint Symposium on Dry SO_2 and Simultaneous SO_2/NO_X control Technologies, EPRI CS-4966,1986.326～332
[26]Lepovitz L.R., Brown C.A., Pearson T.E., et al.10Mw Demonstration of the ADVACATE flue gas desulfurization process.In:Preceedings of the 1993 SO_2 Control Symposium,Boston,1993.278～292
[27]陈甘棠,王樟茂.流态化技术的理论和应用.北京:中国石化出版社,1996:186～210
[28]岑可法,倪明江,骆仲泱,严建华.循环流化床锅炉理论设计与运行.北京:中国电力出版社,1998,63～64
[29] 毕晓涛,金涌,俞芷青.循环流态化(Ⅰ).化学反应工程与工艺,1991,7(2):56～61
[30] Bai D., Jin Y.Flow regimes in circulating fluidized beds.Chemical Engineering and Technology,1993,6:307～313
[31]Bai D., Kato K.1995 Saturation carrying capacity of gas and flow regimes in CFB.Journal of Chemical Engineering of Japan,28:179～185
[32]白丁荣,金涌,俞芷青.循环流化床内颗粒加速作用及气固两相间的动量交换.化学反应工程与工艺,1991,7(3),260～270
[33]金涌,祝京旭,王展文.流态化工程原理.北京:清华大学出版社,2001:123～152
[34]Werther J.Fluid mechanics of large-scale units.Circulating Fluidized Bed Technology, 1994,4:1～14
[35]Tung Y., Li J.Radial voidage profiles in a fast fluidized bed fluidization: Science and Technology.北京:科学出版社,1988,139～145
[36]骆仲泱,倪明江,岑可法.循环流化床流体动力特性的试验研究.浙江大学学报,1987,27(6):84～92
[37]李佑楚,陈丙瑜,王风鸣.快速流态化的试验研究.化工冶金,1980,4:20～45
[38]谢锐生.热力学原理.北京:人民教育出版社,1980,260～262
[39]Neathery James Kyle.A fundamental study of circulating bed absorption for flue gas desulfurization:[Ph.D. dissertation]. University of Kentucky, 1993
[40]V.Dubroveky.Particle interaction in three-phase polydisperse flows. Int.J.Multiphase Flow, 1992,18(3):337～352
[41]Christopher H.Nelli, Gary T.Rochelle.Simultaneous sulfur dioxide and nitrogen dioxide removal by calcium hydroxide and calcium silicate solids.Journal of the Air and Waste Management Association,1998,48 (9):819～828
[42]王乃华.新型半干法烟气脱硫的实验及机理研究:[博士学位论文].杭州:浙江大学,2001
[43]Chiung Fang Liu, Shin Min Shih, Ren Bin Lin.Kinetics of the reaction of Ca(OH)_2/fly ash sorbent with SO_2 at low temperatures. Chemical Engineering Science,2002,57:93～104
[44]A.F. Shaban.Determination of the kinetic parameters of the reaction between SO_2 and using the thermogravimetric technique.Thermochemical Acta, 1991,180:9～21
[45]Gerea.Kinetic of flue gas desulfurization at low temperatures using Ca(OH)_2 with SO_2: Competitive reactions of sulfation and Carbonation. Chemical Engineering Science,2001,56:1387～1393
[46]Newton G.H., Kramlich J., Payne R.Modeling the SO_2-Slurry Droplet Reaction.ACIhE J., 1990,36:1865～1872
[47]Rabe A.E., Harris J.E.Vapor liquid equilibrium data for the binary system.Sulfur dioxide and Water, J.of Chem.Eng.Data, 1963, 8:133～136
[48]樊保国.循环流化床烟气脱硫技术的实验研究:[硕士学位论文].北京:清华大学,1996
[49]黄建军.烟气循环流化床脱硫脱氮技术实验研究:[硕士学位论文].保定:华北电力大学,2003
[50] Chu H., Chien T.W. Simultaneous absorption of SO_2 and NO from flue gas with KMnO4/NaOH solutions. The Science of the Total Environment, 2001,275:127～135
[51] Sada E, Kumazawa H, Hayakawa N, Kudo I, Kondo T. Absorption of NO in aqueous solution of KMnO4. Chemical Engineering Science, 1977,32:1171～1175
[52]李汝辉.传质学基础.北京:北京航空学院出版社,1987,111～112
[53]王志魁.化工原理.北京:化学工业出版社,1987: 210～212