混凝-吸附去除矿井水膜浓缩液中有机物的研究

doi:10.19965/j.cnki.iwt.2024-0927

摘要/Abstract

摘要：

随着对矿井水回收率要求的日益提高，企业普遍采用“混凝沉淀+过滤+反渗透”工艺处理矿井水。经过多级反渗透脱盐，矿井水膜浓缩液中含有大量无机盐离子和有机物。浓缩液直接进入蒸发结晶单元会影响蒸发器运行与结晶盐品质。对比了4种混凝剂、3种介孔活性焦以及混凝剂-活性焦联用去除矿井水膜浓缩液中有机物的效果，同时采用光谱技术分析了混凝法、吸附法、混凝-吸附法对不同有机物组分的去除规律，最后分析了3种方法处理矿井水膜浓缩液的经济效益。结果表明，最优条件下聚合硫酸铁混凝和孔径较大的活性焦对溶解有机碳（DOC）去除率可分别达到38%和61%；矿井水膜浓缩液中有机物主要为腐殖酸，其次为微生物代谢产物、富里酸，也含有少量的类蛋白质；混凝主要去除腐殖酸，而活性焦吸附对膜浓缩液中的有机组分都有去除效果。单独混凝处理对有机物去除效率低，单独吸附处理时活性焦的投加量大，药剂成本高。混凝-吸附处理对DOC去除率可达到59%，与单独吸附处理相当，但药剂成本从1.13元/m³降至0.57元/m³。混凝-吸附处理是利用现有矿井水深度回用工艺（零排放工艺）处理单元去除膜浓缩液中有机物简单有效的方法。

关键词: 混凝, 吸附, 膜浓缩液, 有机物

Abstract:

In response to increasingly stringent requirements for mine water recovery rates, enterprises widely adopt the “coagulation-sedimentation+filtration+reverse osmosis (RO)” process for mine water treatment. After multi-stage reverse osmosis desalination, the reverse osmosis concentrate (ROC) contains high concentrations of inorganic ions and organic substances. The feed of this concentrate directly into the evaporation crystallization unit has been shown a detrimental effect on evaporator operation and the quality of crystallized salts. This study compared the effectiveness of four coagulants, three types of mesoporous activated coke (MAC), and coagulant-activated coke combined use for removing organic matter from mine water ROC. Spectroscopic techniques were employed to analyze the removal patterns of different organic fractions by coagulation adsorption and coagulation-adsorption. Finally, an economic analysis of the three treatment methods for ROC was conducted. The results indicated that under optimal conditions, polyferric sulfate (PFS) coagulation and MAC with larger pore sizes achieved dissolved organic carbon (DOC) removal efficiencies of 38% and 61%, respectively. The organic matter in the mine water ROC primarily consisted of humic acid, followed by microbial metabolites and fulvic acid, with minor amounts of protein-like substances. Coagulation primarily removed humic acid, while MAC adsorption was effective against all organic components in the ROC. Coagulation treatment demonstrated low organic removal efficiency. Adsorption treatment required high MAC dosages, resulting in high reagent costs. The coagulation-adsorption achieved a DOC removal efficiency of 59%, comparable to adsorption alone, while reducing the reagent cost from 1.13 yuan/m³ to 0.57 yuan/m³. The coagulation-adsorption represents a straightforward and effective method for removing organic matter from ROC by utilizing existing treatment units within the advanced mine water reuse (Zero liquid discharge, ZLD) process.

Key words: coagulation, adsorption, membrane concentrate, organic matter

中图分类号:

X703
X52

陈发源, 刘莉莉, 王瑞涵, 许勃笛, 詹亚力, 王庆宏, 陈春茂. 混凝-吸附去除矿井水膜浓缩液中有机物的研究[J]. 工业水处理, 2025, 45(11): 46-52.

Fayuan CHEN, Lili LIU, Ruihan WANG, Bodi XU, Yali ZHAN, Qinghong WANG, Chunmao CHEN. Study on the removal of organic matter from mine water membrane concentrate by coagulation-adsorption[J]. Industrial Water Treatment, 2025, 45(11): 46-52.

https://www.iwt.cn/CN/Y2025/V45/I11/46

图/表 13

表1 矿井水ROC主要水质特征

Table 1 Primary water quality characteristics of ROC from mine water

指标	数值
pH	8.05±0.21
电导率/（mS·cm^-1）	18.30±1.22
COD/（mg·L^-1）	50±5
TOC/（mg·L^-1）	9.11±2.00

图1 不同混凝剂对矿井水ROC中DOC的去除效果

Fig.1 DOC removal from mine water ROC using different coagulants

图2 矿井水ROC混凝前后的紫外-可见光吸收光谱

Fig.2 UV-Vis spectra of mine water ROC before and after coagulation

图3 矿井水ROC混凝前后有机物的荧光强度

Fig.3 Fluorescence intensity of organic matter in mine water ROC before and after coagulation treatment

图4 温度对PFS混凝去除矿井水ROC中DOC效果的影响

Fig.4 Effect of temperature on the removal of DOC from mine water ROC with PFS coagulation

图5 温度对PFS混凝去除矿井水ROC中不同荧光光谱区域有机物的影响

Fig.5 Effect of temperature on the removal of organic matter in different fluorescence regions from ROC in mine water by PFS coagulation

图6 3种不同活性焦对矿井水ROC中DOC的去除效果

Fig.6 DOC removal from ROC in mine water using three different activated cokes

图7 矿井水ROC经3种活性焦吸附后出水的UV₂₅₄变化

Fig.7 Changes in UV₂₅₄ of mine water ROC effluent after adsorption by three types of activated cokes

图8 矿井水ROC经3种活性焦吸附后出水的荧光强度变化

Fig.8 Changes in fluorescence intensity of mine water ROC effluent after adsorption by three types of activated coke

图9 AC-b投加量对ROC中DOC去除效果的影响

Fig.9 Effect of AC-b dosage on DOC removal from mine water ROC

图10 混凝、吸附、混凝-吸附去除矿井水ROC中DOC的效果

Fig.10 Effect of coagulation，adsorption，and coagulation-adsorption on DOC removal from mine water ROC

图11 混凝、吸附、混凝-吸附对矿井水ROC中不同荧光组分的去除情况

Fig.11 Removal of different fluorescent components from mine water ROC by coagulation，adsorption，and coagulation-adsorption

表2 混凝、吸附、混凝-吸附的经济性分析

Table 2 Cost analysis of coagulation，adsorption and coagulation-adsorption

去除方法	药剂	单价/（元·t^-1）	有机物去除率/%	药剂投加量/（mg·L^-1）	单位体积污水处理成本/（元·m^-3）
吸附	AC-a	4 000	40	250	1.00
	AC-b	4 500	60	250	1.13
	AC-c	5 000	61	250	1.25
混凝	PFS	1 200	38	100	0.12
混凝-吸附	PFS-（AC-b）		59	100/100	0.57

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