石灰消化工艺参数及氢氧化钙溶解速率实验研究
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摘要
本论文的研究工作是国家高技术研究发展计划(863)课题“大中型燃煤锅炉双碱法烟气脱硫技术及设备产业化”子课题(课题编号2001AA642030-1)中的一部分，主要是关于石灰消化工艺及再生池中Ca(OH)_2溶解速率的研究。其目的是研究和优化石灰消化工艺，分析石灰消化反应机理，找到最佳的消化操作条件，提高石灰乳的活性。同时研究双碱法再生池中操作条件对Ca(OH)_2溶解速率的影响，通过优化操作条件，提高石灰的利用率和脱硫效率。
对于石灰消化工艺的研究，主要研究了搅拌强度、石灰粒径、消化水温度、H_2O／CaO和一些常见离子等操作参数对石灰消化过程的影响。通过对这些操作参数的研究与优化，为工业装置提供参考数据。同时，探讨用湿法烟气脱硫过程中的废水或过程循环水消化石灰的可行性。
关于双碱法再生池中Ca(OH)_2溶解速率的研究，主要是模拟再生池中的操作条件，通过恒pH值滴定方法和旋转圆盘系统，研究不同旋转圆盘转速(100～2000rpm)、pH值(4～7)和温度(25～45℃)下Ca(OH)_2溶解速率的变化规律，分析操作条件对Ca(OH)_2溶解速率的影响，找出溶解过程的主要影响参数，从而优化操作条件，提高石灰利用率，降低双碱法烟气脱硫成本等。
The study of this paper is one part of 863 Nation Plan of China under project 2001AA642030-1, whose name is "medium and large scale coal burning boiler dual-alkali FGD technology and equipment industrialization". It mainly studied lime slaking process and Ca(OH)2 dissolution rate in regenerated reactor. Through studying and optimizing lime slaking process, it analyzed the mechanism of lime slaking reaction and found the optimum operating conditions to increase the activity of lime milk. In order to increase utilization rate of lime and desulfurization rate, it also studied the influence of operating conditions on the dissolution rate of Ca(OH)2.
In the study of lime slaking process, it mainly studied the influence of operating parameters including agitation intensity, particle diameter, water temperature, H2O/CaO ratio and some common ions(Cl-, F-, SO42- and SO32-) etc. The experimental result can be applied to industrial lime slaker as a reference. And it discussed the feasibility of recycling wastewater and process water in WFGD as lime slaking water.
Simulating the operating conditions in regenerated reactor of the dual-alkali FGD, the dissolution rate of Ca(OH)2 had been studied by using pH-stat method and rotating disc system. It studied the changing rule of dissolution rate of Ca(OH)2 at different operating conditions including rotating rate(100~2000rpm), pH(4.0-7.0) and temperature(25~55 C). According to the effect of operating conditions on the dissolution rate, the most important parameter was found. Optimizing the operating conditions will increase the utilization rate of lime and reduce desulfurization cost of dual-alkali FGD.
对于石灰消化工艺的研究，主要研究了搅拌强度、石灰粒径、消化水温度、H_2O／CaO和一些常见离子等操作参数对石灰消化过程的影响。通过对这些操作参数的研究与优化，为工业装置提供参考数据。同时，探讨用湿法烟气脱硫过程中的废水或过程循环水消化石灰的可行性。
关于双碱法再生池中Ca(OH)_2溶解速率的研究，主要是模拟再生池中的操作条件，通过恒pH值滴定方法和旋转圆盘系统，研究不同旋转圆盘转速(100～2000rpm)、pH值(4～7)和温度(25～45℃)下Ca(OH)_2溶解速率的变化规律，分析操作条件对Ca(OH)_2溶解速率的影响，找出溶解过程的主要影响参数，从而优化操作条件，提高石灰利用率，降低双碱法烟气脱硫成本等。
The study of this paper is one part of 863 Nation Plan of China under project 2001AA642030-1, whose name is "medium and large scale coal burning boiler dual-alkali FGD technology and equipment industrialization". It mainly studied lime slaking process and Ca(OH)2 dissolution rate in regenerated reactor. Through studying and optimizing lime slaking process, it analyzed the mechanism of lime slaking reaction and found the optimum operating conditions to increase the activity of lime milk. In order to increase utilization rate of lime and desulfurization rate, it also studied the influence of operating conditions on the dissolution rate of Ca(OH)2.
In the study of lime slaking process, it mainly studied the influence of operating parameters including agitation intensity, particle diameter, water temperature, H2O/CaO ratio and some common ions(Cl-, F-, SO42- and SO32-) etc. The experimental result can be applied to industrial lime slaker as a reference. And it discussed the feasibility of recycling wastewater and process water in WFGD as lime slaking water.
Simulating the operating conditions in regenerated reactor of the dual-alkali FGD, the dissolution rate of Ca(OH)2 had been studied by using pH-stat method and rotating disc system. It studied the changing rule of dissolution rate of Ca(OH)2 at different operating conditions including rotating rate(100~2000rpm), pH(4.0-7.0) and temperature(25~55 C). According to the effect of operating conditions on the dissolution rate, the most important parameter was found. Optimizing the operating conditions will increase the utilization rate of lime and reduce desulfurization cost of dual-alkali FGD.
引文
[1]国家环境保护总局．2002年中国环境状况公报．环境保护．2003(7)：3～13
[2]National Lime Association. Wet flue gas desulfurization technology evaluation. Project Number 11311-000. 2003.1
[3]郝吉明，王书肖，陆永琪编著．燃煤二氧化硫污染控制技术手册．北京：化学工业出版社．2001
[4]孙文寿，吴忠标，谭天恩．旋流板塔镁强化石灰脱硫过程研究．环境科学．2001，22(3)：104～107
[5]吴忠标，谭天恩等．旋流板塔内石灰湿法烟气脱硫的试验研究．环境科学学报．1995，8(4)：248～251
[6]晏乃强等．双碱法旋流板塔烟气脱硫工艺．环境科学．1998，19(5)：72～74
[7]施耀．浙江大学博士学位论文．1992．4
[8]吴忠标，刘越，余世清等．废大理石粉湿法烟气脱硫工艺实验研究．环境科学．2002，23(1)：44～47
[9]刘越．浙江大学硕士学位论文．2001．3
[10]俞世清．浙江大学硕士学位论文．2002．5
[11]刘精今等．皂化废水和鼓励烟道气的联合处理技术研究．环境保护科学．1997，23[1]：40～42
[12]刘精今等．碱性工业废水在锅炉烟气脱硫除尘中的应用．环境工程．1996，14[2]：24～27
[13]赵强等．染色废水用于除尘脱硫的技术．环境保护．1996，(4)：16～17
[14]武晓莉等．印染废水和烟气脱硫联合治理的实验研究．水利电力环境保护．2000，(1)：21～23
[15]梁宁等．苎麻脱胶废水喷淋锅炉烟气除尘脱硫降碱的实验研究．中国环境科学．1995，15(3)：219～221
[16]王毓秀等．用燃煤烟气处理造纸黑液的研究．污染防治技术．1995，8(1)：41～44
[17]陈德放等．以废治废—制革工业废水净化方法研究．环境工程．1989，7(6)：6～7，16
[18]谭亚军等．旋流板塔在碱性黑液烟气脱硫中的应用．环境工程．1998，2(1)：33～36
[19]赵建海等．粉煤灰在烟气脱硫方面的应用前景．粉煤灰综合利用．2000(2)：50～52
[20]宗润宽等．钙基烟气脱硫剂的生产研究进展．化工进展，2001，12：12～19
[21]Paolo Davini. Investigation of SO_2 adsorption properties of Ca(OH)_2-Fly ash systems. Flue,1996, 75(6):713～716
[22]N Karatepe et al. Effect of hydration conditions on the physical properties of fly ash
Ca(OH)_2 sorbents, Energy Sources, 1998,20:505～511
[23]Anand Srinvasan et al. The adsorption of SO_2 by zeolites synthesized from fly ash. Environ.Sci. Technol. 1999, 33(9): 1464～1469
[24]时黎明等．水合作用对钙基吸收剂脱硫特性的影响．环境工程．1998，16(2)：37～40
[25]庞亚军等．掺加粉煤灰提高含钙脱硫剂的烟气脱硫率的实验研究．工程热物理学报．1992，13(4)：443～447
[26]宗润宽等．钙基烟气脱硫剂制备的实验研究．环境污染治理技术与设备．2001，2(2)：25～30
[27]陆永琪等．提高钙基吸着剂脱硫活性的试验研究．环境工程．1998，16(5)：30～33
[28]Hiroaki Tsuchiai, Tomohiro Ishizuka, et al. Highly active absorbent for SO_2 removal prepared from coal fly ash. Ind. Eng. Chem. Res. 1995, 34(4):1404～1411
[29]Juan Adanez, Vanessa Fierro, et al. Study of modified calcium hydroxides for enhancing SO_2 removal during sorbent injection in pulverized coal boilers.
[30]Anand Srinvasan et al. The adsorption of SO_2 by zeolites synthesized from fly ash.Environ.Sci.Technol. 1999, 33(9): 1464～1469
[31]席勒，贝伦丝著，陆华，武洞明译．石灰．北京：中国建筑工业出版社．1981
[32]冯敏等．工业水处理技术．北京：海洋出版社．1992
[33]Levenspiel O. Chemical reaction engineering(2nd ed.) New York: Wiley, 1972
[34]Ian M Ritchie, Xu BingAn. The kinetic of lime slaking. Hydrometallurgy, 1990, 23:377～396
[35]D E Giles, I M Ritchie, B A Xu. The kinetics of dissolution of slaked lime. Hydrometallurgy,1993, 32:119～128
[36]L Bernard, M Freche, J L Lacout, B Biscan. Modeling of the dissolution of calcium hydroxide in the preparation of hydroxyapatite by neutralization. Chem. Eng. Sci. 2000,55:5683～5692
[37]Johannsen K, Rademacher S. Modelling the kinetics of calcium hydroxide dissolution in water. Acta Hydrochimica et Hydrobiologica. 1999, 27(2), 72-78
[38]Hilja Lohmus, Ahto Rani, A tend to the production of calcium hydroxide and precipitated calcium carbonate with defined properties, The Canadian Journal of Chemical Engineering, v.80 2002.10
[39]ASTM c110-98 Standard test method for physical testing of quicklime, hydrated lime, and limestone. Annual Book of ASTM Standard vol. 04.01
[40]DIN EN 12485—2001饮用水处理用化学品：碳酸钙、高生石灰和半煅烧白云石试验方法
[41]JC／T478．1-92．建筑石灰物理试验方法
[42]D R Glasson. Reactivity of lime and related oxides I : Production of calcium oxide. J. appl.Chem. 1958, December, 8
[43]ZBQ 27002—85．冶金石灰物理检验方法
[44]张海燕，魏绍武，简云川．冶金石灰活性度测定标准及操作要点探讨．理化检验-化学分册．2002，36(2)：86-87
[45]Lund K, Fogler H S, McCune C C. Acidization- I The dissolution of dolomite in hydrochloric acid. Chem. Eng. Sci. 1973,28:691～700
[46]Lund K, Fogler H S, McCune C C, Ault J W. Acidization-Ⅱ The dissolution of calcite in hydrochloric acid. Chem. Eng. Sci. 1975,30:825～835
[47]Wallin M, Bjerle I. A mass tranfer model for limestone dissolution from a rotating cylinder. Chem. Eng. Sci. 1989, 44(1): 61-67
[48]Sjoberg E L, Richard D T. Temperature dependence of calcite dissolution kinetics between 1 and 62℃ at pH2.7 to 8.4 in aqueous solutions. Geochimica et Cosmochimica Acta. 1984, bol.48:485～493
[49]Sjoberg E L, Richard D T. The effect of added dissolved calcium on calcite dissolution in aqueous solution at 25℃. Chem. Geol. 1985, 49:405～413
[50]Bjerle I, Rochelle G T. Limestone dissolution from a plane surface. Chem. Eng. Sci. 1984, 39:183～185
[51]Chan p k, Rochelle G T. Limestone dissolution-effects of pH, CO_2, and buffers modeled by mass transfer. ACS Syrup. Ser. 1982, 188:75
[52]Plummer N L, Wigley T M L, Parkhurst D L. The kinetics of calcium carbonate dissolution in CO_2-water systems at 5-60℃ and 0.0-1.0 atm CO_2. Amer. J. Sci. 1978, 278:179～216
[53]Sjoberg E L, Richard D T. The influence of experimental design on the rate of calcitedissolution. Geochimica et Cosmochimica Acta 1983, 47:2281～2285
[54]Morse J W. Dissolution of calcium carbonate in seawater Ⅲ: A new method for the study of carbonate reaction kinetics. Amer. J. Sci. 1974,274:97～107
[55]Gregory D P, Riddiford A C. Transfort to the surface of a rotating disc. J. Chem. Soc. London, 1956,3:3756～3764
[56]Lehmkuhl G K, Husdon J L. flow and mass transfer near an enclosed rotating disk:experiment. Chem Eng Sci, 1971, 26:1601-1613
[57]H Stephen, T Stephen, et. Solubilities inorganic and metal-organic compounds. Pergamon Press, 1963
[2]National Lime Association. Wet flue gas desulfurization technology evaluation. Project Number 11311-000. 2003.1
[3]郝吉明，王书肖，陆永琪编著．燃煤二氧化硫污染控制技术手册．北京：化学工业出版社．2001
[4]孙文寿，吴忠标，谭天恩．旋流板塔镁强化石灰脱硫过程研究．环境科学．2001，22(3)：104～107
[5]吴忠标，谭天恩等．旋流板塔内石灰湿法烟气脱硫的试验研究．环境科学学报．1995，8(4)：248～251
[6]晏乃强等．双碱法旋流板塔烟气脱硫工艺．环境科学．1998，19(5)：72～74
[7]施耀．浙江大学博士学位论文．1992．4
[8]吴忠标，刘越，余世清等．废大理石粉湿法烟气脱硫工艺实验研究．环境科学．2002，23(1)：44～47
[9]刘越．浙江大学硕士学位论文．2001．3
[10]俞世清．浙江大学硕士学位论文．2002．5
[11]刘精今等．皂化废水和鼓励烟道气的联合处理技术研究．环境保护科学．1997，23[1]：40～42
[12]刘精今等．碱性工业废水在锅炉烟气脱硫除尘中的应用．环境工程．1996，14[2]：24～27
[13]赵强等．染色废水用于除尘脱硫的技术．环境保护．1996，(4)：16～17
[14]武晓莉等．印染废水和烟气脱硫联合治理的实验研究．水利电力环境保护．2000，(1)：21～23
[15]梁宁等．苎麻脱胶废水喷淋锅炉烟气除尘脱硫降碱的实验研究．中国环境科学．1995，15(3)：219～221
[16]王毓秀等．用燃煤烟气处理造纸黑液的研究．污染防治技术．1995，8(1)：41～44
[17]陈德放等．以废治废—制革工业废水净化方法研究．环境工程．1989，7(6)：6～7，16
[18]谭亚军等．旋流板塔在碱性黑液烟气脱硫中的应用．环境工程．1998，2(1)：33～36
[19]赵建海等．粉煤灰在烟气脱硫方面的应用前景．粉煤灰综合利用．2000(2)：50～52
[20]宗润宽等．钙基烟气脱硫剂的生产研究进展．化工进展，2001，12：12～19
[21]Paolo Davini. Investigation of SO_2 adsorption properties of Ca(OH)_2-Fly ash systems. Flue,1996, 75(6):713～716
[22]N Karatepe et al. Effect of hydration conditions on the physical properties of fly ash
Ca(OH)_2 sorbents, Energy Sources, 1998,20:505～511
[23]Anand Srinvasan et al. The adsorption of SO_2 by zeolites synthesized from fly ash. Environ.Sci. Technol. 1999, 33(9): 1464～1469
[24]时黎明等．水合作用对钙基吸收剂脱硫特性的影响．环境工程．1998，16(2)：37～40
[25]庞亚军等．掺加粉煤灰提高含钙脱硫剂的烟气脱硫率的实验研究．工程热物理学报．1992，13(4)：443～447
[26]宗润宽等．钙基烟气脱硫剂制备的实验研究．环境污染治理技术与设备．2001，2(2)：25～30
[27]陆永琪等．提高钙基吸着剂脱硫活性的试验研究．环境工程．1998，16(5)：30～33
[28]Hiroaki Tsuchiai, Tomohiro Ishizuka, et al. Highly active absorbent for SO_2 removal prepared from coal fly ash. Ind. Eng. Chem. Res. 1995, 34(4):1404～1411
[29]Juan Adanez, Vanessa Fierro, et al. Study of modified calcium hydroxides for enhancing SO_2 removal during sorbent injection in pulverized coal boilers.
[30]Anand Srinvasan et al. The adsorption of SO_2 by zeolites synthesized from fly ash.Environ.Sci.Technol. 1999, 33(9): 1464～1469
[31]席勒，贝伦丝著，陆华，武洞明译．石灰．北京：中国建筑工业出版社．1981
[32]冯敏等．工业水处理技术．北京：海洋出版社．1992
[33]Levenspiel O. Chemical reaction engineering(2nd ed.) New York: Wiley, 1972
[34]Ian M Ritchie, Xu BingAn. The kinetic of lime slaking. Hydrometallurgy, 1990, 23:377～396
[35]D E Giles, I M Ritchie, B A Xu. The kinetics of dissolution of slaked lime. Hydrometallurgy,1993, 32:119～128
[36]L Bernard, M Freche, J L Lacout, B Biscan. Modeling of the dissolution of calcium hydroxide in the preparation of hydroxyapatite by neutralization. Chem. Eng. Sci. 2000,55:5683～5692
[37]Johannsen K, Rademacher S. Modelling the kinetics of calcium hydroxide dissolution in water. Acta Hydrochimica et Hydrobiologica. 1999, 27(2), 72-78
[38]Hilja Lohmus, Ahto Rani, A tend to the production of calcium hydroxide and precipitated calcium carbonate with defined properties, The Canadian Journal of Chemical Engineering, v.80 2002.10
[39]ASTM c110-98 Standard test method for physical testing of quicklime, hydrated lime, and limestone. Annual Book of ASTM Standard vol. 04.01
[40]DIN EN 12485—2001饮用水处理用化学品：碳酸钙、高生石灰和半煅烧白云石试验方法
[41]JC／T478．1-92．建筑石灰物理试验方法
[42]D R Glasson. Reactivity of lime and related oxides I : Production of calcium oxide. J. appl.Chem. 1958, December, 8
[43]ZBQ 27002—85．冶金石灰物理检验方法
[44]张海燕，魏绍武，简云川．冶金石灰活性度测定标准及操作要点探讨．理化检验-化学分册．2002，36(2)：86-87
[45]Lund K, Fogler H S, McCune C C. Acidization- I The dissolution of dolomite in hydrochloric acid. Chem. Eng. Sci. 1973,28:691～700
[46]Lund K, Fogler H S, McCune C C, Ault J W. Acidization-Ⅱ The dissolution of calcite in hydrochloric acid. Chem. Eng. Sci. 1975,30:825～835
[47]Wallin M, Bjerle I. A mass tranfer model for limestone dissolution from a rotating cylinder. Chem. Eng. Sci. 1989, 44(1): 61-67
[48]Sjoberg E L, Richard D T. Temperature dependence of calcite dissolution kinetics between 1 and 62℃ at pH2.7 to 8.4 in aqueous solutions. Geochimica et Cosmochimica Acta. 1984, bol.48:485～493
[49]Sjoberg E L, Richard D T. The effect of added dissolved calcium on calcite dissolution in aqueous solution at 25℃. Chem. Geol. 1985, 49:405～413
[50]Bjerle I, Rochelle G T. Limestone dissolution from a plane surface. Chem. Eng. Sci. 1984, 39:183～185
[51]Chan p k, Rochelle G T. Limestone dissolution-effects of pH, CO_2, and buffers modeled by mass transfer. ACS Syrup. Ser. 1982, 188:75
[52]Plummer N L, Wigley T M L, Parkhurst D L. The kinetics of calcium carbonate dissolution in CO_2-water systems at 5-60℃ and 0.0-1.0 atm CO_2. Amer. J. Sci. 1978, 278:179～216
[53]Sjoberg E L, Richard D T. The influence of experimental design on the rate of calcitedissolution. Geochimica et Cosmochimica Acta 1983, 47:2281～2285
[54]Morse J W. Dissolution of calcium carbonate in seawater Ⅲ: A new method for the study of carbonate reaction kinetics. Amer. J. Sci. 1974,274:97～107
[55]Gregory D P, Riddiford A C. Transfort to the surface of a rotating disc. J. Chem. Soc. London, 1956,3:3756～3764
[56]Lehmkuhl G K, Husdon J L. flow and mass transfer near an enclosed rotating disk:experiment. Chem Eng Sci, 1971, 26:1601-1613
[57]H Stephen, T Stephen, et. Solubilities inorganic and metal-organic compounds. Pergamon Press, 1963