Skip to main content
SpringerLink
Log in

DEVELOPING AN EFFICIENT CATALYST BASED ON THERMAL AND ACID-TREATED CLAY FOR THE REMOVAL OF TRACE OLEFINS FROM AROMATIC COMPOUNDS

  • Published:
Clays and Clay Minerals

Abstract

Bentonite is used as a catalyst in the removal of olefins from aromatic compounds and the present study was designed to investigate how its performance might be improved by various treatments. Bentonite from Semnan mine, Iran, was used in the study following initial characterization. In order to investigate the effect of acid and thermal treatments on the removal of olefins from aromatic compounds, bentonite samples were modified using HNO3 at different concentrations (0.15, 0.3, 0.5, 0.7, 1, and 2 M) and were also at temperatures between 100 and 340°C for 3 h. To examine the catalytic activity of bentonite-based catalysts, the samples were evaluated after running batch and continuous experiments. The optimum catalyst was characterized using thermo-programmed desorption (TPD) of NH3 to examine the acidic sites. Scanning Electron Microscopy (SEM) images, nitrogen adsorption-desorption isotherms (BET analysis), and X-ray diffraction (XRD) patterns were used to study the structural changes of the bentonite produced by the acid and thermal activation. The removal of olefins by the catalysts in batch and continuous systems revealed that the sample modified with 0.3 M Nitric acid at 150°C had superior catalytic activity, with olefin conversion remaining at >50% for up to 20 h. Nitrogen adsorption-desorption isotherms showed that acid treatment can produce a mesoporous structure. On the other hand, the TPD analysis indicated that during weak acid treatment, some cations, such as Al3+ and Fe3+, were leached from octahedral sheets and the interlayers of the clay mineral resulting in weak acid sites being generated. Finally, a novel method was proposed and tested for measuring the Bromine Index (BI) using potentiometric titration.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2.
Fig. 3.
Fig. 4.
Fig. 5.
Fig. 6.
Fig. 7.
Fig. 8.
Fig. 9.
Fig. 10.

Similar content being viewed by others

REFERENCES

  • Alothman, Z. A. (2012). A review: Fundamental aspects of silicate mesoporous materials. Materials, 5, 2874–2902.

    Article  Google Scholar 

  • Alsawalha, M., Roessner, F., Novikova, L., & Bel, L. (2011). Acidity of different Jordanian clays characterized by TPD-NH3 and MBOH conversion. International Journal of Chemical and Molecular Engineering, 5, 570–574.

    Google Scholar 

  • Amari, A., Gannouni, H., Khan, M. I., Almesfer, M. K., Elkhaleefa, A. M., & Gannouni, A. (2018). Effect of structure and chemical activation on the adsorption properties of green clay minerals for the removal of cationic dye. Applied Sciences, 8, 2302–2320.

    Article  Google Scholar 

  • Barrett, E. P., Joyner, L. G., & Halenda, P. P. (1951). The determination of pore volume and area distributions in porous substances. I. Computations from nitrogen isotherms. Journal of the American Chemical Society, 73, 373–380.

    Article  Google Scholar 

  • Bradley, W. F., & Grim, R. E. (1951). High temperature thermal effects of clay and related materials. American Mineralogist, 36, 182–201.

    Google Scholar 

  • Centi, G., & Perathoner, S. (2008). Catalysis by layered materials: A review. Microporous and Mesoporous Materials, 107, 3–15.

    Article  Google Scholar 

  • Chen, C., Wu, W., Zeng, X., Jiang, Z., & Shi, L. (2009). Study on several mesoporous materials catalysts applied to the removal of trace olefins from aromatics and commercial sidestream tests. Industrial & Engineering Chemistry Research, 48, 10359–10363.

    Article  Google Scholar 

  • Eisenhour, D. D., & Brown, R. K. (2009). Bentonite and its impact on modern life. Elements, 5, 83–88.

    Article  Google Scholar 

  • Emam, E., Centi, G., Perathoner, S., & Vaccari, A. (2008). Clays as catalysts in petroleum refining industry. Applied Clay Science, 3, 161–198.

    Google Scholar 

  • Franck, H.-G., & Stadelhofer, J. W. (1988). Industrial Aromatic Chemistry. Heidelberg, Berlin: Springer. 460 pp.

    Book  Google Scholar 

  • Genuino, H. C., Muizebelt, I., Heeres, A., Schenk, N. J., Winkelman, J. G. M., & Heeres, H. J. (2019). An improved catalytic pyrolysis concept for renewable aromatics from biomass involving a recycling strategy for co-produced polycyclic aromatic hydrocarbons. Green Chemistry, 21, 3802–3806.

    Article  Google Scholar 

  • Guo, H., Zhang, H., Li, Q., Peng, F., Xiong, L., Wang, C., Hu, A., Yao, S., & Chen, X. (2020). Removal of olefins from reforming aromatic hydrocarbons over metal-halide-modified acid-activated Palygorskite. Energy & Fuels, 34, 9463–9472.

    Article  Google Scholar 

  • Güven, N. (2009). Bentonites – Clays for molecular engineering. Elements, 5, 89–92.

    Article  Google Scholar 

  • Hao, W., Pudasainee, D., Gupta, R., Kashiwabara, T., Alessi, D. S., & Konhauser, K. O. (2019). Effect of acidic conditions on surface properties and metal binding capacity of clay minerals. ACS Earth and Space Chemistry, 3, 2421–2429.

    Article  Google Scholar 

  • Kloprogge, J. T. (1998). Synthesis of smectites and porous pillared clay catalysts: a review. Journal of Porous Materials, 5, 5–41.

    Article  Google Scholar 

  • Kooli, F., Hian, P. C., Weirong, Q., Alshahateet, S. F., & Chen, F. (2006). Effect of the acid-activated clays on the properties of porous clay heterostructures. Journal of Porous Materials, 13, 319–324.

    Article  Google Scholar 

  • Kumar, P., Jasra, R., & Bhat, T. (1995). Evolution of porosity and surface acidity in montmorillonite clay on acid activation. Industrial and Engineering Chemistry Research., 34, 1440–1448.

    Article  Google Scholar 

  • Lagaly, G. (2006). Thermally modified clay minerals. Pp. 289–309 in: Handbook of Clay Science, 1, Elsevier, Amsterdam.

  • Madejová, J., Pentrák, M., Pálková, H., & Komadel, P. (2009). Near-infrared spectroscopy: A powerful tool in studies of acid-treated clay minerals. Vibrational Spectroscopy, 49, 211–218.

    Article  Google Scholar 

  • Mahmoud, S., Hammoudeh, A., & Al-Noaimi, M. (2003). Pretreatment effects on the catalytic activity of Jordanian bentonite. Clays and Clay Minerals, 51, 52–57.

    Article  Google Scholar 

  • Marosz, M., Kowalczyk, A., Gil, B., & Chmielarz, L. (2020). Acid-treated clay minerals as catalysts for dehydration of methanol and ethanol. Clays and Clay Minerals, 68, 23–37.

    Article  Google Scholar 

  • Murilo, F., Luna, T., Cecilia, J. A., Maria, R., & Saboya, A. (2018). Natural and modified montmorillonite clays as catalysts for synthesis of biolubricants. Materials, 11, 1764–1781.

    Article  Google Scholar 

  • Noyan, H., Önal, M., & Sarikaya, Y. (2007). The effect of sulphuric acid activation on the crystallinity, surface area, porosity, surface acidity, and bleaching power of a bentonite. Food Chemistry, 105, 156–163.

    Article  Google Scholar 

  • Pu, X., Liu, N. W., Jiang, Z. H., & Shi, L. (2012). Acidic and catalytic properties of modified clay for removing trace olefin from aromatics and its industrial test. Industrial and Engineering Chemistry Research, 51, 13891–13896.

    Article  Google Scholar 

  • Ross, C., & Shannon, E. (1926). The minerals of bentonite and related clays and their physical properties. Journal of the American Ceramic Society, 9, 77–96.

    Article  Google Scholar 

  • Roth, W. J., Gil, B., Makowski, W., Marszalek, B., & Eliášová, P. (2016). Layer like porous materials with hierarchical structure. Chemical Society Reviews, 45, 3400–3438.

    Article  Google Scholar 

  • Salem, A., & Karimi, L. (2009). Physico-chemical variation in bentonite by sulfuric acid activation. Korean Journal of Chemical Engineering, 26, 980–984.

    Article  Google Scholar 

  • Sulikowski, B. (2006). Nano-structured materials for catalysis. Catalysis Today, 114, 125–332.

    Article  Google Scholar 

  • Tian, Y., Meng, X., Duan, J., & Shi, L. (2012). A novel application of methanesulfonic acid as catalyst for the alkylation of olefins with aromatics. Industrial & Engineering Chemistry Research., 51, 13627–13631.

    Article  Google Scholar 

  • Trombetta, M., Busca, G., Lenarda, M., Storaro, L., Ganzerla, R., Piovesan, L., Lopez, A. J., Alcantara-Rodrìguez, M., & Rodríguez-Castellón, E. (2000). Solid acid catalysts from clays evaluation of surface acidity of mono- and bi-pillared smectites by FT-IR spectroscopy measurements, NH3-TPD and catalytic tests. Applied Catalysis A: General, 193, 55–69.

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, Faculty of Science, Imam Khomeini International University, Qazvin, Iran

    Nooshin Nouri & Hossein Ghasemzadeh

  2. Department of Physical and Computational Chemistry, Faculty of Chemistry and Petroleum Sciences, Shahid Beheshti University, Tehran, Iran

    Mahboubeh Tasviri

Authors
  1. Nooshin Nouri
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Mahboubeh Tasviri
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Hossein Ghasemzadeh
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Mahboubeh Tasviri.

Ethics declarations

Conflict of Interest

The authors declare that they have no conflict of interest.

Additional information

(Received 13 June 2020; revised 11 December 2020; AE: William F. Jaynes)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Nouri, N., Tasviri, M. & Ghasemzadeh, H. DEVELOPING AN EFFICIENT CATALYST BASED ON THERMAL AND ACID-TREATED CLAY FOR THE REMOVAL OF TRACE OLEFINS FROM AROMATIC COMPOUNDS. Clays Clay Miner. 69, 105–116 (2021). https://doi.org/10.1007/s42860-020-00108-3

Download citation

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s42860-020-00108-3

Keywords

Search

Navigation