Effects of Halide Anions on Water Desalination Based on Crystallization Methods: Freezing and Tetrahydrofuran Hydrate Formation

Document Type : Research Article


Faculty of Chemical, Petroleum and Gas Engineering, Semnan University, Semnan, I.R. IRAN


In this study, water desalination was performed using the freezing method and Tetrahydrofuran hydrate formation in a stationary reactor. The experimental setup includes two coaxial cylinders, in which ice crystals deposit outside the cool inner cylinder; thus the salt concentration increases in the residual brine. In order to evaluate the performance of these methods, the removal percentage of salt was measured by the electrical conductivity instrument. The results show that the removal efficiency decreases with an increasing salt concentration in the freezing method while a different trend is observed in the hydrate formation method. As an important result, the salt removal efficiency of the hydrate formation method was higher than the freezing process. Also, to investigate the effect of the anionic size on the salt removal efficiency, the experiments were performed with NaCl, NaBr, NaF, and NaI, which have the same cations. The results show that the performance of desalination improves by increasing the anionic radius. So the dissolved mineral components are removed in the following order: I¯>Br¯>Cl¯>F¯. The removal of salts of a higher size is further by hydrate-based and freezing desalination.


Main Subjects

[1] James E., "Review of Water Resources and Desalination Technologies", Mater. Chem. Dept, Sandia National Laboratories, (2003).
[2] Mandri Y., Rich A., Mangin D., Abderafi S., Bebon C., Semlali N., Klein J.P., Parametric Study of the Sweating Step in the Seawater Desalination Process By Indirect Freezing, Desal., 269:142–147 (2011).
[3] Rich A., Mandri Y., Mangin D., Rivoire A., Abderafi S., Sea Water Desalination by Dynamic Layer Melt Crystallization: Parametric Study of the Freezing and Sweating Steps, J. Cryst. Growth, 342:110-116 (2012).
[4] Williams P.M., Ahmad M., Connolly B.S., Freeze Desalination: An Assessment of an Ice Maker Machine for Desalting Brines, Desal., 308:219 – 224 (2013).
[5] Park K.N., Hong S.Y., Lee J.W., Kang K.C., Lee Y.C., Ha M.G., Lee J.D., A New Apparatus for Seawater Desalination by Gas Hydrate Process and Removal Characteristics of Dissolved Minerals (Na+, Mg2+, Ca2+, K+, B3+), Desal., 274:91-96 (2011).
[6] Khawaji A.D., Kutubkhanah I.K., Wie J.M., Advances in Seawater Desalination Technologies, Desal., 221: 47–69 (2008).
[7] Rahman MS., M Ahmed., XD Chen., Freezing-Melting Process and Desalination: I. Review of the State-of-the-Art, Sep. Purif. Technol. Rev, 35:59-96 (2006).
[8] Hendrickson H.M., Moulton R.W., "Research and Development of Processes for Desalting Water by Freezing", R&D Report 10, Office of Saline Water, US Dept, (1956).
[9] Karnofsky G., Steinhoff P.F., "Saline Water Conversion by Direct Freezing with Butane", R&D Report 40, Office of Saline Water, US Dept, (1960).
[10] Wiegandt H.F., Harriott P., Leinroth J.P., "Desalting of Seawater by Freezing", R&D Report 376, Office of Saline Water US Dept, (1968).
[12] Xie L., Ma J., Cheng F., Li P., Liu J., Chen W., Wang S., Study on Sea Ice Desalination Technology, Desal., 245:146–154 (2009).
[13] Rodriguez R., Luque S., Alvarez J.R., Coca J., A Comparative Study of Reverse Osmosis and Freeze Concentration for the Removal of Valeric Acid from Wastewaters, Desal., 127: 1-11 (2000).
[14] Wakisaka M., Shirai Y., Sakashita S., Ice Crystallization in a Pilot-Scale Freeze Wastewater Treatment System, Chem. Eng. Prog., 40(3):201–208 (2001).
[15] Miyawaki O., Liu L., Shirai Y., Sakashita S., Kagitani K., Tubular Ice System for Scale-up of Progressive Freeze-Concentration, J. Food. Eng., 69(1):107–113 (2005).
[16] Kayansayan N., Acar M.A., Ice Formation Around a Finned-Tube Heat Exchanger for Cold Thermal Energy Storage, Int. J. Therm. Sci., 45(4):405-418 (2006).
[17] Kalista B., Shin H., Cho J.,  Jang A.M., Current Development and Future Prospect Review of Freeze Desalination, Desal., 447:167-181 (2018).
[18] Sloan E.D., Koh C.A., "Clathrate Hydrates of Natural Gases", Third Ed, CRC Press, Taylor & Francis Group, Boca Raton, (2008).
[19] Ballard A.L., Sloan E.D., Hydrate Phase Diagrams for Methane+ Ethane+ Propane Mixtures, Chem. Eng. Sci., 56:6883-6895 (2001).
[20] Aliev A.M., Yusifov R.Y., Kuliev A.R., Yusifov Y.G., Method of Gas Hydrate Formation for Evaluation of Water Desalination, Russ. J. Appl. Chem., 81:588-591 (2008).
[21] Corak D., Barth T., Skodvin T., Larsen R., Skjetne T., Effect of Subcooling and Amount of Hydrate Former on Formation of Cyclopentane Hydrates in Brine, Desal., 278:268-274 (2011).
[22] Parker A., Potable Water from Sea Water, Nature, 149:184-186 (1942).
[23] Ngan Y.T., Englezos P., Concentration of Mechanical Pulp Mill Effluents and NaCl Solutions through Propane Hydrate Formation, Ind. Eng. Chem. Res., 35:1894-1900 (1996).
[24] Javanmardi J., Moshfeghian M., Energy Consumption and Economic Evaluation of Water Desalination by Hydrate Phenomenon, Appl. Therm. Eng., 23(7):845-857 (2003).
[25] Lu H., Mastsumoto R., Tsuji y., Oda H., Anion Plays a More Important Role Than Cation in Affecting Gas Hydrate Stability in Electrolyte Solution? Recognition from Experimental Results, J. Fluid Phase Equilib., 178(1-2):225-232 (2001).
[27] Kang K.C., Linga P., Nam Park K., June Choi S., Lee J.D., Seawater Desalination by Gas Hydrate Process and Removal Characteristics of Dissolved Ions (Na+, K+, Mg2+, Ca2+, B3+, Cl, SO42−), Desal., 353:84–90 (2014).
[28] Sowa B., Zhang X.H., G. Hartley P., Dunstan E.D., Kozielski A.K., Maeda N., Formation of Ice, Tetrahydrofuran Hydrate, and Methane/Propane Mixed Gas Hydrates in Strong Monovalent Salt Solutions, J. Energy. Fuel., 28:6877−6888 (2014).
[29] Farhang F., Nguyen A.V., Hampton M.A., Influence of Sodium Halides on the Kinetics of CO2  Hydrate Formation, J. Energy. Fuel., 28(2): 1220−1229 (2014).
[30] Ho-Van S., Bouillot B., Douzet J., Herri J.M., Cyclopentane Hydrates – A Candidate for Desalination?, J. Environ. Chem.Eng., 7(5):103359 (2019).
[31] Ling Z., Shi Ch., Li F., Fu Y., Song Y., Desalination and Li+ Enrichment Via Formation of Cyclopentane Hydrate, Sep. Purif. Tech., 231: 115921 (2020).
[33] Khan M.N., Peters C.J., Koh C.A., Desalination Using Gas Hydrates: the Role of Crystal Nucleation, Growth and Separation, Desal., 468: 114049 (2019).
[34] Karamoddin M., Varaminian F., Water Desalination Using R141b Gas Hydrate Formation, Desal. Wate. Treat., 1–7 (2013).
[35] Karamoddin M., Varaminian F., “Water Desalination by Gas Hydrate Formation Process via a New Apparatus”, 2nd International Training Workshop, Conference and Exhibition on Desalination, Iran, Tehran, (2014).