聚环氧琥珀酸的相对分子质量控制及相对分子质量与性能间的关系
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摘要
聚环氧琥珀酸(PESA)是世界上公认的绿色水处理剂及更新换代产品。由于其问世较短，产品因垄断而不易获得等原因，关于其阻垢性能的研究较多，但对其它性能尚缺乏研究。本工作首次研究了PESA聚合过程中相对分子质量的控制及相对分子质量与PESA的阻垢性能、缓蚀性能、分散性能之间的关系。鉴于对阻垢剂的需求和阻垢试验方法随应用领域的不同而有很大差别，因而对PESA的阻垢性能的研究采用了不同的研究方法。
通过对PESA聚合过程的研究，找到了影响PESA相对分子质量的关键因素，得出了通过调节引发剂的添加量、改变反应温度等控制PESA相对分子质量及其分布的方法，制备了相对分子质量从400～1200的PESA。
采用鼓泡法研究了PESA的阻垢性能与其相对分子质量的关系，发现当PESA相对分子质量变化时，其性能变化相当大，当相对分子质量在800～1000范围时，钙离子稳定浓度达到120mg·L~(-1)以上；当相对分子质量低于700或高于1000吋，阻垢性能变差。通过静态法研究了聚环氧琥珀酸阻硫酸钡垢的效果，确立了其最佳阻垢效果的分子量范围为700-850，阻垢率在90％以上。
采用动态旋转挂片法研究了PESA的缓蚀性能，发现PESA单独使用时对碳钢即有较好缓蚀作用，其缓蚀作用的本质是在材质表面生成了吸附膜，具有最佳缓蚀效果的分子量范围在750—1000。
采用透光率法和旋转粘度计法研究了PESA的分散性能，发现PESA对氧化铁和碳酸钙均有良好的分散作用，相对分子质量为1000-1200的PESA的分散效果最好。
研究了PESA在油田用水中的阻垢效果，结果表明，PESA对常遇到的硫酸钡、硫酸锶、硫酸钙类难溶垢有着优异的阻垢效果，对碳酸钙也有较好效果。为进一步提高阻垢剂的阻垢性能，对PESA与PBTCA、AA／HPA进行复配，得到的阻垢剂对油田中存在的主要垢盐均有良好的阻垢性能。
Polyepoxysuccinic acid is acknowledged green water treatment agent and new alternative in the world. It appears in recent years and its property of scale inhibition has been studied much more than other properties of PESA. It has been studied the relation between synthesis of polyepoxysuccinic acid and control of molecular weight ,the relation between molecular weight of PESA and its properties such as scale inhibition, corrosion inhibition and dispersion performance. The applications of PESA's scale inhibition property in several fields, so we use differert experiment methods to test the scale inhibition of PESA.
In this study, effect of initiator, pH, temperature and time on products showed that different relative molecular weight were obtained by means of changing these factors.
The standard method was used to study the connection between the scale inhibition and the relative molecular weight of PESA. It had been found that when the relative molecular weight changed, the properties changed also. When the relative molecular weight of PESA is in the range 800 to 1000, the scale inhibitions are best. When the relative molecular weight of PESA is lower than 700 or higher than 1000, the scale inhibition becomes worse. And inhibition of PESA for barium sulfate has been studied, the result show that when the relative molecular weight of PESA is in the range 700 to 850, the scale inhibitions are best, over 90%.
Rotary coupon test has been used to study corrosion inhibition of PESA, it has been found that when PESA was used separately, it has some effect of preventing corrosion.The result show that when the relative molecular weight of PESA is in the range 750 to 1000, the corrosion inhibitions are best.
Translucent rate and rotary viscosimeter method have been used to study the dispersion property of PESA. It has been found that PESA has excellent dispersion property to calcium carbonate and ferric oxide, and the best relative molecular weight range is 1000 to 1200.
The green scale inhibitor polyepoxysuccinic acid's properties of scale inhibition to scale in the oil field were studied. The results indicate that PESA has excellent inhibitive effects to the poor solubility scales such as barium sulfate, calcium sulfate, strontium sulfate and to the calcium carbonate scale is normal. In order to solve the problem of different kind of scale in oilfield water system, we use a combination of PESA and PBTCA and AA/HPA as a water treatment agent add to the oilfield water system. The experiment results show that the complex scaling inhibitors can efficiently control the scale.
通过对PESA聚合过程的研究，找到了影响PESA相对分子质量的关键因素，得出了通过调节引发剂的添加量、改变反应温度等控制PESA相对分子质量及其分布的方法，制备了相对分子质量从400～1200的PESA。
采用鼓泡法研究了PESA的阻垢性能与其相对分子质量的关系，发现当PESA相对分子质量变化时，其性能变化相当大，当相对分子质量在800～1000范围时，钙离子稳定浓度达到120mg·L~(-1)以上；当相对分子质量低于700或高于1000吋，阻垢性能变差。通过静态法研究了聚环氧琥珀酸阻硫酸钡垢的效果，确立了其最佳阻垢效果的分子量范围为700-850，阻垢率在90％以上。
采用动态旋转挂片法研究了PESA的缓蚀性能，发现PESA单独使用时对碳钢即有较好缓蚀作用，其缓蚀作用的本质是在材质表面生成了吸附膜，具有最佳缓蚀效果的分子量范围在750—1000。
采用透光率法和旋转粘度计法研究了PESA的分散性能，发现PESA对氧化铁和碳酸钙均有良好的分散作用，相对分子质量为1000-1200的PESA的分散效果最好。
研究了PESA在油田用水中的阻垢效果，结果表明，PESA对常遇到的硫酸钡、硫酸锶、硫酸钙类难溶垢有着优异的阻垢效果，对碳酸钙也有较好效果。为进一步提高阻垢剂的阻垢性能，对PESA与PBTCA、AA／HPA进行复配，得到的阻垢剂对油田中存在的主要垢盐均有良好的阻垢性能。
Polyepoxysuccinic acid is acknowledged green water treatment agent and new alternative in the world. It appears in recent years and its property of scale inhibition has been studied much more than other properties of PESA. It has been studied the relation between synthesis of polyepoxysuccinic acid and control of molecular weight ,the relation between molecular weight of PESA and its properties such as scale inhibition, corrosion inhibition and dispersion performance. The applications of PESA's scale inhibition property in several fields, so we use differert experiment methods to test the scale inhibition of PESA.
In this study, effect of initiator, pH, temperature and time on products showed that different relative molecular weight were obtained by means of changing these factors.
The standard method was used to study the connection between the scale inhibition and the relative molecular weight of PESA. It had been found that when the relative molecular weight changed, the properties changed also. When the relative molecular weight of PESA is in the range 800 to 1000, the scale inhibitions are best. When the relative molecular weight of PESA is lower than 700 or higher than 1000, the scale inhibition becomes worse. And inhibition of PESA for barium sulfate has been studied, the result show that when the relative molecular weight of PESA is in the range 700 to 850, the scale inhibitions are best, over 90%.
Rotary coupon test has been used to study corrosion inhibition of PESA, it has been found that when PESA was used separately, it has some effect of preventing corrosion.The result show that when the relative molecular weight of PESA is in the range 750 to 1000, the corrosion inhibitions are best.
Translucent rate and rotary viscosimeter method have been used to study the dispersion property of PESA. It has been found that PESA has excellent dispersion property to calcium carbonate and ferric oxide, and the best relative molecular weight range is 1000 to 1200.
The green scale inhibitor polyepoxysuccinic acid's properties of scale inhibition to scale in the oil field were studied. The results indicate that PESA has excellent inhibitive effects to the poor solubility scales such as barium sulfate, calcium sulfate, strontium sulfate and to the calcium carbonate scale is normal. In order to solve the problem of different kind of scale in oilfield water system, we use a combination of PESA and PBTCA and AA/HPA as a water treatment agent add to the oilfield water system. The experiment results show that the complex scaling inhibitors can efficiently control the scale.
引文
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[6] 张建华．冷却水处理剂的应用研制现状及发展趋势[J]，化学与生物工程，2003，1：5-6
[7] 严瑞，胡宇，纪永亮，鲍其鼐．我国水处理剂的现状及发展战略[J]，现代化工，1999，19(2)：3-7
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[12] 郑邦乾，朱清泉．高分子阻垢剂及其阻垢机理[J]，油田化学，1984，2：181．
[13] 姚广致，成荣钊．阻垢剂对CaCO3垢的抑制能力[J]，工业水处理，1986，6(4)：36．
[14] 李裕芳．阻垢剂分散剂控制沉积机理探讨[J]，工业水处理，1984，4(3)：6．
[15] 王平．水解聚马来酸配阻垢性能的研究[J]，工业水处理，1996，16(4)：10
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[33] International workshop on green chemistry and engineering, Global Collaborations, 1998
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[36] Bush, Rodney D, Heinzman, Stephen W, et al. Ether hydroxypolycarboxylate detergency builders[P], US 4654159. 1987-3-31
[37] Benedict, James J, Bush, et al. Oral compositions and methods for reducing dental calculus[P], US 4846650. 1989-7-11
[38] 吕志芳，董伟，夏明珠，等．聚环氧琥珀酸的阻垢缓蚀性能研究[J]，工业水处理，2001，21(3)：23-25
[39] 熊蓉春，魏刚，周娣，等．绿色阻垢剂聚环氧琥珀酸的合成[J]，工业水处理，1999，19(3)：11-13
[40] 熊蓉春，周庆，魏刚．绿色阻垢剂聚环氧琥珀酸的缓蚀协同效应[J]，化工学报，2003，54(9)：1323-1325
[41] 魏刚，许亚男，熊蓉春．阻垢剂的可生物降解性研究[J]，北京化工大学学报，2001，28(1)：59-61
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[56] 周厚安．油气田开发中硫酸盐垢的形成及防垢剂和除垢剂研究与应用进展[J]，石油与天然气化工，1999，28(3)：212-215
[2] 张平．国外水资源管理实践及对我国的借鉴[J]，治淮，2005，03：6-7
[3] 杨彩奎．敞开式循环冷却水系统的水质处理[J]，山西建筑，2003，29(18)：119-120
[4] 王琰，孟兆森，樊守传．工业冷却水系统中的腐蚀问题[J]，氯碱工业，2004，8(8)：43-45
[5] 蔡士杰．绿色水处理剂聚环氧琥珀酸物化性能指标及表征技术[D]，北京：北京化工大学毕业论文，2004
[6] 张建华．冷却水处理剂的应用研制现状及发展趋势[J]，化学与生物工程，2003，1：5-6
[7] 严瑞，胡宇，纪永亮，鲍其鼐．我国水处理剂的现状及发展战略[J]，现代化工，1999，19(2)：3-7
[8] 兰文芝，邵刚，实用环境工程手册[M]，北京：化学工业出版社，2002．282～301
[9] 熊蓉春，董雪玲，魏刚．水处理剂发展趋向绿色化[J]，中国环保产业，2003，06：46-47
[10] 梁克中．水处理剂简介[J]，山东化工，2004，2：37—39
[11] SUITOR J W, MARNER W J, RITTER R B. The history and status of research in fouling of heat exchangers in cooling water service[J], Can J Chem Eng, 1977, 55:374
[12] 郑邦乾，朱清泉．高分子阻垢剂及其阻垢机理[J]，油田化学，1984，2：181．
[13] 姚广致，成荣钊．阻垢剂对CaCO3垢的抑制能力[J]，工业水处理，1986，6(4)：36．
[14] 李裕芳．阻垢剂分散剂控制沉积机理探讨[J]，工业水处理，1984，4(3)：6．
[15] 王平．水解聚马来酸配阻垢性能的研究[J]，工业水处理，1996，16(4)：10
[16] 王睿，张岐，丁洁，等．阻垢剂作用机理研究进展[J]，化学工业与工程，2004，18(2)：79-86
[17] 汪祖模，水质稳定剂，上海：华东化工学院出版社[M]，1991．34
[18] SHAHEEN E I, DIX1T N S. Scale reduction in saline water conversion[J], Desalination, 1973, 13:187
[19] GILL J S, ANDERSON C D, VARSANIK R G. Mechanism of scale inhibition by phosphonates[J], Proc 44th Int Water Conf. Pittsburgh: Pa (USA), 1983, 4: 26.
[20] 梁克中．水处理剂简介[J]，山东化工，2004，02：37
[21] 宋蔚，田禾，张津红．缓蚀剂的成膜机理分析[J]，天津理工学院学报，2004，04：67-70
[22] 王效斌．新型高效铜缓蚀阻垢剂研究[D]，北京：北京化工大学毕业论文，2005
[23] 邓滨才，缓蚀剂的作用及应用[J]，化学下程师，1995，6(51)：43-41
[24] Patel S. Developing a cooling water inhibitor with multifuctionaldeposit control properties[J], Material Performance, 1996, 35(6): 41-45
[25] 马立治．水性涂枓高分子分散剂的合成与性能研究[D]，北京：北京化工大学毕业论文，2003
[26] Anastas P. T., Willianmson T C. Green chemistry-designing chemistry for the environment[C], symposium Series 626th, Washington DC USA, American chemical Society, 1996, 3:254-260
[27] Robert J Poss Kim Low, James E Shannon, Polyaspartate Scale inhibitorsBiodegradable alternatives to Polyacrylates[J], Material Performance, 1997, 36(4): 52-57
[28] Diana Darling, Ram Rakshpal. Green chemistry applied to corrosion and scale inhibitors[J], Material performance, 1998, 37(12): 42-46
[29] 熊蓉春，董雪玲，魏刚．绿色化学与21世纪水处理刑发展战略[J]，环境工程，2000．4，18(2)：22-26
[30] 熊蓉春，董雪玲，魏刚．水处理剂发展趋向绿色化[J]，中国环保产业，2003，06：46-47
[31] FUKUMOTO YASUHISA, TANIGUCHI TAKAO. Water-treating agents for prevention of metal conation and scale generation [P]. JP04166298, 1992-04-08
[32] 魏刚，周庆，熊蓉春，雷晓东．水处理中的绿色化学与绿色技术[J]，现代化工，2002，22(12)：43-46
[33] International workshop on green chemistry and engineering, Global Collaborations, 1998
[34] Brown J, Michiael, Mcdowell, Methods of controlling scale formation in aqueous systems[P], US 5147555.1992-9-15
[35] Brown J, Michiael, Mcdowell, John F. Methods of controlling scale formation in aqueous systems[P], US 5062962. 1991-11-5
[36] Bush, Rodney D, Heinzman, Stephen W, et al. Ether hydroxypolycarboxylate detergency builders[P], US 4654159. 1987-3-31
[37] Benedict, James J, Bush, et al. Oral compositions and methods for reducing dental calculus[P], US 4846650. 1989-7-11
[38] 吕志芳，董伟，夏明珠，等．聚环氧琥珀酸的阻垢缓蚀性能研究[J]，工业水处理，2001，21(3)：23-25
[39] 熊蓉春，魏刚，周娣，等．绿色阻垢剂聚环氧琥珀酸的合成[J]，工业水处理，1999，19(3)：11-13
[40] 熊蓉春，周庆，魏刚．绿色阻垢剂聚环氧琥珀酸的缓蚀协同效应[J]，化工学报，2003，54(9)：1323-1325
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