端羧基超支化型绿色阻垢剂的制备及阻垢性能

doi:10.19491/j.issn.1001-9278.2020.09.007

中国塑料 ›› 2020, Vol. 34 ›› Issue (9): 38-45.DOI: 10.19491/j.issn.1001-9278.2020.09.007

端羧基超支化型绿色阻垢剂的制备及阻垢性能

李美兰¹^,², 贺子纯¹, 穆凯飞¹, 龚伟¹^,²(), 来倩¹, 杨萌¹, 刘白玲²

^1.商洛学院, 陕西省尾矿资源综合利用重点实验室，陕西商洛 726000
^2.中国科学院成都有机化学研究所，成都 610041

收稿日期:2020-03-16 出版日期:2020-09-26 发布日期:2020-09-25
基金资助:
陕西省科技厅自然科学项目（2019JQ⁃907）；陕西省科技厅自然科学项目（2019JQ908）；陕西省教育厅重点项目（19JS024）；陕西省教育厅专项科研计划项目（19JK0252）；商洛学院自然科学项目（16SKY022）

Preparation and Scale Inhibition Performance of Carboxyl-Terminated Hyperbranched Green Scale Inhibitor

LI Meilan¹^,², HE Zichun¹,MU Kaifei¹, GONG Wei¹^,²(), LAI Qian¹, YANG Meng¹, LIU Bailing²

^1.Key Laboratory of Comprehensive Utilization of Tailings Resources in Shaanxi Province, Shangluo University, Shangluo 726000, China
^2.Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, China

Received:2020-03-16 Online:2020-09-26 Published:2020-09-25
Contact: GONG Wei E-mail:gongwei-com@163.com

摘要/Abstract

摘要：

采用熔融聚合法以木糖醇为中心核，成功制备了端羧基超支化型绿色阻垢剂，通过红外光谱仪和核磁共振对其结构进行了表征，采用静态阻垢法探讨了阻垢剂的添加量、水样环境的pH和水样温度对其阻碳酸钙和硫酸钙的能力。结果表明，端羧基超支化型绿色阻垢剂在较宽的温度范围及水体环境的pH=6~9时，对钙垢（CaCO₃和CaSO₄）均具有优异的阻垢性能，且当阻垢剂添加量为24 mg/L时，其对碳酸钙垢的阻垢效率达到了91.6 %；当阻垢剂的添加量为15 mg/L时，其对硫酸钙的阻垢效率达到了94.7 %；端羧基超支化型绿色阻垢剂的使用，均能极大程度地降低了钙垢晶体的规整性，且对于碳酸钙垢而言，端羧基超支化型绿色阻垢剂的使用还可以使碳酸钙垢的晶格发生畸变，从而达到分散阻垢的目的。

关键词: 木糖醇, 超支化聚酯, 阻垢性能, 柠檬酸, 钙垢

Abstract:

A carboxyl-terminated hyperbranched green scale inhibitor based on the xylitol core was successfully prepared by melt polymerization, and its chemical structure was characterized by FTIR and ¹H-NMR. The effects of scale inhibitor dosage, pH of water environment and water temperature on calcium carbonate and calcium sulfate inhibition were investigated by means of a static scale inhibition method. The results indicated that the green scale inhibitor exhibited excellent inhibition efficiency on calcium scale (CaCO₃ and CaSO₄) under a wide range of temperature and a water environment of pH 6~9. The scale inhibition efficiency of calcium carbonate reached 91.6 % at the scale inhibitor dosage of 24 mg/L, while the scale inhibition efficiency of calcium sulfate reached 94.7 % at the dosage of 15 mg/L. Moreover, the SEM observation showed that this green scale inhibitor could greatly reduce the regularity of calcium scale crystal. As for calcium carbonate scale, the green scale inhibitor could promote its lattice distortion of calcium carbonate scale to achieve the purpose of dispersion scale inhibitor.

Key words: xylitol, hyperbranched polyester, scale inhibition, citric acid, calcium scale

中图分类号:

TQ317.4

李美兰, 贺子纯, 穆凯飞, 龚伟, 来倩, 杨萌, 刘白玲. 端羧基超支化型绿色阻垢剂的制备及阻垢性能[J]. 中国塑料, 2020, 34(9): 38-45.

LI Meilan, HE Zichun, MU Kaifei, GONG Wei, LAI Qian, YANG Meng, LIU Bailing. Preparation and Scale Inhibition Performance of Carboxyl-Terminated Hyperbranched Green Scale Inhibitor[J]. China Plastics, 2020, 34(9): 38-45.

图/表 12

图1 端羧基超支化型绿色阻垢剂的合成路线

Fig.1 Synthetic route of carboxy terminated hyperbranched green scale inhibitor

图2 端羧基超支化型绿色阻垢剂的FTIR谱图

Fig.2 FTIR spectra of carboxy terminated hyperbranched green scale inhibitor

图3 端羧基超支化型绿色阻垢剂的1H?NMR谱图

Fig.3 1H?NMR spectra of carboxy terminated hyperbranched green scale inhibitor

图4 端羧基超支化型绿色阻垢剂的添加量对钙垢的阻垢效果

Fig.4 Effect of carboxy terminated hyperbranched green scale inhibitor dosage on calcium scale inhibition performance

图5 pH值对端羧基超支化型绿色阻垢剂阻垢效果的影响

Fig.5 Effect of pH on the carboxy terminated hyperbranched green scale inhibitor calcium scale inhibition performance

图6 水样温度对端羧基超支化型绿色阻垢剂阻垢性能的影响

Fig.6 Effect of water temperature on the carboxy terminated hyperbranched green scale inhibitor calcium scale inhibition performance

阻垢剂类型	透光率/%	Zeta电位/mV
H₂O	83.1	-1.6
柠檬酸	30.2	-11.9
端羧基超支化型绿色阻垢剂	9.5	-22.7

表1 端羧基超支化型绿色阻垢剂的分散性能

Tab.1 Dispersion of carboxy terminated hyperbranched green scale inhibitor

图7 CaSO4垢的SEM照片

Fig.7 SEM images of calcium sulfate scale

图8 混合溶液电导率与CaSO4晶体成核时间的关系

Fig.8 Relationship between the conductivity of mixed solution and the nucleation time of calcium sulfate crystals

图9 CaCO3垢的SEM照片

Fig.9 SEM images of calcium carbonate scale

图10 添加端羧基超支化型绿色阻垢剂后产生CaCO3晶体的FTIR谱图

Fig.10 FTIR spectra of calcium carbonate scale with using carboxy terminated hyperbranched green scale inhibitor

阻垢剂类型	细菌/个·g^-1	放线菌/个·g^-1	真菌/个·g^-1
对照组	7.46×10⁶	2.71×10³	5.03×10⁵
端羧基超支化阻垢剂	6.81×10⁶	2.66×10³	5.19×10⁵

表2 所制备端羧基超支化阻垢剂应用于循环水（模拟）阻垢10 d后的微生物生长情况

Tab.2 Microorganism growth after 10 days of scale inhibition by carboxy terminated hyperbranched green scale inhibitor in circulating water (simulated)

参考文献 27

1	王文波, 陈国力, 王雅珍. 聚合物类阻垢剂的最新研究进展[J]. 应用化工, 2018, 47(5):1 007⁃1 010.
	WANG W B, CHEN G L, WANG Y Z. The Latest Research Progress of Polymer Scale Inhibitors[J]. Applied Chemical Industry, 2018, 47(5):1 007⁃1 010.
2	余伟, 黄牧, 李爱民, 等. 多功能型天然高分子水处理剂的研究[J]. 环境化学, 2018, 37(6):1 293⁃1 310.
	YU W, HUANG M, LI A M, et al．Multi⁃Functional Natural Polymer Based Water Treatment Agents[J]. Environmental Chemistry, 2018, 37(6):1 293⁃1 310.
3	WANG H，ZHOU Y，LIU G，et al． Investigation of Calcium Carbonate Precipitation in The Presence of Fluorescent⁃Tagged Scale Inhibitor for Cooling Water Systems[J]. Desalination & Water Treatment, 2015, 53(13):3 491⁃3 498.
4	张盼盼, 蒋利辉, 孙军萍. 工业循环冷却水用阻垢缓蚀剂的研究进展[J]. 化学研究, 2018, 29(6):642⁃646.
	ZHANG P P, JIANG L H, SUN J P. Research Progress of Scale And corrosion Inhibitor for Industrial Re⁃Circula⁃ting Cooling Water [J]. Chemical Research, 2018, 29(6):642⁃646.
5	YUAN X, DONG S. Novel and Efficient Curcumin Based Fluorescent Polymer for Scale and Corrosion Inhibition[J]. Chemical Engineering Journal, 2020, DOI: 10.1016/j.cej.2020.124296.
6	龚伟, 李美兰, 刘颖, 等. MA/VAc/AA/AMPS四元共聚物的结构特点及其阻垢性能[J]. 现代化工, 2019, 39(4):144⁃148.
	GONG W, LI M L, LIU Y, et al．Structure Characteristics of MA/VAc/AA/AMPS Tetrapolymer And Scale Inhibition Performance[J]. Modern Chemical Industry, 2019, 39(4):144⁃148.
7	ZHAO Y, JIA L, LIU K. Inhibition of Calcium Sulfate Scale by Poly(citric acid)[J]. Desalination, 2016, 392:1⁃7.
8	YOUSEF M, KANEEZ F. Assessment of Novel Maleic Anhydride Copolymers Prepared Via Nitroxide⁃Mediated Radical Polymerization as CaSO₄ Crystal Growth Inhibitors[J]. Environmental Technology, 2017, 38(8):985⁃995.
9	SHI W Y, DING C, YAN J L, et al. Molecular Dynamics Simulation for Interaction of PESA and Acrylic Copolymers with Calcite Crystal Surfaces[J]. Desalination, 2012, 291:8⁃14.
10	王虎传, 杨建军, 彭成军, 等. 改性聚乙二醇多磺酸基水处理剂的制备及性能[J]. 精细化工, 2019, 36(7):1 434⁃1 438.
	WANG C H, YANG J J, PENG J C, et al．Preparation and Properties of Modified PolyethyleneGlycol Polysulfonate Scale Inhibitor[J]. Fine Chemicals, 2019, 36(7):1 434⁃1 438.
11	ISSABAYRV Y A, BOIKO G I, LYUBCHENKO N P, et al. Synthesis of Unexplored Amino Phosphonic Acid and Evaluation as Scale Inhibitor for Industrial Water Applications[J]. Journal of Water Process Engineering, 2018, 22:192⁃202.
12	HUANG H, YAO Q, CHEN H, et al. Scale Inhibitors with Hyper⁃Branched Structure: Preparation, Characterization and Scale Inhibition Mechanism[J]. Rsc Advances, 2016, 6:1⁃22.
13	龚伟, 李美兰, 金振国. 工业循环水用端氨基超支化聚酰胺的阻硫酸钙垢性能[J]. 中国塑料, 2020, 34(1):43⁃50.
	GONG W, LI M L, JIN Z G. Scale Inhibition Performance of Amino‑Terminated Hyperbranched Polyamides for Calcium Sulfate from Circulating Water[J]. China Plastics, 2020, 34(1):43⁃50.
14	LI J, ZHOU Y, YAO Q, et al. Preparation and Evaluation of a Polyether⁃Based Polycar⁃Oxylate As a Kind of Inhibitor for Water Systems[J]. Industrial & Engineering Chemistry Research, 2017, 56:2 624⁃2 633.
15	王淑娜, 康少鑫, 张玉玲, 等. 共聚物PAMA在CaCO₃饱和溶液中的络合性能研究[J].高校化学工程学报, 2018, 32(1):168⁃175.
	WANG S N, KANG S X, ZHANG Y L, et al．Complexation Performance of Aspartic Acid/Malic Acid Copolymer in Supersaturated Calcium Carbonate Solution[J]. Journal of Chemical Engineering of Chinese Universities, 2018, 32(1):168⁃175.
16	WANG H, ZHOU Y, YAO Q, et al. Calcium Sulfate Precipitation Studies with Fluore⁃Scenttagged Scale Inhibitor for Cooling Water Systems[J]. Polymer Bulletin, 2015, 72(9):2 171⁃2 188.
17	WU K, CHEN F, LIU Y, et al. Preparation and Properties of β⁃Cyclodextrins Polymer Used As Calcium Carbonate Scale Inhibitor Containing Fluorescent Groups[J]. Research on Chemical Intermediates, 2015, 41:7 617⁃7 630.
18	WANG C, LI S, LI T. Calcium Carbonate Inhibition by a Phosphonate⁃Terminated Poly (Maleic⁃co⁃Sulfonate) Polymeric Inhibitor[J]. Desalination, 2009, 249(1):1⁃4.
19	李美兰, 龚伟, 武亚楠. 循环水用P(MAH⁃AMPS⁃AM)共聚物阻垢剂的制备及性能[J]. 中国塑料, 2019, 33(2):91⁃96.
	LI M L, GONG W, WU Y N. Preparation and Properties of MA⁃AMPS⁃AM Copolymer Scale Inhibitor for Circulating Water[J]. China Plastics, 2019, 33(2):91⁃96.
20	龚伟, 李美兰, 师明, 等. PPG改性共聚物的结构特点及对阻垢性能的影响[J]. 中国塑料, 2019, 33(11):39⁃44，77.
	GONG W, LI M L, SHI M, et al．Effect of Sturcture Characteristics of Poly(Propylene Glycol)⁃Modified Copolymer on Scale Inhibition Performance[J]. China Plastics, 2019, 33(11):39⁃44，77.
21	KONSTANTIN P, MAXIM O. Synthesis And Properties of Novel Fluorescent Tagged Polyacrylate⁃Based Scale Inhibitors[J]. Journal of Applied Polymer, 2017, 134(26):45 017⁃45 027.
22	龚伟, 李美兰. 苹果酸型端羧基超支化聚酯对矿区重金属污染土壤的淋洗效果[J]. 功能材料, 2019, 50(10):10 149⁃10 155.
	GONG W, LI M L. Effects of Malic Acid Carboxyl⁃Terminated Hyperbranched Polyester Washing Agents for Heavy Metal Removal from Soli[J]. Journal of Functional Materials, 2019, 50(10):10 149⁃10 155.
23	HUANG H H, YAO Q, LIU B L, et al. Synthesis And Characterization of Scale And Corrosion Inhibitors with Hyper⁃Branched Structure and Its Mechanism[J]. New Journal of Chemistry, 2017, 41:12 205⁃12 217.
24	单宁, 陈华林, 刘白玲, 等. 端羧基超支化聚酯的合成及阻垢性能[J]. 高分子材料科学与工程, 2015, 31(1):1⁃6.
	SHAN N, CHEN H L, LIU B L, et al．Synthesis and Scale Inhibition Performance of Carboxyl⁃Terminated Hyperbranched Polyester[J]. Polymer Materials Science & Engineering, 2015, 31(1):1⁃6.
25	CAN H K, ÜNER G. Water⁃Soluble Anhydride Containing Alternating Copolymers as Scale Inhibitors[J]. Desalination, 2015, 355(1):225⁃232.
26	张玉玲, 李伟, 李旭东, 等. 天冬氨酸⁃柠檬酸共聚物对碳酸钙的抑制性能[J]. 精细化工, 2018, 35(11):1 877⁃1 884.
	ZHANG Y L, LI W, LI X D, et al．Scale Inhibition Performance of Copoly (Aspartic Acid⁃Citric Acid) on Calcium Carbonate[J]. Fine Chemicals, 2018, 35(11):1 877⁃1 884.
27	MOHAMMADI Z, RAHSEPAR M. Characterization of Mazuj Galls of Quercus Infectoria, Tree as Green Corrosion and Scale Inhibitor for Effective Treatment of Cooling Water Systems[J]. Research on Chemical Intermediates, 2018, 44(3):2 139⁃2 155.

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端羧基超支化型绿色阻垢剂的制备及阻垢性能

Preparation and Scale Inhibition Performance of Carboxyl-Terminated Hyperbranched Green Scale Inhibitor

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