A Global Kinetic Mechanism for the Prediction of Hg Oxidation by a Chlorine Species

Hans Agarwal, Carlos E. Romero, Fernando Hernandez Rosales, Crisanto Mendoza-Covarrubias


This paper presents a global kinetic model developed from laboratory test results. The model consists of five global reactions - two reversible and three irreversible. The reaction constants for the Arrhenius expression formulation were determined from a set of 35 experiments involving a variety of flue gas compositions that include bulk gases (N2, CO2 and O2.) and trace gases (NO, SO2, Hg, Cl2); at a range of temperatures (from 540 °C to 166 °C) and a variety of residence times (between 2.7 and 3.3 seconds). The values obtained for the reaction constants were further used to predict experimental data from eleven published mercury data sources. The predicted values corresponded very well compared to the observed published data.

Key words:  Kinetics model; Mercury emission; Homogeneous mercury oxidation


Kinetics model; Mercury emission; Homogeneous mercury oxidation

Full Text:



[1] U.S. Environmental Protection Agency, Office of Air Quality Planning and Standards and Office of Research and Development. (1997). Mercury Study Report to Congress: Executive Summary (Vol. I). Report No. EPA-452/R-97-003. Washington, DC: U.S. Environmental Protection Agency.

[2] Brown, Hargis, Smith, D.N., & O’Dowd, W.J. (1999). Mercury Measurement and Its Control: What We Know, have Learned, and Need to Further Investigate. Journal of Air and Waste Management Association, 49, 1-97.

[3] Agarwal, Romero, C.E., & Stenger, H.G. (2007). Comparing and Interpreting Laboratory Results of Hg Oxidation by a Chlorine Species. Fuel Process Technology, 88, 723-730.

[4] Brown, Laudal, D.L., & Nott, B.R. (2000). Effects of Flue Gas Constituents on Mercury Speciation. Fuel Process Technology, 65-66, 157-165.

[5] Brown, Dunham, Eryavec, Laudal, Norton, G.A., & Yang, H. (2002). Heterogeneous Oxidation of Mercury in Simulated Post Combustion Conditions. Fuel, 82, 107-116.

[6] Ghorishi, S.B. (1998). Fundamentals of Mercury Speciation and Control in Coal-Fired Boilers (Report EPA-600/R-98-014). Washington, DC: U.S. Environmental Protection Agency.

[7] Kilgroe, J.D., Lee, C.W., Ryan, J.V., Sedman, C.B., Srivastava, R.K., & Thorneloe, S.A. (2001). Control of Mercury Emissions from Coal-Fired Electric Utility Boilers (Interim Report, No. EPA-600/R-01-109). Washington DC: U.S. Environmental Protection Agency.

[8] Helble, J.J., & Mamani-Paco, R.M. (Eds.). (2000). Bench-Scale Examination of Mercury Oxidation Under Non-Isothermal Conditions: Proc. A&WMA Annual Conference. Salt Lake City, UT.

[9] Helble, J.J., Qiu, J., & Sterling, R.O. (Eds.). (2003). Development of an Improved Model for Determining the Effects of SO2 on Homogeneous Mercury Oxidation: Clear Water Conference. Clearwater, FL.

[10] Cauch, B., Fry, A., Lighty, J.S., Senior, C.L., & Silcox, G.D. (Eds.). (2005). Detailed Kinetic Modeling of Homogeneous Mercury Oxidation Reactions in a 1000 Btu/hr Quartz Furnace: 22nd International Pittsburgh Coal Conference. Pittsburgh, PA.

[11] Hall, Lindqvist, O., & Schager, P. (1991). Chemical Reactions of Mercury in Combustion Flue Gases. Water, Air, Soil Pollut, 56, 3-14.

[12] Kramlich, Marinov, N.M., & Sliger, R.N. (2000). Towards the Development of a Chemical Kinetic Model for the Homogenous Oxidation of Mercury by Chlorine Species. Fuel Process Technology, 65-66, 423-438.

[13] Sliger, R.N. (2001). Development of a Chemical Kinetic Model for the Homogeneous Oxidation of Mercury by Chlorine Species: A Tool for Mercury Emissions Control (Unpublished doctoral dissertation). University of Washington, USA.

[14] Cole, Gaspar, Seeker, W.R., & Widmer, N.C. (1998). Practical Limitation of Mercury Speciation in Simulated Municipal Waste Incinerator Flue Gas. Combustion Science and Technology, 134, 315-326.

[15] Agarwal, Fan, Stenger, H.G., & Wu, S. (2006). The Effects of H2O, SO2 and NO on Homogeneous Hg Oxidation by Cl2. Energy and Fuel, 20, 1068-1075.

[16] Liu, J. (Ed.). (2008). Modeling of Homogeneous Mercury Oxidation in Flue Gas during Coal Combustion: The 42nd Western Regional Meeting. Las Vegas, NV.

[17] Xu, M. (2003). Modeling of Homogeneous Mercury Speciation Using Detailed Chemical Kinetics. Combustion and Flame, 132, 208-218.

[18] Cole, J.A., West, J., & Widmer, N.C. (Eds.). (2000). Thermochemical Study of Mercury Oxidation in Utility Boiler Flue Gases: Proceedings of the Air and Waste Management Association’s 93rd Annual Meeting. Salt Lake City, UT.

[19] Edwards, Kilgroe, J.D., & Srivastava, R.K. (2001) A Study of Gas-Phase Mercury Speciation Using Detailed Chemical Kinetics. Journal of Air & Waste Management Association, 51, 869–877.

[20] Agarwal, H., & Stenger, H.G. (2007). Development of a Predictive Kinetic Model for Homogeneous Hg Oxidation Data. Mathematical and Computer Modeling, 45, 109-125.

[21] Magellan Metals. (2012). Inconel 625. Retrieved from http://www.magellanmetals.com/inconel_625.html

[22] Deacon, H. (1875). Improvement in Manufacture of Chlorine. Patent No. 165802. United States Patent and Trademark Office.

[23] Edwards, J.R., Ghorishi, S.B., Kilgroe, J.D., Lee, C.W., & Srivastava, R.K. (Eds.). (2001). A Computational and Experimental Study of Mercury Speciation as Facilitated by the Deacon Process: The A&WMA Specialty Conference on Mercury Emissions: Fate, Effects and Control. Chicago, IL.

[24] Fujiwara, Helble, J.J., & Niksa, S. (2001). Kinetic Modeling of Homogeneous Mercury Oxidation: The Importance of NO and H­2O in Predicting Oxidation in Coal-Derived Systems. Environ. Sci. Technology, 35, 3701-3706.

DOI: http://dx.doi.org/10.3968/j.est.1923847920120401.332

DOI (PDF): http://dx.doi.org/10.3968/pdf


  • There are currently no refbacks.

Copyright (c)

Share us to:   


If you have already registered in Journal A and plan to submit article(s) to Journal B, please click the CATEGORIES, or JOURNALS A-Z on the right side of the "HOME".

We only use three mailboxes as follows to deal with issues about paper acceptance, payment and submission of electronic versions of our journals to databases: caooc@hotmail.com; est@cscanada.net; est@cscanada.org

 Articles published in Energy Science and Technology are licensed under Creative Commons Attribution 4.0 (CC-BY).


Address: 9375 Rue de Roissy Brossard, Québec, J4X 3A1, Canada 
Telephone: 1-514-558 6138 
Website: Http://www.cscanada.net Http://www.cscanada.org 
E-mailest@cscanada.net; est@cscanada.org

Copyright © 2010 Canadian Research & Development Centre of Sciences and Cultures