一种抑制隧道排水管道中结晶体形成的双层阻垢疏水涂层

doi:10.11949/0438-1157.20241325

摘要/Abstract

摘要：

本研究成功研制了一种新型双层阻垢疏水涂层，目的在于有效抑制隧道排水管道中结晶体的形成。该涂层由纳米二氧化硅、氨基磺酸、水解聚马来酸酐和乙二胺四乙酸二钠（EDTA）等主要成分构成，设计为疏水内层和阻垢外层的结构。疏水内层的功能是阻止结晶颗粒附着于管道内壁，而阻垢外层则保护内层并预防结晶体的形成。通过实验室内的静态和动态模拟实验，发现疏水内层的防结晶率稳定在82%以上，阻垢外层的阻垢率稳定在93%以上。在动态模拟实验中，理论预测疏水内层能够维持428.47 d，阻垢外层能够维持188.57 d，两者合计可维持617.04 d；使用Ansys fluent软件进行仿真计算，结果表明，这种双层阻垢疏水涂层能够保持其性能长达634.72 d。验证实验与仿真结果之间的误差率为2.87%，证明仿真模型预测与涂层性能相符，能够适应不同的流量和流速条件，为各种工况下的仿真模拟提供参考。这种双层涂层不仅实现了疏水与阻垢的双重功能，还展现出了卓越的耐久性和缓释性能，对于抑制隧道排水管道内结晶体的形成具有显著效果，为隧道排水系统的维护提供了一种新的解决方案。

关键词: 隧道排水系统, 结晶堵塞, 阻垢剂, 二氧化硅, 疏水涂层, 模拟

Abstract:

This study successfully developed a new double-layer scale-inhibiting hydrophobic coating, the purpose of which is to effectively inhibit the formation of crystals in tunnel drainage pipes. The coating is composed of nano-silica, sulfamic acid, hydrolyzed maleic anhydride and EDTA, and is designed as a hydrophobic inner layer and a scale-resistant outer layer. The function of the hydrophobic inner layer is to prevent the crystallization particles from adhering to the inner wall of the pipe, while the scale inhibition outer layer protects the inner layer and prevents the formation of crystals. Through the static and dynamic simulation experiments in the laboratory, it is found that the anti-crystallization rate of the hydrophobic inner layer is stable over 82%, and the scale inhibition rate of the outer layer is stable over 93%. In the dynamic simulation experiment, the theory predicts that the hydrophobic inner layer can maintain 428.47 d, the scale inhibition outer layer can maintain 188.57 d, and the total of the two can maintain 617.04 d. Through simulation calculations using Ansys fluent software, the results show that the double-layer scale and hydrophobic coating can maintain its performance for up to 634.72 d. The error rate between the verification experiment and the simulation results is 2.87%, it is proved that the simulation model is consistent with the coating performance and can adapt to different flow and velocity conditions, which provides a reference for simulation under various working conditions. This double-layer coating not only realizes the dual functions of hydrophobic and scale inhibition, but also shows excellent durability and slow release performance, which has a remarkable effect on inhibiting the formation of crystals in tunnel drainage pipes, providing an innovative solution for the maintenance of tunnel drainage systems.

Key words: tunnel drainage system, crystal blockage, scale inhibitor, silica, hydrophobic coating, simulation

中图分类号:

U 45

胡家玮, 王聪, 刘美婧. 一种抑制隧道排水管道中结晶体形成的双层阻垢疏水涂层[J]. 化工学报, 2025, 76(6): 3053-3072.

Jiawei HU, Cong WANG, Meijing LIU. Utility model relates to double - layer anti - scale and hydrophobic coating that inhibits crystal formation in tunnel drainage pipe[J]. CIESC Journal, 2025, 76(6): 3053-3072.

图/表 40

图1 现场取样

Fig.1 On-site sampling

表1 结晶体样品元素种类

Table 1 Crystal sample element species

元素	占比/%
O	55.46
C	24.31
Ca	15.94
Mg	2.13
Fe	1.72
Si	0.3
Na	0.06
S	0.04
K	0.03
Cl	0.01

图2 结晶样品扫描电子显微镜照片

Fig.2 Scanning electron microscope analysis of crystal sample

图3 结晶样品X射线衍射谱图分析

Fig.3 X-ray diffraction analysis of crystal samples

表2 毛垭山隧道排水管水样分析

Table 2 Maoyashan tunnel drainage pipe water sample analysis

检测点位	流速/(m/s)	pH	离子含量/(mg/L)
检测点位	流速/(m/s)	pH	Ca²⁺	Mg²⁺	$C O 3 2 -$	$H C O 3 -$	$S O 4 2 -$
毛垭山LK3+154	0.09	8.2	8.71	11.7	12.9	172	69.9
毛垭山LK3+200	0.12	7.9	24.2	5.63	6.16	244	23.4

表2 毛垭山隧道排水管水样分析

Table 2 Maoyashan tunnel drainage pipe water sample analysis

检测点位	流速/(m/s)	pH	离子含量/(mg/L)
检测点位	流速/(m/s)	pH	Ca²⁺	Mg²⁺	$C O 3 2 -$	$H C O 3 -$	$S O 4 2 -$
毛垭山LK3+154	0.09	8.2	8.71	11.7	12.9	172	69.9
毛垭山LK3+200	0.12	7.9	24.2	5.63	6.16	244	23.4

表3 实验药剂

Table 3 Experimental reagents

实验药剂	药剂纯度	生产厂家
十水合四硼酸钠	分析纯（AR）	烟台市双双化工有限公司
疏水纳米二氧化硅	分析纯（AR）	佛山蓝岭化工有限公司
钛酸酯偶联剂	分析纯（AR）	东莞市康锦新材料有限公司
RTV-2硅橡胶	97%	深圳市立诺德科技有限公司
四氢呋喃	分析纯（AR）	天津市百世化工有限公司
异丙醇	分析纯（AR）	天津市百世化工有限公司
EDTA	分析纯（AR）	天津市大茂化学试剂厂
氨基磺酸	分析纯（AR）	上海阿拉丁生化科技股份有限公司
水解聚马来酸酐(HPMA)	50%	山东优索化工科技有限公司
无水氯化钙	分析纯（AR）	天津市百世化工有限公司
碳酸氢钠	分析纯（AR）	烟台市双双化工有限公司
海藻酸钠	化学纯（AR）	天津百伦斯生物技术有限公司
聚乙烯醇	分析纯（AR）	上海臣启化工科技有限公司
聚乙二醇-600（PEG-600）	分析纯（AR）	无锡市亚泰联合化工有限公司
聚乙烯吡咯烷酮（PVP）	分析纯（AR）	天津市光复科技发展有限公司

表4 实验仪器

Table 4 Experimental instruments

实验仪器	仪器型号	生产厂家
电子分析天平	BCE224I-1CCN	赛多利斯科学仪器（北京）有限公司
超纯水仪	WP-UP-WF-20S	四川沃特尔水处理设备有限公司
便携式pH计	PHBJ-260	上海仪电科学仪器股份有限公司
超纯水仪	WP-UP-WF-20S	四川沃特尔水处理设备有限公司
电热鼓风干燥箱	101-00B	绍兴市沪越仪器设备有限公司
数显恒温水浴锅	HH-6	常州市金坛区西城新瑞仪器厂
接触角测量仪	CA500	广东北斗精密仪器有限公司
光学显微镜	XSP-44X.9	上海光学仪器一厂
便携式浊度仪	WZB-175	上海仪电科学仪器股份有限公司
85-2 数显控温磁力搅拌器	MS-H280-Pro-LED	金坛市大地自动化仪器厂
高精度便携式粗糙度仪	SF200	北京时代山峰科技有限公司
PosiTector200超声波涂层测厚仪	200 B1	美国迪芙斯高公司
SEM扫描电子显微镜	ZR4-6	赛默飞
X射线光电子能谱仪XPS	EDCALAB QXi	赛默飞
X射线衍射仪	D/Max-2400	Rigaku公司

图4 双层阻垢疏水材料研发流程

Fig.4 Double layer scale and hydrophobic material development flow chart

图5 疏水内层作用示意图

Fig.5 Composite paint inner layer action diagram

图6 阻垢外层作用示意图

Fig.6 Scale inhibition outer layer action diagram

图7 接触角、滚动角测量过程

Fig.7 Contact angle, rolling angle measurement process

图8 PE方片附着情况

Fig.8 PE square smear situation

图9 动态模拟实验装置

Fig.9 Diagram of dynamic simulation experiment device

图10 Ansys fluent管道结构示意图

Fig.10 Ansys fluent pipe structural diagram

图11 DPM侵蚀率

Fig.11 DPM erosion rate map

表5 溶剂挥发剂筛选

Table 5 Solvent volatile screening

组号	纳米二氧化硅/g	四氢呋喃/ml	异丙醇/ml	乙醇/ml	甲酸/ml
1	0.1	5	5	—	—
2	0.1	5	—	5	—
3	0.1	5	—	—	5

表6 筛选稀释剂与溶剂挥发剂配比（一）

Table 6 Screening diluent and solvent volatile ratio（Ⅰ）

组号	纳米二氧化硅/g	四氢呋喃/ml	异丙醇/ml
1	0.1	5	5
2	0.1	5	10
3	0.1	10	5

表7 筛选稀释剂与溶剂挥发剂配比（二）

Table 7 Screening diluent and solvent volatile ratio（Ⅱ）

组号	纳米二氧化硅/g	四氢呋喃/ml	异丙醇/ml	滚动角/(°)
1	0.1	5	5	8.017
2	0.1	5	6	8.102
3	0.1	5	7	8.083
4	0.1	5	8	8.052
5	0.1	5	9	8.024
6	0.1	5	10	8.006

表8 筛选界面活性剂

Table 8 Screening interface active agent

组号	纳米二氧化硅/g	四氢呋喃/ml	异丙醇/ml	硅烷偶联剂/ml	酚酞偶联剂/ml	表面情况
1	0.1	5	6	0.05	—
2	0.1	5	6	—	0.05

表9 确定最佳纳米填充剂用量

Table 9 Determine the optimal nano filler dosage

组号	纳米二氧化硅/g	四氢呋喃/ml	异丙醇/ml	硅烷偶联剂/ml
1	0.05	5	6	0.05
2	0.1	5	6	0.05
3	0.15	5	6	0.05
4	0.2	5	6	0.05
5	0.25	5	6	0.05

图12 疏水内层表面接触角的测量

Fig.12 Hydrophobic layer detection

图13 阻垢剂筛选情况

Fig.13 Screening of scale inhibitors

表10 三因素水平响应曲面分析实验设计

Table 10 Three factor horizontal response surface analysis experimental design

因素	水平
因素	-1	0	1
A/ml	3	3.5	4
B/ml	2	2.5	3
C/g	0.4	0.5	0.6

表11 响应曲面优化碳酸钙的结晶量实验设计与结果

Table 11 Experimental design and results of response surface optimization for calcium carbonate crystallization

组号	A/ml	B/ml	C /g	碳酸钙的结晶量/g
1	-1	-1	0	0.1515
2	1	-1	0	0.0937
3	-1	1	0	0.1168
4	1	1	0	0.0272
5	-1	0	-1	0.2172
6	1	0	-1	0.0822
7	-1	0	1	0.0858
8	1	0	1	0.0388
9	0	-1	-1	0.1656
10	0	1	-1	0.1193
11	0	-1	1	0.0897
12	0	1	1	0.0225
13	0	0	0	0.0757
14	0	0	0	0.0808
15	0	0	0	0.0641
16	0	0	0	0.0796
17	0	0	0	0.0627

表12 碳酸钙的结晶量模型及回归系数的回归分析结果

Table 12 The results of regression analysis of calcium carbonate crystal volume model and regression coefficient

来源	离差平方和	自由度	均方	F值	P值	显著性
R² =0.9884, R²(Adj) =0.9735, R² (Pred)=0.9211
模型	0.04	9	0.00441	66.38	< 0.0001	**
A	0.014	1	0.014	204.08	< 0.0001	**
B	0.00576	1	0.00576	86.7	< 0.0001	**
C	0.015	1	0.015	227.12	< 0.0001	**
AB	0.000253	1	0.000253	3.8	0.0921
AC	0.00194	1	0.00194	29.13	0.001	**
BC	0.000109	1	0.000109	1.64	0.2407
A²	0.00104	1	0.00104	15.66	0.0055	**
B²	0.000341	1	0.000341	5.13	0.0579
C²	0.00132	1	0.00132	19.84	0.003	**
残差	0.000465	7	0.0000665
失拟项	0.000169	3	0.0000564	0.76	0.5716	ns
纯误差	0.000296	4	0.000074
总和	0.04	16

图14 阻垢效果实际值与预测值关系

Fig.14 Relationship between actual value and predicted value of scale inhibition effect

图15 各因素的3D曲面图和等高线图

Fig.15 3D surface and contour maps for each factor

表13 聚乙烯醇与壳聚糖混合胶材料

Table 13 Mixed rubber materials of polyvinyl alcohol and chitosan

组号	聚乙烯醇/g	壳聚糖/g	断裂伸长率/%
1	0.5	0.5	30
2	1	0.5	47
3	0.5	1	7

表14 聚乙烯醇和海藻酸钠混合胶材料（一）

Table 14 Polyvinyl alcohol and sodium alginate mixed rubber material（Ⅰ）

组号	聚乙烯醇/g	海藻酸钠/g	断裂伸长率/%
1	0.5	0.5	87.5
2	1	0.5	70.0
3	0.5	1	40

表15 聚乙烯醇和海藻酸钠混合胶材料（二）

Table 15 Polyvinyl alcohol and chitosan mixed rubber material（Ⅱ）

组号	聚乙烯醇/g	海藻酸钠/g	断裂伸长率/%
1	1	0.8	400
2	1	0.5	700
3	1	0.3	1300
4	1	0.1	1700

图16 测试外层药效发挥时间

Fig.16 Test the outer layer for duration of action

图17 疏水内层接触角、滚动角测量

Fig.17 Hydrophobic inner layer contact angle and rolling angle measurement

图18 三种不同界面的管材的内部成垢情况

Fig.18 Internal scaling of pipes with three different interfaces

表16 实验室模拟结晶情况

Table 16 Laboratory simulation of crystallization

界面	原始溶液中Ca²⁺浓度/(mg/L)	（滤纸+垢样）/mg	滤纸/mg	垢样/mg	结晶中Ca²⁺浓度/(mg/L)
原始界面	802	1390.7	987.1	412.6	330.6
疏水界面	802	1765.2	983.7	821.4	660
阻垢界面	802	1000.2	983.1	67.5	54.0

表17 涂覆有疏水内层的管壁粗糙度测量（30 d）

Table 17 Wall roughness measurement with a hydrophobic inner coating （30 d）

管材类型		平均粗糙度/μm
原始管材		11.920
带有疏水内层材料的管材	0 d	7.303
	10 d	6.864
	20 d	6.707
	30 d	6.645

表18 涂覆有阻垢外层的管壁粗糙度测量（30 d）

Table 18 Wall roughness measurement with a hydrophobic inner coating （30 d）

管材类型		平均粗糙度/μm
原始管材		11.920
涂覆阻垢外层材料的管材	0 d	4.214
	10 d	4.212
	20 d	4.212
	30 d	4.212

表19 涂覆有疏水内层的管壁厚度测量（30 d）

Table 19 Wall thickness measurement with a hydrophobic inner coating （30 d）

时间/d	材料平均厚度/μm
0	36.42
10	34.21
20	33.93
30	33.87

表20 涂覆有阻垢外层的管壁厚度测量（30 d）

Table 20 Wall thickness measurement with scale resistant coating （30 d）

时间/d	材料平均厚度/μm
0	987.30
10	867.51
20	843.72
30	830.23

表21 Ansys fluent软件模拟疏水内层耐久时长

Table 21 Ansys fluent software simulates the duration of coating

序号	粗糙度/μm	涂层厚度/m	磨损表面积/m²		平均磨损率/(kg/(m²·s))	时长/d
合计				450.36
1	7.303	0.0000364	1.809557369		3.68×10^-9	123.3937001
2	6.864	0.0000342	1.809557369		4.20×10^-9	101.6899615
3	6.707	0.0000339	1.809557369		3.98×10^-9	106.4081376
4	6.645	0.0000338	1.809557369		3.56×10^-9	118.8659072

表22 Ansys fluent软件模拟阻垢外层耐久时长

Table 22 Ansys fluent software simulates the duration of coating

序号	粗糙度/μm	涂层厚度/m	磨损表面积/m²		平均磨损率/(kg/(m²·s))	时长/d
合计				184.36
1	4.214	0.9873	1.809557369		3.26×10^-4	51.58242594
2	4.212	0.8675	1.809557369		3.26×10^-4	45.32336119
3	4.212	0.8437	1.809557369		3.26×10^-4	44.07990759
4	4.212	0.8302	1.809557369		3.26×10^-4	43.37458727

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