高盐海水中盐度对污垢沉积特性的影响

doi:10.11949/0438-1157.20190649

摘要/Abstract

摘要：

污垢沉积过程十分复杂。管材的种类、海水的成分、盐度和温度等因素都会影响污垢的沉积特性。选用人工海水为工质，在温度为80℃，盐度为6%、8%和10%时，对静态条件下铜管和钛管表面污垢的沉积特性进行对比研究。通过实验得出，金属表面污垢质量增量在盐度为8%时最大。钛管表面污垢主要以片状的Mg(OH)₂和少量的CaCO₃为主，而铜管表面的Mg(OH)₂晶体成团聚形态，并且表面附着大量的方解石CaCO₃和少量的文石CaCO₃。在相同盐度下，两种金属表面污垢的沉积趋势不同。在金属表面没有观察到CaSO₄形态的晶体析出。

关键词: 盐度, 结垢, 结晶, 海水, 脱盐

Abstract:

The process of fouling deposition is complicated. Factors such as the type of pipe, seawater composition, salinity and temperature can affect the deposition characteristics of the fouling. Deposition characteristics of fouling are studied on the surface of titanium tube and copper tube under static conditions with artificial seawater. The seawater temperature is 80℃ and seawater salinity is 6%, 8% and 10%, respectively. The results show that the deposition amount on the metallic surface achieves the highest value at the salinity of 8%. The major composition on the surface of titanium tube is flaky Mg(OH)₂ and minor CaCO₃. Mg(OH)₂is agglomerated on the surface of copper tube. Calcite CaCO₃and_{minor aragonite CaCO₃deposit on the surface of Mg(OH)₂. The deposition trend of fouling on the surface of the two metals is different under the same salinity. CaSO₄ crystals are not observed on the metallic surface.}

Key words: salinity, fouling, crystallization, seawater, desalination

中图分类号:

TK124

倪兵, 沈胜强, 李宜豪, 刘晓华, 李熠桥, 柳山林. 高盐海水中盐度对污垢沉积特性的影响[J]. 化工学报, 2019, 70(11): 4363-4369.

Bing NI, Shengqiang SHEN, Yihao LI, Xiaohua LIU, Yiqiao LI, Shanlin LIU. Effect of salinity on fouling deposition characteristics in hyperhaline seawater[J]. CIESC Journal, 2019, 70(11): 4363-4369.

图/表 9

表1 不同盐度下的离子积

Table 1 Ion product at distinct salinity

Crystal	Salinity
Crystal	6%	8%	10%
CaSO₄	0.90×10^-3	1.66×10^-3	1.95×10^-3
CaCO₃	4.84×10^-5	7.91×10^-5	8.64×10^-5
Mg(OH)₂	1.11×10^-4	1.94×10^-4	2.48×10^-4

表2 不同盐度下的溶度积

Table 2 Solubility product at distinct salinity

Crystal	Salinity
Crystal	6%	8%	10%
CaSO₄	1.16×10^-3	1.35×10^-3	1.52×10^-3
CaCO₃	0.26×10^-5	0.32×10^-5	0.36×10^-5
Mg(OH)₂	4.28×10^-11	4.08×10^-11	3.83×10^-11

表3 不同材料表面能参数

Table 3 Surface energy parameters of different materials

材料	γ ^LW/(mJ?m^-2)	γ⁺/(mJ?m^-2)	γ ^-/(mJ?m^-2)
钛(Ti)	41.32	0.04	41.14
铜(Gu)	42.61	0.03	43.13
CaCO₃	29.67	0.65	30.79
CaSO₄	37.32	1.25	38.57
Mg(OH)₂	32.1	1.07	6.6

图1 实验系统

Fig.1 Experimental system of static condition

图2 铜管表面污垢沉积SEM微观形貌 1—团聚状Mg(OH)2；2—方解石CaCO3；3—不定形晶体；4—方解石CaCO3脱落后；5—文石CaCO3

Fig.2 SEM images of copper tube surface

图3 铜管表面单位面积质量增量随时间的变化

Fig.3 Mass increment of fouling per unit area as a function of time on copper tube surface

图4 晶体成核能垒和晶核尺寸的关系曲线[36]

Fig.4 Relation curve between crystal barrier and crystal nucleus size[36]

图5 不同盐度下钛管表面污垢沉积SEM微观形貌 1—平铺Mg(OH)2；2—文石CaCO3；3—团聚状Mg(OH)2；4—散落Mg(OH)2； 5—方解石CaCO3

Fig.5 SEM images of titanium tube surface

图6 钛管表面单位面积质量增量随时间的变化

Fig.6 Mass increment of fouling per unit area as a function of time on titanium tube surface

参考文献 37

1	刘洁, 袁建军 . 硫酸钙结垢及其防治技术应用进展[J]. 天津化工, 2010, 24(2): 10-14.
	Liu J , Yuan J J . Calcium sulfate scaling and its advances in application of control techniques[J]. Tianjin Chemical Industy, 2010, 24(2): 10-14.
2	董宏光, 丁洁, 沈自求 . 用晶种抑制沉积垢实验研究[J]. 化学工程, 1999, 27(6): 16-19.
	Dong H G , Ding J , Shen Z Q . Experimental research for fouling-proof by introducing seeding crystal[J]. Chemical Engineering, 1999, 27(6): 16-19.
3	熊娅, 王凯军, 阎中 . 诱导结晶工艺中诱晶载体的选择与改性[J]. 环境工程学报, 2013, 7(1): 42-46.
	Xiong Y , Wang K J , Yan Z . Selection and modification of seed crystals in induced crystallization process[J]. Chinese Journal of Enviromental Engineering, 2013, 7(1): 42-46.
4	Linnikov O D . About seed concentration for prevention of scale[J]. Desalination, 2003, 157(1): 235-240.
5	Omar W , Chen J , Ulrich J . Reduction of seawater scale forming potential using the fluidized bed crystallization technology[J]. Desalination, 2010, 250(1): 95-100.
6	Al-Ghandi A , Omar W . Application of pellet softening (PS) as a scale prevention method in seawater desalination plants[J]. Desalination & Water Treatment, 2013, 51(28/29/30): 5509-5515.
7	Omar W , Chen J , Ulrich J . Application of seeded batch crystallization methods for reduction of the scaling tendency of seawater—a study of growth kinetics of calcium carbonate in seawater[J]. Crystal Research & Technology, 2010, 44(5): 469-476.
8	Hasan B O , Nathan G J , Ashman P J , et al . The use of turbulence generators to mitigate crystallization fouling under cross flow conditions[J]. Desalination, 2012, 288(1): 108-117.
9	Hasan B O , Nathan G J , Ashman P J , et al . The effects of temperature and hydrodynamics on the crystallization fouling under cross flow conditions[J]. Applied Thermal Engineering, 2012, 36(2): 210-218.
10	Alsadaie S M , Mujtaba I M . Dynamic modelling of heat exchanger fouling in multistage flash (MSF) desalination[J]. Desalination, 2017, 409(2017): 47-65.
11	Al-Rawajfeh A E , Ihm S , Varshney H , et al . Scale formation model for high top brine temperature multi-stage flash (MSF) desalination plants[J]. Desalination, 2014, 350(2014): 53-60.
12	Pääkkönen T M , Riihimäki M , Simonson C J , et al . Crystallization fouling of CaCO₃—analysis of experimental thermal resistance and its uncertainty[J]. International Journal of Heat & Mass Transfer, 2012, 55(s23/24: 6927-6937.
13	Hofling V , Augustin W , Bohnet M . Crystallization fouling of the aqueous two-component system CaSO₄/CaCO₃ fouling of salt mixtures[J]. International Journal of Transport Phenomena, 2004, 6(2): 99-110.
14	蒋华义, 蔡航航, 梁爱国, 等 . 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.
	Jiang Y H , Cai H H , Liang A G , et al . Effect of alkali about growth characteristics of CaCO₃ on galvanized iron surface[J]. CIESC Journal, 2019, 70(1): 170-178.
15	Peyghambarzadeh S M , Bahrami N . Statistical analysis of calcium sulfate scaling under boiling heat transfer[J]. Applied Thermal Engineering, 2013, 53(1): 108-113.
16	盛健, 张华, 赵萍 . 两种斜翅管表面碳酸钙垢初始阶段结垢特性[J]. 上海理工大学学报, 2014, 36(5): 443-448.
	Sheng J , Zhang H , Zhao P . Characteristics of the initial stage of CaCO₃ crystallization fouling on two kinds of oblique fin tube[J]. Journal of University of Shanghai for Science and Technology, 2014, 36(5): 443-448.
17	Al-Rawajfeh A E . Modeling of alkaline scale formation in falling film horizontal-tube multiple-effect distillers[J]. Desalination, 2007, 205(1): 124-139.
18	Wildebrand C , Glade H , Will S , et al . Effects of process parameters and anti-scalants on scale formation in horizontal tube falling film evaporators[J]. Desalination, 2007, 204(1): 448-463.
19	Al-Anezi K , Johnson D J , Hilal N . An atomic force microscope study of calcium carbonate adhesion to desalination process equipment: effect of anti-scale agent[J]. Desalination, 2008, 220(1): 359-370.
20	Kazi S N , Duffy G G , Chen X D . Fouling and fouling mitigation on heated metal surfaces[J]. Desalination, 2012, 288(1): 126-134.
21	Glade H , Stärk A , Krömer K , et al . Impact of tube surface properties on crystallization fouling in falling film evaporators for seawater desalination[J]. Heat Transfer Engineering, 2017, 38(7/8):207-217.
22	蒋华义, 张定周, 梁爱国, 等 . 材料类型对CaCO₃析晶污垢生长特性的影响机理研究[J]. 表面技术, 2018, 47(12): 255-262.
	Jiang H Y , Zhang D Z , Liang A G , et al . Effect mechanism of material type on crystallization growth of CaCO₃-based scale[J]. Surface Technology, 2018, 47(12): 255-262.
23	Zettler H U , Wei M , Zhao Q , et al . Influence of surface properties and characteristics on fouling in plate heat exchangers[J]. Heat Transfer Engineering, 2005, 26(2): 3-17.
24	Krömer K , Will S , Loisel K , et al . Scale Formation and mitigation of mixed salts in horizontal tube falling film evaporators for seawater desalination[J]. Heat Transfer Engineering, 2014, 36(7/8): 750-762.
25	Stärk A , Loisel K , Odiot K , et al . Wetting behaviour of different tube materials and its influence on scale formation in multiple-effect distillers[J]. Desalination & Water Treatment, 2015, 55(9): 2502-2514.
26	Stephen H , Stephen T . Solubilities of Inorganic and Organic Compounds[M]. Britain: Pergamon Press Ltd., 1963:583.
27	宋彭生, 姚燕, 孙柏, 等 . Li⁺, Na⁺, K⁺, Mg²⁺/Cl^-, S O 4 2 - -H₂O体系Pitzer热力学模型[J]. 中国科学:化学, 2010, 40(9): 1286-1296.
	Song P S , Yao Y , Sun B , et al . Pitzer thermodynamic model of Li⁺, Na⁺, K⁺, Mg²⁺/Cl^-, S O 4 2 - -H₂O system [J]. Scientia Sinica (Chimica), 2010, 40(9): 1286-1296.
28	Wang D , Yang Y Y , Zhang X P , et al . Mean activity coefficients of NaCl in NaCl-CdCl₂-H₂O ternary system at 298.15 K by potential difference method[J]. Journal of Chemical & Engineering Data, 2016, 61(9): 3027-3033.
29	Whitfield M . The extension of chemical models for sea water to include trace components at 25℃ and 1 atm pressure[J]. Geochimica Et Cosmochimica Acta, 1975, 39(11): 1545-1557.
30	Whitfield M . A chemical model for the major electrolyte component of seawater based on the Brønsted-Guggenheim hypothesis[J]. Marine Chemistry, 1973, 1(4): 251-266.
31	王晖, 顾帼华 . 固体的表面能及其亲水/疏水性[J]. 化学通报, 2009, 72(12): 1091-1096.
	Wang H , Gu G H . Surface free energy of solid matter and its hydrophilic hydrophobic nature[J]. Chemistry, 2009, 72 (12): 1091-1096.
32	陈勤芹, 刘代俊 . 微波辐射对硫酸钙粉末表面能影响的研究[J]. 高校化学工程学报, 2009, 23(1): 178-181.
	Chen Q Q , Liu D J . Influence of microwave radiation on the surface free energy of calcium sulfate[J]. Journal of Chemical Engineering of Chinese Universities, 2009, 23(1): 178-181.
33	邱振波, 张精卫, 徐志明 .材料表面能影响污垢诱导期的实验研究与理论分析[J]. 东北电力大学学报, 2008, 28(1): 45-48.
	Qiu Z B , Zhang J W , Xu Z M . Experimenal investigation and theoretical analysis on the effect of surface energy upon the fouling induction peirod[J]. Journal of Northeast Dianli University Natural Science Edition, 2008, 28(1): 45-48.
34	Zhao Q , Müller-Steinhagen H . Intermolecular and adhesion forces of deposits on modified heat transfer surfaces[C]// Proceedings of the 4th International Conference on Heat Exchanger Fouling, Fundamental Approaches & Technical Solutions. Germany: PUBLICO Publications, 2001:41-46.
35	Zhen W , Davidson J H , Francis L F . Effect of water chemistry on calcium carbonate deposition on metal and polymer surfaces[J]. J. Colloid Interface Sci., 2010, 343(1): 176-187.
36	唐睿康 . 表面能与晶体生长/溶解动力学研究的新动向[J]. 化学进展, 2005, 17(2): 368-376.
	Tang R K . Progress in the studies of interfacial energy and kinetics of crystal growth dissolution[J]. Progress in Chemistry, 2005, 17(2): 368-376.
37	刘同海, 窦焰, 方羊, 等 . Al³⁺, Na⁺和Mg²⁺对二水硫酸钙结晶的影响[J]. 化工学报, 2016, 67(S1): 296-301.
	Liu T H , Dou Y , Fang Y , et al . Influence of Al³⁺, Na⁺ and Mg²⁺ on crystallization of calcium sulfate dihydrate[J]. CIESC Journal, 2016, 67(S1): 296-301.

[1]	于宏鑫, 邵双全. 水结晶过程的分子动力学模拟分析[J]. 化工学报, 2023, 74(S1): 250-258.
[2]	傅予, 刘兴翀, 王瀚雨, 李海敏, 倪亚飞, 邹文静, 雷月, 彭永姗. F₃EACl修饰层对钙钛矿太阳能电池性能提升的研究[J]. 化工学报, 2023, 74(8): 3554-3563.
[3]	陈朝光, 贾玉香, 汪锰. 以低浓度废酸驱动中和渗析脱盐的模拟与验证[J]. 化工学报, 2023, 74(6): 2486-2494.
[4]	黄磊, 孔令学, 白进, 李怀柱, 郭振兴, 白宗庆, 李平, 李文. 油页岩添加对准东高钠煤灰熔融行为影响的研究[J]. 化工学报, 2023, 74(5): 2123-2135.
[5]	顾浩, 张福建, 刘珍, 周文轩, 张鹏, 张忠强. 力电耦合作用下多孔石墨烯膜时间维度的脱盐性能及机理研究[J]. 化工学报, 2023, 74(5): 2067-2074.
[6]	苏晓丹, 朱干宇, 李会泉, 郑光明, 孟子衡, 李防, 杨云瑞, 习本军, 崔玉. 湿法磷酸半水工艺考察与石膏结晶过程研究[J]. 化工学报, 2023, 74(4): 1805-1817.
[7]	周璇, 李孟亚, 孙杰, 岑振凯, 吕强三, 周立山, 王海涛, 韩丹丹, 龚俊波. 添加剂对氨基酸晶体生长的影响[J]. 化工学报, 2023, 74(2): 500-510.
[8]	陈毓明, 历伟, 严翔, 王靖岱, 阳永荣. 初生态聚乙烯聚集态结构调控研究进展[J]. 化工学报, 2023, 74(2): 487-499.
[9]	苏伟怡, 丁佳慧, 李春利, 王洪海, 姜艳军. 酶促反应结晶研究进展[J]. 化工学报, 2023, 74(2): 617-629.
[10]	闫军营, 王皝莹, 李瑞瑞, 符蓉, 蒋晨啸, 汪耀明, 徐铜文. 选择性电渗析：机遇与挑战[J]. 化工学报, 2023, 74(1): 224-236.
[11]	黄陆月, 刘畅, 许勇毅, 邢浩若, 王峰, 马双忱. CDI二维浓度传质模型的建立以及实验验证[J]. 化工学报, 2022, 73(7): 2933-2943.
[12]	乃学瑛, 吴鹏, 程远, 肖剑飞, 刘鑫, 董亚萍. 水热生长碱式硫酸镁纳米线结晶动力学研究[J]. 化工学报, 2022, 73(7): 3038-3044.
[13]	孙国鑫, 苟萌萱, 周诚, 常佩, 贺高红, 姜晓滨. 高浓度Na⁺//NO $3 -$ ， SO $4 2 -$ -H₂O溶液的膜蒸馏结晶耦合过程调控[J]. 化工学报, 2022, 73(7): 3078-3089.
[14]	马荣, 孙杰, 李东辉, 魏进家. 基于Cu/TiO₂/C-Wood复合材料的聚光太阳能驱动自漂浮高效海水汽化催化分解制氢体系[J]. 化工学报, 2022, 73(4): 1695-1703.
[15]	张浩, 赵宇, 徐志明, 李晋辉. 羧甲基葡聚糖的快速沉降法阻垢特性研究[J]. 化工学报, 2022, 73(4): 1515-1522.