Acidity of different Jordanian Clays characterized by TPD-NH3 and MBOH Conversion
The acidity of different raw Jordanian clays
containing zeolite, bentonite, red and white kaolinite and diatomite
was characterized by means of temperature programmed desorption
(TPD) of ammonia, conversion of 2-methyl-3-butyn-2-ol (MBOH),
FTIR and BET-measurements. FTIR spectra proved presence of
silanol and bridged hydroxyls on the clay surface. The number of
acidic sites was calculated from experimental TPD-profiles. We
observed the decrease of surface acidity correlates with the decrease
of Si/Al ratio except for diatomite. On the TPD-plot for zeolite two
maxima were registered due to different strength of surface acidic
sites. Values of MBOH conversion, product yields and selectivity
were calculated for the catalysis on Jordanian clays. We obtained that
all clay samples are able to convert MBOH into a major product
which is 3-methyl-3-buten-1-yne (MBYNE) catalyzed by acid
surface sites with the selectivity close to 70%. There was found a
correlation between MBOH conversion and acidity of clays
determined by TPD-NH3, i.e. the higher the acidity the higher the
conversion of MBOH. However, diatomite provided the lowest
conversion of MBOH as result of poor polarization of silanol groups.
Comparison of surface areas and conversions revealed the highest
density of active sites for red kaolinite and the lowest for zeolite and
diatomite.
[1] M. Frenke, "Surface acidity of montmorillonites," Clay Clay Miner.,
vol. 22, pp. 435- 441, 1974.
[2] L.I. Bel-chinskaya, O.Yu. Strel-nikova, L.A. Novikova, F. Roessner,
O.V. Voishcheva, "Enhancement of the Adsorption Selectivity of
Nanoporous Clinoptilolite by Hydrophobization with Organosiloxanes,"
Protect. Met.+, vol. 44, pp. 390-393, Apr. 2008.
[3] L. Rodr─▒guez-Gonzalez, F. Hermes, M. Bertmer, "The acid properties of
H-ZSM-5 as studied by NH3-TPD and 27Al-MAS-NMR spectroscopy,"
Appl. Catal. A-Gen., vol. 328, pp. 174-182. 2007.
[4] L. M. Bull, A. K. Cheetham, T. Anupold, A. Reinhold, A. Samoson, J.
Sauer, B. Bussemer, Y. Lee, S. Gann, J. Shore, A. Pines, R. Dupree, ÔÇ×A
high-resolution (17)O NMR study of siliceous zeolite faujasite," J. Am.
Chem. Soc., vol. 120, pp. 3510-3511. 1998.
[5] H. Knözinger, S. Huber, ÔÇ×Infrared Spectroscopy of Small and Weakly
Interacting Molecular Probes for Acidic and Basic Zeolites," J. Chem.
Soc. Farad. Trans., vol. 94, no. 15, pp. 2047-2059. 1998.
[6] M. Yurdakoc, M. Akcay, Y. Tonbul, K. Yurdakoc, ÔÇ×Acidity of silicaalumina
catalysts by amine titration using Hammett indicators and FT-IR
study of pyridine adsorption," Turk. J. Chem., vol. 23, no. 3, pp. 319-
327. 1999.
[7] M. A. Aramendia, Y. Aviles, J. A. Benitez, V. Borau, C. Jimenez, J. M.
Marinas, J. R. Ruiz, F. J. Urbano, "Comparative Study of Mg/Al and
Mg/Ga Layered Double Hydroxides," Micropor Mesopor Mat, 29, pp.
319-328. 1999.
[8] J. I. Di Cosimo, C. R. Apesteguia, M. J. L. Gines, E. Iglesia, ÔÇ×Structural
Requirements and Reaction Pathways in Condensation Reactions of
Alcohols on MgyAlOx Catalysts," J. Catal., vol. 190, no. 2, pp. 261-275.
2000.
[9] A. BorCave, A. Auroux, C. Guimon, "Nature and strength of acid sites
in HY zeolites: a multitechnical approach," Microporous Mater., pp.
275-291, Nov. 1997.
[10] H. Lauron-Pernot, F. Luck, J. M. Popa, ÔÇ×Methylbutynol: a new and
simple diagnostic tool for acidic and basic sites of solids," Appl. Catal.,
vol. 78, no. 2, pp. 213-225. 1991.
[11] Y. Ono, T. Baba, ÔÇ×Selective reactions over solid base catalysts," Catal.
Today., vol. 38, no. 3, pp. 321-337. 1997.
[12] H. Lauron-Pernot, "Evaluation of surface acido-basic properties of
inorganic-based solids by model catalytic alcohol reaction networks,"
Cat. Rev., vol. 48, pp. 315-361. 2006.
[13] M. Huang, S. Kaliaguine, "Reactions of methylbutynol on alkaliexchanged
zeolites. A Lewis acid-base selectivity study," Catal. Lett.,
vol. 18, pp. 3373-389. 1993.
[14] U. Meyer, W. F. Hoelderich, ÔÇ×Application of basic zeolites in the
decomposition reaction of 2-methyl-3-butyn-2-ol and the isomerization
of 3-carene," J. Mol. Catal. A-Chem., vol. 142, no. 2, pp. 213-222. 1999.
[15] P. Kuśtrowski, L. Chmielarz, E. Bozek, M. Sawalha, F. Roessner,
ÔÇ×Acidity and basicity of hydrotalcite derived mixed Mg-Al oxides
studied by test reaction of MBOH conversion and temperature
programmed desorption of NH3 and CO2," Mater. Res. Bull., vol. 39,
no. 2, pp. 263-281. 2004.
[16] C. Chizallet, G. Costentin, H. Lauron-Pernot, J.M. Krafft, P. Bazin, J.
Saussey, F. Delbecq, P., Sautet, M. Che, "Role of Hydroxyl Groups in
the Basic Reactivity of MgO: a Theoretical and Experimental Study,"
Oil Gas Sci. Technol., vol. 61, no. 4, pp. 479-488. 2006.
[17] N. Abu Salah, A. Mehyar, K. Al-Rousan, M. Tarawneh, E. Nawasreh,
Abu Arar, Natural Resources Authority, Arabic Report, Jordan. pp. 120-
126. 2002.
[18] M. Al-Ghouti, M.A.M. Khraisheh, S.J. Allen, M.N. Ahmad, "The
removal of dyes from textile wastewater: a study of the physical
characteristics and adsorption mechanisms of diatomaceous earth," J.
Environ. Manage, vol. 69, pp. 229-238. 2003.
[19] M. Nawasreh, Y. Al. Omari, J. Sahawneh, M. Madanat, Natural
resources Authority, Jordan, pp. 101-107. 2006.
[20] L.T. Zhuravlev, "The surface chemistry of amorphous silica. Zhuravlev
model," Colloid. surface A, vol. 173, pp. 1-38. 2000.
[21] I. Rushdi Yousef, F. Maha Tutunji, A. Ghazi, W. Derwish, M. Salem
Musleh, "Chemical and structural properties of Jordanian zeolitic tuffs
and their admixtures with urea and thiourea: potential scavengers for
phenolics in aqueous medium," J. Colloid Interf. Sci., vol. 216, pp. 348-
359. 1999.
[22] P. Yuan, D.Q. Wu, Z. Chen, Z. Lin, G. Diao, J. Peng, "1H MAS NMR
spectra of hydroxyl species on diatomite surface," Chinese Sci. Bull.,
vol. 46, no. 13, pp. 1118-1121. 2001.
[23] P. Yuan, D.Q. Wu, H.P. He, Z.Y. Lin, "The hydroxyl species and acid
sites on diatomite surface: a combined IR and Raman study," Appl. Surf.
Sci., vol. 227, no. 1-4, pp. 30-39. 2004.
[24] B. Fubini, V. Bolis, A. Cavenago, M. Volantel, "Physicochemical
properties of crystalline silica dusts and their possible implication in
various biological responses," Scand. J. Work. Env. Hea., vol. 21, pp. 9-
14. 1995.
[25] M. Alsawalha, F. Roessner, ÔÇ×Insight in to the reaction mechanism of the
conversion of methylbutynol on silica-alumina," React. Kinet. Catal.
Lett., vol. 94, no. 1, pp. 63-69. 2008.
[1] M. Frenke, "Surface acidity of montmorillonites," Clay Clay Miner.,
vol. 22, pp. 435- 441, 1974.
[2] L.I. Bel-chinskaya, O.Yu. Strel-nikova, L.A. Novikova, F. Roessner,
O.V. Voishcheva, "Enhancement of the Adsorption Selectivity of
Nanoporous Clinoptilolite by Hydrophobization with Organosiloxanes,"
Protect. Met.+, vol. 44, pp. 390-393, Apr. 2008.
[3] L. Rodr─▒guez-Gonzalez, F. Hermes, M. Bertmer, "The acid properties of
H-ZSM-5 as studied by NH3-TPD and 27Al-MAS-NMR spectroscopy,"
Appl. Catal. A-Gen., vol. 328, pp. 174-182. 2007.
[4] L. M. Bull, A. K. Cheetham, T. Anupold, A. Reinhold, A. Samoson, J.
Sauer, B. Bussemer, Y. Lee, S. Gann, J. Shore, A. Pines, R. Dupree, ÔÇ×A
high-resolution (17)O NMR study of siliceous zeolite faujasite," J. Am.
Chem. Soc., vol. 120, pp. 3510-3511. 1998.
[5] H. Knözinger, S. Huber, ÔÇ×Infrared Spectroscopy of Small and Weakly
Interacting Molecular Probes for Acidic and Basic Zeolites," J. Chem.
Soc. Farad. Trans., vol. 94, no. 15, pp. 2047-2059. 1998.
[6] M. Yurdakoc, M. Akcay, Y. Tonbul, K. Yurdakoc, ÔÇ×Acidity of silicaalumina
catalysts by amine titration using Hammett indicators and FT-IR
study of pyridine adsorption," Turk. J. Chem., vol. 23, no. 3, pp. 319-
327. 1999.
[7] M. A. Aramendia, Y. Aviles, J. A. Benitez, V. Borau, C. Jimenez, J. M.
Marinas, J. R. Ruiz, F. J. Urbano, "Comparative Study of Mg/Al and
Mg/Ga Layered Double Hydroxides," Micropor Mesopor Mat, 29, pp.
319-328. 1999.
[8] J. I. Di Cosimo, C. R. Apesteguia, M. J. L. Gines, E. Iglesia, ÔÇ×Structural
Requirements and Reaction Pathways in Condensation Reactions of
Alcohols on MgyAlOx Catalysts," J. Catal., vol. 190, no. 2, pp. 261-275.
2000.
[9] A. BorCave, A. Auroux, C. Guimon, "Nature and strength of acid sites
in HY zeolites: a multitechnical approach," Microporous Mater., pp.
275-291, Nov. 1997.
[10] H. Lauron-Pernot, F. Luck, J. M. Popa, ÔÇ×Methylbutynol: a new and
simple diagnostic tool for acidic and basic sites of solids," Appl. Catal.,
vol. 78, no. 2, pp. 213-225. 1991.
[11] Y. Ono, T. Baba, ÔÇ×Selective reactions over solid base catalysts," Catal.
Today., vol. 38, no. 3, pp. 321-337. 1997.
[12] H. Lauron-Pernot, "Evaluation of surface acido-basic properties of
inorganic-based solids by model catalytic alcohol reaction networks,"
Cat. Rev., vol. 48, pp. 315-361. 2006.
[13] M. Huang, S. Kaliaguine, "Reactions of methylbutynol on alkaliexchanged
zeolites. A Lewis acid-base selectivity study," Catal. Lett.,
vol. 18, pp. 3373-389. 1993.
[14] U. Meyer, W. F. Hoelderich, ÔÇ×Application of basic zeolites in the
decomposition reaction of 2-methyl-3-butyn-2-ol and the isomerization
of 3-carene," J. Mol. Catal. A-Chem., vol. 142, no. 2, pp. 213-222. 1999.
[15] P. Kuśtrowski, L. Chmielarz, E. Bozek, M. Sawalha, F. Roessner,
ÔÇ×Acidity and basicity of hydrotalcite derived mixed Mg-Al oxides
studied by test reaction of MBOH conversion and temperature
programmed desorption of NH3 and CO2," Mater. Res. Bull., vol. 39,
no. 2, pp. 263-281. 2004.
[16] C. Chizallet, G. Costentin, H. Lauron-Pernot, J.M. Krafft, P. Bazin, J.
Saussey, F. Delbecq, P., Sautet, M. Che, "Role of Hydroxyl Groups in
the Basic Reactivity of MgO: a Theoretical and Experimental Study,"
Oil Gas Sci. Technol., vol. 61, no. 4, pp. 479-488. 2006.
[17] N. Abu Salah, A. Mehyar, K. Al-Rousan, M. Tarawneh, E. Nawasreh,
Abu Arar, Natural Resources Authority, Arabic Report, Jordan. pp. 120-
126. 2002.
[18] M. Al-Ghouti, M.A.M. Khraisheh, S.J. Allen, M.N. Ahmad, "The
removal of dyes from textile wastewater: a study of the physical
characteristics and adsorption mechanisms of diatomaceous earth," J.
Environ. Manage, vol. 69, pp. 229-238. 2003.
[19] M. Nawasreh, Y. Al. Omari, J. Sahawneh, M. Madanat, Natural
resources Authority, Jordan, pp. 101-107. 2006.
[20] L.T. Zhuravlev, "The surface chemistry of amorphous silica. Zhuravlev
model," Colloid. surface A, vol. 173, pp. 1-38. 2000.
[21] I. Rushdi Yousef, F. Maha Tutunji, A. Ghazi, W. Derwish, M. Salem
Musleh, "Chemical and structural properties of Jordanian zeolitic tuffs
and their admixtures with urea and thiourea: potential scavengers for
phenolics in aqueous medium," J. Colloid Interf. Sci., vol. 216, pp. 348-
359. 1999.
[22] P. Yuan, D.Q. Wu, Z. Chen, Z. Lin, G. Diao, J. Peng, "1H MAS NMR
spectra of hydroxyl species on diatomite surface," Chinese Sci. Bull.,
vol. 46, no. 13, pp. 1118-1121. 2001.
[23] P. Yuan, D.Q. Wu, H.P. He, Z.Y. Lin, "The hydroxyl species and acid
sites on diatomite surface: a combined IR and Raman study," Appl. Surf.
Sci., vol. 227, no. 1-4, pp. 30-39. 2004.
[24] B. Fubini, V. Bolis, A. Cavenago, M. Volantel, "Physicochemical
properties of crystalline silica dusts and their possible implication in
various biological responses," Scand. J. Work. Env. Hea., vol. 21, pp. 9-
14. 1995.
[25] M. Alsawalha, F. Roessner, ÔÇ×Insight in to the reaction mechanism of the
conversion of methylbutynol on silica-alumina," React. Kinet. Catal.
Lett., vol. 94, no. 1, pp. 63-69. 2008.
@article{"International Journal of Chemical, Materials and Biomolecular Sciences:60700", author = "M. AlSawalha and F. Roessner and L. Novikova and L. Bel'chinskaya", title = "Acidity of different Jordanian Clays characterized by TPD-NH3 and MBOH Conversion", abstract = "The acidity of different raw Jordanian clays
containing zeolite, bentonite, red and white kaolinite and diatomite
was characterized by means of temperature programmed desorption
(TPD) of ammonia, conversion of 2-methyl-3-butyn-2-ol (MBOH),
FTIR and BET-measurements. FTIR spectra proved presence of
silanol and bridged hydroxyls on the clay surface. The number of
acidic sites was calculated from experimental TPD-profiles. We
observed the decrease of surface acidity correlates with the decrease
of Si/Al ratio except for diatomite. On the TPD-plot for zeolite two
maxima were registered due to different strength of surface acidic
sites. Values of MBOH conversion, product yields and selectivity
were calculated for the catalysis on Jordanian clays. We obtained that
all clay samples are able to convert MBOH into a major product
which is 3-methyl-3-buten-1-yne (MBYNE) catalyzed by acid
surface sites with the selectivity close to 70%. There was found a
correlation between MBOH conversion and acidity of clays
determined by TPD-NH3, i.e. the higher the acidity the higher the
conversion of MBOH. However, diatomite provided the lowest
conversion of MBOH as result of poor polarization of silanol groups.
Comparison of surface areas and conversions revealed the highest
density of active sites for red kaolinite and the lowest for zeolite and
diatomite.", keywords = "Acidity, Jordanian clay, Methylbutynol conversion,Temperature programmed desorption of ammonia", volume = "5", number = "7", pages = "628-5", }
