新型高效除冰剂的开发研究
摘要
在我国和世界上许多国家的高寒地区，冬季冰雪已成为严重的公害，积雪引起的问题不仅给当地人民的生活带来困难，而且阻碍经济的发展；此外，城市高速公路，机场飞机跑道等交通设施对冬季除冰剂的使用也日益迫切，因此，九十年代以来，北美、北欧、日本等多雪地区和国家，对融雪产品的需求量与日俱增，年需求量在2000万吨左右，其中仅日本就需20～30万吨。
除冰剂的类型很多，主要分为以氯化物盐为主的传统型除冰剂和以CMA为代表的新型全有机型除冰剂。以氯化物盐为主的传统型除冰剂虽然原料廉价易得，冰点低，但融解过程吸热，对环境造成污染，对道路设施产生腐蚀。盐水渗入地表，土地盐渍化加重。
而CMA是对氯化物盐除冰剂的重大改进，CMA具有无污染，环保的特点，对金属几乎无腐蚀，但由于原料价格昂贵，使得CMA的价格不菲，CMA对冰的融化能力不如氯化钠，CMA易结块，不宜长期储藏，在撒布时形成的粉尘及刺鼻的酸味亦是需要改进的地方。
针对上述除冰剂的缺点，本课题收集了国内外大量的相关科技文献，通过对主体物料和添加剂两方面的改善，寻找到一种新型除冰剂PAL，它既保留了传统除冰剂的优点，原料廉价易得，低冰点，可达-43.8℃；又兼有CMA的优点，对钢铁几乎无腐蚀，对混凝土无不良影响。基本实现了开发新型除冰剂的初衷，达到了本课题的研究目的。
此次课题开发的产品，丰富了除冰剂的品种，具有一定的应用价值，成为高寒地区冬季冰雪的首选除冰剂之一。
In cold areas in many countries in the world, the winter snow and ice do great harm to the people and public. The problem the snow causes influences the people's lives and impedes the economic development. Meanwhile the transportation infrastructure such as highway intercity and airstrip needs a great amount of deicing salts to maintain the bare road. Therefore from 1980s, many areas and countries such as North American, North Europe, Japan have greater and greater demands on the deicing salts, about 20 million tons per year, only Japan needs 200 to 300 thousand tons per year.
There are all kinds of the deicing salts, mainly divided into two kinds: traditional deicing salt such as sodium chloride and organic deicer such as CMA. While rock salt (NaCl) is relatively abundant and a very cheap deicer, it is endothermic while melting, pollutes the environment and accelerates corrosion of vehicles, bridges, guardrails and reinforcing steel in concrete. As salt is washed from the roadways it infiltrates the surface waters and underlying ground waters.
CMA, as an alternate deicer, tends to inhibit corrosion and appears to be relatively harmless to the environment. But CMA is expensive because of the high price of its material, and it has less ability in melting ice than sodium chloride. Besides these, CMA sticks to wet surfaces and can congeal to form hard chunks, difficult to store for a long time, dusty and a strong vinegar smell when spread. All of these aspects need to be improved.
Considering the disadvantages of the two kinds of the deicers, great amounts of the science data are referred in the research experiment, by developing the main materials and the additives, a new kind of deicer: PAL is founded. Not only does PAL remain the advantages of the traditional deicer such as cheap materials and low freezing point: -43.8 C, but it has the character of CMA, low corrosion to steel and concrete. The primary goal to develop a new highly effective deicer is gained.
The product developed in the experiment enriches the diversity of the deicers, has some application value, and becomes one of the first-choice deicers in cold areas in winter.
除冰剂的类型很多，主要分为以氯化物盐为主的传统型除冰剂和以CMA为代表的新型全有机型除冰剂。以氯化物盐为主的传统型除冰剂虽然原料廉价易得，冰点低，但融解过程吸热，对环境造成污染，对道路设施产生腐蚀。盐水渗入地表，土地盐渍化加重。
而CMA是对氯化物盐除冰剂的重大改进，CMA具有无污染，环保的特点，对金属几乎无腐蚀，但由于原料价格昂贵，使得CMA的价格不菲，CMA对冰的融化能力不如氯化钠，CMA易结块，不宜长期储藏，在撒布时形成的粉尘及刺鼻的酸味亦是需要改进的地方。
针对上述除冰剂的缺点，本课题收集了国内外大量的相关科技文献，通过对主体物料和添加剂两方面的改善，寻找到一种新型除冰剂PAL，它既保留了传统除冰剂的优点，原料廉价易得，低冰点，可达-43.8℃；又兼有CMA的优点，对钢铁几乎无腐蚀，对混凝土无不良影响。基本实现了开发新型除冰剂的初衷，达到了本课题的研究目的。
此次课题开发的产品，丰富了除冰剂的品种，具有一定的应用价值，成为高寒地区冬季冰雪的首选除冰剂之一。
In cold areas in many countries in the world, the winter snow and ice do great harm to the people and public. The problem the snow causes influences the people's lives and impedes the economic development. Meanwhile the transportation infrastructure such as highway intercity and airstrip needs a great amount of deicing salts to maintain the bare road. Therefore from 1980s, many areas and countries such as North American, North Europe, Japan have greater and greater demands on the deicing salts, about 20 million tons per year, only Japan needs 200 to 300 thousand tons per year.
There are all kinds of the deicing salts, mainly divided into two kinds: traditional deicing salt such as sodium chloride and organic deicer such as CMA. While rock salt (NaCl) is relatively abundant and a very cheap deicer, it is endothermic while melting, pollutes the environment and accelerates corrosion of vehicles, bridges, guardrails and reinforcing steel in concrete. As salt is washed from the roadways it infiltrates the surface waters and underlying ground waters.
CMA, as an alternate deicer, tends to inhibit corrosion and appears to be relatively harmless to the environment. But CMA is expensive because of the high price of its material, and it has less ability in melting ice than sodium chloride. Besides these, CMA sticks to wet surfaces and can congeal to form hard chunks, difficult to store for a long time, dusty and a strong vinegar smell when spread. All of these aspects need to be improved.
Considering the disadvantages of the two kinds of the deicers, great amounts of the science data are referred in the research experiment, by developing the main materials and the additives, a new kind of deicer: PAL is founded. Not only does PAL remain the advantages of the traditional deicer such as cheap materials and low freezing point: -43.8 C, but it has the character of CMA, low corrosion to steel and concrete. The primary goal to develop a new highly effective deicer is gained.
The product developed in the experiment enriches the diversity of the deicers, has some application value, and becomes one of the first-choice deicers in cold areas in winter.
引文
[1] R.L .Hanneman. Highway Salt: Bargain of the Century [A]. In: Rob M.Geertman.8TH World Salt Symposium. Holand: 2000.759-765
[2] Dr John E.Thornes. Road Salting-an international benefit/cost review [A]. In: Rob M.Geertman.8TH World Salt Symposium. Holand: 2000.787-791
[3] 张向宇等编．实用化学手册[M]．第一版．北京．国防工业出版社，1986，582-588
[4] 姚允斌等．物理化学手册[M]．第一版．上海．上海科学技术出版社，1985，685-688
[5] Terence E. Peel, METHODS FOR OBTAINING DEICERS [P]. U.S., 4. 728. 393, 1988
[6] 黄士元．21世纪初期我国混凝土技术发展中的几个重点问题[J]．混凝土，2002，149(3)：3-7
[7] 段长强等，第一分册，通用试剂．现代化学试剂手册[M]．北京．化学工业出版社，1986，72-75
[8] 吴天容等．国外化学融雪除冰剂的开发与进展[J]．无机盐工业，1989，102(5)：28-32
[9] 秦炜、赵音延、戴献元．醋酸钙镁盐的应用及开发[J]．现代化工，20(9)：61-63
[10] V.M.Moran, A comparison of conventional and Alternative deicers on environmental Impact Perspective .in: F.M.D'Itri (ED.), Chemical Deicer and the Environment, Lewis Publisher, Chelsea, MI, UCA, 1992,pp, 241-261
[11] H.A.Elliott and J.H.Linn. Effect of Calcium Magnesium Acetate on Heavy Metal Mobility in Soils [J]. J.Environ. Qual. 16 (3), 1987,222-226
[12] Gregory P. Harris, Robert Turner, Richard J.Nelson. Field Test Comparison of Calcium Magnesium Acetate to Salt [J]. Journal of Transportation Engineering, 119(6), 889-905
[13] I.E.Lancaster, Assessment of alterative deicing chemicals to rock salt [J]. Transportation Research Laboratory, UK, 1993
[14] School of Civil Engineering. The effect of CMA deicer on concrete properties[J], Cement and Concrete Research, 2000,30,1389-1394
[15] Olof Peterson, Chemical Effects On Cement Mortarof Calcium Magnesium Acetate as A Deicing Salt [J]. Cement and Concrete Research, 1995,25(3), 617-626
[16] Willam L.Bryan, Research approaches to reduce CMA cost [J]. Resources Conservatin and Recycling, 1992,7,25-42
[17] A.B.Gancy. Water-activateD Exothermic Chemical Formulations [P]. U.S., 4,425,251,1984
[18] Anita His, Test and Evaluation of Calcium Magnesium Acetate-Sodium Chloride Mixtures in Sweden [J]. Snow Removal And Ice Control Technology, 1993,111(6), 53-59
[19] R.L.McCrum, Calcium Magnesium Acetate and Sodium Chloride as Highway Deicing Salts [J]. Environment Treatment & Control, 1989,11,24-28
[20] Cal J.Fritzsche, Calcium Magnesium Acetate Deicer [J]. Water Environment & Technology, 1992,1,44-51
[21] 邓景发 范康年．物理化学[M]．第一版．北京．高教出版社，1993．6
[22] 傅献彩．物理化学[M]．第四版．北京．高等教育出版社，1990．6
[23] 朱文涛．物理化学[M]．第一版．北京．清华大学出版社，1995．6
[24] 贾向群等．高效冰雪融化剂及应用[J]．沈阳工业大学学报，1998，20(1)，50-53
[25] 化学工业部化工机械研究院．腐蚀与防护手册．腐蚀理论．试验及监测[M]．第一版．李志清．北京．化学工业出版社，1989．5(1997第4次印刷)
[26] 李荻主编．电化学原理[M]．修订版．刘宝俊．北京．北京航空航天大学出版社，1999．8(2000年重印)
[27] 祝蓓蓉等．除冰盐对混凝土化学侵蚀机理研究[J]．低温建筑技术，2000，79(1)，3-6
[28] 武汉建筑材料工程学院，硅酸盐物理化学[M]，浙江大学，中国建筑工业出版社，1980，494-495
[29] 卢寿慈．粉体加工技术[M]．第一版．北京．中国轻工业出版社，2000
[30] 中央理研株式会社，不冻性组合物[P]．JP，C09K，0997683．1988
[31] 左景伊、左禹．腐蚀数据与选材手册[M]．第一版．蔡剑秋．北京．化学工业出版社，1995
[32] F.M.Dltri (ED.). Chemical Deicers and the environment [M].Lewis Publishers Chelsea. ML.USA. 1992.
[33] 党弘之、键和田贤一．化学盐防腐剂的开发[C]．第15届寒冷地区技术专题讨论，日本，1999，440-444
[34] 宇士泽光贤等．关于防冻剂对金属腐蚀的研究[C]．第12届寒冷地区技术专题讨论，日本，1996，240-245
[35] 佐佐木胜男，村本诚二，羽根田宽．关于防冻剂对混凝土所产生的物理变化[C]．第12届寒冷地区技术专题讨论，日本，1996，246-251
[36] 日本株式会社．碱性除冰剂[P]，日本公开特许公报，8—73838，1996
[37] Jack L. Simper; Daisy Lane, Salt Composition Containing Calcium Magnesium and Sodium Silicate [P]. WO, C09K, 92/21732,1992
[38] Alfred Lieber; Jack L. Simper, Salt composituion Having Smaller Sized Odium Metasilicate [P]. U. S, C08K 4, 606, 835, 1986
[39] 王凯雄．水化学[M]．北京．第一版．化学工业出版社，2001．5
[40] 武汉大学、吉林大学．无机化学[M]．第二版．北京．高教出版社，1983，318-319
[41] 陈英旭．环境学[M]．第一版．北京．中国环境科学出版社，2001，117-120
[42] 矢野、高志．冻结防止剂的制造方法[P]，日本公开特许公报，2001—11510
[43] 许国话，袁靖．常用热分析仪器[M]．上海科学技术出版社
[44] 合田明美等．关于防冻剂的其他特性[C]．第12届寒冷地区技术专题讨论，日本，1996，219—223
[45] 高存厚等．道路冰雪清除方法及应用[J]．山西交通科技，2000，132(2)，52—53
[46] 王学映译．有关预湿除冰剂须知[J]．市政工程国外动态，1995，(6)．18—19
[2] Dr John E.Thornes. Road Salting-an international benefit/cost review [A]. In: Rob M.Geertman.8TH World Salt Symposium. Holand: 2000.787-791
[3] 张向宇等编．实用化学手册[M]．第一版．北京．国防工业出版社，1986，582-588
[4] 姚允斌等．物理化学手册[M]．第一版．上海．上海科学技术出版社，1985，685-688
[5] Terence E. Peel, METHODS FOR OBTAINING DEICERS [P]. U.S., 4. 728. 393, 1988
[6] 黄士元．21世纪初期我国混凝土技术发展中的几个重点问题[J]．混凝土，2002，149(3)：3-7
[7] 段长强等，第一分册，通用试剂．现代化学试剂手册[M]．北京．化学工业出版社，1986，72-75
[8] 吴天容等．国外化学融雪除冰剂的开发与进展[J]．无机盐工业，1989，102(5)：28-32
[9] 秦炜、赵音延、戴献元．醋酸钙镁盐的应用及开发[J]．现代化工，20(9)：61-63
[10] V.M.Moran, A comparison of conventional and Alternative deicers on environmental Impact Perspective .in: F.M.D'Itri (ED.), Chemical Deicer and the Environment, Lewis Publisher, Chelsea, MI, UCA, 1992,pp, 241-261
[11] H.A.Elliott and J.H.Linn. Effect of Calcium Magnesium Acetate on Heavy Metal Mobility in Soils [J]. J.Environ. Qual. 16 (3), 1987,222-226
[12] Gregory P. Harris, Robert Turner, Richard J.Nelson. Field Test Comparison of Calcium Magnesium Acetate to Salt [J]. Journal of Transportation Engineering, 119(6), 889-905
[13] I.E.Lancaster, Assessment of alterative deicing chemicals to rock salt [J]. Transportation Research Laboratory, UK, 1993
[14] School of Civil Engineering. The effect of CMA deicer on concrete properties[J], Cement and Concrete Research, 2000,30,1389-1394
[15] Olof Peterson, Chemical Effects On Cement Mortarof Calcium Magnesium Acetate as A Deicing Salt [J]. Cement and Concrete Research, 1995,25(3), 617-626
[16] Willam L.Bryan, Research approaches to reduce CMA cost [J]. Resources Conservatin and Recycling, 1992,7,25-42
[17] A.B.Gancy. Water-activateD Exothermic Chemical Formulations [P]. U.S., 4,425,251,1984
[18] Anita His, Test and Evaluation of Calcium Magnesium Acetate-Sodium Chloride Mixtures in Sweden [J]. Snow Removal And Ice Control Technology, 1993,111(6), 53-59
[19] R.L.McCrum, Calcium Magnesium Acetate and Sodium Chloride as Highway Deicing Salts [J]. Environment Treatment & Control, 1989,11,24-28
[20] Cal J.Fritzsche, Calcium Magnesium Acetate Deicer [J]. Water Environment & Technology, 1992,1,44-51
[21] 邓景发 范康年．物理化学[M]．第一版．北京．高教出版社，1993．6
[22] 傅献彩．物理化学[M]．第四版．北京．高等教育出版社，1990．6
[23] 朱文涛．物理化学[M]．第一版．北京．清华大学出版社，1995．6
[24] 贾向群等．高效冰雪融化剂及应用[J]．沈阳工业大学学报，1998，20(1)，50-53
[25] 化学工业部化工机械研究院．腐蚀与防护手册．腐蚀理论．试验及监测[M]．第一版．李志清．北京．化学工业出版社，1989．5(1997第4次印刷)
[26] 李荻主编．电化学原理[M]．修订版．刘宝俊．北京．北京航空航天大学出版社，1999．8(2000年重印)
[27] 祝蓓蓉等．除冰盐对混凝土化学侵蚀机理研究[J]．低温建筑技术，2000，79(1)，3-6
[28] 武汉建筑材料工程学院，硅酸盐物理化学[M]，浙江大学，中国建筑工业出版社，1980，494-495
[29] 卢寿慈．粉体加工技术[M]．第一版．北京．中国轻工业出版社，2000
[30] 中央理研株式会社，不冻性组合物[P]．JP，C09K，0997683．1988
[31] 左景伊、左禹．腐蚀数据与选材手册[M]．第一版．蔡剑秋．北京．化学工业出版社，1995
[32] F.M.Dltri (ED.). Chemical Deicers and the environment [M].Lewis Publishers Chelsea. ML.USA. 1992.
[33] 党弘之、键和田贤一．化学盐防腐剂的开发[C]．第15届寒冷地区技术专题讨论，日本，1999，440-444
[34] 宇士泽光贤等．关于防冻剂对金属腐蚀的研究[C]．第12届寒冷地区技术专题讨论，日本，1996，240-245
[35] 佐佐木胜男，村本诚二，羽根田宽．关于防冻剂对混凝土所产生的物理变化[C]．第12届寒冷地区技术专题讨论，日本，1996，246-251
[36] 日本株式会社．碱性除冰剂[P]，日本公开特许公报，8—73838，1996
[37] Jack L. Simper; Daisy Lane, Salt Composition Containing Calcium Magnesium and Sodium Silicate [P]. WO, C09K, 92/21732,1992
[38] Alfred Lieber; Jack L. Simper, Salt composituion Having Smaller Sized Odium Metasilicate [P]. U. S, C08K 4, 606, 835, 1986
[39] 王凯雄．水化学[M]．北京．第一版．化学工业出版社，2001．5
[40] 武汉大学、吉林大学．无机化学[M]．第二版．北京．高教出版社，1983，318-319
[41] 陈英旭．环境学[M]．第一版．北京．中国环境科学出版社，2001，117-120
[42] 矢野、高志．冻结防止剂的制造方法[P]，日本公开特许公报，2001—11510
[43] 许国话，袁靖．常用热分析仪器[M]．上海科学技术出版社
[44] 合田明美等．关于防冻剂的其他特性[C]．第12届寒冷地区技术专题讨论，日本，1996，219—223
[45] 高存厚等．道路冰雪清除方法及应用[J]．山西交通科技，2000，132(2)，52—53
[46] 王学映译．有关预湿除冰剂须知[J]．市政工程国外动态，1995，(6)．18—19