矿井水反渗透系统阻垢剂成分与阻垢机制  

Antiscalant ingredients and its antiscaling mechanism in mine wastewater reverse osmosis systems

作　　者：李曈 徐梦兰 赵悦 任舒阳 王霄 郭开祥 李从举 LI Tong;XU Menglan;ZHAO Yue;REN Shuyang;WANG Xiao;GUO Kaixiang;LI Congju(State Key Laboratory of Water Resource Protection and Utilization in Coal Mining,China Energy Investment Group,Beijing 102209,China;School of Energy and Environmental Engineering,University of Science and Technology Beijing,Beijing 100083,China)

机构地区：[1]国家能源集团煤炭开采水资源保护与利用国家重点实验室,北京102209 [2]北京科技大学能源与环境工程学院,北京100083

出　　处：《工程科学学报》2024年第6期1004-1011,共8页Chinese Journal of Engineering

基　　金：煤炭开采水资源保护与利用国家重点实验室2021年开放基金课题资助(GJNY-21-219);国家自然科学基金面上资助项目(52270056)。

摘　　要：矿井水反渗透浓水中阻垢剂可以抑制Ca^(2+)、Mg^(2+)结晶沉淀导致双碱法投药量高、除硬效果差,影响后续蒸发结晶分盐效果.探究反渗透系统中阻垢剂成分及阻垢机制是实现Ca^(2+)、Mg^(2+)脱稳、解决深度除硬与零排放问题的关键.本文首先测定反渗透浓水水质条件,通过超滤分级、傅里叶红外光谱(FT-IR)、紫外可见吸收光谱(UV-Vis)和三维荧光光谱(EEM)分析得出溶解性有机物主要为分子量<3 kDa且含有羧基、醇/酚羟基与不饱和烃结构的微生物代谢产物和类腐殖酸物质;根据13C和31P核磁共振(NMR)谱化学位移特征(甲基碳、季碳和C—PO_(3)H_(2)结构),确定阻垢剂主要成分为羟基乙叉二膦酸(HEDP);吸附去除88.55%总磷和38.86%COD后,双碱滴定结果表明,Ca^(2+)沉淀完全所需CO^(2)_(-3)的投加量从2845.8减少至826.8 mg·L^(-1),表明HEDP主要阻止Ca^(2+)结晶成垢;重新利用HEDP复配,CO^(2)_(-3)投加量仅增加至1626.3 mg·L^(-1),说明吸附去除的部分有机物具有一定分散作用,可以抑制溶液中Ca^(2+)结晶团聚.HEDP与溶解性有机物的协同阻垢机制,为矿井水反渗透浓水中Ca^(2+)、Mg^(2+)深度去除提供重要理论依据和调控策略.The use of antiscalants in reverse osmosis(RO)systems is essential to prevent the crystallization and precipitation of Ca^(2+)and Mg^(2+)ions,which can lead to undesirable consequences such as an increase in the required dosages of hydroxide and carbonate for hardness removal,increase operational costs,and negatively impact the evaporation–crystallization of salt.This study aimed to investigate the industrial antiscalant ingredients and antiscaling mechanism in RO systems,which is crucial for achieving thorough hardness removal and no industrial wastewater discharge.We comprehensively analyzed the water quality of RO concentrate and fractionated it using ultrafiltration based on molecular weights.Fourier transform infrared spectroscopy(FT-IR),UV-visible spectrophotometry(UV-Vis),and excitation–emission matrix fluorescence spectroscopy(EEM)results revealed that the primary constituents of the dissolved organic matter(DOM)were microbial metabolites and humic acid substances with a molecular weight of<3 kDa.These substances comprised functional groups such as carboxyl,alcohol/phenol hydroxyl,and unsaturated hydrocarbon structures.We further analyzed the main composition and structure of antiscalants using ^(1)H,^(13)C,and ^(31)P nuclear magnetic resonance(NMR),confirming that the dominant component is hydroxyethylidene-1,1-diphosphonic acid(HEDP)based on the chemical shift characteristics of methyl carbon,quaternary carbon(19.02×10^(-6) and 69.96×10^(-6) in ^(13)C NMR),and C—P structures(19.94×10^(-6) in 31P NMR).Anion exchange adsorption experiments were performed for HEDP removal in RO concentrate to evaluate the effectiveness of the antiscalants.Approximately 88.55%HEDP and 38.86%COD removal substantially reduced the amount of carbonate required for complete Ca^(2+)precipitation,with the needed concentration decreasing from 2845.8 to 826.8 mg·L^(-1).This reduction demonstrates the dominant role of HEDP in hindering Ca^(2+)crystallization rather than Mg^(2+).Interestingly,even upon the reintroduction of

关 键 词：反渗透浓水 阻垢剂 羟基乙叉二膦酸 核磁共振 阻垢机制 

分 类 号：X703[环境科学与工程—环境工程] TD926.5[矿业工程—选矿]