| 300 | 1 | 166 |
| 下载次数 | 被引频次 | 阅读次数 |
磷石膏是湿法磷酸生产过程中产生的固体废弃物，磷石膏中可溶性磷氟限制了磷石膏在建筑行业的应用。通过柠檬酸协同表面活性剂分步去除磷石膏中磷氟杂质，对柠檬酸浓度、表面活性剂种类及工艺流程进行优化，采用激光粒度分析仪、zeta电位仪、扫描电镜-能谱仪（SEM-EDS）对净化前后磷石膏进行微观表征，探究磷石膏在柠檬酸净化和表面活性剂净化过程的除杂机制。研究结果表明：在柠檬酸质量分数为3%、以十六烷基三甲基溴化铵（CTAB）为阳离子表面活性剂时，磷石膏中磷氟杂质的去除率最高，可溶磷去除率可达98.00%，可溶氟去除率可达98.73%，满足井下填充材料及二水磷石膏露天填充材料渗滤液中对P、F及pH的控制要求。
Abstract：Phosphogypsum is a solid waste produced in the production process of phosphoric acid,the soluble phosphorus and fluorine in phosphogypsum limit the application of phosphogypsum in the construction industry.Citric acid synergizes with surfactant method is used to remove phosphorus and fluorine impurities from phosphogypsum in a step-by-step manner,the dosage of citric acid,the type of surfactant and the process flow are optimized,and the laser particle size analyzer meter,zeta potential meter and SEM-EDS are used to characterize phosphogypsum before and after purification, and the impurity removal mechanisms of phosphogypsum in the process of citric acid purification and surfactant purification are explored. The results show that when the mass fraction of citric acid is 3% and CTAB is used as the cationic surfactant,the removal rate of phosphorus and fluorine impurities in phosphogypsum are the highest,the removal rate of soluble phosphorus can reach 98.00%,and the removal rate of soluble fluorine can reach 98.73%, meeting the requirements for phosphorus, fluorine and pH in leachate of phosphogypsum underground and open air filling materials.
[1] LI X,LV X F,XIANG L. Review of the State of Impurity Occurrences and Impurity Removal Technology in Phosphogypsum[J]. Materials,2023,16(16):5630.
[2]柏光山，杨林，曹建新，等.磷石膏预处理工艺对硫酸钙晶须性能影响的研究[J].化工矿物与加工，2011,40(12):14-17.BAI G S,YANG L,CAO J X,et al. Study on effects of the pretreatment technology of phosphogypsum on performance of calcium sulfate whisker[J]. Industrial Minerals&Processing,2011,40(12):14-17.
[3] CAO W X,YI W,PENG J H,et al. Preparation of anhydrite from phosphogypsum:Influence of phosphorus and fluorine impurities on the performances[J]. Construction and Building Materials,2022,318:126021.
[4] CAO W X,YI W,PENG J H,et al. Recycling of phosphogypsum to prepare gypsum plaster:Effect of calcination temperature[J].Journal of Building Engineering,2022,45:103511.
[5] LI X B,ZHANG Q. Dehydration behaviour and impurity change of phosphogypsum during calcination[J]. Construction and Building Materials,2021,311:125328.
[6] XIANG J C,QIU J P,SONG Y Y,et al. Synergistic removal of phosphorus and fluorine impurities in phosphogypsum by enzyme-induced modified microbially induced carbonate precipitation method[J]. Journal of Environmental Management,2022,324:116300.
[7] QI H H,MA B G,TAN H B,et al. Influence of fluoride ion on the performance of PCE in hemihydrate gypsum pastes[J].Journal of Building Engineering,2022,46:103582.
[8] CHEN Q S,SUN S Y,LIU Y K,et al. Immobilization and leaching characteristics of fluoride from phosphogypsum-based cemented paste backfill[J]. International Journal of Minerals,Metallurgy and Materials,2021,28(9):1440-1452.
[9] BELLEFQIH H,BOURGIER V,BILAL E,et al. Effect of HPO42-and brushite on gypsum reactivity and implications for utilization of phosphogypsum in plaster production[J]. Journal of Cleaner Production,2024,451:142013.
[10]白有仙，庞世花，朱云勤.对磷石膏不同处理方法脱磷效果的实验研究[J].磷肥与复肥，2009,24(3):21-22.BAI Y X,PANG S H,ZHU Y Q. Experimental study on the dephosphorization effects of phosphogypsum by different treatment processes[J]. Phosphate&Compound Fertilizer,2009,24(3):21-22.
[11]罗栋源，吴海霞，杨子杰，等.磷石膏水洗液中磷、氟、有机物的去除[J].有色金属（冶炼部分），2023(5):129-137.LUO D Y, WU H X, YANG Z J, et al. Removal of Phosphorus,Fluorine and Organic Matter from Phosphogypsum Washing Solution[J]. Nonferrous Metals(Extractive Metallurgy),2023(5):129-137.
[12] BUMANIS G, ZORICA J, BAJARE D, et al. Effect of water-binder ratio on properties of phosphogypsum binder[J].IOP Conference Series:Materials Science and Engineering,2019,660(1):012071.
[13]张利珍，张永兴，吴照洋，等.脱除磷石膏中水溶磷、水溶氟的实验研究[J].无机盐工业，2022,54(4):40-45.ZHANG L Z,ZHANG Y X,WU Z Y,et al. Experimental study on removal of water-soluble phosphorus and water-soluble fluorine from phosphogypsum[J]. Inorganic Chemicals Industry,2022,54(4):40-45.
[14]王莹，王鹏起，谭丹君，等.磷石膏的预处理及在建材中的应用[J].建设科技，2016(16):164-166.
[15] RUSCH K A, GUO T Z, SEALS R K. Stabilization of phosphogypsum using class C fly ash and lime:assessment of the potential for marine applications[J]. Journal of Hazardous Materials,2002,93(2):167-186.
[16]王进明，董发勤，王肇嘉，等.磷石膏浮选增白净化新工艺研究[J].非金属矿，2019,42(5):1-5.WANG J M,DONG F Q,WANG Z J,et al. Study on a New Technology of Phosphogypsum Whitening and Purification by Flotation[J]. Non-Metallic Mines,2019,42(5):1-5.
[17] MASHIFANA T,NTULI F,OKONTA F. Leaching kinetics on the removal of phosphorus from waste phosphogypsum by application of shrinking core model[J]. South African Journal of Chemical Engineering,2019,27(1):1-6.
[18] SINGH M. Treating waste phosphogypsum for cement and plaster manufacture[J]. Cement and Concrete Research,2002,32(7):1033-1038.
[19] ZHU G Y,YANG Y R,HE L,et al. Novel Synergistic Process of Impurities Extraction and Phophogypsum Crystallization Control in Wet-Process Phosphoric Acid[J].ACS Omega,2023,8(31):28122-28132.
[20] SADRI F,KIM R,YANG Z,et al. The effect of calcium sulfate crystallization and the crystal modification on aqueous REE stability in Ca saturated REE-Ca-SO4-H2O systems[J].Hydrometallurgy,2018,182:82-96.
[21] CAO W X, YI W, PENG J H, et al. Upcycling of phosphogypsum as anhydrite plaster:The positive effect of soluble phosphorus impurities[J]. Construction and Building Materials,2023,372:130824.
[22] LI R, HE W L, DUAN J F, et al. Existing form and distribution of fluorine and phosphorus in phosphate rock acid-insoluble residue[J]. Environmental Science and Pollution Research International,2022,29(5):7758-7771.
[23]唐明珠，王志英，王云山，等. EBSD-XPS法分析磷石膏中杂质物相[J].光谱学与光谱分析，2022,42(1):136-140.TANG M Z,WANG Z Y,WANG Y S,et al. Characterization of the Impurity Phases in Phosphogypsum by the EBSD-XPS Method[J]. Spectroscopy and Spectral Analysis,2022,42(1):136-140.
[24]李绪，朱干宇，宫小康，等.胶磷矿中杂质赋存形式及酸解过程变化[J].光谱学与光谱分析，2019,39(4):1288-1293.LI X,ZHU G Y,GONG X K, et al. Occurrence of the Impurities in Phosphorus Rock and the Research of Acidolysis Process[J]. Spectroscopy and Spectral Analysis,2019,39(4):1288-1293.
[25]杨敏.磷石膏的溶解度研究[J].广州化工，2016,44(15):62-63,72.YANG M. Study on Solubility of Phosphogypsum[J]. Guangzhou Chemical Industry,2016,44(15):62-63,72.
[26]夏桂英，杨柳春，袁治冶.硫酸直接浸出磷石膏中稀土元素的研究[J].无机盐工业，2024,56(1):107-113.XIA G Y,YANG L C,YUAN Z Y.Study on direct leaching of rare earth elements from phosphogypsum with sulfuric acid[J].Inorganic Chemicals Industry,2024,56(1):107-113.
[27] GASSER M S,ISMAIL Z H,ABU ELGOUD E M,et al.Process for lanthanides-Y leaching from phosphogypsum fertilizers using weak acids[J]. Journal of Hazardous Materials,2019,378:120762.
[28] GUAN Q J,ZHOU Y L,YU W J,et al. Efficient removal of impurities from phosphogypsum during preparation ofα-hemihydrate gypsum[J]. Minerals Engineering, 2023,201:108203.
[29] ZHOU Y N,SHI Y,ZHU Q Q. Control of Fluoride Pollution in Cemented Phosphogypsum Backfill by Citric Acid Pretreatment[J]. Materials,2023,16(19):6493.
[30]黄照东，张德明，刘一锴，等.柠檬酸浸法预处理对磷石膏充填体性能的影响[J].黄金科学技术，2020,28(1):97-104.HUANG Z D,ZHANG D M,LIU Y K,et al. Effect of Citric Acid Immersing Pre-treated on the Performance of the Phosphogypsum Cemented Paste Backfill[J]. Gold Science and Technology,2020,28(1):97-104.
[31] CHEN S,CHEN J Z,HE X Y,et al. Micromicelle-mechanical coupling method for high-efficiency phosphorus removal and whiteness improvement of phosphogypsum[J]. Construction and Building Materials,2022,354:129220.
基本信息:
DOI：
中图分类号:TQ177.375
引用信息:
[1]胡强卫,夏举佩.柠檬酸协同表面活性剂去除磷石膏中磷氟杂质[J].生态产业科学与磷氟工程,2025,40(03):9-18.
基金信息:
国家自然科学基金项目（22068019）