Abstract
Cost-effective, efficient and green solid acid catalysts have been synthesized by incipient wetness impregnation of various weight fractions of phosphomolybdic acid (5, 10, 15 and 25 wt. %) on mechanically and thermally activated coal fly ash. N2 adsorption–desorption, XRD, FT-IR, SEM, SEM–EDX, TEM, TGA, UV–Vis DRS, solid state 31P MAS NMR were used for characterization of as synthesized catalysts. Catalytic active sites were developed on inert surface of coal fly ash by using various activation techniques whose performance was assessed over a series of acylation of various aliphatic alcohols. For rapid and higher catalytic activity, reactions were conducted in microwave heating mode. Impregnation of phosphomolybdic acid generates Lewis acidic sites on coal fly ash surface as inferred by pyridine adsorbed FT-IR studies which were then utilized in acylation reactions. Various reaction parameters like weight fraction of catalysts, molar ratio of reactants, time, temperature, etc. were optimized for attaining highest conversion %. The catalyst with 15 wt. % of phosphomolybdic acid was found to be more efficient and could be recycled up to five reaction cycles with analogous conversion %. Negligible leaching of catalyst was confirmed by hot filtration test. This work suggests an alternative approach for valorisation of industrial solid waste, coal fly ash in development of innovative, economical solid catalysts.
Graphic abstract
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Abd El-Wahab MMM, Said AA (2005) Phosphomolybdic acid supported on silica gel and promoted with alkali metal ions as catalysts for the esterification of acetic acid by ethanol. J Mol Catal A Chem 240:109–118. https://doi.org/10.1016/j.molcata.2005.06.038
Ahmed AI, Samra SE, El-Hakam SA, Khder AS, El-Shenawy HZ, Abo El-Yazeed WS (2013) Characterization of 12-molybdophosphoric acid supported on mesoporous silica MCM-41 and its catalytic performance in the synthesis of hydroquinone diacetate. App Surface Sci 282:217–227. https://doi.org/10.1016/j.apsusc.2013.05.105
Aleixo R, Elvas- Leitão R, Ana FM, Carvalho P, Brigas A, Nunes R, Fernandes A, Rochae J, Martinsa A, Nunes N (2019) Zooming in with QSPR on Friedel-Crafts acylation reactions over modified BEA zeolites. Mol Cat 476:110495. https://doi.org/10.1016/j.mcat.2019.110495
Bachiller-Baeza B, Anderson JA (2004) FTIR and reaction studies of the acylation of anisole with acetic anhydride over supported HPA catalysts. J Catal 228:225–233. https://doi.org/10.1016/j.jcat.2004.08.010
Badday AS, Abdullah AZ, Lee KT (2013) Ultrasound-assisted transesterification of crude Jatropha oil using alumina-supported heteropolyacid catalyst. Appl Energy 105:380–388. https://doi.org/10.1016/j.apenergy.2013.01.028
Bai G, Li T, Yang Y, Zhang H, Lan X, Li F, Han J, Ma Z, Chen Q, Chen G (2012) Microwave-assisted Friedel-Crafts acylation of indole with acetic anhydride over tungstophosphoric acid modified Hβ zeolite. Catal Commun 29:114–117. https://doi.org/10.1016/j.catcom.2012.09.028
Bhandari R, Volli V, Purkait MK (2015) Preparation and characterization of fly ash based mesoporous catalyst for transesterification of soyabean oil. J Environ Chem Eng 3(2):906. https://doi.org/10.1016/j.jece.2015.04.008
Bonda S, Mohanty S, Nayak SK (2014) Surface characterization of modified fly ash for polymer filler applications: a case study with polypropylene. Mater Express 4(5):384–392. https://doi.org/10.1166/mex.2014.1187
Borhade AV, Tope DR, Kushare SS, Thakare SV (2018) Fly ash supported NiO as an efficient catalyst for the synthesis of xanthene and its molecular docking study against plasmodium glutathione reductase. Res Chem Intermediat 44:7459–7478. https://doi.org/10.1007/s11164-018-3567-x
Bryzhin AA, Gantman MG, Buryak AK, Tarkhanova IG (2019) Brønsted acidic SILP-based catalysts with H3PMo12O40 or H3PW12O40 in the oxidative desulfurization of fuels. App Catal B Environ 257:117938. https://doi.org/10.1016/j.apcatb.2019.117938
Cardoso LAM, Alves W, Gonzaga ARE, Aguiar LMG, Andrade HMC (2004) Friedel-Crafts acylation of anisole with acetic anhydride over silica-supported heteropolyphosphotungstic acid (HPW/SiO2). J Mol Catal A Chem 209:189–197. https://doi.org/10.1016/j.molcata.2003.08.022
CEA Reports 2017 (2017). www.cea.nic.in/reports/monthly/executivesummary/2017/exe_summary-12.pdf. Accessed 4 July 2020
Chaterjee A, Hu X, Yuk Lam FL (2019) Modified coal fly ash waste as an efficient heterogeneous catalyst for dehydration of xylose to furfural in biphasic medium. Fuel 239:726. https://doi.org/10.1016/j.fuel.2018.10.138
Chen C, Zhou LP, Zhang QH, Ma H, Miao H, Xu J (2007) Design of bifunctionalized hexagonal mesoporous silicas for selective oxidation of cyclohexane. Nanotechnology 18(21):215603. https://doi.org/10.1088/0957-4484/18/21/215603
Condon JB (2006) Surface area and porosity determination by physisorption measurement and theory, 1st edn. Elsevier, Amsterdam. https://doi.org/10.1016/B978-0-444-51964-1.X5000-6
Corma A, Fornes V, Kolodzeiski W, Martineztriguerol J (1994) Orthophosphoric Acid interactions with ultrastable zeolite-y: infrared and NMR studies. J Catal 145(1):27–36. https://doi.org/10.1006/jcat.1994.1004
Dagar A, Narula AK (2018) Visible-light induced photodegradation of organic contaminants in water using Fe3O4 nanoparticles modified polypyrrole/fly ash cenosphere composite. Russ J Phys Chem A 92:2853–2860. https://doi.org/10.1134/S0036024419010060
Deltcheff CR, Aouissi A, Launay S, Fournier M (1996) Silica-supported 12 molybdophosphoric acid catalysts: Influence of the thermal treatments and of the MO contents on their behaviour, from IR Raman, X-ray diffraction studies, and catalytic reactivity in the methanol oxidation. J Mol Catal A Chem 114:331–342. https://doi.org/10.1016/S1381-1169(96)00336-6
Devassy BM, Lefebvre F, Bohringer W, Fletcher J, Halligudi SB (2005) Synthesis of linear alkyl benzenes over zirconia-supported 12-molybdophosphoric acid catalysts. J Mol Catal A Chem 236:162. https://doi.org/10.1016/j.molcata.2005.03.033
Devassy BM, Shanbhag GV, Halligudi B (2006) Phenol tert-butylation over zirconia-supported 12-molybdophosphoric acid catalyst. J Mol Catal A Chem 247:162–170. https://doi.org/10.1016/j.molcata.2005.11.043
El-Naggar MR, Aglan RF, Sayed MS (2013) Direct incorporation method for the synthesis of molybdophosphate/MCM-41 silica composite: adsorption study of heavy metals from aqueous solutions. J Env Chem Eng 1:516–525. https://doi.org/10.1016/j.jece.2013.06.026
Genc M, Genc ZK (2018) Microencapsulated myristic acid–fly ash with TiO2 shell as a novel phase change material for building application. J Therm Anal Calorim 131:2373–2380. https://doi.org/10.1007/s10973-017-6781-7
Ghosh R, Maiti S, Chakraborty A (2005) Facile catalyzed acylation of alcohols, phenols, amines and thiols based on ZrOCl2.8H2O and acetyl chloride in solution and in solvent-free conditions. Tet Lett 46:147–151. https://doi.org/10.1016/j.tetlet.2004.10.164
Gong S, Liu L, Cui Q, Ding J (2010) Liquid phase nitration of benzene over supported ammonium salt of 12-molybdophosphoric acid catalysts prepared by sol–gel method. J Hazard Mater 178:404–408. https://doi.org/10.1016/j.jhazmat.2010.01.095
Green TW, Wuts PGM (1999) Protective groups in organic synthesis, 3rd edn. Wiley, New York
Hada R, Goyal D, Yadav VS, Siddiqui N, Rani A (2020) Synthesis of NiO nanoparticles loaded fly ash catalyst via microwave assisted solution combustion method and application in hydrogen peroxide decomposition. Mat Today: Pro 28(1):119–123. https://doi.org/10.1016/j.matpr.2020.01.411
Heravi MM, Sadjadi S (2009) Recent developments in use of heteropolyacids, their salts and polyoxometalates in organic synthesis. J Iran Chem Soc 6(1):1–54. https://doi.org/10.1007/BF03246501
Herndon JM, Whiteside M (2017) Further evidence of coal fly ash utilization in tropospheric geoengineering: implications on human and environmental health. J Geogr Environ Earth Sci Int 9(1):1–8. https://doi.org/10.9734/JGEESI/2017/31417
Jain D, Mishra M, Rani A (2012) Synthesis and characterization of novel aminopropylated fly-ash catalyst and its beneficial application in base catalyzed Knoevenagel condensation reaction. Fuel Process Technol 95:119. https://doi.org/10.1016/j.fuproc.2011.12.005
Khatri C, Jain D, Rani A (2010) Fly ash-supported cerium triflate as an active recyclable solid acid catalyst for Friedel-Crafts acylation reaction. Fuel 89:3853–3859. https://doi.org/10.1016/j.fuel.2010.07.007
Khayoon MS, Hameed BH (2012) Synthesis of hybrid SBA-15 functionalized with molybdophosphoric acid as efficient catalyst for glycerol esterification to fuel additives. Appl Catal A Gen 433–34:152–161. https://doi.org/10.1016/j.apcata.2012.05.013
Kim H, Jung JC, Park DR, Lee H, Lee J, Lee SH, Baeck SH, Lee KY, Yi J, Song IK (2008) Preparation of H5PMo10V2O40 catalyst immobilized on nitrogen-containing mesostructured cellular foam carbon (N-MCF-C) and its application to the vapor-phase oxidation of benzyl alcohol. Catal Today 132:58–62. https://doi.org/10.1016/j.cattod.2007.12.004
Laila IA, Nashwa S, Abed-Elshafy NS (2006) Influence of counter cation on the thermal stability, the acidity and the catalytic properties in the dehydration of tert-butanol over 12 molybdophosphates. Hungarian J Ind Chem 34:55–62. https://doi.org/10.1515/112
Li M, Shen J, Ge X, Chen X (2001) Characterization and catalytic performance of supported molybdophosphoric acid catalysts for the oxidation of propylene to acetone. Appl Catal A Gen 206:161–169. https://doi.org/10.1016/S0926-860X(00)00597-4
Lin H, Abdullahi A, Changming L, Yunjia L, Chao W, Shiqiu G, Zhouen L, Jian Y (2020) Development of red mud coated catalytic filter for NOx removal in the high temperature range of 300–450 °C. Catal Lett 150:702–712. https://doi.org/10.1007/s10562-019-02953-x
Liu D, Quek XY, Hu S, Li L, Lim HM, Yang Y (2009) Mesostructured TUD-1 supported molybdophosphoric acid (HPMo/TUD-1) catalysts for n-heptane hydroisomerization. Catal Today 147S:S51-57. https://doi.org/10.1016/j.cattod.2009.07.017
Lugemwa FN, Shaikh K, Hochstedt E (2013) Facile and efficient acetylation of primary alcohols and phenols with acetic anhydride catalyzed by dried sodium bicarbonate. Catalysts 3:954–965. https://doi.org/10.3390/catal3040954
Malpani SK, Rani A (2019) A greener route for synthesis of fly ash supported heterogeneous acid catalyst. Mat Today Pro 9:551–559. https://doi.org/10.1016/j.matpr.2018.10.375
Massah AR, Kalbasi RJ, Khalifesoltani M, Kordesofla FM (2013) ZSM-5-SO3H: an efficient catalyst for acylation of sulfonamides, amines, alcohols, and phenols under solvent-free conditions. ISRN Org Chemy. https://doi.org/10.1155/2013/951749
Mazumder NA, Rao R (2015) An efficient solid base catalyst from coal combustion fly ash for green synthesis of dibenzylideneacetone. J Ind Eng Chem 29:359. https://doi.org/10.1016/j.jiec.2015.04.015
Misono M, Konishi Y, Furuta M, Yoneda Y (1978) Surface properties of 12-molybdophosphoric acid catalyst. Chem Lett 7:709–712. https://doi.org/10.1246/cl.1978.709
Mulla SAR, Inamdaar SM, Pathan MY, Chavan SS (2012) Highly efficient cobalt (II) catalyzed O-Acylation of alcohols and phenols under solvent-free conditions. Open J Synth Theory Appl Open J Synth Theory Appl 1:31–35. https://doi.org/10.4236/ojsta.2012.13006
Nakata S, Asoaka S, Takahashi H, Deguchi K (1986) High-resolution solid-state phosphorus-31 MASNMR studies of inorganic phosphates. Anal Sci 2(1):91. https://doi.org/10.2116/analsci.2.91
Ohayama K, Shimada G, Tokumoto Y, Sakamoto K (1995) Process for the preparation of Isopropyl Acetate, 5384426A
Pasha MA, Bhojegowd M, Reddy M, Manjula K (2010) Zinc dust: an extremely active and reusable catalyst in acylation of phenols, thiophenol, amines and alcohols in a solvent-free system. Eur J Chem 1:385–387. https://doi.org/10.5155/eurjchem.1.4.385-387.90
Pawelec B, Damyanova S, Mariscal R, Fierro JLG, Sobrados I, Sanz J, Petrov L (2004) HDS of dibenzothiophene over polyphosphates supported on mesoporous silica. J Catal 223:86–97. https://doi.org/10.1016/j.jcat.2004.01.018
Prasad B, Maity S, Sangita K, Mahato AK, Mortimer RJG (2012) Synthesis and characterisation of zeolite prepared from coal ash by hydrothermal process. Environ Technol 33(1):37. https://doi.org/10.1080/09593330.2010.548532
Preston LJ, Izawa MRM, Banerjee NR (2011) Infrared spectroscopic characterization of organic matter associated with microbial bioalteration textures in basaltic glass. Astrobiology 11:585. https://doi.org/10.1089/ast.2010.0604
Rani A, Khatri C, Hada R (2013) Fly ash supported scandium triflate as an active recyclable solid acid catalyst for Friedel-Crafts acylation reaction. Fuel Process Technol 116:366–373. https://doi.org/10.1016/j.fuproc.2013.08.003
Rocchiccioli-Deltcheff C, Amirouche M, Foumier M (1992) Structure and catalytic properties of silica-supported polyoxomolybdates III. 12-molybdosilicic acid catalysts: vibrational study of the dispersion effect and nature of the mo species in interaction with the silica support. J Catal 138:445–456. https://doi.org/10.1016/0021-9517(92)90296-T
Romanelli G, Vazquez P, Pizzio L, Quaranta N, Autino J, Blanco M, Caceres C (2004) Phenol tetrahydropyranylation catalyzed by silica-alumina supported heteropolyacids with Keggin structure. Appl Catal A Gen 261:16370. https://doi.org/10.1016/j.apcata.2003.10.043
Rupali V, Monika G (2015) Silica-L-proline: An efficient and recyclable heterogeneous catalyst for the Knoevenagel condensation between aldehydes and malononitrile in liquid phase. MonatsheftefürChemie - Chemical Monthly 146:645–652. https://doi.org/10.1007/s00706-014-1331-5
Sartori G, Maggi R (2006) Use of solid catalysts in Friedel-Crafts acylation reactions. Chem Rev 106:1077–1104. https://doi.org/10.1021/cr040695c
Secen H, Kalpar AH (1999) An efficient acetylation of primary and secondary aliphatic alcohols with acetic anhydride in the presence of graphite Bisulphate. Turk J Chem 23:27–30
Shirini F, Seddighi M, Goli-Jolodar O (2016) Facile and efficient synthesis of pyrimido[1,2-a]benzimidazole and tetrahydrobenzimidazo[2,1-b]quinazolin-1(2H)-one derivatives using Brönsted acidic ionic liquid supported on rice husk ash (RHA-[pmim]HSO4). J Iran Chem Soc 13:2013. https://doi.org/10.1007/s13738-016-0918-7
Shu-wen G, Li-jun L, Qian Z, Liang-yin W (2012) Effective Liquid-phase nitration of benzene catalyzed by a stable solid acid catalyst: silica supported Cs2.5H0.5PMo12O40. Bull Kor Chem Soc 33(4):1279–1284. https://doi.org/10.5012/bkcs.2012.33.4.1279
Srivastava K, Devra V, Rani A (2014) Fly ash supported vanadia catalyst: an efficient catalyst for vapor phase partial oxidation of toluene in a micro-reactor. Fuel Process Technol 121:1–8. https://doi.org/10.1016/j.fuproc.2013.12.002
Tayebee R, Cheravi F (2009) Efficient protection of alcohols with carboxylic acids using a variety of heteropolyoxometallates as catalysts Studying Effective Reaction Parameters. Bull Kor Chem Soc 30:2899–2904. https://doi.org/10.5012/bkcs.2009.30.12.2899
Temuujin J, Van Riessen A (2009) Effect of fly ash preliminary calcination on the properties of geopolymer. J Hazard Mater 164:634–639. https://doi.org/10.1016/j.jhazmat.2008.08.065
Thavamani SS, Sudharsan M, Mariya AS, Suresh D, Amali AJ, Rajeswari S, Amaladhas TP (2020) CeO2/Pd nanoparticles incorporated fly ash zeolite: an efficient and recyclable catalyst for Csp2‐Csp2 bond formation reactions. Appl Organomet Chem 2020:e5752. https://doi.org/10.1002/aoc.5752
Toor AP, Sharma M, Kumar G, Wanchoo RK (2011) Kinetic study of esterification of acetic acid with n-butanol and isobutanol catalyzed by ion exchange resin. Bull Chem React Eng Catal 6:23. https://doi.org/10.9767/bcrec.6.1.665.23-30
Umamaheshwari V, Palanichamy M, Arabindoo B, Murugesan V (2001) Acylation of alcohols over solid acid catalysts. Ind J Chem 40A:704–07
Vazquez P, Pizzio L, Caceres C, Blanco M, Thomas H, Alesso E, Finkielsztein L, Lantano B, Moltrasio G, Aguirre J (2000) Silica-supported heteropolyacids as catalysts in alcohol dehydration reactions. J Mol Catal A Chem 161:223–232. https://doi.org/10.1016/S1381-1169(00)00346-0
Vazquez P, Pizzio L, Romanelli G, Autino J, Cáceres C, Blanco M (2002) Mo and W heteropolyacid based catalysts applied to the preparation of flavones and substituted chromones by cyclocondensation of o-hydroxyphenyl aryl 1, 3-propanediones. Appl Catal A Gen 235:233–240. https://doi.org/10.1016/S0926-860X(02)00266-1
Vijaya Shanthi R, Sankaranarayanan TM, Mahalakshmy R, Sivasanker S (2015) Fly ash based Ni catalyst for conversion of sorbitol into glycols. J Environ Chem Eng 3:1752. https://doi.org/10.1016/j.jece.2015.06.024
Winé G, Vanhaecke E, Ivanova S, Ziessel R, Pham-huu C (2009) Microwave heating effects on acylation of anisole, catalyzed by BEA zeolite supported on β-SiC. Catal Commun 10:477–480. https://doi.org/10.1016/j.catcom.2008.10.014
Yamashita H, Mitsukura Y, Kobashi H (2010) Microwave-assisted acylation of aromatic compounds using carboxylic acids and zeolite catalysts. J Mol Catal A Chem 327:80–86. https://doi.org/10.1016/j.molcata.2010.05.016
Zhang X, Zhang Z, Zhang B, Yang X, Chang X, Zhou Z, Wang DH, Zhang MH, Bu XH (2019) Synergistic effect of Zr-MOF on phosphomolybdic acid promotes efficient oxidative desulfurization. App Catal B Environ 256:117804. https://doi.org/10.1016/j.apcatb.2019.117804
Acknowledgements
XRD, UV‒Vis DRS characterizations were performed at UGC-DAE Consortium for Scientific Research, Indore. The authors are thankful to Dr. Mukul Gupta for XRD analysis, Dr. T. Shripathi for UV‒Vis DRS analysis, University of Pune for TGA, BET surface area and SEM analysis, SAIF-Chandigarh for TEM analysis and IIT-Bombay for solid state 31P MAS NMR analysis.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
On behalf of all authors, the corresponding author states that there is no conflict of interest.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Malpani, S.K., Goyal, D., Katara, S. et al. Green, efficient and economical coal fly ash based phosphomolybdic acid catalysts: preparation, characterization and application. Chem. Pap. 75, 3017–3034 (2021). https://doi.org/10.1007/s11696-020-01501-x
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11696-020-01501-x