HEDP、PBTCA、PAA对CaCO<sub>3</sub>垢抑制作用的电化学研究

doi:10.19965/j.cnki.iwt.2020-1207

摘要/Abstract

摘要：

采用线性扫描伏安法、计时电流法、电化学阻抗谱等电化学手段研究羟基亚乙基二膦酸（HEDP）、2-磷酸基-1，2，4-三羧酸丁烷（PBTCA）和聚丙烯酸（PAA）的阻垢效果以及利用剩余电流密度计算阻垢率方法的可行性。结果表明，利用剩余电流密度计算得到的阻垢率与电化学阻抗法得到的阻垢率结果相近，阻垢效果均为PBTCA>HEDP>PAA。机理探究结果表明，CaCO₃垢通过电沉积过程在钛合金电极表面形成文石晶体，阻垢剂的加入可通过晶体畸变作用抑制文石晶体的正常生长，使其转化为不稳定的球霰石晶体，并通过分散作用抑制垢的聚集沉积。

关键词: 计时电流法, 电化学阻抗谱, 电沉积, 阻垢剂, 碳酸钙垢

Abstract:

The anti-scale performance of 1-hydroxyethylidene-1, 1-diphosphonic acid(HEDP), 2-phosphonobutane-1, 2, 4-tricarboxylic acid(PBTCA) and polyacrylic acid(PAA) and the feasibility of calculating the anti-scale rate by using the residual current density were studied by electrochemical techniques including linear sweep voltammetry, chronoamperometry and electrochemical impedance spectroscopy. The results showed the anti-scale rate obtained by residual current density was similar to that obtained by electrochemical impedance method, and the inhibitory effects of three inhibitors followed PBTCA>HEDP>PAA. The mechanism research showed that the CaCO₃ scale with aragonite-shaped structure was successfully formed on the surface of Ti alloy electrode through an electro-deposition process, but the addition of scale inhibitor could inhibit the normal growth of aragonite crystal through the effect of crystal distortion, turning it into unstable aragonite crystalof which the accumulation and deposition was blocked by dispersion effect.

Key words: chronoamperometry, electrochemical impedance spectroscopy, electro-deposition, scale inhibitor, calcium carbonate scale

中图分类号:

TQ085+.4

张可桂,左兆顺,杨文忠,葛峰,陈云,尹晓爽,刘瑛. HEDP、PBTCA、PAA对CaCO₃垢抑制作用的电化学研究[J]. 工业水处理, 2021, 41(9): 117-123.

Kegui Zhang,Zhaoshun Zuo,Wenzhong Yang,Feng Ge,Yun Chen,Xiaoshuang Yin,Ying Liu. Electrochemical investigations of the inhibitory effect of HEDP, PBTCA and PAA on CaCO₃ scale[J]. Industrial Water Treatment, 2021, 41(9): 117-123.

https://www.iwt.cn/CN/Y2021/V41/I9/117

图/表 11

图1 空白测试溶液中TA1电极的电流-电势曲线

Fig.1 The current-potential curves for TA1 electrode testing in blank solution

图2 空白测试溶液中TA1电极的计时电流曲线

Fig.2 The chronoamperometry curves for TA1 electrode testing in blank solution

表1 空白溶液中TA1电极在不同电位下的t_s和i_r

Table 1 The values of t_s and i_r under different potentials for TA1 electrode in blank solution

电位/V	t_s/s	i_r/（μA·cm^-2）
-1.4	3 200	79.1
-1.5	2 100	65.1
-1.6	10 600	511.3

图3 TA1电极在含有不同浓度PBTCA、HEDP和PAA溶液中的计时电流曲线

Fig.3 The chronoamperometry curves for TA1 electrode in the solution containing different concentrations of PBTCA、HEDP and PAA

表2 TA1电极在含有不同浓度PBTCA、HEDP和PAA溶液中的剩余电流密度

Table 2 The residual current density of TA1 electrode in the solution containing different concentrations of PBTCA、HEDP and PAA

阻垢剂浓度/（μmol·L^-1）	i_r/（μA·cm^-2）
阻垢剂浓度/（μmol·L^-1）	PBTCA	HEDP	PAA
0	78.9	78.9	78.9
1.6	132.5	125.4	111.2
6.7	211.3	207.7	181.2
16.7	324.2	307.9	279.1
32	482.8	456.1	380.9

图4 PBTCA、HEDP和PAA在不同浓度时的阻垢率

Fig.4 The scale inhibition efficiency of PBTCA、HEDP and PAA at different concentrations

图5 TA1电极在空白溶液和含有不同浓度阻垢剂溶液中Nyquist图和Bode图

Fig.5 The plots of Nyquist and Bode for TA1 electrode in blank solution in the absence and presence of different concentrations of inhibitors

图6 电化学阻抗等效电路

Fig.6 The equivalent circuit for electrochemical impedance

表3 TA1电极在空白和含有不同浓度阻垢剂溶液中的电化学阻抗参数和阻垢率

Table 3 The electrochemical impedance parameters and scale inhibition efficiency for TA1 electrode in blank solution with and without different concentrations of inhibitors

阻垢剂	浓度/（μmol·L^-1）	Rs/（Ω·cm²）	CPEf/（μF·cm^-2）	nf	Rf/（Ω·cm²）	CPEdl/（μF·cm^-2）	ndl	Rct/（Ω·cm²）	阻垢率/%
空白样	0	27.8	61.6	0.70	5 430	52.7	0.86	14 700	—
PBTCA	1.6	22.7	133.1	0.99	3 786	103.4	0.86	7 924	46.1
	6.7	23.4	185.2	0.96	2 569	633.2	0.86	5 107	65.3
	16.7	17.8	310.4	0.81	1 758	865.2	0.85	2 795	81.0
	32	15.0	504.3	0.87	1 058	889.7	0.83	1 663	88.7
HEDP	1.6	25.4	124.0	0.60	3 828	135.5	0.86	8 472	42.4
	6.7	20.7	217.6	0.74	2 719	230.8	0.80	5 747	60.9
	16.7	18.7	296.2	0.88	2 061	633.7	0.79	4 016	72.7
	32	15.4	418.9	0.70	1 581	730.1	0.76	2 522	82.8
PAA	1.6	26.3	77.9	0.69	3 812	146.0	0.80	10 724	27.1
	6.7	22.3	143.4	0.68	3 040	525.2	0.80	7 184	51.3
	16.7	20.9	198.7	0.58	2 730	831.7	0.86	4 247	71.0
	32	19.6	386.7	0.56	2 017	966.3	0.79	2 830	80.7

图7 空白溶液和含有阻垢剂的溶液中CaCO₃垢的XRD

Fig.7 The XRD pattern of CaCO₃ scale prepared from blank solution and inhibited solution

图8 空白溶液和含有阻垢剂的溶液CaCO₃垢的SEM
（a）空白；（b1）PBTCA，1.6 μmol/L；（b2）PBTCA，6.7 μmol/L；（b3）PBTCA，16.7 μmol/L；（b4）PBTCA，32 μmol/L；（c1）HEDP，1.6 μmol/L；（c2）HEDP，6.7 μmol/L；（c3）HEDP，16.7 μmol/L；（c4）HEDP，32 μmol/L；（d1）PAA，1.6 μmol/L；（d2）PAA，6.7 μmol/L；（d3）PAA，16.7 μmol/L；（d4）PAA，32 μmol/L

Fig.8 SEM pictures of CaCO₃ scale prepared from blank solution and inhibited solution

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HEDP、PBTCA、PAA对CaCO₃垢抑制作用的电化学研究

Electrochemical investigations of the inhibitory effect of HEDP, PBTCA and PAA on CaCO₃ scale