碱对镀锌铁表面CaCO3污垢生长特性的影响机理研究

doi:10.11949/j.issn.0438-1157.20180884

摘要/Abstract

摘要：

为解决因水结垢造成的管线堵塞问题，提出了变被动结垢为主动结垢的思路。针对某油田注入水，以镀锌铁为研究基质，综合动态模拟剪切实验以及SEM、EDS和浊度测试，探究碱类型和浓度对CaCO₃污垢生长特性的影响机理。结果表明5种常用碱——碳酸钠Na₂CO₃、碳酸氢钠NaHCO₃、三乙醇胺TEOA、氢氧化钙Ca(OH)₂和氧化钙CaO对污垢结垢量、失钙率及结垢诱导期影响各异，其中Na₂CO₃对失钙速率影响显著，而CaO对结垢速率影响较为明显。其次，不同碱促使污垢形成不同的晶型晶貌，其中方块状和层状垢物易于在材料表面堆积，即有利于结垢。最后，碱浓度对污垢生长影响具有双重性，存在抑垢和促垢浓度区间。

关键词: 碱, 镀锌铁, 结垢, 失钙率, 晶型晶貌

Abstract:

In order to solve the problem of pipeline blockage due to the water scaling, the key idea that the crystallization fouling process was changed from passive to active was proposed in this research. In view of the injected water form oil field, galvanized iron was selected as the substrate. The mechanisms of the influences of alkali types and concentrations on crystal growth were revealed using dynamic simulation experiments，SEM, EDS and liquid turbidity tests. These results were showed that: The effects of five kinds of alkalis (such as Na₂CO₃, NaHCO₃, TEOA, Ca(OH)₂ and CaO) on scale mass gains, calcium loss rate and scaling induction periods were different. Among them Na₂CO₃ has a significant effeet on the loss of calcium loss, while CaO has a significant effect on the rate of fouling. Secondly, the morphology of the crystal is correlated with the alkali types. If the surface of the material was capable of forming a blocky shape scale or a layered fouling, this material was beneficial for the aggregation and deposition of crystals. Finally, the alkali concentration played a twofold role in the growth of fouling, that was, to promote the aggregation of crystal and to inhibit the scale growth. In other words, there would be a preferred range of alkali concentrations.

Key words: alkali, galvanized iron, fouling, calcium loss rate, crystal morphology

中图分类号:

TE 357.61

蒋华义, 蔡航航, 梁爱国, 张定周, 孙娜娜, 种新民. 碱对镀锌铁表面CaCO₃污垢生长特性的影响机理研究[J]. 化工学报, 2019, 70(1): 170-178.

Huayi JIANG, Hanghang CAI, Aiguo LIANG, Dingzhou ZHANG, Nana SUN, Xinmin CHONG. Effect of alkali about growth characteristics of CaCO₃ on galvanized iron surface[J]. CIESC Journal, 2019, 70(1): 170-178.

图/表 16

表1 注入水离子成分

Table 1 Composition of injected water ions

Cation type	Concentration/ (mg/L)	Anion type	Concentration/ (mg/L)
Na⁺	7150.61	Cl^?	11944.69
K⁺	15.05	HCO₃^?	1338.37
Ca²⁺	644.01	PO₄^3?	299.79
Mg²⁺	183.44	SO₄^2-	40.15

图1 无机碱/有机碱类型对结垢量和失钙率的影响

Fig.1 Effect of inorganic base and organic base type on amount of scale and calcium loss rate

图2 不同碱作用下表面污垢晶体的SEM图

Fig.2 SEM images of fouling crystal under different alkalis action

图3 不同晶型晶貌形成过程

Fig.3 Schematic diagram of formation of different crystal morphologies

表2 不同碱作用下表面污垢晶体的EDS检测表

Table 2 EDS of fouling crystals under different alkalis action

Alkalis	Element /%(mass)
Alkalis	C	O	Na	P	Cl	Ca	Zn
Na₂CO₃	13.01	34.44	1.28	2.52	3.79	38.37	5.59
NaHCO₃	12.42	37.19	7.23	3.46	4.93	30.28	3
TEOA	13.76	33.39	9.72	3.13	2.91	25.24	11
Ca(OH)₂	11.28	37.33	3.34	2.34	2.51	33.87	8.03
CaO	11.26	37.75	4.04	2.25	0.9	32.16	10.57

图4 反应时间对结垢量的影响

Fig.4 Effect of reaction time on amount of scaling

图5 反应时间对失钙率的影响

Fig.5 Effect of reaction time on calcium loss rate

图6 垢物附着示意图

Fig.6 Diagram of scale attachment

图7 剥离和重力作用影响

Fig.7 Effects of peeling and gravity

图8 碱浓度对单位面积结垢量的影响

Fig.8 Effect of alkali concentration on scale formation

图9 碱浓度对失钙率的影响

Fig.9 Effect of alkali concentration on calcium loss rate

图10 均相成核

Fig.10 Homogeneous nucleation diagram

图11 异相成核

Fig.11 Heterogeneous nucleation diagram

表3 液体浊度检测表

Table 3 Result table of liquid turbidity

CaO concentrations/(mg/L)	Turbidity/ NTU	Na₂CO₃ concentrations/(mg/L)	Turbidity/ NTU
50	305.4	50	280.1
150	401.6	150	374.5
250	646.6	250	521
350	1024	350	716
450	1052	450	545
550	1153	550	588

图12 不同Na2CO3浓度作用下试片表面垢物分布

Fig.12 Scale distribution on surface of sample under different concentration of Na2CO3

图13 不同CaO浓度作用下试片表面垢物分布

Fig.13 Scale distribution on surface of sample under different concentration of CaO

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碱对镀锌铁表面CaCO₃污垢生长特性的影响机理研究

Effect of alkali about growth characteristics of CaCO₃ on galvanized iron surface

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