两种锅炉带负荷清洗剂的研究
摘要
本文通过高压釜挂片试验分别对两种锅炉带负荷清洗剂,即新104型、1241型清洗剂进行研究,采用失重法、表面形貌观察分析、炉水全铁测定等方法对清洗效果进行评价;采用水滴实验、酸性硫酸铜点滴实验和湿热实验对成膜效果进行评价。实验详细分析了浓度、温度、恒温时间、pH值等因素分别对新104型清洗剂和1241型清洗剂的清洗和钝化成膜效果的影响,确定了两种清洗剂应用的最佳工艺条件。
实验结果表明:这两种锅炉带负荷清洗剂浓度的升高,有利于试片表面铁锈的清除和钝化成膜,新104型清洗剂在浓度为2.5mL/L时其效果最佳,1241型清洗剂则在浓度为3.0mL/L时其效果最佳;在其他条件不变的情况下,随着温度的升高,清洗剂的清洗和钝化成膜效果都有所增强,360℃时两种清洗剂的清洗和钝化效果达到最佳;而且当两种清洗剂恒温1h时,其清洗成膜效果最佳,随恒温时间的增加,清洗剂的清洗和成膜效果有所下降;pH值在9~10范围内试片的失重速率较稳定,pH值为9.5时清洗及钝化效果最好。
从这两种清洗剂的清洗机理、清洗性能、成膜钝化效果的分析研究来看,新104型带负荷清洗剂在模拟锅炉运行时的高温高压水工况下,成膜钝化效果方面优于1241型清洗剂,但其清洗效果不及1241型清洗剂。而与传统的清洗剂相比,本实验室所研制的带负荷清洗剂在最佳工艺条件下,不论是清洗成膜效果,还是经济效益,都优于传统清洗,是锅炉设备清洗技术的突破,值得推广应用。
Two kinds of on-line cleaning agents, namely New 104 and 1241 cleaning agents, with optimal cleaning and passivation effect were researched by autoclave experiments in this thesis. The corrosive rate,surface analyses,mensuration of stove water were carried out to evaluate the cleaning effect. The passivation effect was valuated by water test,CuSO4 test and humid-heat test. During the experiment,the effects of concentration,temperature,time and pH on cleaning and passivation of cleaning agents New 104 and 1241 were investigated. And the optimum operating conditions were selected.
The experimental results showed that the performances of two cleaning agents were increased with their concentration. The cleaning and passivation effects of New 104 and 1241 cleaning agents were optimum when the concentration were 2.5mL/L and 3mL/L respectively. In addition,the performances of cleaning agents were enhanced with increasing the temperature. The optimum temperature was 360℃for both cleaning agents. However,when the operating time was longer than 1 hour,the cleaning and passivation effect was weakened. At the pH range of 9~10,pH had a little influence on the cleaning and passivation effect. At pH 9.5,the cleaning and passivation effect was the best.
From the performance and mechanism of these on-line cleaning agents under the simulated condition with high temperature,the passivation effect of New 104 cleaning agents was superior to 1241 detergent while the cleaning effect of 1241 cleaning agents was better than New 104. Compared to the conventional cleaning,both on-line cleaning agents showed wonderful cleaning and passivation effect and provided a better economical benefit. It will break through the conventional cleaning technique and be promising in boiler cleaning.
实验结果表明:这两种锅炉带负荷清洗剂浓度的升高,有利于试片表面铁锈的清除和钝化成膜,新104型清洗剂在浓度为2.5mL/L时其效果最佳,1241型清洗剂则在浓度为3.0mL/L时其效果最佳;在其他条件不变的情况下,随着温度的升高,清洗剂的清洗和钝化成膜效果都有所增强,360℃时两种清洗剂的清洗和钝化效果达到最佳;而且当两种清洗剂恒温1h时,其清洗成膜效果最佳,随恒温时间的增加,清洗剂的清洗和成膜效果有所下降;pH值在9~10范围内试片的失重速率较稳定,pH值为9.5时清洗及钝化效果最好。
从这两种清洗剂的清洗机理、清洗性能、成膜钝化效果的分析研究来看,新104型带负荷清洗剂在模拟锅炉运行时的高温高压水工况下,成膜钝化效果方面优于1241型清洗剂,但其清洗效果不及1241型清洗剂。而与传统的清洗剂相比,本实验室所研制的带负荷清洗剂在最佳工艺条件下,不论是清洗成膜效果,还是经济效益,都优于传统清洗,是锅炉设备清洗技术的突破,值得推广应用。
Two kinds of on-line cleaning agents, namely New 104 and 1241 cleaning agents, with optimal cleaning and passivation effect were researched by autoclave experiments in this thesis. The corrosive rate,surface analyses,mensuration of stove water were carried out to evaluate the cleaning effect. The passivation effect was valuated by water test,CuSO4 test and humid-heat test. During the experiment,the effects of concentration,temperature,time and pH on cleaning and passivation of cleaning agents New 104 and 1241 were investigated. And the optimum operating conditions were selected.
The experimental results showed that the performances of two cleaning agents were increased with their concentration. The cleaning and passivation effects of New 104 and 1241 cleaning agents were optimum when the concentration were 2.5mL/L and 3mL/L respectively. In addition,the performances of cleaning agents were enhanced with increasing the temperature. The optimum temperature was 360℃for both cleaning agents. However,when the operating time was longer than 1 hour,the cleaning and passivation effect was weakened. At the pH range of 9~10,pH had a little influence on the cleaning and passivation effect. At pH 9.5,the cleaning and passivation effect was the best.
From the performance and mechanism of these on-line cleaning agents under the simulated condition with high temperature,the passivation effect of New 104 cleaning agents was superior to 1241 detergent while the cleaning effect of 1241 cleaning agents was better than New 104. Compared to the conventional cleaning,both on-line cleaning agents showed wonderful cleaning and passivation effect and provided a better economical benefit. It will break through the conventional cleaning technique and be promising in boiler cleaning.
引文
[1]王战铃.锅炉化学清洗的安全性分析及防护措施[J].电力安全技术,2006,(4):47~48
[2] G D David aniel’s.Good Lay-Up Practice Produces Significant Benefits[J].IWC, 1998, 56:367
[3]王杏卿主编.热力设备的腐蚀与防护[M].北京:水利电力出版社,1988
[4]陈明静,张春雷.火电厂凝汽器不停机清洗工艺的研究[J].工业水处理.2004,7(24):63~66
[5]曹杰玉,姚建涛,邓宇强.电站锅炉盐酸清洗中的腐蚀控制腐蚀科学与防护技术[J].2005,17(2):125～127
[6]H.Kouno, etal Water Control and Management of Thermal Power Plant the Thermal and Nuclear Power. 1992, 43(433)
[7]刘爱忠.电厂化学[M].中国电力出版社,2001(300MW火电机组培训丛书):70~72
[8]窦照英.电力工业清洗技术[M].化学工业出版社,2005:306
[9] E Stven, Kuehn. Battling boiler corrosion[J]. Power Engineering, 1995, 99(3):3740
[10] R Walker.Intergranular Corrosion of Steels and Alloys.Corrosion.1973, 29:290~296
[11]秦国治.清洗剂综述[J].石油化工腐蚀与防护,1995,(4):3~7
[12]秦国治.有机酸洗剂及其应用[J].化工设备与防护腐蚀,2000,(6):29~33
[13]倪关龙.锅炉化学清洗的回顾与思索(Ⅱ)[J].化学清洗,1996,12 (1):47~50
[14]王杏卿主编.热力设备的腐蚀与防护[M].北京:水利电力出版社,1988
[15]敖建平,孙国忠,曾为民.盐酸清洗缓蚀剂的研究进展[J].南昌航空工业学院学报, 2000, 14(1):50～54
[16] R Eilan Arvo, G Bozeka Carl. Blandin Reduces Boil Overheating, Corrosion Through Chemical Cleaning. Pulp&Paper.1992, 66(1)
[17] MU 34-70-113-85.Methodological Recommendations on Pre-Star ChemicalCleaning of Thermal Power Plant Equipment [in Russian], Moscow: Soyuztekheneergo, 1986
[18]宋业林编著.锅炉清洗实用技术[M].北京:中国石化出版社,2003
[19]胡黄卿.锅炉水垢酸洗的探讨(接续)[J].木材加工机械,2003,(1):21~25
[20]李培武.化学清洗技术的研究与应用[J].科技情报开发与经济,2003,3(4):84~85
[21]刘伯东,袁长征.柠檬酸清洗工艺的改进及在运行锅炉上的应用[J].化学清洗,1999,15(6):11~15
[22]鲁彦标. 2000 t/ h汽包锅炉的EDTA化学清洗[J].华东电力,2000,(7):42~44
[23]崔延奎.EDTA化学清洗的理化过程及工艺条件选择[J].内蒙古电力技术,1996,(3):36～40
[24]窦照英.锅炉化学清洗技术的发展(一)—综述及相关问题分析[J].洗净技术,2003,(6):8 ~11
[25]胡锐.EDTA法清洗锅炉的几点体会[J].华北电力技术.1996,(4):57~59
[26]祁利明,张忠义.氨基磺酸清洗镀膜技术在国华准电的应用[J].内蒙古电力技术,2005 23(2):19~20
[27]清洗过程中可能用到的化学药剂的性能[J].洗净技术,2004,10:76
[28] Kobetz P, Lindasy K L.Glycolic Acid [P].US, 3867440, 1975, 2~18
[29]B Brad. Select the Proper Boiler Cleaning Solvent. Chemical Engineering Progress, 2001, (10):22~23
[30]杨汝周,邱武斌等.运行直流炉过热器化学清洗技术研究.中国电力. 2000.11,33(11):30～34
[31]张春雷,陈明静,陈予辉.火力发电厂凝汽器不停机清洗的应用[J].华北电力技术,2001,10(3):28~51
[32]詹约章,喻亚非,彭道元等.锅炉在线清洗的现场应用研究[J].清洗世界,2005.10,21(10):1~4
[33]薛政沈云在等.呼和浩特发电厂通流部分带负荷清洗.内蒙古电力技术. 2003,21(2):47～48
[34]汤延令.汽轮机组带负荷清洗.福建电力与电工. 2004.12,24(2):38～39,51
[35]王胜利.浅析凝汽式汽轮机的清洗. 2004,(1):74～76
[36]Mc Glone,K Anti-Corrs.Methods Mater[J],1987,34(4):6
[37]霍金仙.高压釜腐蚀试验应注意的问题[J].山西电力,2003,1(5):5~8
[38] G W Poling. Environnmentally acceptable methods control pipeline corrosion at lower cost.Corros.Sci.1970.10:357~360
[39] A G Xyla, et al.Colloid and Surfaces.corrosion.1991, 53:241~245
[40] G H Nancollas.J.Development of mechanistic model for predicting corrosion rate in multiphase oil/water/gas flows.Petroleum Technology.1982, 34(3):645~649
[41] Experiences with Hydrazine Substitutes in Boiler Systems,IWC-95-7
[42] P.A.Readon, W.E.Bemald .New Insight into Oxygen Corrosion Control Corrosion, 1987
[43]刘永辉,张佩芬.金属腐蚀学原理[M].北京:航空工业出版社,1993
[44]濮文虹,刘光虹,喻俊芳.水质分析化学[M].武汉:华中科技大学出版社,2004:204~205
[45]武汉大学化学与分子科学学院实验中心.无机及分析化学实验[M].武汉:武汉大学出版社.2005.209~213
[46]李培元,钱达中,王蒙聚.锅炉水处理.武汉:湖北科学技术出版社[M],1989.7
[47]汤海珠,谢学军,傅强等.热力系统新型停用保护缓蚀剂[J].腐蚀科学与防护技术,2002,14(6):356~358
[48]刘建平,李正奉,周晓湘.十八胺乳状液在热力设备停用保护中的应用研究[J].材料保护,2002,35(3):27~29
[49]D Rahner.Fe304 as part of the passive layer on iron, Solid State Ionics, 1996, (86-88):865~871
[50]姚维义,唐谟堂,彭可等.铸造铅腐蚀机理的研究[J].腐蚀科学与防护,2004,7,16(4):203~206
[51]杨道武,张海燕,周琼花.电厂蒸汽导气管室温磷化工艺及其效果[J].材料保护,2005,38(5):54~56
[52]化工部化工机械研究所.腐蚀与防护手册·腐蚀理论·实验及监测[M].北京:化学工业出版社,1994.
[53] J.J Schuck., C.C Nathan.,J.R Metcalf.,Corrosion inhibitors for steam condensate systems. Material Protection and P erformance, 1973, 12(10):42~47
[54] K Azumi., T Ohtsuka., and N Sato., Spectroscopic photoresponse of the passive film formed on iron. J.Electrochem.Soc, 1986, 133(7):1326~1328
[55] J.A Kelly Steam Cycle Passivation and Corrosion Protection in Boiler Systems IWC October 1995:22~24
[2] G D David aniel’s.Good Lay-Up Practice Produces Significant Benefits[J].IWC, 1998, 56:367
[3]王杏卿主编.热力设备的腐蚀与防护[M].北京:水利电力出版社,1988
[4]陈明静,张春雷.火电厂凝汽器不停机清洗工艺的研究[J].工业水处理.2004,7(24):63~66
[5]曹杰玉,姚建涛,邓宇强.电站锅炉盐酸清洗中的腐蚀控制腐蚀科学与防护技术[J].2005,17(2):125～127
[6]H.Kouno, etal Water Control and Management of Thermal Power Plant the Thermal and Nuclear Power. 1992, 43(433)
[7]刘爱忠.电厂化学[M].中国电力出版社,2001(300MW火电机组培训丛书):70~72
[8]窦照英.电力工业清洗技术[M].化学工业出版社,2005:306
[9] E Stven, Kuehn. Battling boiler corrosion[J]. Power Engineering, 1995, 99(3):3740
[10] R Walker.Intergranular Corrosion of Steels and Alloys.Corrosion.1973, 29:290~296
[11]秦国治.清洗剂综述[J].石油化工腐蚀与防护,1995,(4):3~7
[12]秦国治.有机酸洗剂及其应用[J].化工设备与防护腐蚀,2000,(6):29~33
[13]倪关龙.锅炉化学清洗的回顾与思索(Ⅱ)[J].化学清洗,1996,12 (1):47~50
[14]王杏卿主编.热力设备的腐蚀与防护[M].北京:水利电力出版社,1988
[15]敖建平,孙国忠,曾为民.盐酸清洗缓蚀剂的研究进展[J].南昌航空工业学院学报, 2000, 14(1):50～54
[16] R Eilan Arvo, G Bozeka Carl. Blandin Reduces Boil Overheating, Corrosion Through Chemical Cleaning. Pulp&Paper.1992, 66(1)
[17] MU 34-70-113-85.Methodological Recommendations on Pre-Star ChemicalCleaning of Thermal Power Plant Equipment [in Russian], Moscow: Soyuztekheneergo, 1986
[18]宋业林编著.锅炉清洗实用技术[M].北京:中国石化出版社,2003
[19]胡黄卿.锅炉水垢酸洗的探讨(接续)[J].木材加工机械,2003,(1):21~25
[20]李培武.化学清洗技术的研究与应用[J].科技情报开发与经济,2003,3(4):84~85
[21]刘伯东,袁长征.柠檬酸清洗工艺的改进及在运行锅炉上的应用[J].化学清洗,1999,15(6):11~15
[22]鲁彦标. 2000 t/ h汽包锅炉的EDTA化学清洗[J].华东电力,2000,(7):42~44
[23]崔延奎.EDTA化学清洗的理化过程及工艺条件选择[J].内蒙古电力技术,1996,(3):36～40
[24]窦照英.锅炉化学清洗技术的发展(一)—综述及相关问题分析[J].洗净技术,2003,(6):8 ~11
[25]胡锐.EDTA法清洗锅炉的几点体会[J].华北电力技术.1996,(4):57~59
[26]祁利明,张忠义.氨基磺酸清洗镀膜技术在国华准电的应用[J].内蒙古电力技术,2005 23(2):19~20
[27]清洗过程中可能用到的化学药剂的性能[J].洗净技术,2004,10:76
[28] Kobetz P, Lindasy K L.Glycolic Acid [P].US, 3867440, 1975, 2~18
[29]B Brad. Select the Proper Boiler Cleaning Solvent. Chemical Engineering Progress, 2001, (10):22~23
[30]杨汝周,邱武斌等.运行直流炉过热器化学清洗技术研究.中国电力. 2000.11,33(11):30～34
[31]张春雷,陈明静,陈予辉.火力发电厂凝汽器不停机清洗的应用[J].华北电力技术,2001,10(3):28~51
[32]詹约章,喻亚非,彭道元等.锅炉在线清洗的现场应用研究[J].清洗世界,2005.10,21(10):1~4
[33]薛政沈云在等.呼和浩特发电厂通流部分带负荷清洗.内蒙古电力技术. 2003,21(2):47～48
[34]汤延令.汽轮机组带负荷清洗.福建电力与电工. 2004.12,24(2):38～39,51
[35]王胜利.浅析凝汽式汽轮机的清洗. 2004,(1):74～76
[36]Mc Glone,K Anti-Corrs.Methods Mater[J],1987,34(4):6
[37]霍金仙.高压釜腐蚀试验应注意的问题[J].山西电力,2003,1(5):5~8
[38] G W Poling. Environnmentally acceptable methods control pipeline corrosion at lower cost.Corros.Sci.1970.10:357~360
[39] A G Xyla, et al.Colloid and Surfaces.corrosion.1991, 53:241~245
[40] G H Nancollas.J.Development of mechanistic model for predicting corrosion rate in multiphase oil/water/gas flows.Petroleum Technology.1982, 34(3):645~649
[41] Experiences with Hydrazine Substitutes in Boiler Systems,IWC-95-7
[42] P.A.Readon, W.E.Bemald .New Insight into Oxygen Corrosion Control Corrosion, 1987
[43]刘永辉,张佩芬.金属腐蚀学原理[M].北京:航空工业出版社,1993
[44]濮文虹,刘光虹,喻俊芳.水质分析化学[M].武汉:华中科技大学出版社,2004:204~205
[45]武汉大学化学与分子科学学院实验中心.无机及分析化学实验[M].武汉:武汉大学出版社.2005.209~213
[46]李培元,钱达中,王蒙聚.锅炉水处理.武汉:湖北科学技术出版社[M],1989.7
[47]汤海珠,谢学军,傅强等.热力系统新型停用保护缓蚀剂[J].腐蚀科学与防护技术,2002,14(6):356~358
[48]刘建平,李正奉,周晓湘.十八胺乳状液在热力设备停用保护中的应用研究[J].材料保护,2002,35(3):27~29
[49]D Rahner.Fe304 as part of the passive layer on iron, Solid State Ionics, 1996, (86-88):865~871
[50]姚维义,唐谟堂,彭可等.铸造铅腐蚀机理的研究[J].腐蚀科学与防护,2004,7,16(4):203~206
[51]杨道武,张海燕,周琼花.电厂蒸汽导气管室温磷化工艺及其效果[J].材料保护,2005,38(5):54~56
[52]化工部化工机械研究所.腐蚀与防护手册·腐蚀理论·实验及监测[M].北京:化学工业出版社,1994.
[53] J.J Schuck., C.C Nathan.,J.R Metcalf.,Corrosion inhibitors for steam condensate systems. Material Protection and P erformance, 1973, 12(10):42~47
[54] K Azumi., T Ohtsuka., and N Sato., Spectroscopic photoresponse of the passive film formed on iron. J.Electrochem.Soc, 1986, 133(7):1326~1328
[55] J.A Kelly Steam Cycle Passivation and Corrosion Protection in Boiler Systems IWC October 1995:22~24