水合物法处理实际复杂废水及高盐废水

doi:10.16085/j.issn.1000-6613.2022-0319

摘要/Abstract

摘要：

针对复杂废水和高盐废水的处理是目前废水处理领域的难点，常规废水处理技术具有操作复杂、能耗高等问题。本文提出了一种基于水合物处理实际复杂废水及高盐废水的新方法，通过测定水合物分解水中污染物浓度，证实了该技术的可行性。实验中结合中国石化镇海炼化分公司的石油炼化废水和大连市水文局的高浓度实验室废水，在常压、275.15K下进行实验，通过测量水合物法废水处理的脱除效率、产水率及富集因子，评估R141b水合物对废水的处理效果。测定废水处理前后的电导率、总有机碳（TOC）及离子浓度反映对不同种类污染物的去除能力。采用真空抽滤结合离心分离的方法作为后处理方法，提高废水中污染物的脱除效率。结果表明，水合物法废水处理技术可同时去除废水中的无机盐及有机污染物，各污染物的脱除效率可达75%以上，产水量可达78.9%，对高浓度的实验室废水中的铜离子脱除效率达到90.8%。

关键词: 水合物, 脱盐, 废水, R141b, 高浓度

Abstract:

The treatment of complex wastewater and high salt wastewater is the current difficulty in the field of wastewater treatment. The traditional wastewater treatment technology has the disadvantages of complex operation and high energy consumption. An innovative hydrate-based method was proposed in this study to treat actual complex wastewater and high salt wastewater. The feasibility of this technology was confirmed by measuring the concentration of pollutants in purified water through hydrate dissociation. Combined with the petroleum refining wastewater and laboratory wastewater from Sinopec Zhenhai refining & chemical company and Dalian hydrology bureau, the experiment was conducted under atmospheric pressure and 275.15K. The treatment effect of R141b hydrate on wastewater was evaluated by measuring the removal efficiency, water yield, and enrichment factor. The electrical conductivity, total organic carbon and ion concentration before and after treatment were measured to reflect the removal capacity of different kinds of pollutants. Vacuum filtration combined with centrifugal separation was used as the post-treatment method to improve the removal efficiency of pollutants in wastewater. The results showed that the hydrate-based wastewater treatment method can remove inorganic salts and organic pollutants in wastewater simultaneously. The removal efficiency of each pollutant reached more than 75%, with the water yield reaching about 78.9%. For copper ions with high concentrations in laboratory wastewater, the removal efficiency reached 90.8%. The hydrate-based wastewater treatment technology proposed in this study will promote the development of complex wastewater and high salt wastewater treatment.

Key words: hydrate, desalination, waste water, R141b, high concentrations

中图分类号:

X703.1

孙汇莲, 孙灵杰, 赵杨, 孙翔, 张伦祥. 水合物法处理实际复杂废水及高盐废水[J]. 化工进展, 2022, 41(12): 6672-6679.

SUN Huilian, SUN Lingjie, ZHAO Yang, SUN Xiang, ZHANG Lunxiang. Research on the application of hydrate-based method in the treatment of actual complex wastewater and high salt wastewater[J]. Chemical Industry and Engineering Progress, 2022, 41(12): 6672-6679.

图/表 9

参考文献 39

1	江传春, 肖蓉蓉, 杨平. 高级氧化技术在水处理中的研究进展[J]. 水处理技术, 2011, 37(7): 12-16, 33.
	JIANG Chuanchun, XIAO Rongrong, YANG Ping. Research process of advanced oxidation processes in wastewater treatment[J]. Technology of Water Treatment, 2011, 37(7): 12-16, 33.
2	KOLANGARE Irfana Moideen, ISLOOR Arun Mohan, KARIM Zulhairun Abdul, et al. Antibiofouling hollow-fiber membranes for dye rejection by embedding chitosan and silver-loaded chitosan nanoparticles[J]. Environmental Chemistry Letters, 2019, 17(1): 581-587.
3	FERNANDES André, Michał GĄGOL, Patrycja MAKOŚ, et al. Integrated photocatalytic advanced oxidation system (TiO₂/UV/O₃/H₂O₂) for degradation of volatile organic compounds[J]. Separation and Purification Technology, 2019, 224: 1-14.
4	DOTTO G L, MOURA J M, CADAVAL T R S, et al. Application of chitosan films for the removal of food dyes from aqueous solutions by adsorption[J]. Chemical Engineering Journal, 2013, 214: 8-16.
5	WEI Cong, WEI Jingyue, KONG Qiaoping, et al. Selection of optimum biological treatment for coking wastewater using analytic hierarchy process[J]. The Science of the Total Environment, 2020, 742: 140400.
6	SONUNE Amit, GHATE Rupali. Developments in wastewater treatment methods[J]. Desalination, 2004, 167: 55-63.
7	卞晓彤, 黄永明, 郭如涛, 等. 高盐废水单质分盐与资源化利用的研究进展[J]. 无机盐工业, 2019, 51(8): 7-12.
	BIAN Xiaotong, HUANG Yongming, GUO Rutao, et al. Research progress on salt separation and resource utilization in high salinity wastewater[J]. Inorganic Chemicals Industry, 2019, 51(8): 7-12.
8	李柄缘, 刘光全, 王莹, 等. 高盐废水的形成及其处理技术进展[J]. 化工进展, 2014, 33(2): 493-497, 515.
	LI Bingyuan, LIU Guangquan, WANG Ying, et al. Formation and treatment of high-salt wastewater[J]. Chemical Industry and Engineering Progress, 2014, 33(2): 493-497, 515.
9	SUN Yongjun, ZHU Chengyu, ZHENG Huaili, et al. Characterization and coagulation behavior of polymeric aluminum ferric silicate for high-concentration oily wastewater treatment[J]. Chemical Engineering Research and Design, 2017, 119: 23-32.
10	TIAN Wende, WANG Xue, FAN Chenyang, et al. Optimal treatment of hypersaline industrial wastewater via bipolar membrane electrodialysis[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(14): 12358-12368.
11	ZHANG Lunxiang, YANG Lei, WANG Jiaqi, et al. Enhanced CH₄ recovery and CO₂ storage via thermal stimulation in the CH₄/CO₂ replacement of methane hydrate[J]. Chemical Engineering Journal, 2017, 308: 40-49.
12	ZHANG Lunxiang, KUANG Yangmin, DAI Sheng, et al. Kinetic enhancement of capturing and storing greenhouse gas and volatile organic compound: micro-mechanism and micro-structure of hydrate growth[J]. Chemical Engineering Journal, 2020, 379: 122357.
13	SUN Lingjie, WANG Tian, DONG Bo, et al. Pressure oscillation controlled CH₄/CO₂ replacement in methane hydrates: CH₄ recovery, CO₂ storage, and their characteristics[J]. Chemical Engineering Journal, 2021, 425: 129709.
14	Bradshaw ROBERT W, Simmons BLAKE A, Majzoub ERIC H, et al. Clathrate hydrates for production of potable water[J]. MRS Online Proceedings Library, 2006, 930(1): 1-6.
15	PARK Kyeong Nam, HONG Sang Yeon, LEE Jin Woo, et al. A new apparatus for seawater desalination by gas hydrate process and removal characteristics of dissolved minerals (Na⁺, Mg²⁺, Ca²⁺, K⁺, B³⁺)[J]. Desalination, 2011, 274(1/2/3): 91-96.
16	HAN Songlee, SHIN Ju Young, RHEE Young Woo, et al. Enhanced efficiency of salt removal from brine for cyclopentane hydrates by washing, centrifuging, and sweating[J]. Desalination, 2014, 354: 17-22.
17	MCCORMACK R, ANDERSEN R. Clathrate desalination plant preliminary research study. Water treatment technology program report No. 5 (Final) [R]. San Diego: Thermal Energy Storage, Inc., 1995
18	Jong Ho CHA, SEOL Yongkoo. Increasing gas hydrate formation temperature for desalination of high salinity produced water with secondary guests[J]. ACS Sustainable Chemistry & Engineering, 2013, 1(10): 1218-1224.
19	FAKHARIAN Hajar, GANJI Hamid, NADERIFAR Abbas. Saline produced water treatment using gas hydrates[J]. Journal of Environmental Chemical Engineering, 2017, 5(5): 4269-4273.
20	FAKHARIAN Hajar, GANJI Hamid, NADERIFAR Abbas. Desalination of high salinity produced water using natural gas hydrate[J]. Journal of the Taiwan Institute of Chemical Engineers, 2017, 72: 157-162.
21	SONG Yongchen, DONG Hongsheng, YANG Lei, et al. Hydrate-based heavy metal separation from aqueous solution[J]. Scientific Reports, 2016, 6: 21389.
22	DONG Hongsheng, ZHANG Lunxiang, LING Zheng, et al. The controlling factors and ion exclusion mechanism of hydrate-based pollutant removal[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(8): 7932-7940.
23	SUN Huilian, SUN Lingjie, ZHAO Yang, et al. A combined hydrate-based method for removing heavy metals from simulated wastewater with high concentrations[J]. Journal of Environmental Chemical Engineering, 2021, 9(6): 106633.
24	ZHANG Lunxiang, SUN Lingjie, LU Yi, et al. Molecular dynamics simulation and in situ MRI observation of organic exclusion during CO₂ hydrate growth[J]. Chemical Physics Letters, 2021, 764: 138287.
25	YANG Yamei, DU Rui, SHI Changrui, et al. Desalination and enrichment of phosphorus-containing wastewater via cyclopentane hydrate[J]. Journal of Environmental Chemical Engineering, 2021, 9(4): 105507.
26	LI Feng, CHEN Zhijie, DONG Hongsheng, et al. Promotion effect of graphite on cyclopentane hydrate based desalination[J]. Desalination, 2018, 445: 197-203.
27	KANG Kyung Chan, LINGA Praveen, PARK Kyeong nam, et al. Seawater desalination by gas hydrate process and removal characteristics of dissolved ions (Na⁺, K⁺, Mg²⁺, Ca²⁺, B³⁺, Cl^-, SO₄ ^{2 -})[J]. Desalination, 2014, 353: 84-90.
28	ZHENG Jianan, YANG Mingjun. Experimental investigation on novel desalination system via gas hydrate[J]. Desalination, 2020, 478: 114284.
29	LU Hailong, MATSUMOTO Ryo, TSUJI Yoshihiro, et al. Anion plays a more important role than cation in affecting gas hydrate stability in electrolyte solution? ——A recognition from experimental results[J]. Fluid Phase Equilibria, 2001, 178(1/2): 225-232.
30	Amadeu K SUM, Carolyn A KOH, SLOAN E Dendy. Clathrate hydrates: from laboratory science to engineering practice[J]. Industrial & Engineering Chemistry Research, 2009, 48(16): 7457-7465.
31	段睿, 王立和, 杨翠英, 等. 常温中和铁氧体法处理高浓度含铜废水的研究[J]. 工业水处理, 2013, 33(5): 53-56.
	DUAN Rui, WANG Lihe, YANG Cuiying, et al. Treatment of high-concentration copper-containing wastewater by room temperature neutralization ferrite process[J]. Industrial Water Treatment, 2013, 33(5): 53-56.
32	高腾跃, 刘奎仁, 韩庆, 等. 次亚磷酸盐在电解铜氰废液同时回收铜和氰过程中的作用[J]. 工程科学学报, 2017, 39(3): 383-388.
	GAO Tengyue, LIU Kuiren, HAN Qing, et al. Effect of hypophosphite during the recovery of copper and cyanide from high concentration copper-cyanide wastewater by electrodeposition[J]. Chinese Journal of Engineering, 2017, 39(3): 383-388.
33	晋玉秀, 杨秀培, 刘建军, 等. 均匀设计法阴极还原处理含铜废水的研究[J]. 河北冶金, 2005(6): 31-33.
	JIN Yuxiu, YANG Xiupei, LIU Jianjun, et al. Study about using cathodic reduction to treat copper-bearing waste water with even design[J]. Hebei Metallurgy, 2005(6): 31-33.
34	李想, 吴雅琴, 朱圆圆, 等. 电沉积处理含铜强酸废水阴极回收纳米铜[J]. 水处理技术, 2018, 44(3): 34-38.
	LI Xiang, WU Yaqin, ZHU Yuanyuan, et al. Nano-copper recovery at cathode in high acid wastewater containing copper by elcctro-deposition method[J]. Technology of Water Treatment, 2018, 44(3): 34-38.
35	宋永辉, 屈学化, 吴春晨, 等. 硫酸锌沉淀法处理高铜氰化废水的研究[J]. 稀有金属, 2015, 39(4): 357-364.
	SONG Yonghui, QU Xuehua, WU Chunchen, et al. Cyanide wastewater with high density copper treated by zinc sulfate precipitation process[J]. Chinese Journal of Rare Metals, 2015, 39(4): 357-364.
36	肖书虎, 张国芳, 宋永会, 等. 电化学双极法处理高浓度含铜黄连素制药废水[J]. 环境工程技术学报, 2011, 1(4): 295-299.
	XIAO Shuhu, ZHANG Guofang, SONG Yonghui, et al. Treatment of berberine pharmaceutical wastewater containing copper by bipolar-electrochemical process[J]. Journal of Environmental Engineering Technology, 2011, 1(4): 295-299.
37	杨文清, 关念云. 线路板生产络合铜废水的处理研究[J]. 工业用水与废水, 2017, 48(2): 47-49, 76.
	YANG Wenqing, GUAN Nianyun. Study on treatment of wastewater with copper in complex state from circuit board production[J]. Industrial Water & Wastewater, 2017, 48(2): 47-49, 76.
38	PENG Changsheng, LIU Yanyan, BI Jingjing, et al. Recovery of copper and water from copper-electroplating wastewater by the combination process of electrolysis and electrodialysis[J]. Journal of Hazardous Materials, 2011, 189(3): 814-820.
39	MULUNGULUNGU Germain Akonkwa, MAO Tingting, HAN Kai. Efficient removal of high-concentration copper ions from wastewater via 2D g-C₃N₄ photocatalytic membrane filtration[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2021, 623: 126714.

无机物种类	浓度/mg∙L^-1	无机物种类	浓度/mg∙L^-1
Na	2248.04	Cu	0.10
Ca	393.11	Mn	0.06
K	190.71	Hg	0.04
Mg	99.49	Se	0.03
Zn	0.27

无机物种类	浓度/mg∙L^-1	无机物种类	浓度/mg∙L^-1
Na	2248.04	Cu	0.10
Ca	393.11	Mn	0.06
K	190.71	Hg	0.04
Mg	99.49	Se	0.03
Zn	0.27

序号	电导率/mS∙cm^-1				分解质量 /g	抽滤效率 /%	离心效率 /%	产水率 /%	富集因子	平均抽滤效率 /%	平均离心效率 /%	平均产水率 /%	平均富集因子
序号	原废水样	分解水E_d1	分解水E_d2	浓缩废水	分解质量 /g	抽滤效率 /%	离心效率 /%	产水率 /%	富集因子	平均抽滤效率 /%	平均离心效率 /%	平均产水率 /%	平均富集因子
1	11.43	6.32	2.59	19.98	30.88	44.71	77.34	77.19	1.748	44.97	76.00	78.87	1.724
2	11.43	6.37	2.75	20.74	30.77	44.27	75.94	76.93	1.815
3	11.43	6.18	2.89	18.40	33.00	45.93	74.72	82.49	1.610

序号	电导率/mS∙cm^-1				分解质量 /g	抽滤效率 /%	离心效率 /%	产水率 /%	富集因子	平均抽滤效率 /%	平均离心效率 /%	平均产水率 /%	平均富集因子
序号	原废水样	分解水E_d1	分解水E_d2	浓缩废水	分解质量 /g	抽滤效率 /%	离心效率 /%	产水率 /%	富集因子	平均抽滤效率 /%	平均离心效率 /%	平均产水率 /%	平均富集因子
1	11.43	6.32	2.59	19.98	30.88	44.71	77.34	77.19	1.748	44.97	76.00	78.87	1.724
2	11.43	6.37	2.75	20.74	30.77	44.27	75.94	76.93	1.815
3	11.43	6.18	2.89	18.40	33.00	45.93	74.72	82.49	1.610

项目	原水样浓度 /mg∙L^-1	分解水浓度 /mg∙L^-1	分解水质量 /g	浓缩水浓度 /mg∙L^-1	离心效率 /%	产水率 /%	富集因子	平均离心效率 /%	平均产水率 /%	平均富集因子
Cu
1	12895	1102	21.37	21878	91.45	53.43	1.697	90.81	54.99	1.630
2	12895	1239	21.94	20868	90.39	54.87	1.618
3	12895	1216	22.67	20299	90.57	56.68	1.574
As
1	0.065	0.021	21.37	0.166	67.13	53.43	2.562	66.26	54.99	3.035
2	0.065	0.024	21.94	0.179	62.96	54.87	2.761
3	0.065	0.020	22.67	0.245	68.67	56.68	3.782