Chemical Modeling of Nesquehonite Solubility in Li+Na+K+NH4+Mg+Cl+H2O System with a Speciation-based Approach

Chinese Journal of Chemical Engineering ›› 2012, Vol. 20 ›› Issue (2): 267-276.

• CHEMICAL ENGINEERING THERMODYNAMICS • 上一篇下一篇

Chemical Modeling of Nesquehonite Solubility in Li+Na+K+NH₄+Mg+Cl+H₂O System with a Speciation-based Approach

王道广, 李志宝

Key Laboratory of Green Process and Engineering, National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China

收稿日期:2011-03-28 修回日期:2011-08-09 出版日期:2012-04-28 发布日期:2012-05-02
通讯作者: LI Zhibao
基金资助:
Supported by the National Natural Science Foundation of China (21076212,21076213,21146006);the National Basic Research Program of China (2009CB219904);Key Program in Science and Technology of Qinghai Province (2010-G-A4)

Chemical Modeling of Nesquehonite Solubility in Li+Na+K+NH₄+Mg+Cl+H₂O System with a Speciation-based Approach

WANG Daoguang, LI Zhibao

Key Laboratory of Green Process and Engineering, National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China

Received:2011-03-28 Revised:2011-08-09 Online:2012-04-28 Published:2012-05-02
Supported by:
Supported by the National Natural Science Foundation of China (21076212,21076213,21146006);the National Basic Research Program of China (2009CB219904);Key Program in Science and Technology of Qinghai Province (2010-G-A4)

摘要/Abstract

摘要： A chemical model,based on Pitzer activity coefficient model,is developed with a speciation approach to describe the solubility and chemistry of nesquehonite in concentrated chloride solutions.The chemical equilibrium constants for nesquehonite and aqueous species,i.e. MgCO₃⁰ MgHCO₃⁺,and MgOH⁺,are precisely calculated as a function of temperature according to the Van’t Hoff equation by use of standard Gibbs free energy,standard formation enthalpy and heat capacity.The most recent solubility data are regressed to obtain new Pitzer parameters with good agreement.The predictive ability of the new model is improved significantly in comparison with previous models.The behavior of speciation chemistry for nesquehonite in various chloride media is explained through this modeling work on the basis of the Mg/CO₃^2- bearing species distribution,activity coefficient and pH changes.

关键词: chemical modeling, speciation, equilibrium, nesquehonite solubility

Abstract: A chemical model,based on Pitzer activity coefficient model,is developed with a speciation approach to describe the solubility and chemistry of nesquehonite in concentrated chloride solutions.The chemical equilibrium constants for nesquehonite and aqueous species,i.e. MgCO₃⁰ MgHCO₃⁺,and MgOH⁺,are precisely calculated as a function of temperature according to the Van’t Hoff equation by use of standard Gibbs free energy,standard formation enthalpy and heat capacity.The most recent solubility data are regressed to obtain new Pitzer parameters with good agreement.The predictive ability of the new model is improved significantly in comparison with previous models.The behavior of speciation chemistry for nesquehonite in various chloride media is explained through this modeling work on the basis of the Mg/CO₃^2- bearing species distribution,activity coefficient and pH changes.

Key words: chemical modeling, speciation, equilibrium, nesquehonite solubility

王道广, 李志宝. Chemical Modeling of Nesquehonite Solubility in Li+Na+K+NH₄+Mg+Cl+H₂O System with a Speciation-based Approach[J]. Chinese Journal of Chemical Engineering, 2012, 20(2): 267-276.

WANG Daoguang, LI Zhibao. Chemical Modeling of Nesquehonite Solubility in Li+Na+K+NH₄+Mg+Cl+H₂O System with a Speciation-based Approach[J]. Chin.J.Chem.Eng., 2012, 20(2): 267-276.

参考文献

1 Hänchen,M.,Prigiobbe,V.,Baciocchil,R.,Mazzotti,M.,“Precipitation in the Mg-carbonate system-effects of temperature and CO₂ pressure”,Chem.Eng.Sci.,63,1012-1028(2008).
2 Königsberger,E.,Königsberger,L.C.,Gamsjäger,H.,“Low-temperature thermodynamic model for the system Na₂CO₃-MgCO₃-CaCO₃-H₂O”, Geochim.Cosmochim.Acta,63,3105-3119(1999).
3 Hopkinson,L.,Rutt,K.,Cressey,G.,“The transformation of nesquehonite to hydromagnesite in the system CaO-MgO-H₂O-CO₂: An experimental spectroscopic study”,The Journal of Geology,116,387-400(2008).
4 Kloprogge,J.T.,Martens,W.N.,Nothdurft,L.,Duong,L.V.,Webb, G.E.,“Low temperature synthesis and characterization of nesquehonite”,Journal of Materials Science Letters,22,825v829(2003).
5 Giester,G.,Lengauer,C.L.,Rieck,B.,“The crystal structure of nesquehonite,MgCO₃·3H₂O,from Lavrion,Greece”,Mineralogy and Petrology,70,153-163(2000).
6 Wang,Y.,Li,Z.B.,Demopoulos,G.P.,“Controlled precipitation of nesquehonite by the reaction of MgCl₂ with(NH₄)₂CO₃ at 303 K”,J. Cryst.Growth,310,1220-1227(2007).
7 Cheng,W.T.,Li,Z.B.,“Precipitation of nesquehonite from homogeneous supersaturated solutions”,Cryst.Res.Technol.,44,937-947 (2009).
8 Cheng,W.T.,Li,Z.B.,Demopoulos,G.P.,“Effect of temperature on the preparation of magnesium carbonate hydrates by reaction of MgCl₂ with Na2CO₃”,Chin.J.Chem.Eng.,17,661-669(2009).
9 Park,A.A.,“Carbon dioxide sequestration:Chemical and physical activation of aqueous carbonation of Mg-bearing minerals and pH swing process”,Ph.D.Dissertation,The Ohio State University,USA (2005).
10 Ferrini,V.,Vito,C.D.,Mignardi,S.,“Synthesis of nesquehonite by reaction of gaseous CO₂ with Mg chloride solution:Its potential role in the sequestration of carbon dioxide”,J.Hazardous Materials,168,832-837(2009).
11 Ballirano,P.,Vito,C.D.,Ferrini,V.,Mignardi,S.,“The thermal behavior and structural stability of nesquehonite,MgCO₃·3H₂O,evaluated by in situ laboratory parallel-beam X-ray powder diffraction: New constraints on CO₂ sequestration within minerals”,J.Hazardous Materials,178,522-528(2010).
12 Demopoulos,G.P.,“Aqueous precipitation and crystallization for the production of particulate solids with desired properties”,Hydrometallurgy,96,199-214(2009).
13 Dong,M.,Li,Z.B.,Mi,J.G.,Demopoulos,G.P.,“Solubility and stability of nesquehonite(MgCO₃·3H₂O)in mixed NaCl,KCl,MgCl₂ and NH₄Cl solutions”,J.Chem.Eng.Data,53,2586-2593(2008).
14 Dong,M.,Li,Z.B.,Mi,J.G.,Demopoulos,G.P.,“Solubility and stability of nesquehonite(MgCO₃·3H₂O)in mixed NaCl+MgCl₂, NH₄Cl+MgCl₂,LiCl and LiCl+MgCl₂ solutions”,J.Chem.Eng. Data,54,3002-3007(2009).
15 Harvie,C.E.,M?ller,N.,Weare,J.H.,“The prediction of mineral solubilities in natural waters:Na-K-Mg-Ca-H-Cl-SO₄-OH-HCO₃CO₃-CO₂-H₂O system to high ionic strengths at 25°C”,Geochim. Cosmochim.Acta,48,723-751(1984).
16 Marion,G.M.,“Carbonate mineral solubility at low temperatures in the Na-K-Mg-Ca-H-Cl-SO₄-OH-HCO₃-CO₃-CO₂-H₂O system”,Geochim.Cosmochim.Acta,65,1883-1896(2001).
17 Nakayama,F.S.,“Magnesium complex and ion-pair in MgCO₃-CO₂ solution system”,J.Chem.Eng.Data,16,178-181(1971).
18 McGee,K.A.,Hostetler,P.B.,“Studies in the system MgO-SiO₂-CO₂-H₂O.IV:The stability of MgOH + from 10 to 90°C”, Am.J.Sci.,275,304-317(1975).
19 Millero,F.J.,Thurmond V.,“The ionization of carbonic acid in Na-Mg-Cl solutions at 25°C”,J.Solution Chem.,12,401-412 (1983).
20 He,S.,Morse,J.W.,“The carbonic acid system and calcite solubility in aqueous Na-K-Ca-Mg-Cl-SO₄ solutions form 0 to 90°C”,Geochim. Cosmochim.Acta.,57,3533-3555(1993).
21 Siebert,R.M.,Hostetler,P.B.,“The stability of the magnesium carbonate ion pair from 10°to 90°C”,Am.J.Sci.,277,716-734 (1977).
22 Bauman,J.E.Jr.,“Thermodynamic measurements of carbonate equilibria involving metal ions”,Inf.Circ.Bur.Mines U.S.Dep.Inter. No,8853,268-274(1981).
23 Harvie,C.E.,Weare,J.H.,“The prediction of mineral solubilities in natural waters:The Na-K-Mg-Ca-Cl-SO₄-H₂O systems from zero to high concentration at 25°C”,Geochim.Cosmochim.Acta,44,981-997(1980).
24 Li,Z.B.,Demopoulos,G.P.,“Speciation-based chemical equilibrium model of CaSO₄ solubility in the H+Na+Ca+Mg+Al+Fe(Ⅱ)+ Cl+SO₄+H₂O system”,Ind.Eng.Chem.Res.,46,6385-6392(2007).
25 Azimi,G.,Papangelakis,V.G.,Dutrizac,J.E.,“Development of an MSE-based chemical model for the solubility of calcium sulphate in mixed chloride-sulphate solutions”,Fluid Phase Equilibria,266,172-186(2008).
26 Azimi,G.,Papangelakis,V.G.,“Thermodynamic modeling and experimental measurement of calcium sulphate solubility in complex aqueous solutions”,Fluid Phase Equilibria,290,88-94(2010).
27 Azimi,G.,Papangelakis,V.G.,“The solubility of gypsum and anhydrite in simulated laterite pressure acid leach solutions up to 250°C”, Hydrometallurgy,102,1-13(2010).
28 Wang,D.G.,Li,Z.B.,“Modeling solid-liquid equilibrium of NH₄Cl-MgCl₂-H₂O system and its application to recovery of NH₄Cl in MgO production”,AIChE J.,57,1595-1606(2011).
29 Pabalan,R.T.,Pitzer,K.S.,“Thermodynamics of concentrated electrolyte mixtures and the prediction of mineral solubilities to high temperatures for mixtures in the system Na-K-Mg-Cl-SO₄-OH-H₂O”, Geochim.Cosmochim.Acta,51,2429-2443(1987).
30 Pitzer,K.S.,“Thermodynamics of electrolytes.I.Theoretical basis and general equations”,J.Phys.Chem.,77,268-277(1973).
31 Pitzer,K.S.,“Theory:Ion interaction approach”,In:Activity Coefficients in Electrolyte Solutions,CRC Press,Boca Raton,75-154 (1991).
32 Zemaitis,J.F.,Clark,D.M.,Rafal,M.,Scrivner,N.C.,Handbook of Aqueous Electrolyte Thermodynamics,Des.Inst.for Phys.Prop. Res.,AIChE,New York(1986).
33 Robie,R.A.,“The heat capacities at low temperatures and entropies at 298.15 K of nesquehonite,MgCO₃·3H₂O,and hydromagnesite”, American Mineralogist,57,1768-1781(1972).
34 Shock,E.L.,Helgeson,H.C.,“Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures:Correlation algorithms for ionic species and equation of state predictions to 5 Kb and 1000°C”,Geochim.Cosmochim. Acta,52,2009-2036(1988).
35 Shock,E.L.,Sassani,D.C.,Willis,M.,Sverjensky,D.A.,“Inorganic species in geologic fluids:Correlations among standard molar thermodynamic properties of aqueous ions and hydroxide complexes”, Geochim.Cosmochim.Acta,61,907-950(1997).
36 Johnson,J.W.,Oelkers,R.H.,Helgeson,H.C.,“Supcrt92:A software package for calculating the standard molal thermodynamic properties of minerals,gases,aqueous,and reactions from 1 to 5000 bar and 0 to 1000°C”,Computers and Geosciences,18,899-947(1992).
37 Song,P.S.,Yao,Y.,“On Pitzer parameters of LiCl and Li2SO₄”, Journal of Salt Lake Science,4,55-63(1996).
38 Balarew,C.,Christov,C.,Valyashko,V.,Petrenko,S.,“Thermodynamics of formation of carnallite type double salts”,J.Solution Chem.,22,173-181(1993).
39 Christov,C.,“Thermodynamics of formation of double salts and mixed crystals from aqueous solutions”,J.Chem.Thermodynamics,37,1036-1060(2005).

[1]	Zhonghao Li, Yuanyuan Yang, Huanong Cheng, Yun Teng, Chao Li, Kangkang Li, Zhou Feng, Hongwei Jin, Xinshun Tan, Shiqing Zheng. Measurement and model of density, viscosity, and hydrogen sulfide solubility in ferric chloride/trioctylmethylammonium chloride ionic liquid[J]. 中国化学工程学报, 2023, 59(7): 210-221.
[2]	Yun-Zhang Liu, Lu-Yao Zhang, Dan He, Li-Zhen Chen, Zi-Shuai Xu, Jian-Long Wang. Solubility measurement, correlation and thermodynamic properties of 2, 3, 4-trichloro-1, 5-dinitrobenzene in fifteen mono-solvents at temperatures from 278.15 to 323.15 K[J]. 中国化学工程学报, 2023, 58(6): 224-233.
[3]	Pengbao Lian, Lizhen Chen, Dan He, Guangyuan Zhang, Zishuai Xu, Jianlong Wang. Crystallization thermodynamics of 2,4(5)-dinitroimidazole in binary solvents[J]. 中国化学工程学报, 2023, 57(5): 173-182.
[4]	Youqi Li, Xiaopeng Chen, Linlin Wang, Xiaojie Wei, Weijian Nong, Xuejuan Wei, Jiezhen Liang. Measurement and prediction of isothermal vapor–liquid equilibrium of α-pinene + camphene/longifolene + abietic acid + palustric acid + neoabietic acid systems[J]. 中国化学工程学报, 2023, 53(1): 155-169.
[5]	Yimin Zhang, Ruiming Zeng, Yun Zu, Linhua Zhu, Yi Mei, Yongming Luo, Dedong He. Low-temperature dry reforming of methane tuned by chemical speciations of active sites on the SiO₂ and γ-Al₂O₃ supported Ni and Ni-Ce catalysts[J]. 中国化学工程学报, 2022, 48(8): 76-90.
[6]	Pengbao Lian, Lizhen Chen, Daozhen Huang, Jianxin Xu, Zishuai Xu, Cai Cao, Jiaxiang Zhao, Jianlong Wang. Crystallization thermodynamics of 2,4(5)-dinitroimidazole in eleven pure solvents[J]. 中国化学工程学报, 2022, 48(8): 236-243.
[7]	Zhijie Shen, Jingchun Min. Non-equilibrium thermodynamic analysis of coupled heat and moisture transfer across a membrane[J]. 中国化学工程学报, 2022, 44(4): 497-506.
[8]	Lianzheng Zhang, Jie Wang, Lin Yang, Dongmei Xu, Yixin Ma, Jun Gao, Yinglong Wang. Separation of isopropyl alcohol + isopropyl acetate azeotropic mixture: Selection of ionic liquids as entrainers and vapor-liquid equilibrium validation[J]. 中国化学工程学报, 2022, 50(10): 326-334.
[9]	Zhengyu Chen, Xinhui Yao, Dong Guan, Suoqi Zhao, Linzhou Zhang, Chunming Xu. Vacuum residue coking process simulation using molecular-level kinetic model coupled with vapor-liquid phase separation[J]. 中国化学工程学报, 2022, 41(1): 301-310.
[10]	Yonglin Li, He'an Luo, Qiuhong Ai, Kuiyi You, Fei Zhao, Wenlong Xiao. Efficient separation of phenols from coal tar with aqueous solution of amines by liquid-liquid extraction[J]. 中国化学工程学报, 2021, 35(7): 180-188.
[11]	Yang Liu, Yangbo Deng, Junrui Shi, Rujie Xiao, Houping Li. Pore-level numerical simulation of methane-air combustion in a simplified two-layer porous burner[J]. 中国化学工程学报, 2021, 34(6): 87-96.
[12]	Xingang Li, Chuanrui Pang, Hong Li, Xin Gao. Microwave energy inductive fluidized metal particles discharge behavior and its potential utilization in reaction intensification[J]. 中国化学工程学报, 2021, 33(5): 256-267.
[13]	Pengbao Lian, Qiang Liu, Lizhen Chen, Cai Cao, Jiaxiang Zhao, Jianlong Wang. Determination and correlation solubility of 4-nitroimidazole in twelve pure solvents from 278.15 K to 323.15 K[J]. 中国化学工程学报, 2020, 28(10): 2634-2639.
[14]	Yonghui Dou, Huanxin Li, Xiaoqiang Gao, Guoji Liu, Li Xu. Investigation of liquid-liquid equilibrium of the ternary system (water+1,6-diaminohexane+2-methyl-1-propanol or 3-methyl-1-butanol) at different temperatures[J]. 中国化学工程学报, 2020, 28(1): 191-197.
[15]	Peiyao Zheng, Chong Li, Naixin Wang, Jie Li, Quanfu An. The potential of pervaporation for biofuel recovery from fermentation: An energy consumption point of view[J]. 中国化学工程学报, 2019, 27(6): 1296-1306.

Chemical Modeling of Nesquehonite Solubility in Li+Na+K+NH₄+Mg+Cl+H₂O System with a Speciation-based Approach

Chemical Modeling of Nesquehonite Solubility in Li+Na+K+NH₄+Mg+Cl+H₂O System with a Speciation-based Approach

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价