Effect of Hydrochloric Acid on the Structural of Sodic-Bentonite Clay
ABSTRACT
The objective of this work is to determine changes of surface properties of a bentonite after acid activation, using hydrochloric acid solutions (HCl) at room temperature. XRD, FX, FTIR, MEB, and BET analyses of the samples have been carried out to examine the structure of bentonite before and after acid activation. It is found that the raw bentonite is composed of dioctahedral montmorillonite with predominant quantity and certain amounts of quartz, albite and illite, etc. It has an cation exchange capacity (CEC) of 74.32 meq/g which allows it to be characterized as typical sodium bentonite. The changes, at low acid concentrations, are the result from from cation exchange (exchangeable cations with H+ ions). Differences of surface area at high acid concentrations (0.25 - 0.4 M) were caused by structural changes and partial decomposition of the samples. Data of surface area measurements have showed that with increase of concentration of hydrochloric acid, the surface area increased. The maximum value (837.11 m2/g) was reached by the sample activated with 0.4 M HCl. By against, activation with higher concentration (0.6 M) caused a decrease in the surface area.
The objective of this work is to determine changes of surface properties of a bentonite after acid activation, using hydrochloric acid solutions (HCl) at room temperature. XRD, FX, FTIR, MEB, and BET analyses of the samples have been carried out to examine the structure of bentonite before and after acid activation. It is found that the raw bentonite is composed of dioctahedral montmorillonite with predominant quantity and certain amounts of quartz, albite and illite, etc. It has an cation exchange capacity (CEC) of 74.32 meq/g which allows it to be characterized as typical sodium bentonite. The changes, at low acid concentrations, are the result from from cation exchange (exchangeable cations with H+ ions). Differences of surface area at high acid concentrations (0.25 - 0.4 M) were caused by structural changes and partial decomposition of the samples. Data of surface area measurements have showed that with increase of concentration of hydrochloric acid, the surface area increased. The maximum value (837.11 m2/g) was reached by the sample activated with 0.4 M HCl. By against, activation with higher concentration (0.6 M) caused a decrease in the surface area.
Cite this paper
Bendou, S. and Amrani, M. (2014) Effect of Hydrochloric Acid on the Structural of Sodic-Bentonite Clay. Journal of Minerals and Materials Characterization and Engineering, 2, 404-413. doi: 10.4236/jmmce.2014.25045.
Bendou, S. and Amrani, M. (2014) Effect of Hydrochloric Acid on the Structural of Sodic-Bentonite Clay. Journal of Minerals and Materials Characterization and Engineering, 2, 404-413. doi: 10.4236/jmmce.2014.25045.
References
[1] Stephen, G. and Martin, R.T. (1995) Definition of Clay and Clay Minerals: Joint Report of the Aipea Nomenclature and CMS Nomenclature Committees. Clay and Clay Minerals, 43, 255-256.
http://dx.doi.org/10.1346/CCMN.1995.0430213 [2] Grim, R.E. and Güven, N. (1978) Bentonites, Geology, Mineralogy, Properties and Uses, Development in Sedimentology. Vol. 24, Elsevier, Amsterdam. [3] Murray, H.H. (1991) Some Application of Clay Minerals. Applied Clay Science, 5, 379-395.
http://dx.doi.org/10.1016/0169-1317(91)90014-Z [4] Pauling, L. (1967) The Nature of the Chemical Bond. Cornell University Press, New York. [5] Murray, H.H. (2000) Traditional and New Applications for Kaolin, Smectite Andpalygorskite: A General Overview. Applied Clay Science, 17, 207-221. http://dx.doi.org/10.1016/S0169-1317(00)00016-8 [6] Ayari, F., Srasra, E. and Trabelsi-Ayadi, M. (2005) Characterization of Bentonitic Clays and Theiruse as Adsorbent. Desalination, 185, 391-397. http://dx.doi.org/10.1016/j.desal.2005.04.046 [7] Murray, H.H. (1999) Applied Clay Mineralogy Today and Tomorrow. Clay Miner, 34, 39-49.
http://dx.doi.org/10.1180/000985599546055 [8] Christidis, G.E., Scott, P.W. and Dunham, A.C. (1997) Acid Activation and Bleaching Capacity of Bentonitesfrom the Islands of Milos and Chios, Aegean, Greece. Applied Clay Science, 12, 329-347.
http://dx.doi.org/10.1016/S0169-1317(97)00017-3 [9] Joshi, R.C., Achari, G., Horfield, D. and Nagaraj, T.S. (1994) Effect of Heat Treatment on Strength of Clays. Journal of Geotechnical Engineering, 120, 1080-1088, http://dx.doi.org/10.1061/(ASCE)0733-9410(1994)120:6(1080) [10] Juang, R.-S., Lin, S.-H. and Tsao, K.-H. (2002) Mechanism of the Sorption of Phenols from Aqueous Solutions into Surfactant-Modified Montmorillonite. Journal of Colloid and Interface Science, 254, 234-241. http://dx.doi.org/10.1006/jcis.2002.8629 [11] Noyan, H., Önal, M. and Sarikaya, Y. (2007) The Effect of Sulfuric Acid Activation on Crystallinity, Surface Area, Porosity, Surface Acidity and Bleaching Power of a Bentonite. Food Chemistry, 105, 156-163. http://dx.doi.org/10.1016/j.foodchem.2007.03.060 [12] Hassan, M.S. and Abdel-Khalek, N.A. (1998) Beneficiation and Applications of an Egyptian Bentonite. Applied Clay Science, 13, 99-115. http://dx.doi.org/10.1016/S0169-1317(98)00021-0 [13] Jovanovic, N. and Janackovic, J. (1991) Pore Structure and Adsorption Properties of an Acid Activated Bentonite. Applied Clay Science, 6, 59-68. http://dx.doi.org/10.1016/0169-1317(91)90010-7 [14] Komadel, P., Schmidt, D., Madejova, J. and Cicel, B. (1990) Alteration of Smectites by Treatments with Hydrochloric Acid and Sodium Carbonate Solutions. Applied Clay Science, 5, 113-122.
http://dx.doi.org/10.1016/0169-1317(90)90017-J [15] Banat, F.A., Al-Bashir, B., Al-Asheh, S. and Hayajneh, O. (2000) Adsorption of Phenol by Bentonite. Environmental Pollution, 107, 391-398. http://dx.doi.org/10.1016/S0269-7491(99)00173-6 [16] Tyagi, B., Chudasama, C.D. and Jasra, R.V. (2006) Determination of Structural Modification in Acid Activated Montmorillonite Clay by FT-IR Spectroscopy. Spectrochimica Acta Part A, 64, 273-278. [17] Van Olphen, H. and Fripiat, J.J. (1979) Data Handbook for Clay Materials and Other Non-Metallic Minerals. Pergamon Press, Oxford. [18] Novak, I. and Cicel, B. (1978) Dissolution of Smectites in Hydrochloric Acid: II Dissolution Rate as a Function of Crystallochemical Composition. Clays and Clay Minerals, 26, 341-344. [19] Önal, M., Sarikaya, Y. and Alemdaroglu, T. (2002) The Effect of Acid Activation on Some Physicochemical Properties of a Bentonite. Turkish Journal of Chemistry, 26, 409-416. [20] Park, S.J., Seo, D.I. and Lee, J.R. (2002) Surface Modification of Montmorillonite on Surface Acid-Base Characteristics of Clay and Thermal Stability of Epoxy/Clay Nanocomposites. Journal of Colloid and Interface Science, 251, 160-165. http://dx.doi.org/10.1006/jcis.2002.8379 [21] Venaruzzo, J.L., Volzone, C., Rueda, M.L. and Ortiga, J. (2002) Modified Bentonitic Clay Minerals as Adsorbents of CO, CO2 and SO2 Gases. Microporous and Mesoporous Materials, 56, 73-80. http://dx.doi.org/10.1016/S1387-1811(02)00443-2 [22] Carrado, K.A. and Komadel, P. (2009) Bentonites-Versatile Clays: Acid Activation of Bentonites and Polymer-Clay Nanocomposites. Elements, 5, 111-116. [23] Amari, A., Chlendi, M., Gannouni, A. and Bellagi, A. (2010) Optimised Activation of Bentonite for Toluene Adsorption. Applied Clay Science, 47, 457-461. http://dx.doi.org/10.1016/j.clay.2009.11.035 [24] Diaz, F.C. and Sanctos, P.S. (2001) Studies on the Acid Activation of Brazilian Smectitic Clays. Química Nova, 24, 345-353. [25] Pesquera, C., Gonzalez, F., Benito, I., Blanco, C., Mendioroz, S. and Pajares, J. (1992) Passivation of a Montmorillonite by the Silica Created in Acid Activation. Journal of Materials Chemistry, 2, 907-912. http://dx.doi.org/10.1039/jm9920200907 [26] Temuujin, J., Jadamobaa, T., Burmaa, G., Erdenechimeg, S., Amarsanaa, J. and Mackenzie, K.J.D. (2004) Characterization of Acid Activated Montmorillonite from Tuulant (Mongolia). Ceramics International, 30, 251-255. http://dx.doi.org/10.1016/S0272-8842(03)00096-8 [27] Önal, M. and Sarikaya, Y. (2007) Preparation and Characterization of Acid-Activated Bentonite Powders. Powder Technology, 172, 14-18. http://dx.doi.org/10.1016/j.powtec.2006.10.034 [28] Kashani Motlagh, M.M., Youzbashi, A.A. and Amiri Rigi, Z. (2011) Effect of Acid Activation on Structural and Bleaching Properties of Bentonite. Iranian Journal of Materials Science and Engineering, 8, 50-56. [29] Zorica, P.T., Svetlana, B.A., Biljana, M.B., Vesna, A.P., Aleksandar, R.Ð. and Svjetlana, B.C. (2011) Modification of Smectite Structure by Sulphuric Acid and Characteristics of the Modified Smectite. Journal of Agricultural Sciences, 56, 25-35. [30] Kumar, P., Jasra, R.V. and Bhat, T.S.G. (1995) Evolution of Porosity and Surface Acidity in Montmorillonite Clay on Acid Activation. Industrial & Engineering Chemistry Research, 34, 1440-1448.
http://dx.doi.org/10.1021/ie00043a053 [31] Emmerich, K., Madsen, F.T. and Kahr, G. (1999) Dehydroxylation Behavior of Heat-Treated and Steam-Treated Homoionic CIS-Vacant Montmorillonites. Clays and Clay Minerals, 47, 591-604.
http://dx.doi.org/10.1346/CCMN.1999.0470506 [32] Steudel, A., Batenburgm, L.F., Fisher, H.R., Weidler, P.G. and Emmerich, K. (2009) Alteration of Swelling Clays by Acid Treatment. Applied Clay Science, 44, 105-115. http://dx.doi.org/10.1016/j.clay.2009.02.002 [33] Madejová, J., Bujdák, J., Janek, M. and Komadel, P. (1998) Comparative FT-IR Study of Structural Modifications during Acid Treatment of Dioctahedral Smectites and Hectorite. Spectrochimica Acta Part A, 54, 1397-1406. [34] Madejovà, J. (2003) FTIR Techniques in Clay Mineral Studies. Vibrational Spectroscopy, 31, 1-10. http://dx.doi.org/10.1016/S0924-2031(02)00065-6 [35] Kooli, F. and Liu, Y. (2013) Chemical and Thermal Properties of Organoclays Derived from Highly Stable Bentonite in Sulfuric Acid. Applied Clay Science, 83-84, 349-356.
http://dx.doi.org/10.1016/j.clay.2013.07.022 [36] Morgan, D.A., Shaw, D.B., Sidebottom, T.C., Soon, T.C. and Taylor, R.S. (1985) The Function of Bleaching Earths in the Processing of Palm, Palm Kernel and Coconut Oils. Journal of the American Oil Chemists’ Society, 62, 292-299. http://dx.doi.org/10.1007/BF02541394 [37] Kheok, S.C. and Lim, E.E. (1982) Mechanism of Palm Oil Bleaching by Montmorillonites Clay Activated at Various Acid Concentrations. Journal of the American Oil Chemists’ Society, 59, 129-131.
http://dx.doi.org/10.1007/BF02662259
[1] Stephen, G. and Martin, R.T. (1995) Definition of Clay and Clay Minerals: Joint Report of the Aipea Nomenclature and CMS Nomenclature Committees. Clay and Clay Minerals, 43, 255-256.
http://dx.doi.org/10.1346/CCMN.1995.0430213 [2] Grim, R.E. and Güven, N. (1978) Bentonites, Geology, Mineralogy, Properties and Uses, Development in Sedimentology. Vol. 24, Elsevier, Amsterdam. [3] Murray, H.H. (1991) Some Application of Clay Minerals. Applied Clay Science, 5, 379-395.
http://dx.doi.org/10.1016/0169-1317(91)90014-Z [4] Pauling, L. (1967) The Nature of the Chemical Bond. Cornell University Press, New York. [5] Murray, H.H. (2000) Traditional and New Applications for Kaolin, Smectite Andpalygorskite: A General Overview. Applied Clay Science, 17, 207-221. http://dx.doi.org/10.1016/S0169-1317(00)00016-8 [6] Ayari, F., Srasra, E. and Trabelsi-Ayadi, M. (2005) Characterization of Bentonitic Clays and Theiruse as Adsorbent. Desalination, 185, 391-397. http://dx.doi.org/10.1016/j.desal.2005.04.046 [7] Murray, H.H. (1999) Applied Clay Mineralogy Today and Tomorrow. Clay Miner, 34, 39-49.
http://dx.doi.org/10.1180/000985599546055 [8] Christidis, G.E., Scott, P.W. and Dunham, A.C. (1997) Acid Activation and Bleaching Capacity of Bentonitesfrom the Islands of Milos and Chios, Aegean, Greece. Applied Clay Science, 12, 329-347.
http://dx.doi.org/10.1016/S0169-1317(97)00017-3 [9] Joshi, R.C., Achari, G., Horfield, D. and Nagaraj, T.S. (1994) Effect of Heat Treatment on Strength of Clays. Journal of Geotechnical Engineering, 120, 1080-1088, http://dx.doi.org/10.1061/(ASCE)0733-9410(1994)120:6(1080) [10] Juang, R.-S., Lin, S.-H. and Tsao, K.-H. (2002) Mechanism of the Sorption of Phenols from Aqueous Solutions into Surfactant-Modified Montmorillonite. Journal of Colloid and Interface Science, 254, 234-241. http://dx.doi.org/10.1006/jcis.2002.8629 [11] Noyan, H., Önal, M. and Sarikaya, Y. (2007) The Effect of Sulfuric Acid Activation on Crystallinity, Surface Area, Porosity, Surface Acidity and Bleaching Power of a Bentonite. Food Chemistry, 105, 156-163. http://dx.doi.org/10.1016/j.foodchem.2007.03.060 [12] Hassan, M.S. and Abdel-Khalek, N.A. (1998) Beneficiation and Applications of an Egyptian Bentonite. Applied Clay Science, 13, 99-115. http://dx.doi.org/10.1016/S0169-1317(98)00021-0 [13] Jovanovic, N. and Janackovic, J. (1991) Pore Structure and Adsorption Properties of an Acid Activated Bentonite. Applied Clay Science, 6, 59-68. http://dx.doi.org/10.1016/0169-1317(91)90010-7 [14] Komadel, P., Schmidt, D., Madejova, J. and Cicel, B. (1990) Alteration of Smectites by Treatments with Hydrochloric Acid and Sodium Carbonate Solutions. Applied Clay Science, 5, 113-122.
http://dx.doi.org/10.1016/0169-1317(90)90017-J [15] Banat, F.A., Al-Bashir, B., Al-Asheh, S. and Hayajneh, O. (2000) Adsorption of Phenol by Bentonite. Environmental Pollution, 107, 391-398. http://dx.doi.org/10.1016/S0269-7491(99)00173-6 [16] Tyagi, B., Chudasama, C.D. and Jasra, R.V. (2006) Determination of Structural Modification in Acid Activated Montmorillonite Clay by FT-IR Spectroscopy. Spectrochimica Acta Part A, 64, 273-278. [17] Van Olphen, H. and Fripiat, J.J. (1979) Data Handbook for Clay Materials and Other Non-Metallic Minerals. Pergamon Press, Oxford. [18] Novak, I. and Cicel, B. (1978) Dissolution of Smectites in Hydrochloric Acid: II Dissolution Rate as a Function of Crystallochemical Composition. Clays and Clay Minerals, 26, 341-344. [19] Önal, M., Sarikaya, Y. and Alemdaroglu, T. (2002) The Effect of Acid Activation on Some Physicochemical Properties of a Bentonite. Turkish Journal of Chemistry, 26, 409-416. [20] Park, S.J., Seo, D.I. and Lee, J.R. (2002) Surface Modification of Montmorillonite on Surface Acid-Base Characteristics of Clay and Thermal Stability of Epoxy/Clay Nanocomposites. Journal of Colloid and Interface Science, 251, 160-165. http://dx.doi.org/10.1006/jcis.2002.8379 [21] Venaruzzo, J.L., Volzone, C., Rueda, M.L. and Ortiga, J. (2002) Modified Bentonitic Clay Minerals as Adsorbents of CO, CO2 and SO2 Gases. Microporous and Mesoporous Materials, 56, 73-80. http://dx.doi.org/10.1016/S1387-1811(02)00443-2 [22] Carrado, K.A. and Komadel, P. (2009) Bentonites-Versatile Clays: Acid Activation of Bentonites and Polymer-Clay Nanocomposites. Elements, 5, 111-116. [23] Amari, A., Chlendi, M., Gannouni, A. and Bellagi, A. (2010) Optimised Activation of Bentonite for Toluene Adsorption. Applied Clay Science, 47, 457-461. http://dx.doi.org/10.1016/j.clay.2009.11.035 [24] Diaz, F.C. and Sanctos, P.S. (2001) Studies on the Acid Activation of Brazilian Smectitic Clays. Química Nova, 24, 345-353. [25] Pesquera, C., Gonzalez, F., Benito, I., Blanco, C., Mendioroz, S. and Pajares, J. (1992) Passivation of a Montmorillonite by the Silica Created in Acid Activation. Journal of Materials Chemistry, 2, 907-912. http://dx.doi.org/10.1039/jm9920200907 [26] Temuujin, J., Jadamobaa, T., Burmaa, G., Erdenechimeg, S., Amarsanaa, J. and Mackenzie, K.J.D. (2004) Characterization of Acid Activated Montmorillonite from Tuulant (Mongolia). Ceramics International, 30, 251-255. http://dx.doi.org/10.1016/S0272-8842(03)00096-8 [27] Önal, M. and Sarikaya, Y. (2007) Preparation and Characterization of Acid-Activated Bentonite Powders. Powder Technology, 172, 14-18. http://dx.doi.org/10.1016/j.powtec.2006.10.034 [28] Kashani Motlagh, M.M., Youzbashi, A.A. and Amiri Rigi, Z. (2011) Effect of Acid Activation on Structural and Bleaching Properties of Bentonite. Iranian Journal of Materials Science and Engineering, 8, 50-56. [29] Zorica, P.T., Svetlana, B.A., Biljana, M.B., Vesna, A.P., Aleksandar, R.Ð. and Svjetlana, B.C. (2011) Modification of Smectite Structure by Sulphuric Acid and Characteristics of the Modified Smectite. Journal of Agricultural Sciences, 56, 25-35. [30] Kumar, P., Jasra, R.V. and Bhat, T.S.G. (1995) Evolution of Porosity and Surface Acidity in Montmorillonite Clay on Acid Activation. Industrial & Engineering Chemistry Research, 34, 1440-1448.
http://dx.doi.org/10.1021/ie00043a053 [31] Emmerich, K., Madsen, F.T. and Kahr, G. (1999) Dehydroxylation Behavior of Heat-Treated and Steam-Treated Homoionic CIS-Vacant Montmorillonites. Clays and Clay Minerals, 47, 591-604.
http://dx.doi.org/10.1346/CCMN.1999.0470506 [32] Steudel, A., Batenburgm, L.F., Fisher, H.R., Weidler, P.G. and Emmerich, K. (2009) Alteration of Swelling Clays by Acid Treatment. Applied Clay Science, 44, 105-115. http://dx.doi.org/10.1016/j.clay.2009.02.002 [33] Madejová, J., Bujdák, J., Janek, M. and Komadel, P. (1998) Comparative FT-IR Study of Structural Modifications during Acid Treatment of Dioctahedral Smectites and Hectorite. Spectrochimica Acta Part A, 54, 1397-1406. [34] Madejovà, J. (2003) FTIR Techniques in Clay Mineral Studies. Vibrational Spectroscopy, 31, 1-10. http://dx.doi.org/10.1016/S0924-2031(02)00065-6 [35] Kooli, F. and Liu, Y. (2013) Chemical and Thermal Properties of Organoclays Derived from Highly Stable Bentonite in Sulfuric Acid. Applied Clay Science, 83-84, 349-356.
http://dx.doi.org/10.1016/j.clay.2013.07.022 [36] Morgan, D.A., Shaw, D.B., Sidebottom, T.C., Soon, T.C. and Taylor, R.S. (1985) The Function of Bleaching Earths in the Processing of Palm, Palm Kernel and Coconut Oils. Journal of the American Oil Chemists’ Society, 62, 292-299. http://dx.doi.org/10.1007/BF02541394 [37] Kheok, S.C. and Lim, E.E. (1982) Mechanism of Palm Oil Bleaching by Montmorillonites Clay Activated at Various Acid Concentrations. Journal of the American Oil Chemists’ Society, 59, 129-131.
http://dx.doi.org/10.1007/BF02662259