A Thermodynamic Study of Parameters That Affect the Nitration of Glycerol with Nitric Acid

Authors: Erna Astuti, Supranto, Rochmadi, Agus Prasetya

Abstract:

Biodiesel production from vegetable oil will produce glycerol as by-product about 10% of the biodiesel production. The amount of glycerol that was produced needed alternative way to handling immediately so as to not become the waste that polluted environment. One of the solutions was to process glycerol to polyglycidyl nitrate (PGN). PGN is synthesized from glycerol by three-step reactions i.e. nitration of glycerol, cyclization of 13- dinitroglycerine and polymerization of glycosyl nitrate. Optimum condition of nitration of glycerol with nitric acid has not been known. Thermodynamic feasibility should be done before run experiments in the laboratory. The aim of this study was to determine the parameters those affect nitration of glycerol and nitric acid and chose the operation condition. Many parameters were simulated to verify its possibility to experiment under conditions which would get the highest conversion of 1, 3-dinitroglycerine and which was the ideal condition to get it. The parameters that need to be studied to obtain the highest conversion of 1, 3-dinitroglycerine were mol ratio of nitric acid/glycerol, reaction temperature, mol ratio of glycerol/dichloromethane and pressure. The highest conversion was obtained in the range of mol ratio of nitric acid /glycerol between 2/1 – 5/1, reaction temperature of 5-25oC and pressure of 1 atm. The parameters that need to be studied further to obtain the highest conversion of 1.3 DNG are mol ratio of nitric acid/glycerol and reaction temperature.

Keywords: Nitration, glycerol, thermodynamic, optimum condition.

Digital Object Identifier (DOI): doi.org/10.5281/zenodo.1107864

References:

[1] V.K. Shahir, C.P. Jawahar, and P.R. Suresh, “Comparative study of diesel and biodiesel on CI engine with emphasi to emissions—A review, Renewable and Sustainable Energy Reviews, Vol. 45, pp. 686–697, 2015.
[2] Y.H. Tan, M.O. Abdullah, and C. Nolasco-Hipolito, “The potential of waste cooking oil-based biodiesel using heterogeneous catalyst derived from various calcined eggshells coupled with an emulsification technique: A review on the emission reduction and engine performance”, Renewable and Sustainable Energy Reviews, Vol. 47, pp. 589–603, 2015.
[3] R.W.M. Pott, C. J. Howe, and J. S. Dennis, “The purification of crude glycerol derived from biodiesel manufacture and its use as a substrate by Rhodopseudomonaspalustris to produce hydrogen”, Bioresource Technology, Vol. 152, pp. 464–470, 2014.
[4] M. Ayoub, and A.Z. Abdullah, ”Critical Review on the Current Scenario and Significance of Crude glycerol resulting from biodiesel industry towards more sustainable renewable energy industry”, Renewable and Sustainable Energy Reviews, Vol. 16, pp. 2671-2686, 2012.
[5] H. Rastegari, and H.S. Ghaziaskar, “From glycerol as the by-product of biodiesel production to value-added monoacetin by continuous and selective esterification in acetic acid”, Journal of Industrial and Engineering Chemistry, Vol. 21, pp. 856–861, 2015.
[6] Z. Mufrodi, A. Budiman, Rochmadi, and Sutijan, “Continuous Process of Reactive Distillation to Produce Bio-additive Triacetin from Gliserol”, Vol. 7, No. 10, Modern Applied Science, pp.70-78, 2013.
[7] Z. Mufrodi, A. Budiman, Rochmadi, and Sutijan, “Synthesis Acetylation of Glycerol Using Batch Reactor and Continuous Reactive Distillation Column, Engineering Journal, Vol. 18, No. 2, pp. 29-39,2014.
[8] S.V. Dammea, S. Brama, and F. Continoa,”Comparison of biodiesel production scenarios with coproduction of triacetin according to energy and GHG emissions”, Energy Procedia, Vol. 61, pp.1852 – 1859, 2014.
[9] M.A. Dasari, , et al, ”Low-pressure Hydrogenolysis of Glycerol to Propylene Glycol”, Applied Catalysis A : General, Vol. 281, pp. 225- 231, 2005,
[10] E.P. Marris, W.C. Ketchie, M. Murayama, and R.J. Davis, “Glycerol Hydrogenolysis on Carbon Supported PtRu and AuRu Bimetallic Catalysts”, Journal of Catalysis, Vol.251, pp. 281-294, 2007.
[11] T. Kurosaka, H.Maruyama, I. Naribayashi, and Y. Sasaki,”Production of 1,3Propanediol by Hydrogenolysis of Glycerol Catalyzed by Pt/WO3/ZrO2, Catalysis Communication, Vol. 9, pp.1360-1363, 2008.
[12] E. A. de Souza, D. M. Rossi, M.A.Z. Ayub,”Bioconversion of residual glycerol from biodiesel synthesis into 1, 3-propanediol using immobilized cells of Klebsiellapneumoniae BLh-1, Renewable Energy, Vol. 72 , pp.253-257, 2014.
[13] T.K., Highsmith, A.J., Sanderson, L.F., Cannizzo, and R.M., Hajik, “Polymerization of Poly (glycidyl Nitrate) from High Purity Glycidyl Nitrate Synthesized from Glycerol”, US Patent 6362311, 2002.
[14] T.K Highsmith, and H.E., Johnston, “Continuous Process and System for Production of glycidyl nitrate from glycerin, nitric acid and caustic and conversion of glycidyl nitrate to poly(glycidyl nitrate”, US Patent 6870061, 2005.
[15] E. Astuti, Supranto, Rochmadi, A. Prasetya, K. Ström, and B. Andersson, “determination of the temperature effect on glycerol nitration processes using the hysys predictions and the laboratory experiment”, Indo. J. Chem., Vol. 14, No. 1, pp. 57 – 62, 2014.
[16] A.I. Kazakov, G.V. Lagodzinskaya, L.P. Andrienku, N.G.Yunda, A.M.Korolev, Y.I. Rubtsov, G.B. Manelis. And L. T Eremenko, “Study of nitration equilibrium in the glycerin—aqueous nitric acid system.1. Dependence of the equilibrium constants of nitration reactions on the temperature, acidity of the medium, and structure of the nitrated compound”, Russian Chemical Bulletin. Vol. 39, No. 8, pp. 1560-1565, 1990.
[17] A.J. Sanderson, and L.J., Martins, “Process for Making Stable cured poly (glycidyl nitrate”, US Patent 6730181, 2004.
[18] A.J., Sanderson, L.J. Martins, and M.A., Dewey, ”Process for Making Stable cured poly (glycidyl nitrate) and Energetic Compositions Comprising Same”, US Patent 6.861.501, 2005.
[19] P. Atkins, and J. de Paula, Atkins’ Physical Chemistry, 7thed, Oxford University Press, Oxford, 2002.
[20] W.J. Moore, Physical Chemistry, 4th ed, Longmans Green and Co Ltd, London, 1965.
[21] K. Denbigh, the Principles of Chemical Equilibrium, 2nd ed., the Cambridge University Press, London. Pp.298-299, 309, 1968.