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Tuning the Acidity of Montmorillonite by H3PO4-Activation and Supporting WO3 for Catalytic Dehydration of Glycerol to Acrolein

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Clays and Clay Minerals

Abstract

Montmorillonite (Mnt)-based solid acids have a wide range of applications in catalysis and adsorption of pollutants. For such solid acids, the acidic characteristic often plays a significant role in these applications. The objective of the current study was to examine the effects of H3PO4-activation and supporting WO3 on the textural structure and surface acidic properties of Mnt. The Mnt-based solid acid materials were prepared by H3PO4 treatment and an impregnation method with a solution of ammonium metatungstate (AMT) and were examined as catalysts in the dehydration of glycerol to acrolein. The catalysts were characterized by nitrogen adsorption-desorption, powder X-ray diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy, scanning electronic microscopy (SEM), X-ray photoelectron spectroscopy (XPS), diffuse reflectance ultraviolet-visible (DR UV-Vis) spectroscopy, temperature programmed desorption of NH3 (NH3-TPD), diffuse reflectance Fourier-transform infrared (DR FTIR) spectroscopy of adsorbed pyridine, and thermogravimetric (TG) analyses. The phosphoric acid treatment of Mnt created Brönsted and Lewis acid sites and led to increases in specific surface areas, porosity, and acidity. WO3 species influenced total acidity, acid strength, the numbers of Brönsted and Lewis acid sites, and catalytic performances. A high turnover frequency (TOF) value (31.2 h−1) based on a maximal 60.7% yield of acrolein was reached. The correlation of acrolein yield with acidic properties indicated that the cooperative role of Brönsted and Lewis acid sites was beneficial to the formation of acrolein and a little coke deposition (<3.3 wt.%). This work provides a new idea for the design of solid acid catalysts with cooperative Brönsted and Lewis acidity for the dehydration of glycerol.

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References

  • Ali, B., Lan, X. C., Arslan, M. T., Gilani, S. Z. A., Wang, H. J., & Wang, T. F. (2020). Controlling the selectivity and deactivation of H-ZSM-5 by tuning b-axis channel length for glycerol dehydration to acrolein. Journal of Industrial and Engineering Chemistry, 88, 127–136.

    Article  Google Scholar 

  • Baertsch, C. D., Soled, S. L., & Iglesia, E. (2001). Isotopic and chemical titration of acid sites in tungsten oxide domains supported on zirconia. Journal of Physical Chemistry B, 105(7), 1320–1330.

    Article  Google Scholar 

  • Bokade, V. V., & Yadav, G. D. (2011). Heteropolyacid supported on montmorillonite catalyst for dehydration of dilute bio-ethanol. Applied Clay Science, 53, 263–271.

    Article  Google Scholar 

  • Carriço, C. S., Cruz, F. T., Santos, M. B., Pastore, H. O., Andrade, H. M. C., & Mascarenhas, A. J. S. (2013). Efficiency of zeolite MCM-22 with different SiO2/Al2O3 molar ratios in gas phase glycerol dehydration to acrolein. Microporous Mesoporous Materials, 181, 74–82.

    Article  Google Scholar 

  • Catuzo, G. L., Possato, L. G., Sad, M. E., Padro, C., & Martins, L. (2021). Progress of the catalytic deactivation of H-ZSM-5 zeolite in glycerol dehydration. ChemCatChem, 13(20), 4419–4430.

    Article  Google Scholar 

  • Chai, S. H., Wang, H. P., Liang, Y., & Xu, B. G. (2007). Sustainable production of acrolein: Investigation of solid acid–base catalysts for gas-phase dehydration of glycerol. Green Chemistry, 9, 1130–1136.

    Article  Google Scholar 

  • Corà, F., Patel, A., Harrison, N. M., Dovesi, R., & Catlow, C. R. A. (1996). An ab initio Hartree-Fock study of the cubic and tetragonal phases of bulk tungsten trioxide. Journal of the American Chemical Society, 118, 12174–12182.

    Article  Google Scholar 

  • Corma, A., Huber, G. W., Sauvanaud, L., & O’Connor, P. (2008). Biomass to chemicals: Catalytic conversion of glycerol/water mixtures into acrolein, reaction network. Journal of Catalysis, 257, 163–171.

    Article  Google Scholar 

  • Dalil, M., Carnevali, D., Dubois, J. L., & Patience, G. S. (2015). Transient acrolein selectivity and carbon deposition study of glycerol dehydration over WO3/TiO2 catalyst. Chemical Engineering Journal, 270, 557–563.

    Article  Google Scholar 

  • Dalil, M., Carnevali, D., Edake, M., Auroux, A., Jean-Luc Dubois, J. L., & Patience, G. S. (2016). Gas phase dehydration of glycerol to acrolein: Coke on WO3/TiO2 reduces by-products. Journal of Molecular Catalysis A: Chemical, 421, 146–155.

    Article  Google Scholar 

  • Deleplanque, J., Dubois, J. L., Devaux, J. F., & Ueda, W. (2010). Production of acrolein and acrylic acid through dehydration and oxydehydration of glycerol with mixed oxide catalysts. Catalysis Today, 157, 351–358.

    Article  Google Scholar 

  • Ding, J., Wang, L. H., Zhang, Z. Q., Zhao, S. F., Zhao, J. H., Lu, Y., & Huang, J. (2019). Microstructured ZSM-11 catalyst on stainless steel microfibers for improving glycerol dehydration to acrolein. ACS Sustainable Chemistry & Engineering, 7, 16225–16232.

    Article  Google Scholar 

  • García-Fernández, S., Gandarias, I., Requies, J., Güemez, M. B., Bennici, S., Auroux, A., & Arias, P. L. (2015). New approaches to the Pt/WOx/Al2O3 catalytic system behavior for the selective glycerol hydrogenolysis to 1,3-propanediol. Journal of Catalysis, 323, 65–75.

    Article  Google Scholar 

  • Ginjupalli, S. R., Mugawar, S., Pethan, R. N., Balla, P. K., & Komandur, V. R. C. (2014). Vapour phase dehydration of glycerol to acrolein over tungstated zirconia catalysts. Applied Surface Science, 309, 153–159.

    Article  Google Scholar 

  • Ginjupalli, S., Balla, P., Shaik, H., Nekkala, N., Ponnala, B., & Mitta, H. (2019). Comparative study of vapour phase glycerol dehydration over different tungstated metal phosphate acid catalysts. New Journal of Chemistry, 43, 16860–16869.

    Article  Google Scholar 

  • Guo, C. S., Yin, S., Dong, Q., & Sato, T. (2012). Simple route to (NH4)xWO3 nanorods for near infrared absorption. Nanoscale, 4, 3394–3398.

    Article  Google Scholar 

  • Gregg, S. J., & Sing, K. S. W. (1982). Adsorption, surface area and porosity (2nd ed.). Academic Press.

    Google Scholar 

  • Huang, W. J., Liu, J. H., She, Q. M., Zhong, J. Q., Christidis, G. E., & Zhou, C. H. (2021). Recent advances in engineering montmorillonite into catalysts and related catalysis. Catalysis Reviews. https://doi.org/10.1080/01614940.2021.1995163

  • Hunyadi, D., Sajó, I., & Szilágyi, I. M. (2014). Structure and thermal decomposition of ammonium metatungstate. Journal of Thermal Analysis Calorimetry, 116, 329–337.

    Article  Google Scholar 

  • Jiang, X. C., Zhou, C. H., Tesser, R., Serio, M. D., Tong, D. S., & Zhang, J. R. (2018). Coking of catalysts in catalytic glycerol dehydration to acrolein. Industrial Engineering Chemistry Research, 57, 10736–10753.

    Article  Google Scholar 

  • Kalpakli, A. O., Arabaci, A., Kahruman, C., & Yusufoglu, I. (2013). Thermal decomposition of ammonium paratungstate hydrate in air and inert gas atmospheres. International Journal of Refractory Metals & Hard Materials, 37, 106–116.

    Article  Google Scholar 

  • Katryniok, B., Paul, S., Bellière-Baca, V., Rey, P., & Dumeignil, F. (2010). Glycerol dehydration to acrolein in the context of new uses of glycerol. Green Chemistry, 12, 2079–2098.

    Article  Google Scholar 

  • Kim, T., Burrows, A., Kiely, C. J., & Wachs, I. E. (2007). Molecular/electronic structure-surface acidity relationships of model-supported tungsten oxide catalysts. Journal of Catalysis, 246, 370–381.

    Article  Google Scholar 

  • Kruk, M., & Jaroniec, M. (2001). Gas adsorption characterization of ordered organic-inorganic nanocomposite materials. Chemistry of Materials, 13, 3169–3183.

    Article  Google Scholar 

  • Kumar, J. P., Ramacharyulu, P. V. R. K., Prasad, G. K., & Singh, B. (2015). Montmorillonites supported with metal oxide nanoparticles for decontamination of sulfur mustard. Applied Clay Science, 116, 263–272.

    Article  Google Scholar 

  • Lauriol-Garbey, P., Postole, G., Loridant, S., Auroux, A., Belliere-Baca, V., Rey, P., & Millet, J. M. M. (2011). Acid-base properties of niobium-zirconium mixed oxide catalysts for glycerol dehydration by calorimetric and catalytic investigation. Applied Catalysis B: Environmental, 106, 94–102.

    Google Scholar 

  • Liu, D., Yuan, P., Liu, H. M., Tan, D. Y., He, H. P., Zhu, J. X., & Chen, T. H. (2013). Quantitative characterization of the solid acidity of montmorillonite using combined FTIR and TPD based on the NH3 adsorption system. Applied Clay Science, 80, 407–412.

    Article  Google Scholar 

  • Liu, H., Tao, K., Yu, H. B., Zhou, C., Ma, Z., Mao, D. S., & Zhou, S. H. (2015). Effect of pretreatment gases on the performance of WO3/SiO2 catalysts in the metathesis of 1-butene and ethene to propene. Comptes Rendus Chimie, 18, 644–653.

    Article  Google Scholar 

  • Liu, S., Yu, Z. Q., Wang, Y., Sun, Z. C., Liu, Y. Y., Shi, C., & Wang, A. J. (2021). Catalytic dehydration of glycerol to acrolein over unsupported MoP. Catalysis Today, 379, 132–140.

    Article  Google Scholar 

  • Lu, X., Cui, X., & Song, M. (2003). Study on the alteration of chemical composition and structural parameters of modified montmorillonite. Minerals Engineering, 16, 1303–1306.

    Article  Google Scholar 

  • Madejová, J., & Komadel, P. (2001). Baseline studies of the clay minerals society source clays: Infrared methods. Clays and Clay Minerals, 49(5), 410–432.

    Article  Google Scholar 

  • Madejová, J. (2003). FTIR techniques in clay mineral studies. Vibrational Spectroscopy, 31, 1–10.

    Article  Google Scholar 

  • Massa, M., Andersson, A., Finocchio, E., & Guido, B. (2013a). Gas-phase dehydration of glycerol to acrolein over Al2O3-, SiO2-, and TiO2-supported Nb- and W-oxide catalysts. Journal of Catalysis, 307, 170–184.

    Article  Google Scholar 

  • Massa, M., Andersson, A., Finocchio, E., Busca, G., Lenrick, F., & Wallenberg, L. R. (2013b). Performance of ZrO2-supported Nb- and W-oxide in the gas-phase dehydration of glycerol to acrolein. Journal of Catalysis, 297, 93–109.

    Article  Google Scholar 

  • Mojović, Z., Banković, P., Milutinović-Nikolić, A., Nedić, B., & Jovanović, D. (2010). Co-aluminosilicate based electrodes. Applied Clay Science, 48, 179–184.

    Article  Google Scholar 

  • Nadji, L., Massó, A., Delgado, D., Issaadi, R., Rodriguez-Aguado, E., Rodriguez-Castellón, E., & LópezNieto, J. M. L. (2018). Gas phase dehydration of glycerol to acrolein over WO3-based catalysts prepared by non-hydrolytic sol-gel synthesis. RSC Advances, 8, 13344–13352.

    Article  Google Scholar 

  • Palcheva, R., Spojakina, A., Tyuliev, G., Jiratova, K., & Petrov, L. (2007). The effect of nickel on the component state and HDS activity of alumina supported heteropolytungstates. Kinetics and Catalysis, 48(6), 847–852.

    Article  Google Scholar 

  • Pentrák, M., Hronský, V., Pálková, H., Uhlík, P., Komadel, P., & Madejová, J. (2018). Alteration of fine fraction of bentonite from Kopernica (Slovakia) under acid treatment: A combined XRD, FTIR, MAS NMR and AES study. Applied Clay Science, 163, 204–213.

    Article  Google Scholar 

  • Rao, G. S., Rajan, N. P., Sekhar, M. H., Ammaji, S., & Chary, K. V. R. (2014). Porous zirconium phosphate supported tungsten oxide solid acid catalysts for the vapour phase dehydration of glycerol. Journal of Molecular Catalysis A: Chemical, 395, 486–493.

    Article  Google Scholar 

  • Ravindra Reddy, C., Bhat, Y. S., Nagendrappa, G., & Jai Prakash, B. S. (2009). Brønsted and Lewis acidity of modified montmorillonite clay catalysts determined by FT-IR spectroscopy. Catalysis Today, 141, 157–160.

    Article  Google Scholar 

  • Rožić, L., Novaković, T., & Petrović, S. (2010). Modeling and optimization process parameters of acid activation of bentonite by response surface methodology. Applied Clay Science, 48, 154–158.

    Article  Google Scholar 

  • Song, K. S., Zhang, H. B., Zhang, Y. H., Tang, Y., & Tang, K. J. (2013). Preparation and characterization of WOx/ZrO2 nanosized catalysts with high WOx dispersion threshold and acidity. Journal of Catalysis, 299, 119–128.

    Article  Google Scholar 

  • Song, C. W., Li, C., Yin, Y. Y., Xiao, J. K., Zhang, X. N., Song, M. Y., & Dong, W. (2015). Preparation and gas sensing properties of partially broken WO3 nanotubes. Vacuum, 114, 13–16.

    Article  Google Scholar 

  • Soriano, M. D., Concepciόn, P., Nieto, J. M. L., Cavani, F., Guidetti, S., & Trevisanut, C. (2011). Tungsten-vanadium mixed oxides for the oxidehydration of glycerol into acrylic acid. Green Chemistry, 13, 2954–2962.

    Article  Google Scholar 

  • Szilágyi, I. M., Santala, E., Heikkilä, M., Kemell, M., Nikitin, T., Khriachtchev, L., Räsänen, M., Ritala, M., & Leskelä, M. (2011). Thermal study on electrospun polyvinylpyrrolidone/ammonium metatungstate nanofibers: Optimising the annealing conditions for obtaining WO3 nanofibers. Journal of Thermal Analysis and Calorimetry, 105, 73–81.

    Article  Google Scholar 

  • Tong, D. S., Zheng, Y. M., Yu, W. H., Wu, L. M., & Zhou, C. H. (2014). Catalytic cracking of rosin over acid-activated montmorillonite catalysts. Applied Clay Science, 100, 123–128.

    Article  Google Scholar 

  • Ulgen, A., & Hoelderich, W. F. (2011). Conversion of glycerol to acrolein in the presence of WO3/TiO2 catalysts. Applied Catalysis A: General, 400, 34–38.

    Article  Google Scholar 

  • van Olphen, H. V. (1964). Internal mutual flocculation in clay suspensions. Journal of Colloid Science, 19, 313–322.

    Article  Google Scholar 

  • Varadwaj, G. B. B., Rana, S., & Parida, K. (2013). Cs salt of co substituted lacunary phosphotungstate supported K10 montmorillonite showing binary catalytic activity. Chemical Engineering Journal, 215–216, 849–858.

    Article  Google Scholar 

  • Viswanadham, B., Vishwanathan, V., Chary, K. V. R., & Satyanarayana, Y. (2021). Catalytic dehydration of glycerol to acrolein over mesoporous MCM-41 supported heteropolyacid catalysts. Journal of Porous Materials, 28, 1269–1279.

    Article  Google Scholar 

  • Wang, T. H., Liu, T. Y., Wu, D. C., Li, M. H., Chen, J. R., & Teng, S. P. (2010). Performance of phosphoric acid activated montmorillonite as buffer materials for radioactive waste repository. Journal of Hazardous Materials, 173, 335–342.

    Article  Google Scholar 

  • Wang, Z. H., & Liu, L. C. (2021). Mesoporous silica supported phosphotungstic acid catalyst for glycerol dehydration to acrolein. Catalysis Today, 376, 55–64.

    Article  Google Scholar 

  • Wang, Z. H., Lu, X. H., Liang, X., & Ji, J. B. (2020). Improving the stability and efficiency of dimeric fatty acids production by increasing the Brønsted acidity and basal spacing of montmorillonite. European Journal of Lipid Science and Technology, 122, 1900342.

    Article  Google Scholar 

  • Wu, L. M., Tong, D. S., Zhao, L. Z., Yu, W. H., Zhou, C. H., & Wang, H. (2014). Fourier transform infrared spectroscopy analysis for hydrothermal transformation of microcrystalline cellulose on montmorillonite. Applied Clay Science, 95, 74–82.

    Article  Google Scholar 

  • Wu, S. T., She, Q. M., Tesser, R., Serio, M. D., & Zhou, C. H. (2020). Catalytic glycerol dehydration-oxidation to acrylic acid. Catalysis Reviews-Science and Engineering, 62(4), 481–523.

    Article  Google Scholar 

  • Yadav, M. K., Chudasama, C. D., & Jasra, R. V. (2004). Isomerisation of α-pinene using modified montmorillonite clays. Journal of Molecular Catalysis A: Chemical, 216, 51–59.

    Article  Google Scholar 

  • Yu, W. H., Ren, Q. Q., Tong, D. S., Zhou, C. H., & Wang, H. (2014). Clean production of CTAB-montmorillonite: Formation mechanism and swelling behavior in xylene. Applied Clay Science, 97, 222–234.

    Article  Google Scholar 

  • Zatta, L., Ramos, L. P., & Wypych, F. (2013). Acid-activated montmorillonites as heterogeneous catalysts for the esterification of lauric acid with methanol. Applied Clay Science, 80−81, 236–244.

    Article  Google Scholar 

  • Zhou, C. H., Li, G. L., Zhuang, X. Y., Wang, P. P., Tong, D. S., Yang, H. M., Lin, C. X., Li, L., Zhang, H., Ji, S. F., & Yu, W. H. (2017). Roles of texture and acidity of acid-activated sepiolite catalysts in gas-phase catalytic dehydration of glycerol to acrolein. Molecular Catalysis, 434, 219–231.

    Article  Google Scholar 

  • Zhao, H., Zhou, C. H., Wu, L. M., Lou, J. Y., Li, N., Yang, H. M., Tong, D. S., & Yu, W. H. (2013). Catalytic dehydration of glycerol to acrolein over sulfuric acid-activated montmorillonite catalysts. Applied Clay Science, 74, 154–162.

    Article  Google Scholar 

  • Zhao, S. F., Wang, W. D., Wang, L. Z., Wang, W., & Huang, J. (2020). Cooperation of hierarchical pores with strong Brønsted acid sites on SAPO-34 catalysts for the glycerol dehydration to acrolein. Journal of Catalysis, 389, 166–175.

    Article  Google Scholar 

  • Zhao, Y. H., Wang, Y. J., Hao, Q. Q., Liu, Z. T., & Liu, Z. W. (2015). Effective activation of montmorillonite and its application for Fischer-Tropsch synthesis over ruthenium promoted cobalt. Fuel Processing Technology, 136, 87–95.

    Article  Google Scholar 

  • Zhu, R. L., Zhu, L. H., Zhu, J. X., & Xu, L. H. (2008). Structure of cetyltrimethylammonium intercalated hydrobiotite. Applied Clay Science, 42(1–2), 224–231.

    Article  Google Scholar 

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Acknowledgments

This work was supported by the National Natural Scientific Foundation of China (22072136, 21506188), Engineering Research Center of Non-metallic Minerals of Zhejiang Province, Zhejiang Institute of Geology and Mineral Resource, Hangzhou, China (ZD2020K09), and the Zhejiang Provincial Natural Scientific Foundation of China (LY16B030010, LQ19F050004).

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Authors and Affiliations

  1. Zhijiang College, Zhejiang University of Technology, Shaoxing, 312030, China

    Wei Hua Yu & Tian Hao Huang

  2. Research Group for Advanced Materials & Sustainable Catalysis (AMSC), Research Center for Clay Minerals, Breeding Base of State Key Laboratory of Green Chemistry Synthesis Technology, Discipline of Industrial Catalysis, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, 310032, China

    Wei Hua Yu, Bao Zhu, Dong Shen Tong, Kai Deng, Chao Peng Fu & Chun Hui Zhou

  3. Engineering Research Center of Non-metallic Minerals of Zhejiang Province, Zhejiang Institute of Geology and Mineral Resource, Hangzhou, 310007, China

    Chun Hui Zhou

  4. Qing Yang Institute for Industrial Minerals, Youhua, Qingyang, 242804, Anhui, China

    Chun Hui Zhou

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  1. Wei Hua Yu
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Yu, W.H., Zhu, B., Tong, D.S. et al. Tuning the Acidity of Montmorillonite by H3PO4-Activation and Supporting WO3 for Catalytic Dehydration of Glycerol to Acrolein. Clays Clay Miner. 70, 460–479 (2022). https://doi.org/10.1007/s42860-022-00193-6

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