循环冷却水用绿色阻垢剂的研究进展

doi:10.3976/j.issn.1002-4026.2023.05.013

摘要/Abstract

摘要：

近年来,为缓解水资源匮乏,循环冷却水系统得到了广泛应用。冷却水中通常含有钙、镁等多种矿物离子,容易形成不溶性盐,在设备表面结垢。使用阻垢剂是解决结垢问题最有效的方法之一。综述了近年来国内外绿色阻垢剂的研究进展,介绍了绿色阻垢剂的开发与应用现状,分析了不同类型阻垢剂的特点和阻垢性能,从螯合增溶、晶格畸变和凝聚分散作用等方面阐述了阻垢机理,可为未来绿色阻垢剂研究发展提供借鉴。

关键词: 循环冷却水, 绿色阻垢剂, 阻垢性能, 阻垢机理

Abstract:

Recently, circulating cooling water systems have been widely used to alleviate water shortage.However, cooling water usually contains various mineral ions,such as calcium and magnesium, which can easily form insoluble salts and scale on the surface of the equipment. The use of scale inhibitors in cooling water systems is one of the most effective methods to solve the scaling problem. In this paper, the recent research progress on green scale inhibitors at home and abroad was reviewed. The development and applications of green scale inhibitors were introduced here. The characteristics and scale inhibition performance of different types of scale inhibitors are also analyzed.Moreover,the scale inhibition mechanism was explained from different aspects,such as chelation and solubilization, coagulation and dispersion, and lattice distortion.Therefore,this review would provide an excellent reference for future research and development of green scale inhibitors.

Key words: circulating cooling water, green scale inhibitor, scale inhibition performance, scale inhibition mechanism

中图分类号:

何振波, 张厉, 高铭心, 栾玲玉. 循环冷却水用绿色阻垢剂的研究进展[J]. 山东科学, 2023, 36(5): 102-120.

HE Zhenbo, ZHANG Li, GAO Mingxin, LUAN Lingyu. Research progress of green scale inhibitors for circulating cooling water[J]. Shandong Science, 2023, 36(5): 102-120.

图/表 3

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阻垢剂	化学结构式	主要特性
2-膦酸基-1,2,4-三羧酸丁烷 (PBTCA)^[9]		有机膦酸,含有羧酸和膦酸官能团,与Ca²⁺有较好的络合能力,具有良好的阻垢、分散性能和耐高温性能,可作螯合剂和分散剂。
羟基乙叉二膦酸 (HEDP)^[9]		有机膦酸,含有膦酸和羟基官能团,能与Ca²⁺生成稳定的络合物,具有良好的阻垢缓蚀性能,毒性小和抗氧化性强,可作阻垢缓蚀剂和螯合剂。
氨基三亚甲基膦酸 (ATMP)^[10]		有机膦酸,含有膦酸官能团,化学性质稳定且较难水解,对Ca²⁺具有良好的螯合能力,在较低浓度时就引起晶格畸变,具有良好的阻垢性能和阈值效应。
乙二胺四乙酸 (EDTA)^[10]		含有羧酸官能团,能与Ca²⁺形成稳定的络合物,是螯合剂的典型代表物质,常被用作螯合剂和滴定指示剂。
聚丙烯酸 (PAA)^[9]		水溶性聚羧酸类阻垢剂,含有羧基,能与Ca²⁺螯合,具有阻垢和分散性能,不可降解。
氨三乙酸 (NTA)^[9]		含有羧酸官能团,单个分子能提供4个配位键,具有非常强的络合能力,可以与Ca²⁺形成稳定的螯合物,可作阻垢剂和洗涤剂。

阻垢剂		主要特性
生姜提取物^[36]		含有羟基和羰基等官能团,羟基可与Ca²⁺螯合,对钙垢的形成有一定的抑制作用
褐藻提取物^[37]		褐藻酸含有羧基和羟基等官能团,对Ca²⁺有很强的结合能力,具有良好的阻垢性能,可作阻垢剂和食品添加剂
橄榄叶提取物^[32]		橄榄苦柑含有羟基和酯基等官能团,能够络合Ca²⁺,具有良好的阻垢性能
萝卜提取物^[38]	提取物中可与Ca²⁺相互作用的主要化合物的活性官能团有羟基和羧基,醚键会提高聚合物在钙垢晶体的吸附性


单宁酸^[39]	多酚类化合物,无磷且易降解,含有酚羟基、羰基等官能团,易与Ca²⁺形成可溶性较大的螯合物
柠檬酸^[3]	环境友好型天然有机酸,结构中含有羧基和羟基,能与Ca²⁺螯合,具有阻垢性能,可用作阻垢剂、芳香剂和防腐剂
淀粉^[40],纤维素^[41-42]	天然有机高分子阻垢剂,含有羟基和醚键官能团,能够络合Ca²⁺,具有一定的阻垢性能,但自身阻垢效果不够好,高温下易分解
壳聚糖^[43]	天然多糖,无毒生物可降解,含有羟基和氨基官能团,能与Ca²⁺发生螯合反应,具有阻垢和缓蚀性能,但分散性能和抗菌活性差

阻垢剂	化学结构式	主要特性
聚天冬氨酸^[101]		无磷无毒,具有生物可降解性,侧链含有羧基官能团,可以螯合Ca²⁺,主要通过改变钙垢晶体结构来抑制钙垢的生长,具有良好的阻垢性能,但在高温或高硬度水体中阻垢效果不够好。
聚环氧琥珀酸^[101]	n=2~10 M为Na⁺或H⁺,K⁺,NH₄⁺ R为H或C_1-4烷基	无磷无毒,生物降解性好,能与Ca²⁺螯合,主要通过延缓晶体成核时间来抑制钙垢的形成,可做阻垢缓蚀剂。但存在投加量大、Ca²⁺耐受性差和耐温性差等缺点。
苹果酸^[102]		无毒,生物可降解,含有羧基和羟基官能团,具有一定的阻垢性能,可作食品添加剂和阻垢剂。
羧基甲菊粉^[103]		属于多糖,无毒,不含氮、磷,具有可再生和生物降解性,含有羧基和羟基官能团,可以与Ca²⁺发生螯合反应,引起晶格畸变,能够有效地抑制钙垢的形成。可用于石油勘探、药物输送和抑制钙垢。