Abstract
Phenol methylation is an acid-base catalysed reaction that produces valuable chemicals that are used in fine chemical synthesis. Methylation of phenol was studied over iron, vanadium and zirconium doped cerium nano oxides under optimized reaction conditions such as catalyst weight 0.5 g, phenol/methanol molar ratio 1/3 and WHSV 1.4 h−1 at 300 °C and 2 h. 80-90% conversion and 90% ortho selectivity are achieved with all prepared mixed oxides. o-cresol and 2,6-xylenol are the major products of the reaction. Catalytic activity depends on the number and strength of moderate and strong acidic sites on the surface which in turn depends on the nature and composition of the catalyst. Structural stability of the catalyst substantiates the heterogeneous nature of the catalyst.
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Barrett J A, Gao Y, Bernt C M, Chui M, Tran A T, Foston M B and Ford P C 2016 Enhancing aromatic production from reductive lignin disassembly: in situ O-Methylation of phenolic intermediates ACS Sustain. Chem. Eng. 4 6877
Xie J, Zhuang W, Yan N, Du Y, Xi S, Zhang W, Tang J, Zhou Y and Wang J 2017 Directly synthesized V-containing BEA zeolite: Acid-oxidation bifunctional catalyst enhancing C-alkylation selectivity in liquid-phase methylation of phenol Chem. Eng. J. 328 1031
Bhadra K H and Yadav G D 2018 Controlled manipulation of selectivity between O- versus C-alkylation in methylation of phenol using ZrO2-WO3-SiO2 catalysts Appl. Catal. A Gen. 562 67
Zukowski W, Berkowicz G, Baron J, Kanderfer S, Jamanek D and Szarlik S 2014 Selective phenol methylation to 2,6-dimethylphenol in a fluidized bed of iron-chromium mixed oxide catalyst with o–cresol circulation Chem. Central J. 8 1
Grabowska H, Klimkiewicz R, Tylus W and Godowski P J 2003 A search for reason for deactivation of alkylation iron catalyst Appl. Catal. A Gen. 240 111
Cavani F, Maselli L, Passeri S and Lercher J A 2010 Catalytic methylation of phenol on MgO – Surface chemistry and mechanism J. Catal. 269 340
Tabanelli T, Cocchi S, Gumina B, Izzo L, Mella M, Passeri S, Cavani F, Lucarelli C, Schutz J, Bonrath W and Netscher T 2018 Mg/Ga mixed-oxide catalysts for phenol methylation: Outstanding performance in 2,4,6-trimethylphenol synthesis with co-feeding of water Appl. Catal. A Gen. 552 86
Reddy K R, Ramesh K, Seela K K, Rao V V and Chary K V R 2003 Alkylation of phenol with methanol over molybdenum oxide supported on NaY zeolite Catal. Commun. 4 112
Wang Y, Yang P, Liu G, Xu L, Jia M, Zhang W and Jiang D 2008 Stability and deactivation of spinel-type cobalt chromite catalysts for ortho-selective alkylation of phenol with methanol Catal. Commun. 9 2044
Crocella V, Cerrato G, Magnacca G, Morterra C, Cavani F, Cocchi S, Passeri S, Scagliarini D, Flego C and Perego C 2010 The balance of acid, basic and redox sites in Mg/Me-mixed oxides: The effect on catalytic performance in the gas-phase alkylation of m-cresol with methanol J. Catal. 270 125
Klimkiewicz R, Grabowska H and Teterycz H 2003 Sn–Ce–Rh–O monophase system as a new type of ortho-selective catalyst for phenol alkylation Appl. Catal. A Gen. 246 125
Malshe K M, Patil P T, Umbarkar S B and Dongare M K 2004 Selective C-methylation of phenol with methanol over borate zirconia solid catalyst J. Mol. Catal. A Chem. 212 337
Kirichenko G N, Glazunova V I, Balaev A V and Dzhemilev U M 2008 Catalytic vapor-phase alkylation of phenol with methanol Petrol. Chem. 48 389
Chary K V R, Ramesh K, Naresh D, Rao P V R, Rao A R and Rao V V 2009 The effect of zirconia polymorphs on the structure and catalytic properties of V2O5/ZrO2 catalysts Catal. Today 141 187
Sad M E, Padro C L and Apesteguia C R 2010 Study of the phenol methylation mechanism on zeolites HBEA, HZSM5 and HMCM22 J. Mol. Catal. A Chem. 327 63
Tabanelli T, Passeri S, Guidetti S, Cavani F, Lucarelli C, Cargnoni F and Mella M 2019 A cascade mechanism for a simple reaction: The gas-phase methylation of phenol with methanol J. Catal. 370 447
Ballarini N, Cavani F, Passeri S, Pesaresi L, Lee A F and Wilson K 2009 Phenol methylation over nanoparticulate CoFe2O4 inverse spinel catalysts: The effect of morphology on catalytic performance Appl. Catal. A Gen. 366 184
Gholipour F, Rahmani M and Panahi F 2019 Efficient and selective microwave-assisted O-methylation of phenolic compounds using tetramethylammonium hydroxide (TMAH) Green Process. Synth. 8 584
Molleti J and Yadav G D 2017 Potassium modified La-Mg mixed oxide as active and selective catalyst for mono-methylation of phenylacetonitrile with dimethyl carbonate Mol. Catal. 438 66
Liu J, Huang H, Liu X, Xiao J, Zhong S, She X, Fu Z, Kirk S R and Yin D 2017 Preparation of Fe2O3 doped SBA-15 for vapor phase ortho-position C-alkylation of phenol with methanol Catal. Commun. 92 90
Choi W C, Kim J S, Lee T H and Woo S I 2000 Balancing acidity and basicity for highly selective and stable modified MgO catalysts in the alkylation of phenol with methanol Catal. Today 63 229
Barman S, Pradhan N C and Basu J K 2006 Kinetics of alkylation of phenol with methanol over Ce-exchanged NaX zeolite Catal. Lett. 111 67
Sad M E, Padro C L and Apesteguia C R 2008 Selective synthesis of p-cresol by methylation of phenol Appl. Catal. A Gen. 342 40
Wang Y, Song Y, Huo W, Jia W, Jing X, Yang P, Yang Z, Liu G and Zhang W 2012 Vapor phase ortho-selective alkylation of phenol with methanol over silica–manganese mixed oxide catalysts Chem. Eng. J. 181–182 630
Beutel T and Su B 2005 Behavior of phenol (phenol-d5) on NaX zeolite as studied by 1H NMR and FT-IR techniques Chem. Phy. Lett. 416 51
Kurian M and Kunjachan C 2015 Effect of lattice distortion on physical properties and surface morphology of nanoceria framework with incorporation of iron/zirconium Nano-Struct. Nano Obj. 1 15
Kurian M and Kunjachan C 2016 CexV1−xO2 (x: 0, 0.25–1) nanocomposites as efficient catalysts for degradation of 2,4 dichlorophenol J. Environ. Chem. Eng. 4 1359
Kunjachan C, Sreevalsan A and Kurian M 2017 Effect of vanadium on the catalytic activity of ceria towards wet peroxide oxidation of persistent and biorecalcitrant chlorinated organics J. Water Process Eng. 19 42
Kunjachan C, Sreevalsan A and Kurian M 2018 On the redox nature of ceria-zirconia mixed nanocatalysts and its effect on catalytic wet peroxide oxidation of chlorinated organic pollutants J. Environ. Chem. Eng. 6 4151
Kurian M, Kunjachan C and Sreevalsan A 2017 A 2017 Catalytic degradation of chlorinated organic pollutants over CexFe1−xO2 (x: 0, 0.25, 0.5, 0.75, 1) nanocomposites at mild conditions Chem. Eng. J. 308 67
Sreekumar K and Sugunan S 2002 A comparison on the catalytic activity of Zn1−xCoxFe2O4 (x = 0, 0.2, 0.5, 0.8 and 1.0)-type ferrospinels prepared via a low temperature route for the alkylation of aniline and phenol using methanol as the alkylating agent Appl. Catal. A Gen. 230 245
Sreekumar K and Sugunan S 2002 Ferrospinels based on Co and Ni prepared via a low temperature route as efficient catalysts for the selective synthesis of o-cresol and 2,6-xylenol from phenol and methanol J. Mol. Catal. A Chem. 185 259
Dixit R, Saxena S, Raghuvanshi D and Dwivedi R 2013 Kinetic studies and mechanism evolution of the methylation of phenol over Al-Fe2O4 catalyst Int. J. Chem. Sci. 11 1737
Gupta R K, Prasad R, Pawan S and Singh S 2007 Vapour phase methylation of phenol over Ni1−xMnxFe2O4 type ferrospinels Asian J. Chem. 19 3780
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Kunjachan, C., Kurian, M. Mixed cerium nanooxides as efficient and selective C-alkylation catalysts for gas phase methylation of phenol. J Chem Sci 132, 55 (2020). https://doi.org/10.1007/s12039-020-1757-8
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DOI: https://doi.org/10.1007/s12039-020-1757-8