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Submicron arsenic fumes are dicult to control in conventional air pollution control devices.
Abstract
Direct measurement of arsenic release requires a good sampling and analysis procedure in order to capture and detect the total
amount of metals emitted. The literature is extensively reviewed in order to evaluate the eciency of full eld-scale and laboratory
scale techniques for capturing particulate and gaseous emissions of arsenic from the thermo-chemical treatment of dierent sources
of arsenic. Furthermore, trace arsenic concentrations in ambient air, national standard sampling methods and arsenic analysis
methods are considered. Besides sampling techniques, the use of sorbents is also reviewed with respect to both approaches (1) to
prevent the metals from exiting with the ue gas and (2) to react or combine with the metals in order to be collected in air pollution
control systems. The most important conclusion is that submicron arsenic fumes are dicult to control in conventional air pollution
control devices. Complete capture of the arsenic species requires a combination of particle control and vapour control devices.
2005 Elsevier Ltd. All rights reserved.
Keywords: Arsenic; Sampling; Air pollution control device; Gaseous emissions; Particulate emissions; Literature review
1. Introduction
Since thermal processes that use arsenic containing
sources inherently lead to volatilisation of arsenic,
appropriate arsenic capturing devices have to be installed or arsenic capturing methods have to be applied.
These devices are said to be commercially available, but
very few successful tests have been carried out on
industrial scale for the specic case of thermal conversion of chromated copper arsenate (CCA)-treated wood.
In the frame of a study that aims at identifying the best
available thermochemical conversion technology (pyrolysis, gasication or (co-)combustion) for CCA impregnated wood waste (Helsen and Van den Bulck, 2005),
the literature is critically reviewed with respect to the
* Tel.: C32 16 322505; fax: C32 16 322985.
E-mail address: lieve.helsen@mech.kuleuven.ac.be.
0269-7491/$ - see front matter 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.envpol.2005.01.025
306
As mass
balance
Tauw Infra
Consult, 1987
MulticycloneCcellulose
nitrate lter
!50%
Pasek and
McIntyre, 1993
Two bubblers:
20e90%
emptyC2% NaOH
or glass beadsC
2% monoethanolamine
Corneld et al.,
1993
NA
Hirata et al.,
1993
50e80%
McMahon
et al., 1985
61e104%
307
308
Table 2
Arsenic (%) retained in the dierent parts of the INDAVER rotary kiln incineration plant (Wauters, 1998)
Collected in
Temperature ( C)
As (wt%)
Bottom ash
Boiler ash
Fly ash
Sludge
Exhaust gas
Rotary kiln
1120
14.6
Boiler
280e240
5
Electrolter
260
75
Scrubber
250e60
5.4
!60
0.02
309
Table 3
Sorbents studied with respect to their eectiveness to reduce arsenic
emissions during coal combustion
Reference
Sorbent
Comments
Sterling and
Helble, 2003
Ca compounds
in y ash:
CaO
2CaO$SiO2
CaO$SiO2
Jadhav and
Fan, 2001
Activated carbon
Fly ash
Minerals
Silica
Alumina
Kaolinite
Minerals: lower
emission and products
of lower leachability
interaction CaOCAs2O3
depends on T
!600 C: amount captured
increases with T and
Ca3As2O8 is formed
700e800 C: amount
captured decreases with
T and Ca2As2O7 is formed
No signicant
effect of SO2 or HCl
Emathlite
Lime
Soda ash
Wu and
Barton, 2001
Afnity to adsorb As
(500e1750 K): LiOKO
NaOAlOCaOMgO
FeOBe
Effectiveness may be reduced
when Cl or S is present
Products with
high alumina content: low
leaching
high silica content: high
leaching
Gullett and
Raghunathan,
1994
Hydrated lime
As capture is function of
sorbent type and injection
mode (1000e1150e1300 C):
kaoliniteOlimestoneO
hydrated lime
Not a simple condensation
mechanism, the particles
external surface area or
pore diffusion is important
to the capture mechanism
Limestone
Kaolinite
Bauxite
310
311
Metal compound
Sampling system
Eciency
As
concO1 mg m3
17e65%
46.7e97%
99.2e99.8%
98.2e99.9%
Lower
conc!1 mg m3
Lao et al., 1974
As2O3
Low (10e24%)
Higher
Crecelius and
Sanders, 1980
part. AsCinorg.
As As2O3 vapour
NA
MDHS, 1995
part. AsCinorg. As
As2O3
NA
Complies EN 482
NIOSH, 1984
part AsCAs2O3
93%
NIOSH, 1985
AsH3
89%
NA, eciency is not available; MDHS, Methods for the Determination of Hazardous Substances.
Glass bre
40e60
Membrane
0.1e4
Teon
0.3
312
3. Conclusions
From the literature review the following conclusions
are drawn:
1. A simple cooling and/or condensation process does
not succeed in collecting all the arsenic.
2. Since most of the arsenic is released as very small
particles, venturi scrubbers are generally not ecient in capturing arsenic.
3. Physical methods (adsorption on particulate surfaces) seem attractive but only surface-active agents,
such as activated carbons, silica gel, and molecular
sieves, adsorb arsenic oxide vapour strongly.
4. Filtration through a quartz bre, glass bre or
Teon lter collects the arsenic only partly; for
Nuclepore and Millipore lters, on the other hand,
high lter eciencies were reported; good collection
eciencies were reported for alkali impregnated
(cellulose ester membrane) lters; impregnation
(with an aqueous glycerol-polyethylenimine solution, sodium carbonate or TBAH) seems to be
necessary, resulting in a chemical reaction between
the arsenic compound and the chemical agent on the
lter.
5. The lower the arsenic concentration to be measured
(e.g. low concentrations in the ambient air), the
lower the lter eciency.
6. Also the combination of lters and impingers
(containing acids or alkali) seems to be ecient.
7. Water and dilute sodium hydroxide are equally
eective collection media for arsenic trioxide vapour
in impingers; however, some arsenic compounds
adsorbed to the impinger walls need to be thoroughly washed with sodium hydroxide.
8. In the case of a sampling train consisting of a series
of impingers, the amount caught by the last
impinger should be close to zero to obtain a high
overall eciency.
9. In big chimneys a small part of the total emitted
ow is isokinetically sampled and forced through
a heated lter and at least three impingers that
contain an acid solution.
10. To collect arsine (AsH3) a charcoal tube or a silver
nitrate impregnated lter is used.
11. In coal red power plants ne y ash particles that
are enriched with arsenic are collected in an ESP;
however, ESPs are found to be insucient to capture
all arsenic released when incinerating arsenic containing waste.
313
Acknowledgements
L. Helsen is a post-doctoral research fellow of the
Fund for Scientic Research of Flanders (Fonds voor
Wetenschappelijk Onderzoek d Vlaanderen) (Belgium).
The authors are grateful to the company ARCH Timber
Protection Limited (UK) for the nancial support of the
research work.
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315