Fuel 89 (2010) 1323–1325

Contents lists available at ScienceDirect

Fuel
journal homepage: www.elsevier.com/locate/fuel

Surface characterization of palladium–alumina sorbents for high-temperature

capture of mercury and arsenic from fuel gas
John P. Baltrus a,*, Evan J. Granite a, Henry W. Pennline a, Dennis Stanko a, Hugh Hamilton b,
Liz Rowsell b, Stephen Poulston b, Andrew Smith b, Wilson Chu c
a
U.S. Department of Energy, National Energy Technology Laboratory, P.O. Box 10940, Pittsburgh, PA 15236-0940, USA
b
Johnson Matthey Plc, Technology Centre, Blounts Court, Sonning Common, Reading RG4 9NH, UK
c
Johnson Matthey, 400 Lapp Road, Malvern, PA 19355, USA

a r t i c l e i n f o a b s t r a c t

Article history: Coal gasification with subsequent cleanup of the resulting fuel gas is a way to reduce the impact of mer-
Received 23 June 2009 cury and arsenic in the environment during power generation and on downstream catalytic processes in
Received in revised form 25 August 2009 chemical production. The interactions of mercury and arsenic with Pd/Al2O3 model thin film sorbents and
Accepted 25 September 2009
Pd/Al2O3 powders have been studied to determine the relative affinities of palladium for mercury and
Available online 14 October 2009
arsenic, and how they are affected by temperature and the presence of hydrogen sulfide in the fuel
gas. The implications of the results on strategies for capturing the toxic metals using a sorbent bed are
Keywords:
discussed.
Mercury
Arsenic
Published by Elsevier Ltd.
Surface characterization
Fuel gas
Sorbent

1. Introduction
Conversion of coal into electricity, hydrogen, and other valuable
energy products can be accomplished through coal gasification.
Coal gasification electric power plants are now operating commer-
cially in the United States and in other nations, and it is predicted
that coal gasification will be at the heart of future generations of
clean coal technology plants.
In addition to the efficiency benefits in power generation
through coal gasification, there are environmental benefits as well.
Traditionally these include reductions in SOx, NOx and particulate
emissions. Recently it has been shown that sorbents composed of
noble metals supported on alumina are effective in removing mer-
cury and other toxic metals from fuel gas [1–3]. Palladium sup-
ported on alumina has been found to be an attractive sorbent
candidate for the removal of mercury from fuel gases at elevated
temperatures [3,4]. In addition, recent results suggest that palla-
dium also has excellent potential for arsenic, phosphorus, and sele-
nium capture from fuel gases, making it capable of multi-pollutant
capture [5]. Ideally, the sorbent should also be minimally affected
by other impurities such as hydrogen sulfide.
Previously, X-ray photoelectron spectroscopy (XPS) has been
used to characterize the surfaces of a series of Pd/Al2O3 sorbents
* Corresponding author. Tel.: +1 412 386 4570; fax: +1 412 386 5870.
E-mail address: john.baltrus@netl.doe.gov (J.P. Baltrus).
and Pd/Al2O3 model thin film sorbents [6]. Both temperature and
dispersion affected the ability of palladium to adsorb mercury. It
was also found that the presence of H2S in the fuel gas promoted
the adsorption of mercury through its association with mercury
in the palladium lattice. The present study extends the earlier work
to examination of the surface properties of Pd/Al2O3 exposed to ar-
senic in a simulated fuel gas, and finally to systems containing both
arsenic and mercury. Development of a sorbent that can also re-
move arsenic from fuel gas is important because gaseous arsenic
can cause deactivation of catalysts used in selective catalytic
reduction (SCR) systems for NOx control [7] and may end up in
waste streams. Arsenic also poisons the methanol synthesis cata-
lysts employed in syngas streams. In February 2009, the US Su-
preme Court cleared the way for the US Environmental
Protection Agency to issue new regulations on emissions of mer-
cury, lead, arsenic, and other pollutants from coal-fired power
plants.
2. Materials and methods
2.1. Materials and gas exposures
Model surfaces comprised of Pd/alumina were prepared by vac-
uum deposition of an approximate 0.5 lm-thick palladium film on
flat alpha alumina pieces that are made for vacuum deposition
(Alfa Aesar). The vacuum-deposited Pd/alumina was treated with

0016-2361/$ - see front matter Published by Elsevier Ltd.

doi:10.1016/j.fuel.2009.09.030
1324 J.P. Baltrus et al. / Fuel 89 (2010) 1323–1325
a simulated fuel gas containing 5% CO2, 35% H2, 45% CO, and bal-
ance N2 (SFG-A), to which AsH3 alone or in combination with Hg
and/or H2S (0.2%) was added. The 350-min adsorption capacity of
a 10% Pd/alumina powder (Johnson Matthey) for Hg alone was
measured in a simulated fuel gas of composition 2% CO2, 10% H2,
14% CO, 1% H2O, 0.2% H2S, 180 ppb Hg, and balance N2 (SFG-B),
while its capacity for simultaneous adsorption of mercury and ar-
senic was measured in a fuel gas of composition: 2% CO2, 10% H2,
14% CO, 0.2% H2S, 180 ppb Hg, 795 ppb AsH3, and balance N2
(SFG-C). All treatments were conducted for 350 min in a packed-
bed reactor described elsewhere [1,2] to avoid contamination of
the spectrometer’s analysis chamber. The reacted Pd films were ex-
posed to air during transfer to the XPS instrument. It appeared that
the information gained from the films was not compromised by
exposure to air as evidenced by the lack of formation of sulfate
on the surfaces of films treated with H2S.
2.2. Analysis
XPS measurements were carried out using a PHI 5600ci instru-
ment. The XPS instrument employed monochromatic Al Ka X-rays
and the pass energy of the analyzer was 58.7 eV. Elemental surface
concentrations were calculated from peak areas based on manufac-
turer-provided sensitivity factors. In order to avoid possible influ-
ence of the XPS results by surface contamination of the very-top
layer, the samples were sputter-profiled with argon ions and the
reported atomic ratios were those calculated by averaging the
intensity ratios measured at 6.8 Å intervals over the sputtering
depth of 34–102 Å.
XRD analysis of the palladium films coated on alumina was
accomplished by removing the films from the crystals by carefully
scraping the coating off onto a zero-background quartz slide using
a scalpel. A drop of ethanol was used for some samples to aid
manipulation of the thin foil-like fragments, and to improve adhe-
sion to the slide. Samples were characterized using a PANalytical
X’Pert Pro MPD powder diffractometer equipped with a monochro-
matic Cu X-ray source operated at 45 kV and 40 mA. Diffraction
patterns were recorded over a 2h range of 10–90° at a step size
of 0.017° 2h. Data collection times varied with total collection
times up to about 16 h.
3. Results and discussion
As in a previous study [6], thin palladium films deposited on
alumina served as model sorbents and were exposed to a simu-
lated fuel gas to determine how toxic elements present in fuel
gas might interact with the surface of Pd/Al2O3 sorbents. In this
study, the films were exposed to a simulated fuel gas containing
3.8 ppm AsH3 at progressively higher temperatures. The results
are reported in Table 1. It can be seen that the surface As/Pd ratios
increase with exposure temperature. This is opposite to the behav-
ior that was observed for mercury under similar conditions [6].
Two distinct regions could be observed on the palladium film trea-
ted at 288 °C. When the analysis area of the spectrometer was fo-
cused on each of these areas, two different As/Pd ratios were
measured. One ratio was close to that measured following treat-
ment at 204 °C, while the other was close to the ratio measured fol-
lowing treatment at 371 °C.
X-ray diffraction was used to detect crystalline phases that
formed during exposure to AsH3. The data in Table 1 show that
As3Pd8 is formed at 204 °C while AsPd2 is formed at 371 °C. Forma-
tion of such compounds is reasonable based on As–Pd phase dia-
grams and the amount of arsenic captured [8]. The As/Pd atomic
ratio increases in going from As3Pd8 to AsPd2, which is consistent
with what was observed for the surface As/Pd atomic ratios
Table 1
XPS-determined As/Pd atomic ratios and XRD-determined composition of Pd films on
alumina crystals exposed to SFG-A + 3.8 ppm AsH3.
Temperature (°C) As/Pd atomic ratio As–Pd phase
204 0.240 As3Pd8
288 0.258 (phase 1), 0.398 (phase 2) n.d.
371 0.403 AsPd2
204 (SFG + H2S) 0.163 As3Pd8
n.d.: Distinct phases were not detected.
measured using XPS. No distinct As–Pd phases were detected by
XRD for the sorbent treated at 288 °C. The small areas of the dis-
tinct regions that could be observed on the surface of this sample
limited the material that was available for XRD detection, plus it
was not possible to focus on the separate distinct areas. Based on
the above information, it is believed that 288 °C must lie in a tem-
perature range for transition between the As3Pd8 and AsPd2
phases.
The effect of typical fuel gas contaminants such as hydrogen
sulfide on the adsorption of toxic metals is of interest because
H2S is known for poisoning the activity of Pd/Al2O3 catalysts for
methane oxidation [9]. The affect of adding H2S to the fuel gas con-
taining AsH3 that was used to treat the Pd/Al2O3 sorbent at 204 °C
can be seen in Table 1. The surface As/Pd atomic ratio decreased by
about 30% when adsorption took place in the presence of H2S. This
is in contrast to the two and a half fold increase in mercury uptake
observed under identical conditions [6]. It was also noted that the
S/Pd atomic ratio of 0.242 determined by XPS for the sample trea-
ted with AsH3 was twice the ratio (0.120) previously measured for
the sample treated with Hg under identical conditions. Formation
of an As3Pd8 phase for the sample treated with AsH3 was still ob-
served in the presence of H2S, indicating that not all of the palla-
dium was bound to sulfur. However, even though the surface of
the sample treated with AsH3 and H2S had a surface S/Pd atomic
ratio twice that of the sample treated with mercury, no discrete
Pd–S phase was detected using XRD, while such a phase was de-
tected for the sample treated with mercury. Clearly two different
mechanisms exist when comparing the adsorption of mercury
and arsenic in the presence of H2S. As previously suggested [6],
adsorption of mercury in the presence of H2S through sharing of
sulfur bridge atoms with palladium is consistent with the data.
In the case of arsenic, it appears that arsenic adsorption may be
facilitated by direct bonding with palladium that has not reacted
with sulfur.
Following the separate treatments of the supported palladium
films with AsH3 or mercury, a simultaneous exposure to AsH3
and Hg in SFG-A at 204 °C was completed. The results are summa-
rized in Table 2. It can be seen that concentrations of adsorbed
mercury and arsenic moved in different directions compared to
the treatments with the individual species. Following the simulta-
neous exposure to AsH3 and mercury, the mercury concentration
was significantly reduced to slightly above the detection limit of
the XPS compared to treatment with mercury alone. The opposite
was true with respect to the arsenic concentration. Once again,
As3Pd8 was observed following the simultaneous exposure. It ap-
pears that palladium has a preference for bonding with arsenic
over mercury and that what little mercury that is adsorbed may
have altered the mechanism of the As–Pd interaction enough to
promote the adsorption of arsenic.
To round out the study, Table 3 contains the mercury and ar-
senic 350-min adsorption capacities of a 10% Pd/Al2O3 sorbent
powder from an earlier study [6]. The capacities were measured
at 204 °C during exposure to SFG-B, which contained mercury
and H2S, and during exposure to SFG-C, which contained Hg,
AsH3, and H2S. The relative capacities for arsenic and mercury were
 J.P. Baltrus et al. / Fuel 89 (2010) 1323–1325 1325

Table 2 4. Conclusions
XPS-determined Hg/Pd and As/Pd atomic ratios and XRD-determined composition of
Pd films on alumina crystals exposed to SFG-A combined with 240 ppb Hg and/or
3.8 ppm AsH3 at 204 °C. The interactions leading to the capture of the toxic metals mer-
cury and arsenic from fuel gas by Pd/Al2O3 sorbents are distinct.
Toxic gas XPS atomic ratio XRD phase
The adsorption of mercury is favored by lower temperatures while
Hg/Pd As/Pd arsenic adsorption is favored at higher temperatures within the
Hg 0.0413 n.d. temperature range of 204–371 °C. The relative adsorption of mer-
AsH3 0.240 As3Pd8 cury is greatly suppressed in the presence of an excess of arsenic.
Hg + AsH3 Trace 0.338 As3Pd8 However, the presence of H2S in the fuel gas helps to mitigate this
n.d.: Distinct phases were not detected. imbalance by moderately inhibiting the adsorption of arsenic
while enhancing the adsorption of mercury. The results of this
study suggest that differences in affinity of the Pd/Al2O3 sorbent
towards mercury and arsenic can be overcome by adjusting the
length and temperature of the adsorption bed.

Table 3
Mercury and arsenic 350 min capacities for 10% Pd/Al2O3 powder exposed to
simulated fuel gas at 204 °C.
Fuel gas Hg (lg/g) As (lg/g)
SFG-B 2610 ± 235
SFG-C 1686 ± 277 4743 ± 238
consistent with what might be expected based on the results re-
ported above for the study of model Pd films supported on alu-
mina. For the powder, the mercury capacity was reduced by
approximately 36% in the presence of AsH3. Even though the
capacity for arsenic was a little over 2.5 times that of mercury on
a weight basis, which is equivalent to 7.5:1 on an atom basis, the
sorbent was still capable of absorbing some mercury in the
presence of arsenic, probably due to the co-presence of H2S,
which was demonstrated above to promote the adsorption of
mercury.
The apparent preference of Pd/Al2O3 for adsorption of arsenic
over mercury may lead to concerns that this may be a detriment
to using it as a sorbent for mercury in fuel gas containing the
two species. However, such concerns may be alleviated by sug-
gesting that any preference can be overcome by extending the
length of the adsorption bed so that a majority of the arsenic is ad-
sorbed in the first part of the bed and mercury is captured further
along the bed. The above results also suggest that one can use tem-
perature to manipulate the adsorption of arsenic and mercury. Ar-
senic adsorption may be enhanced in the first part of the bed by
maintaining a higher temperature there and then as the gas flows
along the bed either the gas can be cooled or the sorbent can be
held at a somewhat lower temperature to facilitate the adsorption
of mercury.
It is noted that in recent slipstream tests at a pilot coal gasifica-
tion facility, a sorbent bed containing ten pounds of Pd/Al2O3 held
at 260 °C removed nearly 100% of the mercury, arsenic, and sele-
nium present within the fuel gas during extended test periods last-
ing several weeks [10].
Acknowledgements
The authors thank Bret Howard for assisting with the X-ray dif-
fraction analysis and interpretation, and Gary Stiegel, Gasification
Program Manager, for supporting the research. Reference herein
to any specific commercial product, process, or service by trade
name, trademark, manufacturer, or otherwise does not necessarily
constitute or imply its endorsement, recommendation, or favoring
by the United State Government or any agency thereof.
References
[1] Granite EJ, Pennline HW. Method for high temperature mercury capture from
gas streams. US Patent No. 7,033,419; April 25, 2006.
[2] Granite EJ, Myers CR, King WP, Stanko DC, Pennline HW. Sorbents for mercury
capture from fuel gas with application to gasification systems. Ind Eng Chem
Res 2006;45:4844–8.
[3] Poulston S, Granite EJ, Pennline HW, Myers CR, Stanko DP, Hamilton H, et al.
Metal sorbents for high temperature mercury capture from fuel gas. Fuel
2007;86:2201–3.
[4] Sasmaz E, Aboud S, Wilcox J. Hg binding on Pd binary alloys and overlays. J
Phys Chem C 2009;113:7813–20.
[5] Granite EJ, Pennline HW, Stanko D, Baltrus JP, Hamilton H, Roswell L, et al.
Poulston S, Smith A, Chu W. Palladium sorbents for high temperature capture
of mercury, arsenic, selenium and phosphorus from fuel gas. In: Proc 2009
AIChE Spring National Meeting. CD-ROM ISBN: 978-0-8169-1052-6.
OmniPress. <http://www.aicheproceedings.org>.
[6] Baltrus JP, Granite EJ, Stanko DC, Pennline HW. Surface characterization of Pd/
Al2O3 sorbents for mercury capture from fuel gas. Main Group Chem
2008;7:217–25.
[7] Senior CL, Lignell DO, Sarofim AF, Mehta A. Modeling arsenic partitioning in
coal-fired power plants. Combust Flame 2006;147:209–21.
[8] Okamoto H. The As–Pd (arsenic–palladium) system. J Phase Equilib
1990;11:503–7.
[9] Yu T-C, Shaw H. The effect of sulfur poisoning on methane oxidation over
palladium supported on c-alumina catalysts. Appl Catal B-Environ
1998;18:105–14.
[10] Vimalchand P, Morton FC, Datta S, Lambrecht RC, Granite EJ, Pennline HW,
et al. Slipstream tests of palladium sorbents for high temperature capture of
mercury, arsenic, selenium and phosphorous from fuel gas. In: Proc 2009
AIChE Spring National Meeting. CD-ROM ISBN: 978-0-8169-1052-6.
OmniPress. <http://www.aicheproceedings.org>.