亚硫酸钙脱硫法研究
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摘要
本文是针对目前国内应用最为广泛的石灰湿法脱硫存在的设
备易结垢和堵塞问题而进行的亚硫酸钙脱硫法的研究。其实质是
以全钙基物质为脱硫剂的新型间接石灰法，它不象“双碱法”、“碱
式硫酸铝法”等间接石灰法那样消耗钠或铝。因此该法能连续、
稳定、高效率、低费用地脱硫。课题旨在从理论上解释、实践上
解决石灰湿法脱硫过程中设备结垢的问题，以期促进国内烟气湿
法脱硫的发展。
笔者导师较早前在国内外首次进行了不同pH值下石灰湿法
脱硫反应机理的研究，指出pH值不同时，脱硫的主要反应是不
同的，在此基础上提出了亚硫酸钙脱硫法。本项研究进一步深入
研究了不同pH值下石灰湿法脱硫的反应机理，并通过单因素实
验，探讨了影响这种新方法脱硫效率的各项因素，确定了适宜的
操作条件，并对大量的实验数据进行综合分析，建立了亚硫酸钙
脱硫效率的预测模型，可供脱硫工程设计和脱硫效率预测参考。
在适宜的操作条件下进行的中试结果表明，亚硫酸钙悬浮液脱硫
效率可达87％以上，排气中SO_2可以达到国家排放标准。
同时本项研究在国内外首次测定了作为亚硫酸钙脱硫法中间
产物的亚硫酸氢钙的饱和浓度（30℃时的饱和浓度为0.6126mol/L）
及不同温度和浓度下的分解性能，建立了分解温度与对应浓度的
函数关联式，具有一定理论和实际意义，为亚硫酸钙脱硫法的实
际应用提供了理论依据和重要设计参数。
本项研究还考察了影响CaSO_3·1/2H_2O氧化反应的多种因
素，结果表明pH值是影响CaSO_3·1/2H_2O氧化反应的最主要因
素，反应温度对氧化率的影响仅次于pH值，在实验确定的适宜
操作条件下，氧化率可达96％以上。连续运行时，氧化塔内物料
始终处于高氧化率状态，几乎没有HSO_3~-分解副反应发生，可
以实现工业化。
Abstract
Aiming for the scaling problem lying in wet desulfuriZation with
lime slurry which has been widely aPplied, a method of
desulfuriZation with calcium sulfite is stUdied. The method can insure
desulfuriZation system to be run economically and teliab1y, which is
a novel indirect lime-method with Ca-contalned material as
desulfuriZation agent. Our research aims at theoretica1ly and
practically solving the scaling problems and pushing wet
desulfuriZation to be developed in our country
Reaction mechanism of lime wet desulfuriZation under varying
the value of pH has been studied by Penman teacher for the first time
before. The exPerirnental results show that main reactions during
desulfuriZation are different under varying the value of pH. Based on
the study, a method of calcium sulfite desulfurization is put forward,
and reaction mechanism is thorough studied in the paPeL via single
factof, the effectS of different conditions on desulfuriZaion efficiency
with the new method are probed into, and the optdrim conditions are
obtained. On the basis of many exPeriment datu, a math model is
raised, Which is a reference for engineering design and predicting
desulfuriZaion efficiency. The pilot-plant exPerimefltal results show
that desulfurization efficiency can be over 87% under the optimum
conditions.
The saforation concentration (0.6126 moljL under the
tempertae of 30C) and decomPose caPability of calcium bisulfite
under different temPeratUre and concentration are studied for the first
time, and a math model is developed correlating decomPosed
temPerthee and correspondence concentration, which provide
theoretic basis and imPortan design parameter for having been
aPplied method of calcium sulfite desulhozation in industry
Moreover, the study on the effects of different conditions on calcium sulfite oxidation reaction is carried out, and the experimental results indicate that the value of p1-I and reaction temperature are the most principal factors. Under the optimum conditions, the oxidation efficiency is more than 96%. When keeping on operating, the concentration of calcium sulfite is lower in oxidation tower and no decompose side reaction of HSO7 begets. So the craft may be industrialized.
备易结垢和堵塞问题而进行的亚硫酸钙脱硫法的研究。其实质是
以全钙基物质为脱硫剂的新型间接石灰法，它不象“双碱法”、“碱
式硫酸铝法”等间接石灰法那样消耗钠或铝。因此该法能连续、
稳定、高效率、低费用地脱硫。课题旨在从理论上解释、实践上
解决石灰湿法脱硫过程中设备结垢的问题，以期促进国内烟气湿
法脱硫的发展。
笔者导师较早前在国内外首次进行了不同pH值下石灰湿法
脱硫反应机理的研究，指出pH值不同时，脱硫的主要反应是不
同的，在此基础上提出了亚硫酸钙脱硫法。本项研究进一步深入
研究了不同pH值下石灰湿法脱硫的反应机理，并通过单因素实
验，探讨了影响这种新方法脱硫效率的各项因素，确定了适宜的
操作条件，并对大量的实验数据进行综合分析，建立了亚硫酸钙
脱硫效率的预测模型，可供脱硫工程设计和脱硫效率预测参考。
在适宜的操作条件下进行的中试结果表明，亚硫酸钙悬浮液脱硫
效率可达87％以上，排气中SO_2可以达到国家排放标准。
同时本项研究在国内外首次测定了作为亚硫酸钙脱硫法中间
产物的亚硫酸氢钙的饱和浓度（30℃时的饱和浓度为0.6126mol/L）
及不同温度和浓度下的分解性能，建立了分解温度与对应浓度的
函数关联式，具有一定理论和实际意义，为亚硫酸钙脱硫法的实
际应用提供了理论依据和重要设计参数。
本项研究还考察了影响CaSO_3·1/2H_2O氧化反应的多种因
素，结果表明pH值是影响CaSO_3·1/2H_2O氧化反应的最主要因
素，反应温度对氧化率的影响仅次于pH值，在实验确定的适宜
操作条件下，氧化率可达96％以上。连续运行时，氧化塔内物料
始终处于高氧化率状态，几乎没有HSO_3~-分解副反应发生，可
以实现工业化。
Abstract
Aiming for the scaling problem lying in wet desulfuriZation with
lime slurry which has been widely aPplied, a method of
desulfuriZation with calcium sulfite is stUdied. The method can insure
desulfuriZation system to be run economically and teliab1y, which is
a novel indirect lime-method with Ca-contalned material as
desulfuriZation agent. Our research aims at theoretica1ly and
practically solving the scaling problems and pushing wet
desulfuriZation to be developed in our country
Reaction mechanism of lime wet desulfuriZation under varying
the value of pH has been studied by Penman teacher for the first time
before. The exPerirnental results show that main reactions during
desulfuriZation are different under varying the value of pH. Based on
the study, a method of calcium sulfite desulfurization is put forward,
and reaction mechanism is thorough studied in the paPeL via single
factof, the effectS of different conditions on desulfuriZaion efficiency
with the new method are probed into, and the optdrim conditions are
obtained. On the basis of many exPeriment datu, a math model is
raised, Which is a reference for engineering design and predicting
desulfuriZaion efficiency. The pilot-plant exPerimefltal results show
that desulfurization efficiency can be over 87% under the optimum
conditions.
The saforation concentration (0.6126 moljL under the
tempertae of 30C) and decomPose caPability of calcium bisulfite
under different temPeratUre and concentration are studied for the first
time, and a math model is developed correlating decomPosed
temPerthee and correspondence concentration, which provide
theoretic basis and imPortan design parameter for having been
aPplied method of calcium sulfite desulhozation in industry
Moreover, the study on the effects of different conditions on calcium sulfite oxidation reaction is carried out, and the experimental results indicate that the value of p1-I and reaction temperature are the most principal factors. Under the optimum conditions, the oxidation efficiency is more than 96%. When keeping on operating, the concentration of calcium sulfite is lower in oxidation tower and no decompose side reaction of HSO7 begets. So the craft may be industrialized.
引文
[1] Kohl A L and Riesenfeld F C, Gas Purification, Third Edition, Gulf Publishing Company, 1979, 278-302。
[2] Stem C, Air Pollution-Engineering Control of Air Pollution, Third Edition, VolumeⅣ, Academic Press., 1977, 411-500。
[3] Wark K and Warner C F, Air Pollution-Its Origin and Control, Thomas Y. Crowell Company Inc., 1976, 343-345。
[4] Mogami and Koichi, Wet lime-gypsum scrubber for flue gas desulfurization, JP 63 49,229, 1988。
[5] Nakao and Motoroku, PH adjustment for recycling of flue gas desulfurizing slurry, JP 62,273,037, 1987。
[6] Ishiguro and Okikazu, Scrubbing solution control for flue gas desulfurization, JP 62,204,829, 1987。
[7] 《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，1981，93～101。
[8] Paul N. Cheremisinoff & Richard A. Young, Air Pollution Control and Design Handbook, Part 2, Marcel Dekker Inc., New York and Basel, 1977。
[9] Seinfeld J H , Air Pollution: : Physical and Chemical Fundamentals, McGraw-Hill Inc. , 1975, 439-442。
[10] Homer W and Parker P E, Air pollution, Prentice-Hall Inc. , 1977, 269-271。
[11] Calvert S and Englund H M, Handbook of Air Pollution Technology, John Wileyand Sons Inc. , 1984, 653-654。
[12] Flagan R C and Seinfeld J H, Fundamentals of Air Polluton Engineering, PRENTICE HALL, Englewood Cliffs, New Jersey, 1976, 505-512。
[13] P.Zannetti, C.A.Brebbia, J.E.Garcia, Gardea and G.Ayala
Milian, Air Pollution, Computational Mechanics Publications, 1993, 693～697。
[14] Albert Parker, Industrial Air Pollotion Handbook, MCGRAWHILL BOOK Company(uk), 1978, 285～287。
[15] 林肇信，童志权等，大气污染控制工程，北京：高等教育出版社，1991，445～446。
[16] 内韦尔，大气污染控制工程，北京：清华大学出版社，2000，414～421。
[17] 郝吉明，马广大等，大气污染控制工程，北京：高等教育出版社，1999，329～337。
[18] 童志权，陈焕钦，工业废气污染控制与利用，北京：化学工业出版社，1989，317。
[19] 张天生，杨新建，化工环保，(6)(1983)，339～342。
[20] 蒲恩奇等，大气污染控制工程，北京：高等教育出版社，1999，218～219。
[21] 季学李，大气污染控制工程，上海：同济大学出版社，1992，392～393。
[22] 陈昭琼，童志权，pH值对石灰(石灰石)湿法脱硫反应机理的影响，环境科学，17(5)(1996)，42～44。
[23] Huss A et. al, Oxidation of Aqueous Sulfur Dioxide, 1.Homogeneous Manganese(Ⅱ) and Iron(Ⅱ) Catalysis at Low pH, J. Phys. Chem., 86(1982), 4225。
[24] 曾昭掄，陶坤，无机物和有机化合物的主要性质，苏联化学手册(第二册)，科学出版社，1956，90。
[25] CRC Handbook of Chemistry and Physics, 第70版，1989～1990。
[26] 天津化工研究院等，无机盐工业手册，第二版，下册，化工出版社，1996，1342。
[27] 顾庆超等，化学用表，江苏科学技术出版社，1979，2～70。
[28] Shinoda, Tatani, Takashina and Onizuka, Method for desulfurizing smoke[P], JP: 0263057, 1988。
[29] John W, Method of sulfur dioxide removal from gaseous streams with alphy-hemihydate gypsum product formation[P], US: 5,312,609, 1994。
[30] Bang M. Kim, Effluent gas desulfurization with conversion to gypsum of large partical size[p], US. 4,587,112, 1986。
[31] Ronald J. Rathi, Flue gas desulfurization with oxidation of calcium sulfite in FGD discharges[P], US: 4,976,936, 1990。
[32] Ronald J. Rathi, Flue gas desulfurization with oxidation of calcium sulfite in FGD discharges[P], US: 4,976,936, 1990。
[33] 童志权，陈昭琼，“旋风水膜—XP型塔板”二级脱硫除尘装置的工业实践，见：中国环境科学学会编，燃煤烟气脱硫技术(全国燃煤烟气脱硫技术交流会论文集)，青岛：1988。
[2] Stem C, Air Pollution-Engineering Control of Air Pollution, Third Edition, VolumeⅣ, Academic Press., 1977, 411-500。
[3] Wark K and Warner C F, Air Pollution-Its Origin and Control, Thomas Y. Crowell Company Inc., 1976, 343-345。
[4] Mogami and Koichi, Wet lime-gypsum scrubber for flue gas desulfurization, JP 63 49,229, 1988。
[5] Nakao and Motoroku, PH adjustment for recycling of flue gas desulfurizing slurry, JP 62,273,037, 1987。
[6] Ishiguro and Okikazu, Scrubbing solution control for flue gas desulfurization, JP 62,204,829, 1987。
[7] 《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，1981，93～101。
[8] Paul N. Cheremisinoff & Richard A. Young, Air Pollution Control and Design Handbook, Part 2, Marcel Dekker Inc., New York and Basel, 1977。
[9] Seinfeld J H , Air Pollution: : Physical and Chemical Fundamentals, McGraw-Hill Inc. , 1975, 439-442。
[10] Homer W and Parker P E, Air pollution, Prentice-Hall Inc. , 1977, 269-271。
[11] Calvert S and Englund H M, Handbook of Air Pollution Technology, John Wileyand Sons Inc. , 1984, 653-654。
[12] Flagan R C and Seinfeld J H, Fundamentals of Air Polluton Engineering, PRENTICE HALL, Englewood Cliffs, New Jersey, 1976, 505-512。
[13] P.Zannetti, C.A.Brebbia, J.E.Garcia, Gardea and G.Ayala
Milian, Air Pollution, Computational Mechanics Publications, 1993, 693～697。
[14] Albert Parker, Industrial Air Pollotion Handbook, MCGRAWHILL BOOK Company(uk), 1978, 285～287。
[15] 林肇信，童志权等，大气污染控制工程，北京：高等教育出版社，1991，445～446。
[16] 内韦尔，大气污染控制工程，北京：清华大学出版社，2000，414～421。
[17] 郝吉明，马广大等，大气污染控制工程，北京：高等教育出版社，1999，329～337。
[18] 童志权，陈焕钦，工业废气污染控制与利用，北京：化学工业出版社，1989，317。
[19] 张天生，杨新建，化工环保，(6)(1983)，339～342。
[20] 蒲恩奇等，大气污染控制工程，北京：高等教育出版社，1999，218～219。
[21] 季学李，大气污染控制工程，上海：同济大学出版社，1992，392～393。
[22] 陈昭琼，童志权，pH值对石灰(石灰石)湿法脱硫反应机理的影响，环境科学，17(5)(1996)，42～44。
[23] Huss A et. al, Oxidation of Aqueous Sulfur Dioxide, 1.Homogeneous Manganese(Ⅱ) and Iron(Ⅱ) Catalysis at Low pH, J. Phys. Chem., 86(1982), 4225。
[24] 曾昭掄，陶坤，无机物和有机化合物的主要性质，苏联化学手册(第二册)，科学出版社，1956，90。
[25] CRC Handbook of Chemistry and Physics, 第70版，1989～1990。
[26] 天津化工研究院等，无机盐工业手册，第二版，下册，化工出版社，1996，1342。
[27] 顾庆超等，化学用表，江苏科学技术出版社，1979，2～70。
[28] Shinoda, Tatani, Takashina and Onizuka, Method for desulfurizing smoke[P], JP: 0263057, 1988。
[29] John W, Method of sulfur dioxide removal from gaseous streams with alphy-hemihydate gypsum product formation[P], US: 5,312,609, 1994。
[30] Bang M. Kim, Effluent gas desulfurization with conversion to gypsum of large partical size[p], US. 4,587,112, 1986。
[31] Ronald J. Rathi, Flue gas desulfurization with oxidation of calcium sulfite in FGD discharges[P], US: 4,976,936, 1990。
[32] Ronald J. Rathi, Flue gas desulfurization with oxidation of calcium sulfite in FGD discharges[P], US: 4,976,936, 1990。
[33] 童志权，陈昭琼，“旋风水膜—XP型塔板”二级脱硫除尘装置的工业实践，见：中国环境科学学会编，燃煤烟气脱硫技术(全国燃煤烟气脱硫技术交流会论文集)，青岛：1988。
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