Efficient and selective nitration of xylenes over MoO3/SiO2 supported phosphoric acid

Joanna Adamiak; Michal Chmielarek

Journal of Industrial and Engineering Chemistry, Vol.27, 175-181, July, 2015

DOI10.1016/j.jiec.2014.12.032 Export Citation

Efficient and selective nitration of xylenes over MoO3/SiO2 supported phosphoric acid

Joanna Adamiak^†, and Michal Chmielarek

Industrial Chemistry Research Institute, Rydygiera 8, 01-793 Warsaw, Poland

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Silica supported molybdenum oxide modified with phosphoric acid (P/Mo/SiO2) is a very active solid acid catalyst in ortho-xylene nitration. At room temperature and with a small excess of fuming nitric acid, ortho-xylene conversion is 79 wt%. In nitration with 65% HNO3 at 80 °C and with fivefold molar excess of acid, almost complete ortho-xylene conversion is achieved. The P/Mo/SiO2 is also an excellent catalyst for nitration in the continuous process with using 65% HNO3 under solventless conditions. Hence, the process is eco-friendly, cheaper and leads to 60 wt% of selectivity to 4-nitro-ortho-xylene with ca. 90 wt% conversion for long time.

Keywords:Nitration;Ortho-xylene;Supported heteropolyacid

[References]

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[1] Olah GA, Malhotra R, Narang SC, Nitration Methods and Mechanism, VCH, New York, 1989.

[2] Ono N, The Nitro Group in Organic Synthesis, Wiley-VCH, New York, 2001.

[3] Carey AF, Sundberg RJ, Advanced Organic Chemistry, Part A: Structure and Mechanisms, fourth ed, Kluwer Academic/Plenum Publishers, New York, 2000.

[4] Hoggett JG, Moodie RB, Penton JR, Schofield K, Nitration and Aromatic Reactivity, Rhandon, Cambridge, 1971.

[5] Kemdeo SM, Bull. Chem. React. Eng. Catal., 7, 92 (2012)

[6] Kemdeo SM, Sapkal VS, Chaudhari GN, J. Mol. Catal. A-Chem., 323(1-2), 70 (2010)

[7] Ganjala VSP, Neeli CKP, Pramod CV, Hagga MK, Rao KSR, Burri DR, Catal. Commun., 49, 82 (2014)

[8] Yadav GD, Bisht PM, Lande SV, Catal. Today, 141, 56 (2009)

[9] Sheemol VN, Tyagi B, Jasra R, J. Mol. Catal. A-Chem., 252(1-2), 194 (2006)

[10] Kantam ML, Choudary BM, Kumar NS, Ramprasad KV, J. Mol. Catal. A-Chem., 229(1-2), 67 (2005)

[11] Patil PT, Malshe KM, Dagade SP, Dongare MK, Catal. Commun., 4, 429 (2003)

[12] Sengupta SK, Schultz JA, Walck KR, Corbin DR, Ritter JC, Top. Catal., 55, 601 (2012)

[13] Miłczak T, Jacniacki J, Zawadzki J, Malesa M, Skupinski W, Synth. Commun., 31, 173 (2001)

[14] Skupinski W, Malesa M, Appl. Catal. A: Gen., 236(1-2), 223 (2002)

[15] Adamiak J, Kalinowska-Alichnewicz D, Maksimowski P, Skupinski W, J. Mol. Catal. A-Chem., 351, 62 (2011)

[16] Adamiak J, Kalinowska-Alichnewicz D, Szadkowski M, Skupinski W, J. Hazard. Mater., 195, 195 (2011)

[17] Adamiak J, Skupinski W, Cent. Eur. J. Energ. Mater., 7, 301 (2010)

[18] Gong SW, Liu LJ, Cui QX, Ding JH, J. Hazard. Mater., 178(1-3), 404 (2010)

[19] Wang P, Yao K, Lu M, RSC Adv., 3, 2197 (2013)

[20] Gong S, Liu L, Zhang J, Proc QC, Safety Environ. Prot., http://dx.doi.org/10.1016/j.psep.2013.03.005. (2013)

[21] Girgsdies F, Schlogl R, Trunschke A, Catal. Commun., 18, 37 (2012)

[22] Cid R, Pecchi G, Appl. Catal., 14, 15 (1985)

[23] Pizzio LR, Vazquez PG, Caceres CV, Blanco MN, Appl. Catal. A: Gen., 256(1-2), 125 (2003)

[24] Mizushima T, Moriya Y, Phuc NHH, Ohkita H, Kakuta N, Catal. Commun., 13, 10 (2011)

[25] Srilakshmi C, Chew W, Ramesh K, Garland M, Inorg. Chem., 48(5), 1967 (2009)

[26] Rocchiccioli-Deltcheff C, Aouissi A, Launay S, Fournier M, J. Mol. Catal. A-Chem., 114, 331 (1996)