磷石膏中杂质深度脱除技术
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摘要
以深度脱除磷石膏中的杂质,提高其品质为目的,采用XRF、XRD、SEM以及白度分析仪等多种分析表征手段,对水洗、硫酸酸洗以及硫酸酸洗耦合溶剂萃取等3种磷石膏净化除杂方法进行了比较分析研究。结果表明,磷石膏表面粘附的少量可溶性磷、镁化合物以及部分可溶性含硅及氟化合物可采用水洗除去,而磷石膏中几乎全部含有可溶性硅、铝、铁、氟、钾等杂质元素的化合物可采用硫酸酸洗除去。在水洗和酸洗过程中,磷石膏中的二水硫酸钙均经历了溶解再结晶成无水硫酸钙的晶型转变过程,并且在硫酸体系中可有效促进其晶型转变速率。此外,在硫酸酸洗过程中添加磷酸三丁酯,不仅可有效脱除磷石膏中的石英、硫化亚铁、无机炭黑等酸不可溶性杂质,还可有效脱除溶解度较小的氟硅酸钾和带结晶水的氟化铝等杂质,由此可以获得纯度大于99%、白度大于92%,并且分散性较好的棒状细小无水硫酸钙颗粒。采用硫酸酸洗耦合有机溶剂磷酸三丁酯萃取深度净化磷石膏,将为磷石膏资源实现高效利用提供了新途径。
To deeply remove the impurities and improve the quality of phosphogypsum(PG),three PG purification methods,including water washing,acid pickling,and acid pickling coupling solvent extraction,were comparatively analyzed according to the results of characterization by XRF,XRD,SEM and whiteness. Results showed that a small amount of soluble phosphorus,magnesium compounds and part of soluble silicon,fluorine compounds on the surface of PG could be removed by water washing,while almost all of the acid soluble compounds containing Si,Al,Fe,F and K impurity elements in PG could be removed by acid pickling. It was found that the main mineral phase of CaSO_4·2H_2O in PG underwent the dissolution and recrystallization to form CaSO_4 both in water washing and acid pickling process,while the transformation speed was much faster in the latter.Moreover,when the organic solvent tributyl phosphate(TBP)was added to the acid pickling process,all of the impurities in PG involving the acid insoluble impurities,such as quartz,iron sulfide,inorganic carbon black,and the barely soluble impurities,such as K_2SiF_6 and aluminum fluoride with crystal water,can be effectively removed.The clubbed CaSO_4 with the purity and whiteness of more than 99%and 92%,respectively,could be obtained by this acid pickling coupling with solvent extraction technique,which would provide a new way for the comprehensive utilization of PG.
To deeply remove the impurities and improve the quality of phosphogypsum(PG),three PG purification methods,including water washing,acid pickling,and acid pickling coupling solvent extraction,were comparatively analyzed according to the results of characterization by XRF,XRD,SEM and whiteness. Results showed that a small amount of soluble phosphorus,magnesium compounds and part of soluble silicon,fluorine compounds on the surface of PG could be removed by water washing,while almost all of the acid soluble compounds containing Si,Al,Fe,F and K impurity elements in PG could be removed by acid pickling. It was found that the main mineral phase of CaSO_4·2H_2O in PG underwent the dissolution and recrystallization to form CaSO_4 both in water washing and acid pickling process,while the transformation speed was much faster in the latter.Moreover,when the organic solvent tributyl phosphate(TBP)was added to the acid pickling process,all of the impurities in PG involving the acid insoluble impurities,such as quartz,iron sulfide,inorganic carbon black,and the barely soluble impurities,such as K_2SiF_6 and aluminum fluoride with crystal water,can be effectively removed.The clubbed CaSO_4 with the purity and whiteness of more than 99%and 92%,respectively,could be obtained by this acid pickling coupling with solvent extraction technique,which would provide a new way for the comprehensive utilization of PG.
引文
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[18]赵志曼,刘子瑜,李帅,等.磷石膏炒制-酸浸法脱色增白研究[J].低温建筑技术,2016,38(5):9-11.ZHAO Z M,LIU Z Y,LI S,et al.Study on decoloring and whitening of phosphogypsum by coupling stir frying and acid leaching[J].Low Temperature Architecture Technology,2016,38(5):9-11.
[19]师梦,杨保俊,刘磊,等.磷石膏脱色增白工艺条件的研究[J].合肥工业大学学报:自然科学版,2013,36(2):212-216.SHI M,YANG B J,LIU L,et al.Study of technological conditions of decoloring and whitening of phosphogypsum[J].Journal of Hefei University of Technology(Natural Science),2013,36(2):212-216.
[20]曾亚平,党亚固,费德君.制备高品质磷石膏的湿法磷酸新工艺的开发[J].化工进展,2015,34(1):167-172.ZENG Y P,DANG Y G,FEI D J.Development of the new wet phosphoric process of preparing high-quality phosphogypsum[J].Chemical Industry and Engineering Progress,2015,34(1):167-172.
[21]ZHI Y,LIU J.Surface modification of activated carbon for enhanced adsorption of perfluoroalkyl acids from aqueous solutions[J].Chemosphere,2016,144:1224-1232.
[22]RECHNIA P,MALAIKA A,KOZ?OWSKI M.Synthesis of tert-amyl methyl ether(TAME)over modified activated carbon catalysts[J].Fuel,2015,154:338-345.
[2]EI-DIDAMONY H,GADO H S,AWWAD N S,et al.Treatment of phosphogypsum waste produced from phosphate ore processing[J].Journal of Hazardous Materials,2013,244:596-602.
[3]谢和平,谢凌志,王昱飞,等.全球二氧化碳减排不应是CCS,应是CCU[J].四川大学学报(工程科学版),2012,44(4):1-5.XIE H P,XIE L Z,WANG Y F,et al.CCU:a more feasible and economic strategy than CCS for reducing CO2 emissions[J].Journal Sichuan University(Engineering Science Edition),2012,44(4):1-5.
[4]XIE H P,YUE H R,ZHU J H,et al.Scientific and engineering progress in CO2 mineralization using industrial waste and natural minerals[J].Engineering,2015,1(1):150-157.
[5]MATTILA H P,ZEVENHOVEN R.Mineral carbonation of phosphogypsum waste for production of useful carbonate and sulfate salts[J].Frontiers in Energy Research,2015,3:1-8.http://dx.doi.org/10.3389/fenrg.2015.00048
[6]ZHAO H T,LI H Q,BAO W J,et al.Experimental study of enhanced phosphogypsum carbonation with ammonia under increased CO2pressure[J].Journal of CO2 Utilization,2015,11:10-19.
[7]CONTRERAS M,PéREZ-LóPEZ R,GáZQUEZ M J,et al.Fractionation and fluxes of metals and radionuclides during the recycling process of phosphogypsum wastes applied to mineral CO2sequestration[J].Waste Management,2015,45:412-419.
[8]徐爱叶,李沪萍,罗康碧.磷石膏中杂质及除杂方法研究综述[J].化工科技,2011,18(6):59-64.XU A Y,LI H P,LUO K B.An overview of the study on the impurities and the method of eliminating the impurity in the phosphogypsum[J].Science&Technology in Chemical Industry,2010,18(6):59-64.
[9]孔霞,罗康碧,李沪萍,等.硫酸酸浸法除磷石膏中杂质氟的研究[J].化学工程,2012,40(8):65-68.KONG X,LUO K B,LI H P,et al.Removing impurity flourine from phosphogypsum by sulfuric acid leaching method[J].Chemical Engineering(China),2012,40(08):65-68.
[10]付全军,罗蜀峰,马先林,等.浸取中和法脱除磷石膏中杂质的研究[J].无机盐工业,2015,47(7):44-47.FU Q J,LUO S F,MA X L,et al.Impurities removal from phosphogypsum by leaching neutralization method[J].Inorganic Chemicals Industry,2015,47(7):44-47.
[11]李会泉,赵红涛,包炜军,等.一种由磷石膏制备高白、高纯无水硫酸钙的方法:201510029369.X[P].2015-01-21.LI H Q,ZHAO H T,BAO W J,et al.Method for preparing high white,high purity anhydrous calcium sulfate from phosphorusgypsum:201510029369.X[P].2015-01-21.
[12]WANG W L,ZENG D W,YIN X,et al.Prediction and measurement of gypsum solubility in the systems Ca SO4+HMSO4+H2SO4+H2O(HM=Cu,Zn,Ni,Mn)at 298.15 K[J].Industrial&Engineering Chemistry Research,2012,51(14):5124-5134.
[13]CHRISTENSEN A N,OLESEN M,CERENIUS Y,et al.Formation and transformation of five different phases in the Ca SO4-H2O system:crystal structure of the subhydrateβ-Ca SO4·0.5 H2O and soluble anhydrite Ca SO4[J].Chemistry of Materials,2008,20(6):2124-2132.
[14]GROENEWOLD G S,INGRAM J C,DELMORE J E,et al.Static secondry ionization mass spectrometry analysis of tributyl phosphate on mineral surfaces:effect of Fe(Ⅱ)[J].Journal of the American Society for Mass Spectrometry,1995,6(3):165-174.
[15]LI H,GUO F,ZHANG Z,et al.A new hydrometallurgical process for extracting rare earths from apatite using solvent extraction with P350[J].Journal of Alloys and Compounds,2006,408:995-998.
[16]EI-MAJDOUB L,SHI Y,YUAN Y,et al.Preparation,characterization,and catalytic activity of zirconocene bridged on surface of silica gel[J].Applied Surface Science,2015,353:376-381.
[17]赵红涛,李会泉,包炜军,等.磷石膏中微量含氟物相的光谱分析[J].光谱学与光谱分析,2015,35(8):2333-2338.ZHAO H T,LI H Q,BAO W J,et al.Spectral analysis of trace fluorine phase in phosphogypsum[J].Spectroscopy and Spectral Analysis,2015,35(8):2333-2338.
[18]赵志曼,刘子瑜,李帅,等.磷石膏炒制-酸浸法脱色增白研究[J].低温建筑技术,2016,38(5):9-11.ZHAO Z M,LIU Z Y,LI S,et al.Study on decoloring and whitening of phosphogypsum by coupling stir frying and acid leaching[J].Low Temperature Architecture Technology,2016,38(5):9-11.
[19]师梦,杨保俊,刘磊,等.磷石膏脱色增白工艺条件的研究[J].合肥工业大学学报:自然科学版,2013,36(2):212-216.SHI M,YANG B J,LIU L,et al.Study of technological conditions of decoloring and whitening of phosphogypsum[J].Journal of Hefei University of Technology(Natural Science),2013,36(2):212-216.
[20]曾亚平,党亚固,费德君.制备高品质磷石膏的湿法磷酸新工艺的开发[J].化工进展,2015,34(1):167-172.ZENG Y P,DANG Y G,FEI D J.Development of the new wet phosphoric process of preparing high-quality phosphogypsum[J].Chemical Industry and Engineering Progress,2015,34(1):167-172.
[21]ZHI Y,LIU J.Surface modification of activated carbon for enhanced adsorption of perfluoroalkyl acids from aqueous solutions[J].Chemosphere,2016,144:1224-1232.
[22]RECHNIA P,MALAIKA A,KOZ?OWSKI M.Synthesis of tert-amyl methyl ether(TAME)over modified activated carbon catalysts[J].Fuel,2015,154:338-345.