二水硫酸钙在硫酸铵溶液中的溶解度测定
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摘要
采用电感耦合等离子体发射光谱法(ICP-AES)测定了二水硫酸钙在硫酸铵溶液中(298.15~348.15 K)的溶解度,利用E-DH方程对实验数据进行关联,总平均相对偏差为2.81%;并考察了E-UDH方程的理论预测值,与实验值对比,总平均相对偏差为4.13%。实验和理论研究结果表明:在同离子效应和盐效应协同影响下,二水硫酸钙在(NH4)_2SO_4-H_2O体系中溶解度随硫酸铵浓度增加先降低后又增大,在298.15~348.15 K温区内,溶解度突变点硫酸铵浓度为0.07~0.08 mol·kg~(-1);随溶液中硫酸铵浓度增加,温度对二水硫酸钙溶解度的影响更趋显著。研究结果对磷石膏矿化烟气CO_2的过程设计具有指导意义。
The effect of the concentration(0—2.5 mol·kg~(-1)) of ammonium sulfate on the solubility of calcium sulfate dihydrate is measured in inductively coupled plasma-atomic emission spectrometry(ICP-AES) under the conditions of 298.15—348.15 K. The activity coefficient model of extended Debye-Hückel was applied to correlate the experimental data, and the averaged relative deviation were found at 2.81%. Meanwhile, the activity coefficient model of extended UNIQUAC-Debye-Hückel was applied to calculate the solubility of calcium sulfate dihydrate in ammonium sulfate solution, and the experimental data agreed well with the model prediction, with an averaged relative deviation of 4.13%. The theoretical and experimental results show that the solubility of calcium sulfate dihydrate can firstly decrease and then increase with the increasing of the concentration of ammonium sulfate under the conditions of 298.15—348.15 K. At the solubility mutation point the concentration of ammonium sulfate is 0.07—0.08 mol·kg~(-1) under the synergetic effect of common-ion effect and salt effect. There are strong effects of temperature on the solubility of calcium sulfate dihydrate under higher ammonium sulfate concentrations(0.3—2.5 mol·kg~(-1)). The results provide better understanding and theoretical guidance for process design of CO_2 mineralization with phosphogypsum.
The effect of the concentration(0—2.5 mol·kg~(-1)) of ammonium sulfate on the solubility of calcium sulfate dihydrate is measured in inductively coupled plasma-atomic emission spectrometry(ICP-AES) under the conditions of 298.15—348.15 K. The activity coefficient model of extended Debye-Hückel was applied to correlate the experimental data, and the averaged relative deviation were found at 2.81%. Meanwhile, the activity coefficient model of extended UNIQUAC-Debye-Hückel was applied to calculate the solubility of calcium sulfate dihydrate in ammonium sulfate solution, and the experimental data agreed well with the model prediction, with an averaged relative deviation of 4.13%. The theoretical and experimental results show that the solubility of calcium sulfate dihydrate can firstly decrease and then increase with the increasing of the concentration of ammonium sulfate under the conditions of 298.15—348.15 K. At the solubility mutation point the concentration of ammonium sulfate is 0.07—0.08 mol·kg~(-1) under the synergetic effect of common-ion effect and salt effect. There are strong effects of temperature on the solubility of calcium sulfate dihydrate under higher ammonium sulfate concentrations(0.3—2.5 mol·kg~(-1)). The results provide better understanding and theoretical guidance for process design of CO_2 mineralization with phosphogypsum.
引文
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[16]刘仕忠,朱家骅,周加贝,等.(NH4)2SO4-H2O体系中Ca SO4·2H2O溶解度的突变现象[J].磷肥与复肥,2017,32(4):5-8.LIU S Z,ZHU J H,ZHOU J B,et al.Saltation phenomenon of lean production of Ca SO4·2H2O solubility in(NH4)2SO4-H2O system[J].Phosphate&Compound Fertilizer,2017,32(4):5-8.
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[18]李以圭,陆九芳.电解质溶液理论[M].清华大学出版社,2005:62,105-107.LI Y G,LU J F.Theory for Electrolyte Solutions[M].Beijing:Tsinghua University Press,2005:62,105-107.
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[22]WILLIAM L M,RUTH S.Thermodynamics of calcium sulfate dihydrate in aqueous sodium chloride solutions,0-110°1,2[J].Journal of Physical Chemistry,1966,70(12):4015-4027.
[23]吉晓燕,张吕正,陆小华,等.混合电解质水溶液固液平衡计算[J].化工学报,1997,48(5):532-539.JI X Y,ZHANG L Z,LU X H,et al.The solid-liquid equilibrium calculation of mixed electrolyte aqueous solution[J].Journal of Chemical Industry and Engineering(China),1997,48(5):532-539.
[24]孔令启,王渊朴,曹婺,等.乙酸乙酯-间苯二酚-酸性盐水液液相平衡测定及关联[J].化工学报,2016,67(4):1098-1102.KONG L Q,WANG Y P,CAO W,et al.Measurement and correlation of liquid-liquid equilibrium data for acetic ether-resorcinol-acid brine system[J].CIESC Journal,2016,67(4):1098-1102.
[25]CHRISTENSEN C,SANDER B,FREDENSLUND A,et al.Towards the extension of UNIFAC to mixtures with electrolytes[J].Fluid Phase Equilibria,1983,13:297-309.
[26]YAN W,TOPPHOFF M,ROSE C,et al.Prediction of vapor-liquid equilibria in mixed-solvent electrolyte systems using the group contribution concept[J].Fluid Phase Equilibria,1999,162(1/2):97-113.
[27]GARAIA A V,THOMSON K,STENBY E H.Prediction of mineral scale formation in geothermal and oilfield operations using the extended UNIQUAC model(Ⅱ):Carbonate-scaling minerals[J].Geothermics,2006,34(1):61-97.
[28]THOMSON K.Aqueous electrolytes:model parameters and process simulation[D].Denmark:Department of Chemical Engineering Technical University of Denmark,1997.
[29]HAGHTALAB A,PEYVANDI K.Electrolyte-UNIQUAC-NRF model for the correlation of the mean activity coefficient of electrolyte solutions[J].Fluid Phase Equilibria,2009,281(2):163-171.
[30]THOMSON K,RASMUSSEN P,GANI R.Correlation and prediction of thermal properties and phase behavior for a class of aqueous electrolyte systems[J].Chemical Engineering Science,1996,51(14):3675-3683.
[31]MESSNAOUI B,OUIAZZANE S,BOUHAOUSS A,et al.A modified electrolyte-UNIQUAC model for computing the activity coefficient and phase diagrams of electrolytes systems[J].Calphad-computer Coupling of Phase Diagrams&Thermochemistry,2008,32(3):566-576.
[32]BISGAARD T,KADHIM A S.Aktivitetsko efficient model for saltopl?sninger:udvikling af et nyt parameter s?t for ammoniumionen til extended UNIQUAC[D].Denmark:Technical University of Denmark Kgs Lyngby Denmark,2010.
[33]付雪梅.尿素生产解吸及水解系统热力学研究与设备模拟[D].重庆:重庆大学,2011.FU X M.Thermodynamic model and simulation for desorber and hydrolyzer of urea process[D].Chongqing:Chongqing University,2011.
[34]TIAN P,NING P G,CAO K B,et al.Determination and modeling of solubility for Ca SO4·2H2O-NH+4-Cl--SO42--NO3-H2O system[J].Journal of Chemical&Engineering Data,2012,57(12):3664-3671.
[35]HASHEMI S H,DEHGHANI S,DINMOHANNAD M,et al.Prediction of water activity of electrolyte solutions with extended UNIQUAC model[J].Journal of Chemical and Pharmaceutical Research,2017,9(1):247-252.
[2]中华人民共和国国家统计局.中华人民共和国2015年国民经济和社会发展统计公报[N].人民日报,2016-02-29(10).National Bureau of Statistics,the People’s Republic of China.Statistical bulletin of the national economic and social development of the People’s Republic of China in 2015[N].People’s Daily,2016-02-29(10).
[3]张琦,吴佳艺,卢平,等.磁场对氨水吸收烟气中CO2的促进作用[J].化工学报,2017,68(6):2555-2562.ZHANG Q,WU J Y,LU P,et al.CO2 absorption by aqueous ammonia solution with use of external magnetic field[J].CIESC Journal,2017,68(6):2555-2562.
[4]喻健良,郑阳光,闫兴清,等.工业规模CO2管道大孔泄漏过程中的射流膨胀及扩散规律[J].化工学报,2017,68(6):2298-2305.YU J L,ZHENG Y G,YAN X Q,et al.Under-expanded jest and dispersion during big hole leakage of high pressure CO2 pipeline in industrial scale[J].CIESC Journal,2017,68(6):2298-2305.
[5]Al-HWAITI M,Al-KHASHMAN O.Health risk assessment of heavy metals contamination in tomato and green pepper plants grown in soils amended with phosphogypsum waste materials[J].Environmental Geochemistry&Health,2015,37(2):287-304.
[6]包炜军,赵红涛,李会泉,等.磷石膏加压碳酸化转化过程中平衡转化率分析[J].化工学报,2016,68(3):1155-1162.BAO W J,ZHAO H T,LI H Q,et al.Equilibrium conversion analysis of pressurized carbonation with phosphogypsum[J].CIESC Journal,2016,68(3):1155-1162.
[7]ZHU J H,XIE H P,XIA S L,et al.One step conversion technology of carbon dioxide and phosphogypsum:201210223218.4[P].2012-10-22.
[8]李季,周加贝,朱家骅,等.磷石膏强化氨法CO2捕集机理与模型[J].化工学报,2015,66(8):3218-3224.LI J,ZHOU J B,ZHU J H,et al.Mechanism and model of ammoniabased carbon dioxide trapping enhanced by gypsum particles[J].CIESC Journal,2015,66(8):3218-3224.
[9]王子宁,周加贝,朱家骅,等.二水硫酸钙溶解动力学[J].化工学报,2015,66(3):1001-1006.WANG Z N,ZHOU J B,ZHU J H,et al.Dissolution kinetics of calcium sulfate dihydrate[J].CIESC Journal,2015,66(3):1001-1006.
[10]RAINES M A,DEWERS T A.Mixed transport/reaction control of gypsum dissolution kinetics in aqueous solutions and initiation of gypsum karst[J].Chemical Geology,1997,140(1/2):29-48.
[11]DEWERS T,RAINES M.Reply to comment on:mixed transport/reaction control of gypsum dissolution kinetics[J].Chemical Geology,2000,168(3):275-278.
[12]LASAGA A C.Kinetic Theory in the Earth Sciences[M].Princeton:Princeton University Press,1998:2-15.
[13]HILL A E,YANICK N S.Ternary systems.XX.calcium sulfate,ammonium sulfate and water[J].Journal of the American Chemical Society,2002,56(5):1071-1078.
[14]SULLIVAN E C.Calcium sulfate in ammonium sulfate solution1[J].Journal of the American Chemical Society,1905,27(5):529-539.
[15]BELL J M,TABER W C.The solubility of gypsum in solutions of ammonium sulfate[J].J.Phys.Chem.,1906,10(2):121-122.
[16]刘仕忠,朱家骅,周加贝,等.(NH4)2SO4-H2O体系中Ca SO4·2H2O溶解度的突变现象[J].磷肥与复肥,2017,32(4):5-8.LIU S Z,ZHU J H,ZHOU J B,et al.Saltation phenomenon of lean production of Ca SO4·2H2O solubility in(NH4)2SO4-H2O system[J].Phosphate&Compound Fertilizer,2017,32(4):5-8.
[17]顾雪萍,田璐璐,冯连芳,等.基于新UNIFAC基团的尼龙66盐溶解度的计算方法[J].化工学报,2016,67(2):435-441.GU X P,TIAN L L,FENG L F,et al.Thermodynamic modeling with new UNIFAC groups for solubility of Nylon66-salt in water system[J].CIESC Journal,2016,67(2):435-441.
[18]李以圭,陆九芳.电解质溶液理论[M].清华大学出版社,2005:62,105-107.LI Y G,LU J F.Theory for Electrolyte Solutions[M].Beijing:Tsinghua University Press,2005:62,105-107.
[19]BROMLEY L A.Approximate individual ion values ofβ(or B)in extended Debye-Hückel theory for univalent aqueous solutions at298.15 K1[J].Journal of Chemical Thermodynamics,1972,4(5):669-673.
[20]BROMLEY L A.Thermodynamic properties of strong electrolytes in aqueous solutions[J].AICh E Journal,1973,19(2):313-320.
[21]WILLIAM L M,RUTH S,ERNEST V J.Aqueous systems at high temperatures,XIV.solubility and thermodynamic relationships for Ca SO4 in Na Cl-H2O solutions from 40 to 200℃.0 to 4 mole Na Cl[J].Journal of Chemical and Engineering Data,1964,9(2):1467-1468.
[22]WILLIAM L M,RUTH S.Thermodynamics of calcium sulfate dihydrate in aqueous sodium chloride solutions,0-110°1,2[J].Journal of Physical Chemistry,1966,70(12):4015-4027.
[23]吉晓燕,张吕正,陆小华,等.混合电解质水溶液固液平衡计算[J].化工学报,1997,48(5):532-539.JI X Y,ZHANG L Z,LU X H,et al.The solid-liquid equilibrium calculation of mixed electrolyte aqueous solution[J].Journal of Chemical Industry and Engineering(China),1997,48(5):532-539.
[24]孔令启,王渊朴,曹婺,等.乙酸乙酯-间苯二酚-酸性盐水液液相平衡测定及关联[J].化工学报,2016,67(4):1098-1102.KONG L Q,WANG Y P,CAO W,et al.Measurement and correlation of liquid-liquid equilibrium data for acetic ether-resorcinol-acid brine system[J].CIESC Journal,2016,67(4):1098-1102.
[25]CHRISTENSEN C,SANDER B,FREDENSLUND A,et al.Towards the extension of UNIFAC to mixtures with electrolytes[J].Fluid Phase Equilibria,1983,13:297-309.
[26]YAN W,TOPPHOFF M,ROSE C,et al.Prediction of vapor-liquid equilibria in mixed-solvent electrolyte systems using the group contribution concept[J].Fluid Phase Equilibria,1999,162(1/2):97-113.
[27]GARAIA A V,THOMSON K,STENBY E H.Prediction of mineral scale formation in geothermal and oilfield operations using the extended UNIQUAC model(Ⅱ):Carbonate-scaling minerals[J].Geothermics,2006,34(1):61-97.
[28]THOMSON K.Aqueous electrolytes:model parameters and process simulation[D].Denmark:Department of Chemical Engineering Technical University of Denmark,1997.
[29]HAGHTALAB A,PEYVANDI K.Electrolyte-UNIQUAC-NRF model for the correlation of the mean activity coefficient of electrolyte solutions[J].Fluid Phase Equilibria,2009,281(2):163-171.
[30]THOMSON K,RASMUSSEN P,GANI R.Correlation and prediction of thermal properties and phase behavior for a class of aqueous electrolyte systems[J].Chemical Engineering Science,1996,51(14):3675-3683.
[31]MESSNAOUI B,OUIAZZANE S,BOUHAOUSS A,et al.A modified electrolyte-UNIQUAC model for computing the activity coefficient and phase diagrams of electrolytes systems[J].Calphad-computer Coupling of Phase Diagrams&Thermochemistry,2008,32(3):566-576.
[32]BISGAARD T,KADHIM A S.Aktivitetsko efficient model for saltopl?sninger:udvikling af et nyt parameter s?t for ammoniumionen til extended UNIQUAC[D].Denmark:Technical University of Denmark Kgs Lyngby Denmark,2010.
[33]付雪梅.尿素生产解吸及水解系统热力学研究与设备模拟[D].重庆:重庆大学,2011.FU X M.Thermodynamic model and simulation for desorber and hydrolyzer of urea process[D].Chongqing:Chongqing University,2011.
[34]TIAN P,NING P G,CAO K B,et al.Determination and modeling of solubility for Ca SO4·2H2O-NH+4-Cl--SO42--NO3-H2O system[J].Journal of Chemical&Engineering Data,2012,57(12):3664-3671.
[35]HASHEMI S H,DEHGHANI S,DINMOHANNAD M,et al.Prediction of water activity of electrolyte solutions with extended UNIQUAC model[J].Journal of Chemical and Pharmaceutical Research,2017,9(1):247-252.