无磷有机阻垢剂的性能和作用机理

摘要/Abstract

摘要： 综述了羧酸盐型聚合物、磺酸盐型聚合物和聚醚型聚合物3种无磷有机阻垢剂对碳酸钙、磷酸钙的阻垢性能和阻垢机理，从结构和阻垢性能的关系方面探讨了3类阻垢剂的阻垢特点。羧酸根与碳酸钙晶体表面的钙离子螯合，使碳酸钙晶体畸变为松散结构，抑制了碳酸钙的结垢；羧酸根与磺酸根或聚乙烯氧基链的协同作用抑制了磷酸钙的结垢。其中，羧酸根通过螯合作用锚定在无定型磷酸钙纳米颗粒的表面，磺酸根使无定型磷酸钙带负电荷从而分散磷酸钙垢，聚乙烯氧基链增加了磷酸钙的溶解性。对无磷有机阻垢剂的发展趋势进行了展望。

关键词: 无磷有机阻垢剂, 羧酸盐, 磺酸盐, 聚醚

Abstract: The scale inhibition properties and mechanism of three kinds of phosphate-free organic scale inhibitors, including carboxylate polymer, sulfonate polymer and polyether polymer, on calcium carbonate and calcium phosphate were reviewed from the relationship between structure and scale inhibition performance. The carboxylate chelates with the calcium ions on the surface of the calcium carbonate crystal, which distorts the calcium carbonate crystal into a loose structure and inhibits the scaling of calcium carbonate. The carboxylate is anchored to the surface of amorphous calcium phosphate nanoparticles by chelation, the sulfonate makes amorphous calcium phosphate negatively charged and disperses calcium phosphate scale, and the polyvinyl oxy chain increases the solubility of calcium phosphate. In this context, the directions of developing scale inhibitors were prospected.

Key words: non-phosphorus scale inhibitors, carboxylates, sulfonates, polyethers

中图分类号:

窦孟然高嵩. 无磷有机阻垢剂的性能和作用机理[J]. 石油炼制与化工, 2020, 51(5): 105-109.

参考文献

[1]姜文; 万志强, 石化污水回用于循环水系统处理技术探讨[J]. 石油化工设计 2012, 29 (01), 7-9.
[2]李婷婷; 郝燕; 郭贵宝, AA-AMPS-HPA的合成及其阻垢性能研究[J]. 内蒙古科技大学学报 2015, 34 (01), 29-32.
[3]吴海福; 文明通; 蒋铭明; 黄淋佳, 几种工业循环水用缓蚀阻垢剂静态阻垢性能对比研究[J]. 广东化工 2016, 43 (03), 1-2+7.
[4]Amjad, Z.; Koutsoukos, P. G., Evaluation of maleic acid based polymers as scale inhibitors and dispersants for industrial water applications[J]. Desalination 2014, 335 (1), 55-63.
[5]李晓梅. 聚环氧琥珀酸阻垢缓蚀性能及机理研究[J]. 黑龙江大学, 2008.
[6]Shen, Z.; Li, J.; Xu, K.; Ding, L.; Ren, H., The effect of synthesized hydrolyzed polymaleic anhydride (HPMA) on the crystal of calcium carbonate[J]. Desalination 2012, 284, 238-244.
[7]Shi, W.-Y.; Ding, C.; Yan, J.-L.; Han, X.-Y.; Lv, Z.-M.; Lei, W.; Xia, M.-Z.; Wang, F.-Y., Molecular dynamics simulation for interaction of PESA and acrylic copolymers with calcite crystal surfaces[J]. Desalination 2012, 291, 8-14.
[8]Shen, X.; Tong, H.; Zhu, Z.; Wan, P.; Hu, J., A novel approach of homogenous inorganic/organic composites through in situ precipitation in poly-acrylic acid gel[J]. Materials Letters 2007, 61 (3), 629-634.
[9]Bar-Yosef Ofir, P.; Govrin-Lippman, R.; Garti, N.; Füredi-Milhofer, H., The Influence of Polyelectrolytes on the Formation and Phase Transformation of Amorphous Calcium Phosphate[J]. Crystal Growth & Design 2004, 4 (1), 177-183.
[10]Watanabe, K.; Nishida, I.; Imai, H., Dispersion of hydroxyapatite nanocrystals stabilized by polymeric molecules bearing carboxy and sulfo groups[J]. Colloid and Polymer Science 2017, 295 (9), 1491-1498.
[11]符嫦娥; 周钰明; 薛蒙伟; 谢洪涛; 吴文导; 孙伟, 新型无磷无氮阻垢剂的阻磷酸钙垢及分散Fe(III)性能[J]. 化工学报 2011, 62 (2), 525-531.
[12]Krogstad, D. V.; Wang, D.; Lin-Gibson, S., Kinetics of Aggregation and Crystallization of Polyaspartic Acid Stabilized Calcium Phosphate Particles at High Concentrations[J]. Biomacromolecules 2015, 16 (5), 1550-1555.
[13]Dietzsch, M.; Barz, M.; Schuler, T.; Klassen, S.; Schreiber, M.; Susewind, M.; Loges, N.; Lang, M.; Hellmann, N.; Fritz, M.; Fischer, K.; Theato, P.; Kuhnle, A.; Schmidt, M.; Zentel, R.; Tremel, W., PAA-PAMPS copolymers as an efficient tool to control CaCO3 scale formation[J]. Langmuir : the ACS journal of surfaces and colloids 2013, 29 (9), 3080-8.
[14]李海花; 高美玲; 张利辉; 高玉华; 刘振法, 含磺酸基团的环氧琥珀酸类共聚物的合成及性能比较[J]. 化工进展 2017, 36 (04), 1491-1498.
[15]赵彦生; 武丽丽; 魏文珑, 磺酸盐类共聚物阻垢分散剂的研究进展[J]. 太原理工大学学报 2002, (02), 125-127+136.
[16]符嫦娥; 胡大华; 韩承辉; 刘海霞; 仓理; 周钰明, 两种封端聚醚大单体及其共聚物制备与阻磷酸钙垢应用[J]. 化工学报 2013, 64 (7), 2687-2895.
[17]Wang, L.-C.; Cui, K.; Wang, L.-B.; Li, H.-X.; Li, S.-F.; Zhang, Q.-l.; Liu, H.-B., The effect of ethylene oxide groups in alkyl ethoxy carboxylates on its scale inhibition performance[J]. Desalination 2016, 379, 75-84.
[18]Wang, L. C.; Zhu, C. G.; Liu, H. B.; Zhao, W. D.; Che, Y.; Zhang, Q. L.; Wang, L. B., Evaluation of maleic acid‐based copolymers containing polyoxyethylene ether as inhibitors for CaCO3 scale[J]. Journal of Applied Polymer Science 2019, 136 (19).
[19]Fu, C.; Zhou, Y.; Liu, G.; Huang, J.; Wu, W.; Sun, W., Carboxylate-Ended Poly(ethylene glycol) Macromonomers and their Copolymers as Inhibitors for Calcium Phosphate and Calcium Sulfate[J]. International Journal of Polymeric Materials 2012, 61 (5), 341-356.
[20]Ling, L.; Zhou, Y.; Huang, J.; Yao, Q.; Liu, G.; Zhang, P.; Sun, W.; Wu, W., Carboxylate-terminated double-hydrophilic block copolymer as an effective and environmental inhibitor in cooling water systems[J]. Desalination 2012, 304, 33-40.
[21]Change, F.; Yuming, Z.; Guangqing, L.; Jingyi, H.; Wei, S.; Wendao, W., Inhibition of Ca3(PO4)2, CaCO3, and CaSO4Precipitation for Industrial Recycling Water[J]. Industrial & Engineering Chemistry Research 2011, 50 (18), 10393-10399.
[22]Li, J.; Zhou, Y.; Yao, Q.; Wang, T.; Zhang, A.; Chen, Y.; Wu, W.; Sun, W., Preparation and Evaluation of a Polyether-Based Polycarboxylate as a Kind of Inhibitor for Water Systems[J]. Industrial & Engineering Chemistry Research 2017, 56 (10), 2624-2633.
[23]Liu, G.; Xue, M.; Liu, Q.; Yang, H.; Yang, J.; Zhou, Y., Maleic anhydride–allylpolyethoxy carboxylate copolymer as an effective and environmentally benign inhibitor for calcium carbonate in industrial cooling systems[J]. RSC Advances 2017, 7 (40), 24723-24729.
[24]Fu, C.; Zhou, Y.; Xie, H.; Sun, W.; Wu, W., Double-Hydrophilic Block Copolymers as Precipitation Inhibitors for Calcium Phosphate and Iron(III) [J]. Industrial & Engineering Chemistry Research 2010, 49 (19), 8920-8926.
[25]符嫦娥; 向奇志; 秦品珠; 丁任丽; 薛晓婷; 周钰明, 聚羧酸系无磷阻垢剂阻磷酸钙垢的对比研究[J]. 工业水处理 2015, 35 (2), 34-37.
[26]符嫦娥; 胡大华; 韩承辉; 刘海霞; 仓理; 周钰明, 两种封端聚醚大单体及其共聚物制备与阻磷酸钙垢应用[J]. 化工学报 2013, 64 (07), 2687-2695.
[27]符嫦娥; 秦品珠; 向奇志; 刘海霞; 谢洪涛; 周钰明, 高效无磷聚醚型阻垢剂合成与阻垢分散性能[J]. 水处理技术 2014, 40 (08), 16-19+24.
[28]Chen, Y. J.; Xu, G. Y., Improvement of Ca2+-tolerance by the introduction of EO groups for the anionic surfactants: Molecular dynamics simulation[J]. Colloid Surf. A-Physicochem. Eng. Asp. 2013, 424, 26-32.