Energy Technology & Innovation Initiative

FACULTY OF ENGINEERING

Mercury oxidation

Alastair Clements
13/06/2012

Outline

Introduction to mercury Mercury oxidation Oxidation modelling Summary Further work

Mercury
Toxicity Methyl mercury ([HgCH3 ]+ ) forms in the environment. Potent neurotoxin; RfD = 0.1-0.3g/kg per day. Bioaccumulates through the food web into lethal doses. Transport 6-18 months atmospheric lifetime. Global distribution from source. Corrosion Mercury forms amalgams with many metals, including aluminium.

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Mercury oxidation
Elemental Hg thermodynamically favoured at high temperatures.
Hg is volatile, relatively inert and has low solubility.

Oxidised at moderate temperatures by halides.

Oxidised to HgCl2 or HgBr2 . Mercuric halides are soluble and so can be captured.

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Relative abundance of Cl
4500 4000 3500

Chlorine Bromine

Coal content (ppmw )

3000 2500 2000 1500 1000 500 0

B ul ria ga U kr ai ne A us tr al ia U SA Ca na da Ja pa n Ch a in So ut h A fri ca U K

[Vassilev et al. 2000] [Spears and Zheng 1999]

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Correlation of Hg2+ and HCl

180 160 HgE (g /dscm) / HgT (ppmw ) 140 120 100 80 60 40 20 0 0 500 1000 1500 2000 2500 Chlorine (ppmw ) 3000 3500 4000

[EPA 2011]
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Oxidation pathways
Gas-phase
Focus of early work. Unable to model in all situations.

Paricle-bound
Activated carbon and y ash. Inuenced by O/S/halogen species.

Surface-catalysed
Uncoated surface eects observed. Speculative mechanisms.

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Gas phase oxidation

Widmer et al. mechanism:
Hg + Cl + M HgCl + M Hg + Cl2 HgCl + Cl Hg + HCl HgCl + H Hg + HOCl HgCl + OH (R 1) (R 2) (R 3) (R 4) HgCl + Cl + M HgCl2 + M (R 5) HgCl + Cl2 (R 6) HgCl2 + Cl HgCl + HCl (R 7) HgCl2 + H HgCl + HOCl HgCl2 + OH (R 8)

Reaction R 1-R 4 produce the unstable HgCl intermediate. Only R 1 can proceed at an appreciable rate. Reactions R 5-R 8 complete mercury oxidation and occur much faster. [Widmer et al. 2000]
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H r p 00 (4 p 00 (1 pp 00 (4 p 0p 10 ) m ) m ) pm pm 5 (2 m pp )

Cl H Cl H Cl H ( Cl

B H r 0p (5 r pm ) H 5p B H r (2 pm ) + Cl (4 (5 p 0p m ) +

(5 H

0p

pm

Oxy-ring

B H )

[Buitrago 2011]
Alastair Clements Mercury oxidation

(5

p 0p

) m

pp 00

) m

B H

B H

(2

5p

pm

Oxidation levels

r B

(2

5p

pm

Cl H Cl H

(4

p 00

pm

(1

pp 00

80

60

40

100

20

Air ring

Cl

(1

p 00

pm

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Percentage Hg oxidation

Chlorine modelling
Leeds mercury-chlorine model:
Reaction Hg + Cl + M HgCl + M Hg + Cl2 HgCl + Cl Hg + HCl HgCl +H Hg + HOCl HgCl + OH HgCl + Cl + M HgCl2 + M HgCl + Cl2 HgCl2 + Cl HgCl + HCl HgCl2 + H HgCl + HOCl HgCl2 + OH Ref. Donohoue et al. Widmer et al. Wilcox Wilcox Niksa et al. Wilcox Wilcox Wilcox Method PLP/PLIF TST/ab initio TST/ab initio TST/ab initio Collision limited TST/ab initio TST/ab initio TST/ab initio

[Gharabaghi et al. 2011]

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Chlorine modelling results

10 Percentage Hg oxidation

Experimental 440K/s Experimental 220 K/s Model 440 K/s Model 220 K/s 0 100 200 300 HCl concentration (ppmv ) 400 500

Experimental data from [Cauch 2008]

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Bromine modelling
Leeds mercury-bromine model:
Reaction Hg + Br + M HgBr + M Hg + Br2 HgBr + Br Hg + HBr HgBr +H Hg + HOBr HgBr + OH HgBr + Br + M HgBr2 + M HgBr + Br2 HgBr2 + Br HgBr + HBr HgBr2 + H HgBr + HOBr HgBr2 + OH Ref. Donohoue et al. Okano Okano Niksa et al. Goodsite et al. Niksa et al. Okano Niksa et al. Method PLP/PLIF TST/ab initio TST/ab initio Collision limited TST/ab initio Collision limited TST/ab initio Collision limited

[Hughes et al. 2011]

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Bromine modelling results

100

80 Percentage Hg oxidation

60

40

20

Experimental 440K/s Experimental 220 K/s Model 440 K/s Model 220 K/s 0 10 20 30 HBr concentration (ppmv ) 40 50

Experimental data from [van Otten et al. 2011]

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Summary
Mercury oxidation chemistry has proven challenging for modellers. Existing gas-phase oxidation models have failed to be validated across datasets. Experimental data only covers the atomic recombination reactions. Not all potential gas-phase pathways have been fully investigated. Work has also started on identifying surface-catalysed and particle-bound mechanisms.

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Further work
Continue to improve and validate current model.

Measure reaction rates under ue gas temperatures.

Using ash photolysis and adsorption spectroscopy.

Analyse and integrate models for heterogeneous reactions.

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References
Buitrago, P. A. Gas-phase mercury oxidation: eects of bromine, chlorine and SO2 under air ring and oxy-fuel conditions, experimental and modeling study The University of Utah, 2011 Cauch, B. Experimental Investigation And Kinetic Modeling Of Homogeneous Mercury Oxidation By Halogens The University of Utah, 2008 Donohoue, D. L.; Bauer, D. & Hynes, A. J. Temperature and Pressure Dependent Rate Coecients for the Reaction of Hg with Cl and the Reaction of Cl with Cl: A Pulsed Laser Photolysis-Pulsed Laser Induced Fluorescence Study The Journal of Physical Chemistry A, 2005, 109, 7732-7741 Donohoue, D. L.; Bauer, D.; Cossairt, B. & Hynes, A. J. Temperature and Pressure Dependent Rate Coecients for the Reaction of Hg with Br and the Reaction of Br with Br: A Pulsed Laser Photolysis-Pulsed Laser Induced Fluorescence Study The Journal of Physical Chemistry A, 2006, 110, 6623-6632 Donohoue, D. L. Kinetic Studies of the Oxidation Pathways of Gaseous Elemental Mercury University of Miami, 2008 Environmental Protection Agency, http://www.epa.gov/ accessed 11/06/2012

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References
Gharebaghi, M.; Hughes, K.; Porter, R.; Pourkashanian, M. & Williams, A. Mercury speciation in air-coal and oxy-coal combustion: A modelling approach Proceedings of the Combustion Institute, 2011, 33, 1779 - 1786 Goodsite, M. E.; Plane, J. M. C. & Skov, H. A Theoretical Study of the Oxidation of Hg0 to HgBr2 in the Troposphere Environmental Science & Technology, 2004, 38, 1772-1776 Hughes, K. J.; Ma, L.; Porter, R. T. & Pourkashanian, M. E.N. Pistikopoulos, M. G. & Kokossis, A. (Eds.) Mercury Transformation Modelling with Bromine Addition in Coal Derived Flue Gases 21st European Symposium on Computer Aided Process Engineering, Elsevier, 2011, 29, 171 - 175 Niksa, S.; Helble, J. & Fujiwara, N. Kinetic modeling of homogeneous mercury/oxidation: The importance of NO and H2O in predicting oxidation in coal-derived systems Environmental Science and Technology, 2001, 35, 3701-3706 Niksa, S.; Padak, B.; Krishnakumar, B. & Naik, C. V. Process Chemistry of Br Addition to Utility Flue Gas for Hg Emissions Control Energy & Fuels, 2010, 24, 1020-1029 Okano, T. High Temperature Mercury Oxidation Kinetics via Bromine Mechanisms Worcester Polytechnic Institute, 2009 van Otten, B.; Buitrago, P. A.; Senior, C. L. & Silcox, G. D. Gas-Phase Oxidation of Mercury by Bromine and Chlorine in Flue Gas Energy & Fuels, 2011, 25, 3530-3536
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References
Spears, D. & Zheng, Y. Geochemistry and origin of elements in some UK coals International Journal of Coal Geology, 1999, 38, 161 - 179 Vassilev, S.; Eskenazy, G. & Vassileva, C. Contents, modes of occurrence and origin of chlorine and bromine in coal Fuel, 2000, 79, 903 - 921 Widmer, N. C.; West, J. & Cole, J. A. Proceedings of the Air & Waste Management Association Annual Conference, 2000 Wilcox, J. A kinetic investigation of high-temperature mercury oxidation by chlorine Journal of Physical Chemistry A, 2009, 113, 6633-6639

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