常压水热法下钛白石膏的脱水速率与产物形貌
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摘要
采用常压水热法将工业副产钛白石膏转化为晶体形貌规整的α-半水钛石膏,利用XRD确定了反应产物的相态组成,利用TGA分析了不同条件下不同时刻产物的结晶水含量,利用SEM观测了不同条件下得到的产物晶体形貌,掌握了不同的工艺参数对钛白石膏的脱水速率及其产物形貌的影响。研究结果表明:随着氯化钙含量增加,钛白石膏脱水速率逐渐加快,当氯化钙含量为15%时,40 min内其脱水程度可以达到90%以上,并获得规整的六棱短柱状晶体;而反应物浓度对钛白石膏脱水速率和产物晶体形貌影响不大,但浓度过大时,会造成晶体轻微团聚;随着反应温度的升高,钛白石膏脱水速率加快,当温度为100℃时,40 min内其脱水程度可以达到90%以上,产物呈现规整的六棱短柱状晶体;溶液pH值对钛白石膏脱水速率影响不大,但可以影响晶体的形貌,当pH值为5时,产物呈现规整的六棱短柱状晶体。
The α-hemihydrate titanium gypsum was prepared from titanium gypsum through atmospheric hydrothermal method,XRD test was used to analysis the phase composition of the products,TGA test was used to analysis the crystal water content of products at different time and conditions,SEM test was used to observe the morphology of products.Effects of different factors on the dehydrating rate of titanium gypsum and the crystal morphology of α-hemihydrate titanium gypsum were investigated.The results show that,the dehydrating rate of titanium gypsum increased gradually as the increase of the calcium chloride,when calcium chloride content was15% by mass,the dehydrating rate of titanium gypsum could reach 90% in 40 min and the crystal morphology ofα-hemihydrate titanium gypsum would be short hexagonal prism.However,the content of titanium gypsum played little role on the dehydrating rate of titanium gypsum and the crystal morphology of α-hemihydrate titanium gypsum,but when titanium gypsum was much more enough,the α-hemihydrate titanium gypsum may be conglobation.Moreover,the dehydrate rate of titanium gypsum increased gradually as the increase of reaction temperature,when it is 100 ℃,the dehydrating rate of titanium gypsum could reach 90% in 40 min and the crystal morphology of α-hemihydrate titanium gypsum would be short hexagonal prism.The pH value may also have nothing to do with dehydrating rate of titanium gypsum,but it could control the crystal morphology of α-hemihydrate titanium gypsum.When pH value was 5,the crystal morphology of α-hemihydrate titanium gypsum would be short hexagonal prism.
The α-hemihydrate titanium gypsum was prepared from titanium gypsum through atmospheric hydrothermal method,XRD test was used to analysis the phase composition of the products,TGA test was used to analysis the crystal water content of products at different time and conditions,SEM test was used to observe the morphology of products.Effects of different factors on the dehydrating rate of titanium gypsum and the crystal morphology of α-hemihydrate titanium gypsum were investigated.The results show that,the dehydrating rate of titanium gypsum increased gradually as the increase of the calcium chloride,when calcium chloride content was15% by mass,the dehydrating rate of titanium gypsum could reach 90% in 40 min and the crystal morphology ofα-hemihydrate titanium gypsum would be short hexagonal prism.However,the content of titanium gypsum played little role on the dehydrating rate of titanium gypsum and the crystal morphology of α-hemihydrate titanium gypsum,but when titanium gypsum was much more enough,the α-hemihydrate titanium gypsum may be conglobation.Moreover,the dehydrate rate of titanium gypsum increased gradually as the increase of reaction temperature,when it is 100 ℃,the dehydrating rate of titanium gypsum could reach 90% in 40 min and the crystal morphology of α-hemihydrate titanium gypsum would be short hexagonal prism.The pH value may also have nothing to do with dehydrating rate of titanium gypsum,but it could control the crystal morphology of α-hemihydrate titanium gypsum.When pH value was 5,the crystal morphology of α-hemihydrate titanium gypsum would be short hexagonal prism.
引文
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[2]赵玉静,施惠生.粉煤灰-钛白石膏路基材料的研究[J].建筑材料学报,2000,3(4):328-334
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[12]郭会宾,张兴儒.Na Cl盐溶液制备半水石膏的工艺条件研究[J].青海大学学报(自然科学版),2013,31(2):24-31
[13]JIANG G,WANG H,CHEN Q,et al.Preparation of alpha-calcium sulfate hemihydrate from FGD gypsum in chloride-free Ca(NO3)2solution under mild conditions[J].Fuel,2016,174:235-241
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[15]THOMAS F,DEMOPOULOS G P.The crystal growth kinetics of alpha calcium sulfate hemihydrate in concentrated Ca Cl2-HCl solutions[J].Journal of Crystal Growth,2012,351:9-18
[16]LI Zhibao,DEMOPOULOS G P.Solubility of Ca SO4phase in aqueous HCl+Ca Cl2solutions from 283 K to 353 K[J].Journal of Chemical and Engineering Data,2005,50:1971-1982
[17]刘红霞,彭家惠,瞿金东,等.柠檬酸和p H值对α-半水脱硫石膏晶体形貌的调控及影响[J].硅酸盐通报,2010,29(3):518-523
[18]段珍华,秦鸿根,李岗,等.脱硫石膏制备高强α-半水石膏的晶形改良剂与工艺参数研究[J].新型建筑材料,2008,35(8):1-4
[19]GUAN Baohong,SHEN Zhuoxian,WU Zhongbiao,et al.Effect of pH on the preparation ofα-calcium sulfate hemihydrate from FGD gypsum with the hydrothermal method[J].Journal of the American Ceramic Society,2008,91(12):546-566
[20]LI F,LIU J,YANG G,et al.Effect of p H and succinic acid on the morphology ofα-calcium sulfate hemihydrate synthesized by a salt solution method[J].Journal of Crystal Growth,2013,374:31-36
[21]杭州大学分析化学教研室.化学分析手册:第1册:基础知识与安全知识[M].2版.北京:化学工业出版社,1997:162
[2]赵玉静,施惠生.粉煤灰-钛白石膏路基材料的研究[J].建筑材料学报,2000,3(4):328-334
[3]付克明,朱虹.钛白渣作水泥缓凝剂的应用研究[J].中国矿业,2007,16(2):96-99
[4]茹晓红,李海涛,张新爱,等.可溶磷对常压水热法制备高强α-半水石膏的影响[J].化工学报,2015,66(5):1983-1988
[5]胡宏,何兵兵,薛绍秀.α-半水石膏的制备与应用研究进展[J].新型建筑材料,2015,42(4):44-48
[6]GUAN Baohong,YANG Liuchun,WU Zhongbiao.Preparation of alpha-calcium sulfate hemihydrate form FGD gypsum in KMg containing concentrated Ca Cl2solution under mild conditions[J].Fuel,2009,88:1286-1293
[7]GUAN B,KONG B,FU H,et al.Pilot scale preparation ofα-calcium sulfate hemihydrate from FGD gypsum in Ca-K-Mg aqueous solution under atmospheric pressure[J].Fuel,2012,98:48-54
[8]刘丽丽.脱硫石膏常压盐溶液法制备α-半水石膏影响因素研究[D].绵阳:西南科技大学,2009
[9]邹辰阳.α-半水脱硫石膏常压盐溶液法制备工艺及调晶剂技术机理研究[D].重庆:重庆大学,2011
[10]李林,李琳,孙元喜.常压盐溶液法制备α-半水石膏的工艺参数研究[J].湖南文理学院学报(自然科学版),2005,17(1):31-33
[11]马宪法,官宝红.常压KCl溶液中α-半水石膏的脱水过程[J].硅酸盐学报,2009,37(10):1654-1659
[12]郭会宾,张兴儒.Na Cl盐溶液制备半水石膏的工艺条件研究[J].青海大学学报(自然科学版),2013,31(2):24-31
[13]JIANG G,WANG H,CHEN Q,et al.Preparation of alpha-calcium sulfate hemihydrate from FGD gypsum in chloride-free Ca(NO3)2solution under mild conditions[J].Fuel,2016,174:235-241
[14]THOMAS F,DEMOPOULOS G P.Phase transformation kinetics of calcium sulfate phases in strong Ca Cl2-HCl solutions[J].Hydrometallurgy,2012,129-130:126-134
[15]THOMAS F,DEMOPOULOS G P.The crystal growth kinetics of alpha calcium sulfate hemihydrate in concentrated Ca Cl2-HCl solutions[J].Journal of Crystal Growth,2012,351:9-18
[16]LI Zhibao,DEMOPOULOS G P.Solubility of Ca SO4phase in aqueous HCl+Ca Cl2solutions from 283 K to 353 K[J].Journal of Chemical and Engineering Data,2005,50:1971-1982
[17]刘红霞,彭家惠,瞿金东,等.柠檬酸和p H值对α-半水脱硫石膏晶体形貌的调控及影响[J].硅酸盐通报,2010,29(3):518-523
[18]段珍华,秦鸿根,李岗,等.脱硫石膏制备高强α-半水石膏的晶形改良剂与工艺参数研究[J].新型建筑材料,2008,35(8):1-4
[19]GUAN Baohong,SHEN Zhuoxian,WU Zhongbiao,et al.Effect of pH on the preparation ofα-calcium sulfate hemihydrate from FGD gypsum with the hydrothermal method[J].Journal of the American Ceramic Society,2008,91(12):546-566
[20]LI F,LIU J,YANG G,et al.Effect of p H and succinic acid on the morphology ofα-calcium sulfate hemihydrate synthesized by a salt solution method[J].Journal of Crystal Growth,2013,374:31-36
[21]杭州大学分析化学教研室.化学分析手册:第1册:基础知识与安全知识[M].2版.北京:化学工业出版社,1997:162