Synthesis, Characterization and Application of ZS/HMS Catalyst in the Esterification of Gossypol

Abstract

A solid acid catalyst of zirconium sulfate (ZS) on a pure hexagonal mesoporous silica (HMS) sieve was prepared and characterized by small angle X-ray diffraction, NH3-temperature programmed desorption, and thermogravimetric analysis. The obtained ZS/HMS catalyst displayed a typical mesoporous structure, ZS was well dispersed on the HMS support, and the acidity increased with the amount of ZS loading. Gossypol was extracted from cottonseed cake with acetone as solvent, and then the gossypol solution was esterified with ZS/HMS as catalyst to yield products of acetic acid gossypol. Under the optimal conditions, the conversion efficiency of gossypol was as high as 96.7%.

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S. Dong, M. Zhu and B. Dai, "Synthesis, Characterization and Application of ZS/HMS Catalyst in the Esterification of Gossypol," Green and Sustainable Chemistry, Vol. 2 No. 1, 2012, pp. 8-13. doi: 10.4236/gsc.2012.21002.

Conflicts of Interest

The authors declare no conflicts of interest.

References

[1] R. D. Stipanovic, D. W. Altman, D. L. Begin, G. A. Green- blatt and J. H. Benedict, “Terpenoid Aldehydes in Upland Cottons: Analysis by Aniline and HPLC Methods,” Jour- nal of Agri-cultural and Food Chemistry, Vol. 36, No. 3, 1988, pp. 509-515. doi:10.1021/jf00081a026
[2] A. A. Nomeir, M. B. Abou-Donia and J. Am, “Photode- composition of Gossypol by Ultraviolet Irradiation,” Jour- nal of the American Oil Chemists Society, Vol. 62, No. 1, 1985, pp. 87-89. doi:10.1007/BF02541497
[3] L. L. Hua, J. J. Zhou and H. Y. Han, “Direct Electro- chemiluminescence of CdTe Quantum Dots Based on Room Temperature Ionic Liquid Film and High Sensitiv- ity Sensing of Gossypol,” Electrochimica Acta Elec-tron, Vol. 55, No. 3, 2010, pp. 1265-1271. doi:10.1016/j.electacta.2009.10.038
[4] W. A. Pons, J. Po-minski, W. H. King, J. A. Harris and T. H. Hopper, “Recovery of Gossypol from Cottonseed Gums,” Journal of the American Oil Chemists Society, Vol. 36, No. 8, 1959, pp. 328-332. doi:10.1007/BF02640046
[5] R. D. Stipanovic, J. C. Donovan, A. A. Bell and F. W. Martin, “Factors Interfering in Gossypol Analysis of Okra and Glandless Cottonseed Using Direct Aniline Extrac- tion,” Journal of Agricultural and Food Che-mistry, Vol. 32, No. 4, 1984, pp. 809-810. doi:10.1021/jf00124a027
[6] W. A. Pons, R. A. Pittman and C. L. Hoffpauir, “3-Amino- 1-propanol as a Complexing agent in the Determination of Total Gossypol,” Journal of the American Oil Chem- ists Society, Vol. 35, No. 2, 1958, pp. 93-97. doi:10.1007/BF02672661
[7] S. Furuta, H. Matsuhashi and K. Arata, “Catalytic Action of Sulfated Tin Oxide for Etherification and Esterification in Comparison with Sulfated Zirconia,” Applied Catalysis A: General, Vol. 269, No. 2, 2004, pp. 187-191. doi:10.1016/j.apcata.2004.04.017
[8] J. C. Juan, J. C. Zhang, Y. J. Jiang, W. L. Cao and M. A. Yarmo, “Zirconium Sulfate Supported on Activated Carbon as Catalyst for Esterification of Oleic Acid by n-Bu- tanol under Solvent-Free Conditions,” Catalysis Letters, Vol. 117, No. 3-4, 2007, pp. 153-158. doi:10.1007/s10562-007-9128-3
[9] J. R. Sohn and D. H. Seo, “Preparation of New Solid Superacid Catalyst, Zirconium Sulfate Supported on γ-Alu- mina and Activity for Acid Catalysis,” Catalysis Today, Vol. 87, No. 1-4, 2003, pp. 219-226. doi:10.1016/j.cattod.2003.09.010
[10] C. L. Chen, T. Li, S. Cheng, H. P. Lin, C. J. Bhongale and C. Y. Mou, “Direct Im-pregnation Method for Preparing Sulfated Zirconia Supported on Mesoporous Silica,” Mi- croporous and Mesoporous Materials, Vol. 50, No. 2-3, 2001, pp. 201-208. doi:10.1016/S1387-1811(01)00453-X
[11] J. C. Juan, Y. Jiang, X. J. Meng, W. L. Cao, M. A. Yarmo and H. C. Zhang, “Sup-ported Zirconium Sulfate on Car- bon Nanotubes as Wa-ter-Tolerant Solid Acid Catalyst,” Materials Research Bulletin, Vol. 42, No. 7, 2007, pp. 1278-1285. doi:10.1016/j.materresbull.2006.10.017
[12] C. L. Chen, S. Cheng, H. P. Lin, S. T. Wong and C. Y. Mou, “Sulfated Zirco-nia Catalyst Supported on MCM-41 Mesoporous Molecular Sieve,” Applied Catalysis A: Gen- eral, Vol. 215, No. 1-2, 2001, pp. 21-30. doi:10.1016/S0926-860X(01)00504-X
[13] T. R. Pauly and T. J. Pinnavaia, “Pore Size Modification of Mesoporous HMS Molecular Sieve Silicas with Worm- hole Framework Struc-tures,” Chemistry of Materials, Vol. 13, No. 3, 2001, pp. 987-993. doi:10.1021/cm000762t
[14] J. C. Juan, J. C. Zhang and M. A. Yarmo, “Study of Catalysts Comprising Zirconium Sulfate Supported on a Me- soporous Molecular Sieve HMS Foresterification of Fatty Acids under Solvent-Free Condition,” Applied Catalysis A: General, Vol. 347, No. 2, 2008, pp. 133-141. doi:10.1016/j.apcata.2008.06.004
[15] P. T. Tanev and T. J. Pinnavaia, “A Neutral Templating Route to Mesoporous Mo-lecular Sieves,” Science, Vol. 267, No. 5199, 1995, pp. 865-867. doi:10.1126/science.267.5199.865
[16] S. M. Rlseman, F. E. Massoth, G. M. Dhar and E. M. Eyring, “Fourier Transform Infrared Photoacoustic Spec- troscopy of Pyridine Adsorbed on Silica-Alumina and γ- Alumina,” The Journal of Chemical Physics, Vol. 86, No. 10, 1982, pp.1760-1763.
[17] L. Forni, “Comparison of the Methods for the Determina- tion of Surface Acidity of Solid Catalysts,” Catalysis Re- views—Science and Engineering, Vol. 8, No. 1, 1974, pp. 65-115. doi:10.1080/01614947408071857
[18] G. D. Yadav and A. D. Murkute, “Preparation of the Novel Mesoporous Solid Acid Catalyst UDCaT-4 via Synergism of Persulfated Alumina and Zirconia into Hex- agonal Mesoporous Silica for Alkylation Reactions,” Ad- vanced Synthesis and Catalysis, Vol. 346, No. 4, 2004, pp. 389-394. doi:10.1002/adsc.200303212
[19] D. P. Quintanilla, A. Sánchez, I. Hierro, M. Fajardo and I. Sierra, “Functionalized HMS Mesoporous Silica as Solid Phase Ex-tractant for Pb(II) Prior to Its Determination by Flame Atomic Absorption Spectrometry,” Journal of Se- paration Science, Vol. 30, No. 10, 2007, pp. 1556-1567. doi:10.1002/jssc.200600540

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