A Thermodynamic Study of Parameters That Affect the Nitration of Glycerol with Nitric Acid
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.
[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.
[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.
@article{"International Journal of Chemical, Materials and Biomolecular Sciences:70553", author = "Erna Astuti and Supranto and Rochmadi and Agus Prasetya", title = "A Thermodynamic Study of Parameters That Affect the Nitration of Glycerol with Nitric Acid", 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.", volume = "9", number = "8", pages = "1010-4", }
