混合及活化脱硫剂在CFBA装置中的应用研究
摘要
本文研究了以生石灰、电厂废料粉煤灰、烧结机头除尘灰等原料通过物理混合及活化手段制备适用于CFBA装置的新型脱硫剂。其中生石灰为吸收剂,而电厂废料粉煤灰、烧结机头除尘灰为添加剂。
以混合方式制备的脱硫剂称之为混合型脱硫剂。三种混合脱硫剂A、B、C均为生石灰与不同添加剂简单混合制得。试验结果表明,添加剂的确可以增加CaO利用率,尤其是添加含氧化铁的机头灰脱硫效果最为明显。添加机头灰的B脱硫剂组与添加粉煤灰的A脱硫剂对照组比较,氧化钙利用率平均提高近38%。说明钢厂就地取材的机头灰是一种优秀的脱硫添加剂,将其用于烧结机烟气脱硫能充分体现以废治废、循环利用的原则。
以活化方式制备的脱硫剂称为活化型脱硫剂。活化脱硫剂D、E、F为生石灰与粉煤灰添加剂经水合、水合加蒸汽活化、直接蒸汽活化三种方法分别制成的活化型脱硫剂,其中尤其以脱硫剂D、E的制备方式最为复杂。试验表明,高温活化对于CaO利用率提高贡献极大,低温水合基本没有生成大量高活性的硅钙中间体,表现为脱硫剂D的CaO利用率较脱硫剂A提高不大。而经蒸汽活化过的脱硫剂F较水合脱硫剂D的CaO利用率提高近50%。表明蒸汽活化方法具有很好的应用前景。
本文还进行了CFBA装置的运行参数试验和腐蚀试验研究。结果表明:70-110kg/m~2床重可作为CFBA系统适宜床重范围,而流化床压力降又与床重成正比关系;采用脱硫剂F的连续性试验在Ca/S=1.3时脱硫率大于80%;流化床塔体金属腐蚀速度约6.51mg/dm~2·d,腐蚀深度约300 μm/a,不足湿法脱硫设备平均腐蚀深度的四分之一。
这些成果对于烧结机烟气CFBA脱硫装置工业化运行提供了新型脱硫剂和操作参数。
This paper selects calces ,coke breeze and sinter ash etc. as material which were mixed and experienced activation, in the end, getting a new desulfurizing agents on CFBA. Desulfurizing agent is calces,and additives agents are coke breeze and sinter ash.As far as desulfurizing agents are concerned,when they are mixed they are called mixture desulfurizing agents.There are three kinds agents: A ,B , C. The experimental results indicate that additive can increase the usage efficiency of CaO.Fe_2O_3 is the best desulfurizing agent.Agent B is better in the usage efficiency of CaO than agent A, 38% higher. So the experiment gives a expected result.The Active Desulfurizing Agent is made by hydration method . Through hydration , steam and hydration steam methods produce three Active Desulfurizing Agent — D,E and F. The study shows that high temperature is benefit to increase the usage efficiency of CaO. Agent F by steam activation perform more efficiency of using CaO than agent D,approximately 49%. Therefore, we can see perfect prospect.In the CFBA's rotten experiment, the study indicates that the erode velocity of metal is about 6. 51mg/dm~2 · d and the erode depth is 300μm/a.The experimental results provide reference to CFBA.
以混合方式制备的脱硫剂称之为混合型脱硫剂。三种混合脱硫剂A、B、C均为生石灰与不同添加剂简单混合制得。试验结果表明,添加剂的确可以增加CaO利用率,尤其是添加含氧化铁的机头灰脱硫效果最为明显。添加机头灰的B脱硫剂组与添加粉煤灰的A脱硫剂对照组比较,氧化钙利用率平均提高近38%。说明钢厂就地取材的机头灰是一种优秀的脱硫添加剂,将其用于烧结机烟气脱硫能充分体现以废治废、循环利用的原则。
以活化方式制备的脱硫剂称为活化型脱硫剂。活化脱硫剂D、E、F为生石灰与粉煤灰添加剂经水合、水合加蒸汽活化、直接蒸汽活化三种方法分别制成的活化型脱硫剂,其中尤其以脱硫剂D、E的制备方式最为复杂。试验表明,高温活化对于CaO利用率提高贡献极大,低温水合基本没有生成大量高活性的硅钙中间体,表现为脱硫剂D的CaO利用率较脱硫剂A提高不大。而经蒸汽活化过的脱硫剂F较水合脱硫剂D的CaO利用率提高近50%。表明蒸汽活化方法具有很好的应用前景。
本文还进行了CFBA装置的运行参数试验和腐蚀试验研究。结果表明:70-110kg/m~2床重可作为CFBA系统适宜床重范围,而流化床压力降又与床重成正比关系;采用脱硫剂F的连续性试验在Ca/S=1.3时脱硫率大于80%;流化床塔体金属腐蚀速度约6.51mg/dm~2·d,腐蚀深度约300 μm/a,不足湿法脱硫设备平均腐蚀深度的四分之一。
这些成果对于烧结机烟气CFBA脱硫装置工业化运行提供了新型脱硫剂和操作参数。
This paper selects calces ,coke breeze and sinter ash etc. as material which were mixed and experienced activation, in the end, getting a new desulfurizing agents on CFBA. Desulfurizing agent is calces,and additives agents are coke breeze and sinter ash.As far as desulfurizing agents are concerned,when they are mixed they are called mixture desulfurizing agents.There are three kinds agents: A ,B , C. The experimental results indicate that additive can increase the usage efficiency of CaO.Fe_2O_3 is the best desulfurizing agent.Agent B is better in the usage efficiency of CaO than agent A, 38% higher. So the experiment gives a expected result.The Active Desulfurizing Agent is made by hydration method . Through hydration , steam and hydration steam methods produce three Active Desulfurizing Agent — D,E and F. The study shows that high temperature is benefit to increase the usage efficiency of CaO. Agent F by steam activation perform more efficiency of using CaO than agent D,approximately 49%. Therefore, we can see perfect prospect.In the CFBA's rotten experiment, the study indicates that the erode velocity of metal is about 6. 51mg/dm~2 · d and the erode depth is 300μm/a.The experimental results provide reference to CFBA.
引文
[1] 赵旭东,等.75t/h锅炉双循环流化床烟气脱硫装置研制及应用,中国电力,35(3):62-65.2002
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[1] 国家环境保护总局.2002年中国环境状况公报.
[3] 郝吉明,马广大.大气污染控制工程[M].高等教育出版社.2002.
[4] 肖文德,吴志泉.二氧化硫去除与回收[M].化学工业出版社.
[5] Graf R. First operation experience with a dry flue gas desulfurization process using a circulating fluidized bed (FGD-CFB), Lecture at he "First international conference on circulating fluidized beds" in Halifax Nova Scotia, Canada in November 1985
[6] Graf, R., Riley, J. D.: Dry/semi dry flue gas desulfurization using the LURGI circulating fluid bed absorption process. Lecture at the EPA/EPRI fourth symposium on flue gas desulphurization in Atlanta, Georgia from 18th to21 th November, 1986
[7] 马果骏.烟气循环流化床脱硫技术简介.电力环境保护.10(1):46-48.1994.
[8] R. E. Gra, 1000 hours commercial operating experience with advanced design reflux circulating fluid bed scrubbing employing slaked lime reagent. EPRI/EPA/DOE SO_2 control symposium, march 28-31, 1995, Miami, Florida, USA.
[9] Rgraf. 70000 hours of commercial operating experience with advanced-design, reflux circulating fluid bed flue gas desulfurization[A]. Proceedings Air & Waste Management association's 90th Annual Meeting & exhibition[C]. Toronto, Ontario, Canada, June 8-13, 1997.
[10] 黎在时,刘卫平.德国WULFF公司的干法脱硫技术.中国环保产业CEPI.:2:74-76.2002
[11] 米浩林,马果骏.回流式烟气循环流化床脱硫技术.热力发电.2:57-59.1998.
[12] 薛建明,马果骏.欧洲三种烟气循环流化床脱硫技术及经济分析.中国环保产业 CEPI.1:36-38.2003
[13] 徐贤忠.高效回流式循环流化床烟气脱硫及除尘技术.国际电力.6(2):60-63.2002
[14] 张凤兰,程岩.小龙潭发电厂烟气循环流化床脱硫工程评述.电力环境保护.19(1):22-24.2003
[15] 吴必科,李云峰,曹宇飞.内回流循环流化床烟气脱硫运行特性分析.中国电力.36(8):55-58.2003
[16] 肖文德,吴志泉.二氧化硫去除与回收[M].化学工业出版社.2001.
[17] 葛介龙,王新龙.NID脱硫工艺在国内的应用研究.电力环境保护.18(1):10-12.2002
[18] 刘颖昊。循环流化床烧结烟气脱硫半工业性试验研究[硕士学位论文].西安建筑科技大学,1999.
[19] 谢建军,钟秦。循环流化床烟气脱硫实验研究.南京理工大学学报.25(6).2002
[20] 赵旭东,吴少华,等。循环流化床烟气悬浮脱硫技术中试及机理分析.环境科学.23(2):109-112.2002
[21] 樊保国,等。循环流化床烟气脱硫机理研究.环境科学.19(3):14-17.1998
[22] 黄震,等。首套国产循环流化床烟气脱硫装置投入运行,建筑热能通风空调,(1),56～58.2001
[23] 赵旭东,等。75t/h锅炉双循环流化床烟气脱硫装置研制及应用,中国电力,35(3):62-65.2002
[24] UNEP(1987) Environmental Aspects of Iron and Steel production An Overview.
[25] 刘培善.日本五大钢铁公司企业概况.冶金工业部安全环保公司、冶金部建筑研究院编.1988.9.
[26] 贝加·尼汉宁·坚生,彼得·波·奥生.采用FLS式气悬吸收剂半干法吸收装置的高效脱硫技术.国际电力环境保护学术研讨会论文集.1996.10.
[27] Borgwardt R H kinetics of the Reaction of SO_2 with Calcined Limestone, Environ Sci. Technol, 1970, 4(1):59
[28] Borwardt R H and Harvey R D. Properties of Carbonate Rocks Related to SO_2 Reactivity, Engviron, Sci, Technol. 1972, 6147:350
[29] Dean J A. Lamge's Handbook of chemistry 12th, New York:Mc Graw-hill, 1979
[30] Al-sheawabkeh A, Matsuda H and Hastatani M. Comparratire Reactivity of Ca(OH)_2-Derived Oxides for SO_2 Capture J, Chem Eng. 1994, 27(5):650
[31] Davis W I and Keener T C chemical Studies on Dry Sorbents Final Report, Doe/FC/10/84-1, 1982
[32] 张蕴璧.流态化选论.西安.西北大学出版社.1989.
[33] 金涌,祝京旭,汪展文,俞芷青.流态化工程原理.北京.清华大学出版社.2001,8.
[34] 范浩杰,姚强,曹欣玉等,碱金属化合物添加剂对氧化钙固硫影响的试验研究。燃烧科学与技术,1997,3(1):105-111
[35] 高翔,骆仲泱,陈亚非等。金属氧化物对脱硫影响的试验研究。工程热物理学报,1997,18 (4):517-520
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