钛石膏硫酸浸取法提取铁质氧化物及石膏的物相变化
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摘要
硫酸法生产钛白粉副产大量钛石膏,因其含有较多杂质而无法直接利用,目前可采用硫酸酸浸处理提高钛石膏的品质。本文以硫酸为浸取剂,研究钛石膏中铁质氧化物在不同硫酸浓度、反应温度、固液比、反应时间条件下的溶出规律以及酸浸产物的物相变化;采用XRD、XRF、SEM等分析手段,对钛石膏酸浸前后样品的物相、化学成分、形态等进行分析。结果表明,硫酸酸浸可以有效去除钛石膏中铁质氧化物,最佳工艺条件下去除率可达93.14%,白度由原来的8.1提高至54.4。在酸浸过程中随着硫酸浓度、反应温度、固液比等浸取条件的改变,钛石膏中的二水石膏脱水形成半水石膏和无水石膏。采用硫酸酸浸法处理钛石膏,滤液经处理可获得Fe(OH)3,废液可循环利用,将为钛石膏的资源化利用提供新途径。
Titanium gypsum is a by-product in the production of titanium dioxide by sulfuric acid method. The impurities in titanium gypsum limit the usage of it. Sulfuric acid leaching processing can be used to improve the quality of titanium gypsum. Using sulfuric acid as a leaching agent, the dissolution rules of iron oxide in titanium gypsum and the phase change of acid leaching products were investigated under different sulfuric acid concentration, reaction temperature, solid-liquid ratio and reaction time.XRD, XRF, SEM and other analytical methods were used to analyze the phase, chemical composition and morphology of the samples before and after the acid leaching of titanium gypsum. The results show that the sulfuric acid leaching can effectively remove the iron oxide from titanium gypsum, and the removal rate can reach 93.14% under the optimum conditions, and the whitenes increases from 8.1 to 54.4. During the acid leaching process, dehydration of dihydrate gypsum in titanium gypsum forms hemihydrate gypsum and anhydrite as sulfuric acid concentration, reaction temperature, solid-liquid ratio, reaction time changed. Titanium gypsum is treated by sulfuric acid leaching method, Fe(OH)3 can be obtained from the filtrate after treatment. The waste liquid can be recycled, which will provide a new way for the resource utilization of titanium gypsum.
Titanium gypsum is a by-product in the production of titanium dioxide by sulfuric acid method. The impurities in titanium gypsum limit the usage of it. Sulfuric acid leaching processing can be used to improve the quality of titanium gypsum. Using sulfuric acid as a leaching agent, the dissolution rules of iron oxide in titanium gypsum and the phase change of acid leaching products were investigated under different sulfuric acid concentration, reaction temperature, solid-liquid ratio and reaction time.XRD, XRF, SEM and other analytical methods were used to analyze the phase, chemical composition and morphology of the samples before and after the acid leaching of titanium gypsum. The results show that the sulfuric acid leaching can effectively remove the iron oxide from titanium gypsum, and the removal rate can reach 93.14% under the optimum conditions, and the whitenes increases from 8.1 to 54.4. During the acid leaching process, dehydration of dihydrate gypsum in titanium gypsum forms hemihydrate gypsum and anhydrite as sulfuric acid concentration, reaction temperature, solid-liquid ratio, reaction time changed. Titanium gypsum is treated by sulfuric acid leaching method, Fe(OH)3 can be obtained from the filtrate after treatment. The waste liquid can be recycled, which will provide a new way for the resource utilization of titanium gypsum.
引文
[1]钛石膏资源化是钛白粉行业可持续发展的关键[J].中国粉体工业,2012(3):32-33.Titanium gypsum resource is the key to the sustainable development of titanium dioxide industry[J]. China Powder Industry, 2012(3):32-33.
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[6]彭志辉,刘巧玲,彭家惠,等.钛石膏作水泥缓凝剂研究[J].重庆建筑大学学报, 2004(1):93-96.PENG Zhihui, LIU Qiaoling, PENG Jiahui, et al. Study on titanium gypsum as set retarder for cement[J]. Journal of Chongqing Jianzhu University, 2004(1):93-96.
[7]杜传伟,李国忠,陈娟.利用天然石膏形态组成模拟钛石膏及其性能研究[J].建筑材料学报, 2014, 17(3):511-516.DU Chuanwei, LI Guozhong, CHEN Juan. Simulation of tianium gypsum with morphology and composition of natural gypsum and its property[J]. Journal of Building Materials, 2014, 17(3):511-516.
[8]丁明,黄俊俊,王凌云,等.一种钛石膏中铁元素的分离去除工艺:CN105502464A[P]. 2016.DING Ming, HUANG Junjun, WANG Lingyun, Titanium gypsum iron element seperation and remocval process:CN105502464A[P]. 2016.
[9]江莹.钛石膏除铁试验研究[J].化工管理, 2015(34):199-200.JIANG Ying. Experimental study on iron removal from titanium gypsum[J]. Chemical Enterprise Management, 2015(34):199-200.
[10] PéREZ-MORENO S M, GáZQUEZ M J, BOLíVAR J P. CO2sequestration by indirect carbonation of artificial gypsum generated in the manufacture of titanium dioxide pigments[J]. Chemical Engineering Journal, 2015, 262:737-746.
[11]汪潇,刘强,杨留栓,等.钛石膏颗粒物特性及其热重分析[J].硅酸盐通报, 2014, 33(1):212-215.WANG Xiao, LIU Qiang, YANG Liushuan, et al. Analysis of particle characteristics and TG of titanium gypsum[J]. Bulletin of the Chinese Ceramic Society, 2014, 33(1):212-215.
[12] AZDARPOUR A, ASADULLAH M, JUNIN R, et al. Extraction of calcium from red gypsum for calcium carbonate production[J]. Fuel Processing Technology, 2015, 130:12-19.
[13]刘民荣,田颖,赵帅.碱性激发剂对钛石膏-粉煤灰复合胶结材料性能的影响[J].粉煤灰, 2008, 20(6):15-17.LIU Mingrong, TIAN Ying, ZHAO Shuai, et al. Effect of alkali activator on properties of titanium gypsum/fly ash compound cementitious material[J]. Fly Ash, 2008, 20(6):68-74.
[14] FAUZIAH I, ZAUYAH S, JAMAL T. Characterization and land application of red gypsum:a waste product from the titanium dioxide industry[J]. Science of the Total Environment, 1996, 188(2/3):243-251.
[15] WANG W L, ZENG D W, YIN X, et al. Prediction and measurement of gypsum solubility in the systems CaSO4+HMSO4+H2SO4+H2O(HM=Cu, Zn, Ni, Mn)at 298.15K[J]. Industrial&Engineering Chemistry Research, 2012, 51(14):5124-5134.
[16] WANG W L, ZENG D W, CHEN Q Y, et al. Experimental determination and modeling of gypsum and insoluble anhydrite solubility in the system CaSO4-H2SO4-H2O[J]. Chemical Engineering Science, 2013, 101(14):120-129.
[17]倪丽娜,李沪萍,罗康碧,等.磷石膏在低浓度硫酸中的溶解及相态变化[J].化工进展, 2014, 33(3):769-772.NI Lina, LI Huping, LUO Kangbi, et al. Research of the dissolution and phase behavior change on the phosphogypsum in the low concentration of sulfuric acid[J]. Chemical Industry and Engineering Progress, 2014, 33(3):769-772.
[2] AZDARPOUR A, ASADULLAH M, JUNIN R, et al. Direct carbonation of red gypsum to produce solid carbonates[J]. Fuel Processing Technology, 2014, 126(1):429-434.
[3]刘长春,李荣军,刘磊,钛石膏作水泥缓凝剂的试验研究[J].水泥,2006(11):4-6.LIU C C, LI R J,LIU L. Study on application of titanium gypsum as cement retarder[J]. Cement, 2006(11):4-6..
[4] QU D Y, WANG J. Research on titanium gypsum for light-quality wall material[J]. Bulletin of the Chinese Ceramic Society, 2009, 28(5):1064-1070.
[5] AZDARPOUR A, ASADULLAH M, MOHAMMADIAN E, et al.Mineral carbonation of red gypsum via pH-swing process:effect of CO2pressure on the efficiency and products characteristics[J].Chemical Engineering Journal, 2015, 264:425-436.
[6]彭志辉,刘巧玲,彭家惠,等.钛石膏作水泥缓凝剂研究[J].重庆建筑大学学报, 2004(1):93-96.PENG Zhihui, LIU Qiaoling, PENG Jiahui, et al. Study on titanium gypsum as set retarder for cement[J]. Journal of Chongqing Jianzhu University, 2004(1):93-96.
[7]杜传伟,李国忠,陈娟.利用天然石膏形态组成模拟钛石膏及其性能研究[J].建筑材料学报, 2014, 17(3):511-516.DU Chuanwei, LI Guozhong, CHEN Juan. Simulation of tianium gypsum with morphology and composition of natural gypsum and its property[J]. Journal of Building Materials, 2014, 17(3):511-516.
[8]丁明,黄俊俊,王凌云,等.一种钛石膏中铁元素的分离去除工艺:CN105502464A[P]. 2016.DING Ming, HUANG Junjun, WANG Lingyun, Titanium gypsum iron element seperation and remocval process:CN105502464A[P]. 2016.
[9]江莹.钛石膏除铁试验研究[J].化工管理, 2015(34):199-200.JIANG Ying. Experimental study on iron removal from titanium gypsum[J]. Chemical Enterprise Management, 2015(34):199-200.
[10] PéREZ-MORENO S M, GáZQUEZ M J, BOLíVAR J P. CO2sequestration by indirect carbonation of artificial gypsum generated in the manufacture of titanium dioxide pigments[J]. Chemical Engineering Journal, 2015, 262:737-746.
[11]汪潇,刘强,杨留栓,等.钛石膏颗粒物特性及其热重分析[J].硅酸盐通报, 2014, 33(1):212-215.WANG Xiao, LIU Qiang, YANG Liushuan, et al. Analysis of particle characteristics and TG of titanium gypsum[J]. Bulletin of the Chinese Ceramic Society, 2014, 33(1):212-215.
[12] AZDARPOUR A, ASADULLAH M, JUNIN R, et al. Extraction of calcium from red gypsum for calcium carbonate production[J]. Fuel Processing Technology, 2015, 130:12-19.
[13]刘民荣,田颖,赵帅.碱性激发剂对钛石膏-粉煤灰复合胶结材料性能的影响[J].粉煤灰, 2008, 20(6):15-17.LIU Mingrong, TIAN Ying, ZHAO Shuai, et al. Effect of alkali activator on properties of titanium gypsum/fly ash compound cementitious material[J]. Fly Ash, 2008, 20(6):68-74.
[14] FAUZIAH I, ZAUYAH S, JAMAL T. Characterization and land application of red gypsum:a waste product from the titanium dioxide industry[J]. Science of the Total Environment, 1996, 188(2/3):243-251.
[15] WANG W L, ZENG D W, YIN X, et al. Prediction and measurement of gypsum solubility in the systems CaSO4+HMSO4+H2SO4+H2O(HM=Cu, Zn, Ni, Mn)at 298.15K[J]. Industrial&Engineering Chemistry Research, 2012, 51(14):5124-5134.
[16] WANG W L, ZENG D W, CHEN Q Y, et al. Experimental determination and modeling of gypsum and insoluble anhydrite solubility in the system CaSO4-H2SO4-H2O[J]. Chemical Engineering Science, 2013, 101(14):120-129.
[17]倪丽娜,李沪萍,罗康碧,等.磷石膏在低浓度硫酸中的溶解及相态变化[J].化工进展, 2014, 33(3):769-772.NI Lina, LI Huping, LUO Kangbi, et al. Research of the dissolution and phase behavior change on the phosphogypsum in the low concentration of sulfuric acid[J]. Chemical Industry and Engineering Progress, 2014, 33(3):769-772.