Fuel Processing Technology 120 (2014) 5460

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Fuel Processing Technology

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Trace metals emission in syngas from biomass gasication

Deepak Pudasainee , Hanns-Rudolf Paur, Sabine Fleck, Helmut Seifert
Karlsruhe Institute of Technology, Institute of Technical Chemistry, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany

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

Article history: In this paper, trace metals (As, Be, Cd, Cr, Hg Ni, Pb, Se and V) emission from the atmospheric entrained ow
Received 12 September 2013 gasier REGA at Karlsruhe Institute of Technology, Germany is presented. Elemental composition and metals
Received in revised form 9 December 2013 concentration in glycol (model fuel) and straw char samples were determined. In order to achieve well dened
Accepted 13 December 2013
and reproducible operating conditions, gasication experiments were carried out with glycol and slurry (straw
Available online 29 December 2013
char mixed with glycol) as fuel. Trace metals emission and distribution into particle and gas phase in syngas
Keywords:
from gasication were measured according to US EPA method 29. During glycol gasication, metals concentra-
Biomass gasication tion in syngas ranged from 0.1 g/Nm3 (V) to 4.6 g/Nm3 (Cr). In slurry gasication, metals concentration in syn-
Mercury gas ranged from 2.4 g/Nm3 (Hg) to 53.2 g/Nm3 (Ni). Trace metals tend to volatilize more in reducing
Minamata convention gasication environment. Tendency of metals to speciate into particle phase increased in slurry gasication
Renewable energy than glycol gasication due to increased in particle concentration and unburned carbon content in syngas. The
Syngas increase of particle and carbon content in syngas possessed strong inuence in distribution behavior of As, Be
Trace metals and Pb, however, such inuence was less for other metals studied. Mercury in syngas was speciated predomi-
nantly into elemental form followed by oxidized form whereas share of particle bond mercury was the least.
2013 Elsevier B.V. All rights reserved.

1. Introduction
Biomass is a renewable, low carbon fuel that can be used as a substi-
tute of fossil fuels promoting environmental and social benets.
Biomass is the fourth major sources of primary energy uses following
coal, petroleum and natural gas [1]. The simplest utilization of biomass
i.e. burning, largely practiced in the developing countries, is an unsus-
tainable combustion practice which releases pollutants of serious
health and environmental concern. Bio-chemical processes like bio-
methanization and thermo-chemical methods such as combustion,
pyrolysis and gasication are used in recovering energy from biomass
[24]. Biomass gasication is one of such promising technologies to
produce syngas in an energy efcient manner. The gasication of
ligno-cellulosic biomass has high conversion efciency among various
thermo-chemical conversion technologies [5]. Due to several advan-
tages, biomass gasication technology has drawn an attention around
the world [3,5,6]. As for example, over the past decades the North
Dakota Energy and Environmental Research Center has developed and
applied the gasication of solid fuels (coal, biomass, coalbiomass
blends), cleaned syngas and converted syngas to useful energy [7].
Biomass based energy has been prioritized in current European
Union (EU) strategies to mitigate climate change and improve energy
Corresponding author. Tel.: +49 721 608 23832; fax: +49 721 608 24303.
E-mail addresses: deepak.pudasainee@itc-tab.fzk.de, deepu003@hotmail.com
(D. Pudasainee).
security. The member states of the EU are committed to acquire 20%
of their energy requirements from renewable sources, including bio-
mass, by the year 2020 [8]. German government's Energy Concept
(2010) aims to increase the share of regenerative energies up to 18%
of the end-use energy by the year 2020. Inuenced by these activities,
biomass gasication research and development work has increased
intending on improving efciency; reduce pollutants release during
the process utilization. In spite increasing use, one of the environmental
aspects that have not been studied comprehensively is the fate of trace
metals during biomass gasication process.
Biomass contains trace quantity of metals [9]. Biomass burning, both
natural and anthropogenic means has been reported as a source of
atmospheric metals including mercury emissions [1012]. Trace metals
introduced into a gasication system, mainly from feedstocks, undergo
transformation and removal within the system and the left over enters
the chemical conversion steps together with syngas or if syngas is used
as fuel in gas engines leaves the system with ue gas. Some trace metals
in syngas cause fouling and corrosion of the gas turbine blades [13].
Trace metals in syngas also affect the catalyst in the system and results
in low biomass to fuel conversion. Specically, as for example, alkali
metals (Na, K) and heavy metals V, and Zn species can damage materials
in heat and power plants, cause abrasion, corrosion and erosion of inter-
nal parts, inuences energy and mass ow in the system. Further, depo-
sition of alkali species such as NaCl, Na2SO4, and Na2CO3, can poison and
deactivate catalysts [14] and fuel cells. To achieve an economically
acceptable service lifetime of catalyst, Hg and As concentration in
syngas at the inlet should be reduced to b 5 ppb [15,16]. The catalyst
deactivation by other trace heavy metals such as Pb and Cd in off-gas

0378-3820/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.fuproc.2013.12.010
 D. Pudasainee et al. / Fuel Processing Technology 120 (2014) 5460
has been reported, however, the quantitative data is lacking. Never-
theless, trace metals in biomass gasication are to be controlled, as
minimum as possible, to increase the lifetime of the facility itself,
increase biomass to fuel conversion and to create the cleaner
environment.
To some extent, trace metals emission in combustion ue gas is
known [1719]. However, their behavior in gasication environment
is unclear. Considering the difference in off gas chemistry, an apparent
difference in trace metal emission behavior between combustion and
gasication atmosphere can be rationally anticipated. Behavior of
trace metals during gasication process utilization has been studied by
some researchers [20,21]. However, most of these studies are carried
with fuels containing relatively higher amount of trace metals, mainly
coal. Very few studies [9] have investigated trace metals emission dur-
ing gasication from fuels with relatively lower content of trace metals
such as biomass and thus their behavior is still scarcely known. Before
biomass gasication technology is used widely, understanding biomass
characteristics and metals content in feedstocks and behavior in pro-
duction process, input and output streams are vitally important, which
is lacking in the existing literature. In this paper for the rst time we
have presented trace metals emission and distribution from gasication
of straw char at 60 kW atmospheric entrained gasier.
The Karlsruhe Institute of Technology (KIT), Germany has developed
a two-stage process bioliq for the production of synfuel from
biomass [22,23]. The process involves: 1) pyrolysis of straw and other
lignocellulosic agricultural byproducts at a regional plant, 2) bio-
syncrude gasication and syngas conversion in a central plant. The
energy-rich suspension, obtained from pyrolysis plants is gasied in
an entrained-ow gasier and converted into syngas, a chemically reac-
tive mixture of CO and H2. Pyrolysis is the starting point in the bio-
mass gasication process, bioliq. The biomass char, oil obtained
from pyrolysis are gasied to produce fuel gas that can be used to
produce heat, electricity, or converted into syngas. In this paper
characteristic of feedstocks namely glycol (model fuel) and straw
char is presented. Further, experiments were carried out to deter-
mine emission concentration of trace metals in syngas and their dis-
tribution into particle and gas phases at the atmospheric entrained
ow gasier REGA.
Fig. 1. Process ow diagram of the pilot-scale gasier REGA [22].
55
2. Experimental
2.1. Pilot-scale gasier-REGA
Fig. 1 shows the process conguration of a 60 kW pilot-scale atmo-
spheric entrained ow gasier REGA (Research Entrained Flow GAsi-
er) at Karlsruhe Institute of Technology (KIT), Germany. At REGA basic
research on the inuence of atomization and fuel specication on the
syngas quality is carried out. The ceramic tube reactor of the gasier
is 3 m long with inner diameter of 28 cm. The gasier walls can be
heated up to 1200 C. The adiabatic temperatures were 2000 C
(Test 11), 1700 C (Tests 12, 13) and 1700 C (Tests 21, 22, 2
3). Experiments were carried out with fuels: i) glycol ii) and slurry
(glycol + straw char 10 wt.%), with feeding rate of 12.6 kg/h and
12.4 kg/h in Test 1 and 10.05 kg/h in Test 2. The air numbers were
0.57 and 0.46 in Test 1 and 0.52 in Test 2. Air enriched with oxygen
(53.8 vol.% and 69.3 vol.% in Test 1 and 41.2 vol.%. in Test 2) were
used as gasication agent. Syngas after the reactor was cooled by a
tube-in-tube heat exchanger and a scrubber. During experiment, the
gasication process was monitored by the reactor temperature and
syngas composition. Experimental parameters and syngas composition
in this study are summarized in Table 1. The syngas composition differs
due to different feedstocks: glycol and slurry and different experimental
conditions in Test 1 and Test 2.
2.2. Feedstocks characteristic
The feedstocks employed for biomass gasication were straw char
and glycol. In order to achieve well dened operating conditions glycol
was considered as model feedstock. The energy-rich straw char (mixed
with glycol) obtained from pyrolysis were gasied in an entrained-ow
gasier and converted into synthesis gas, a chemically reactive mixture
of CO, H2 and so on. The main reason to use glycol as a model fuel was
the oxygen content, which is comparable to pyrolysis oil from biomass
[24]. The physico-chemical characteristics: elemental (C, H, N, S, O)
composition, heating value, chlorine content, and volatiles in feedstocks
used in the gasication process were analyzed.
56 D. Pudasainee et al. / Fuel Processing Technology 120 (2014) 5460

Table 1 Table 2
Experimental parameters and syngas composition in this study. Elemental composition, heating value, chlorine content in straw char and glycol used in
gasication.
Parameters Glycol (Test 1) Slurry (Test 2)
(Straw char 10 wt.%) Parameters Mass (%, dry basis)

Test 11 Tests 12, 13 Test 21 Tests 22, 23 Straw char Glycol

Fuel ow rate (Kg/h.) 12.60 12.42 10.05 10.05 C 60.4 38

Stoichiometric ratio () 0.57 0.46 0.523 0.523 H 3.4 8.9
O2 content of gasication 53.70 69.3 41.82 41.82 N 1.2 0.3
agent (%) S 0.2 b0.0001
CO (%) 22.86 29.41 21.79 21.36 O 22.0 43.6
CO2 (%) 21.98 19.17 16.59 16.18 Higher heating value (MJ/kg) 23.2 18.8
H2 (%) 20.77 30.03 18.91 18.71 Chlorine (mg/kg) 4183 36.5
CH4 (%) 0.019 0.49 0.44 0.52
Corg (mg C/Nm3) 60 1990 1950 2200
Syngas ow rate (Nm3/h.) 29 26 26 26 heating value of straw char (23.2 MJ/kg) and glycol (18.8 MJ/kg) was
higher than of biomass (1415 MJ/kg). Chlorine content in straw char
and glycol were 4183 and 36.5 mg/kg, respectively. Average chlorine
2.3. Sampling and determination of selected metals in feedstocks and content of coal, biomass and straw pellets are reported 901100 mg/kg,
syngas 1006000 mg/kg [25] and 2700 mg/kg [26], respectively. Noticeably,
chlorine content in straw char is much higher than coal. With the increas-
Selected alkali, alkaline, trace metals content in straw char and eth- ing use of biomass, mainly agricultural residues, the problem of chloride
ylene glycol (glycol) used for gasication and in resulting syngas were induced corrosion is increasing. Chlorine concentration in biomass has
determined. Concentration of selected alkali and alkaline metals (Na, an important role in determining alkali vaporization and corrosion. Chlo-
K, Ca and Mg) in feedstocks were high enough to be analyzed by rine aids the movement of many inorganic compounds, mainly K. Thus,
Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES) high chlorine concentration in fuel possesses higher risk since alkali act
(Optima 4300 DV, PerkinElmer Inc.). Trace metals concentrations as a Cl carrier to super heater, where elemental chlorine is released. Ash
were determined using Inductively Coupled Plasma Mass Spectroscopy content of straw char at 815 C was 19%. Volatile matters in straw char
(ICP-MS) (X Series 2, Thermo Scientic). on an average were 25.6% to 25.8%. Moisture content and x carbon in
Particulate and gas samples were collected to determine selected straw char sample were 4.3% and 51%, respectively. In general, volatile
trace metals, including Hg speciation, in syngas according to US EPA matter was higher in straw char compared to coal whereas heating
method 29. US EPA method 29 is a multi metals analysis method, in- value and xed carbon were lower.
cluding mercury analysis with speciation at the same time. Syngas sam- Elemental content in straw char and glycol were, C 60.4% and 38%,
ple was withdrawn from the duct after gasier (after cooler). Particulate S 0.25% and b0.0001%, H 3.4% and 8.9%, N 1.2% and b 0.1% and O 22.0%
matter was collected in a heated lter at the front end of the probe. and 43.6%, respectively. Sulfur content was lower. Sulfur content in
Syngas withdrawn was passed through the ltration system followed fuel has been reported effecting Hg emission and speciation in combus-
by a series of impingers in an ice bath. All metals including oxidized tion ue gas. Sulfur content in fuel and the SO2 concentration in ue gas
Hg were collected in an aqueous acidic solution of hydrogen peroxide have an inuential role on Hg0 oxidation in ue gas. The low sulfur fuel
(5%HNO3/10%H2O2) solution. Elemental Hg was collected in an acidic is more preferred because rstly it reduces SO2 emission and secondly it
solution of potassium permanganate (4%KMNO4/10%H2SO4) solution. promotes Hg removal in control devices.
Any remaining moisture was removed in the last impinger, in a series
containing silica gel. Syngas temperature at the sampling point ranged 3.2. Metals content in feedstocks
169196C. Recovery of samples was carried out immediately after
sampling. The recovered samples were pre-treated, digested and ana- Trace metals concentration in biomass differs with place of origin,
lyzed using ICP-MS. Syngas components such as CO, CO2, H2, Corg, CH4, types, geology etc. Metals emission concentration in syngas from bio-
were measured with analyzers installed at the gasier. mass gasication is without doubt related to their content in biomass.
Alkali and alkaline metals are abundant in biomass. In general, K, Na,
2.4. Morphology of particulate matter in syngas Ca and Mg content in biomass are higher than coal. Metals content in
straw char and glycol used in gasication is presented in Table 3. Metals
Fly ash particles were analyzed by scanning electron microscope content in glycol and straw char were Na (1.5 and 395 mg/kg), K (b1
(SEM) for morphological analysis. ZEISS Supra 55 VP SEM, eld emission and 42,800 mg/kg), Mg (b1 and 3560 mg/kg), and Ca (b1 and
gun (FEG), secondary electron detector type instrument was used. 16,800 mg/kg). Reported value of Na and K in straw/grass ranged be-
Samples preparation and handling for particle analysis by SEM were tween 7015,000 mg/kg and 500030,000 mg/kg. Generally, biomass
done according to standard operating procedures. Different magnica-
tions were applied to clearly view the morphology of particles.
Table 3
3. Results and discussion Trace metals content in straw char and glycol used in gasication.

Metals Concentration (mg/kg)

3.1. Feedstocks characteristic
Straw char Glycol

Feedstocks characteristics are important parameter determining As b1 b0.1

metals distribution, transformation and emission during biomass gasi- Be b0.5 b0.05
Cd 0.2 b0.05
cation. The physico-chemical characteristics: elemental (C, H, N, S, O)
Cr 1390 b0.5
composition, higher heating value, chlorine content, in straw char and V b1 b0.1
glycol used in the gasication process are shown in Table 2. From ele- Ni 2190 b0.05
mental analysis it can be seen that straw char from pyrolysis has higher Pb 41 b0.1
carbon content, even higher than biomass because during pyrolysis vola- Se b1 b0.1
Hg 0.002 0.0002
tiles are removed from the straw and carbon remains in the char. Higher
 D. Pudasainee et al. / Fuel Processing Technology 120 (2014) 5460 57

has high alkali content that may have catalytic inuence in gasication 11) and 1900 mg C/Nm3 (Tests 12,13), whereas 1950 mg C/Nm3
process [27,28]. Similarly, trace metals concentration in straw char and (Test 21) and 2200 mg C/Nm3 (Tests 22, 23). Unburned carbon con-
glycol were Cr (b0.5 and 1390 mg/kg), Ni (b0.05 and 2190 mg/kg), Pb tains active carbon sites where metals can bind [31]. The increase in y
(b0.1 and 41 mg/kg), As (b 0.1 and b 1), Be (b0.05 and b 0.5), Cd (b0.05 ash particles in syngas increased the sorption sites for metals resulting
and 0.2), V (b0.1 and b1 mg/kg), and Se (b 0.1 and b1). Hg increased particle bond metals in Test 2 compared to Test 1. V and Se
concentration in glycol and straw char ranged 0.0002 mg/kg, and were speciated more into gas phase even though the carbon content in
0.002 mg/kg, respectively. Documented metal concentrations in bio- syngas increased (Test 2). No signicant differences in distribution behav-
mass are As (0.16 mg/kg), Cr (0.1525 mg/kg), Cd (0.10.3 mg/kg), ior into particle and gas phase (in Test 1 and Test 2) were measured for Ni,
Ni (0.210 mg/kg), Pb (15 mg/kg), V (0.13 ppmw), and Hg (0.01 Cd and As. However, it is to be noted that metals in syngas, in general,
0.05 mg/kg) [29,30]. were distributed more in gas phase compared to combustion ue gas.
Metals distribution into particle and gas phase in syngas from bio-
3.3. Trace metals emission, distribution into particle and gas phase in mass gasication is affected by several possible factors such as operating
syngas temperature, reactor conguration, chlorine, sulfur, moisture content,
oxygen availability, element constituents and so forth [32]. Considering
Trace metals introduced into a gasier, mainly from feedstocks the fact that trace metals behave differently in different gasication
(straw char and glycol) undergo transformation and removal within environment (syngas components, operating conditions), the behavior
the system (boiler, cooler, syngas cleaning devices) and the remaining of metals species during gasication cannot be generalized for wider
enters the chemical synthesis process (in case of bioliq). Table 4 implications. The effects of syngas constituents on metals distribution
shows trace metals concentration and distribution in syngas at two into gas and particle phase are to be considered in the future study.
different gasication feedstocks (i) glycol and (ii) slurry. The emission However, one possible factor contributing higher portion of gas phase
concentration of trace metals from glycol gasication were in the metals in Test 1 is availability of very less amount of particle matter
order of Cr N Pb N Ni N Hg N As N Se N Be N V N Cd. In Test 1 (i.e. glycol for metals to be adsorbed. Whereas, might be due to formation of
gasication), metals concentration in syngas ranged from 0.1 g/Nm3 more metals chlorides species attributed by higher amount of chlorine
(V) to 4.6 g/Nm3 (Cr). In Test 2 (slurry gasication) the emission content in straw char (Table 2), in Test 2.
concentration of trace metals were in the order of Ni N Cr N Pb N As N
V N Be N Se N Cd N Hg. Metals concentration in syngas ranged from 3.4. Mercury emission and speciation in syngas
2.4 g/Nm3 (Hg) to 53.2 g/Nm3 (Ni). Metals concentration in syngas
increased moving from Test 1 to Test 2 because there were higher Mercury, unlike other trace metals behaved differently due to high
content of metals in straw char compared to glycol. The measured emis- volatility. Hg speciation generally refers to its distribution into various
sion concentrations of metals in syngas are less compared to emission chemical forms. Emission of Hg compounds in gasication syngas exists
from coal gasication. However, it should be noted that with the in three main forms: elemental (Hg0), oxidized (Hg2 +) and particle
increasing portion of char in glycol (future target of bioliq) trace bond (Hgp). (i) Gaseous elemental mercury (Hg0): mostly associated
metals emission concentration will increase. Unlike combustion system, with minerals, relatively non-reactive and insoluble in water. Thus, usu-
gasication system is more sensitive with increased trace metals con- ally escapes emission control equipment and emitted into the atmo-
centration considering their effect in catalyst deactivation, so efforts sphere. (ii) Reactive gaseous or oxidized mercury (Hg2+): is soluble in
need to be directed to control trace metals as minimum as possible, water and can be removed in wet scrubbers. (iii) Particulate mercury
e.g., Hg and As b 5 ppb [15,16]. In order to meet the safe limit highly ef- (Hgp): associated with particles (ash). Hgp can be removed in particu-
cient gas cleaning system is required. Based on the present study, re- late control devices. These all together comprises total Hg (HgT).
moval efciency more than 78% is required for As, which is one of the As expected, Hg in syngas was speciated predominantly in elemental
challenges to meet. form (63.0% to 71.5%) followed by oxidized form (27.5% to 32.7%). The
All the heavy metals were more enriched in y ash from slurry share of particle bond mercury was less (1 to 4.4%). Decreasing tenden-
gasication compared to glycol gasication. In general, more portions cy of Hgp in glycol than slurry gasication, which is due to the reduction
of trace metals were distributed into gas phase. In Test 1, V, As and Be of y ash particles and carbon content in it, as discussed in Section 3.3.
were mainly distributed into particulate phase whereas, Ni, Cd and Hg Elevated temperature and reducing atmosphere in gasier resulted
were mainly distributed in gas phase (Fig. 2). Tendency of metals (Be, most of the Hg in elemental form. Hg in fuel/feedstocks is believed to
Pb, Cr, Hg) to speciate into particle phase increased in Test 2 than Test vaporize completely and converted into Hg0 in gasication zone, since
1, which is related to increase in y ash particle and the unburned Hg0 is thermodynamically stable at high temperature in boiler. In com-
carbon content in it. In average, y ash particles in syngas were bustion ue gas, as Hg0 passes the ue gas stream it may further react
59.5 mg/Nm3 (Tests 11, 12, 13) and 1511.7 mg/Nm3 (Tests 21, 2 with acid gases, halogens, and thus mostly mercury in downstream of
2, 23). Similarly, carbon content in syngas were 60 mg C/Nm3 (Tests boiler is found as Hg2 + compounds. The degree of conversion of Hg0
to Hg2+ and Hgp primarily depends on ue gas components, operating
conditions, process conguration, quenching rate, air pollution control
Table 4
devices (APCDs) conguration etc.
Trace metals concentration (g/Nm3) and distribution into particle and gas phase in
syngas, average value of 3 measurements. In contrast to combustion environment, in gasication environment,
due to the reducing atmosphere and reactions with syngas components
Metals Glycol gasication Slurry (straw char such as CO and SO2; Hg2+ compounds may be reduced to Hg0 as it pass
10 wt.%) gasication
downstream of the boiler. Lack of oxygen at reducing atmosphere in the
Particulate Gas Particulate Gas gasier prevents the formation of chlorine (which may oxidize Hg)
V 0.1 0.02 9.9 4.8 from hydrogen chloride. These might be the likely explanation for
As 0.8 0.1 18.5 3.8 higher portion of Hg0 in our measurements. The present measurement
Be 0.3 0.1 9.9 0.04
is also in agreement with the study by Li et al., [20] where it is reported
Se 0.3 0.3 3.0 4.8
Pb 1.4 1.9 27.3 4.5 that at the gasier outlet mercury content in coal were released mainly
Cr 1.8 2.8 28.7 5.8 as Hg0. Variation in Hg emission concentration and speciation within
Ni 0.7 1.8 15.1 38.1 the samples is related to the non-uniform distribution of Hg in feed-
Cd 0.03 0.1 0.9 4.3 stock, fuel composition (especially Cl, S content), operating parameters,
Hg 0.01 2.2 0.5 1.9
interaction with syngas components, y ash properties etc.
58 D. Pudasainee et al. / Fuel Processing Technology 120 (2014) 5460
Fig. 2. Trace metals distribution into particle and gas phase in syngas. T#1: Glycol gasication; T#2: Slurry (straw char 10 wt.% gasication.
Theoretical chemical equilibrium calculation provides a valuable
insight to the stable species that are formed during combustion process
as a function of temperature. Thermodynamic model estimation shows
that mercury was more volatile in reducing gasication condition than
oxidizing conditions [21]. This might be because volatile gaseous com-
pounds like Cl, SO4, and OH are more stable in reducing environ-
ment. Study has shown that Hg0 oxidation by gas-phase reaction with
individual syngas components is very less. However, in simulated
syngas conditions, Hg0 oxidation in gas phase reactions occurred only
either Cl2 or HCl + COS was introduced in syngas mixture. Hg0 oxida-
tion was more notable after involvement of y ash in syngas [33].
Hg distribution into particle phase was lesser. The adsorbing ability
of y ash particles determines Hg speciation into particle and gas
phase. The absorption capacity can be increased with treating y ash
with chemicals such as bromine [34]. Fly ash (with unburned carbon)
contains active carbon sites where Hg2 + can bind. Cl and S in y ash
(Hg\Cl and Hg\S bond respectively) and the temperature of ue gas
are important in determining Hg sorption capacity [35]. On the other
hand, sulfur oxides such as SO2 and SO3 can bind to these active sites
inhibiting the binding of Hg [36]. Thus, sorption and desorption of Hg
in y ash depends on syngas condition and interaction with several spe-
cies which is bit complex, needs further studies in controlled conditions.
3.5. Relative enrichment of metals in y ash
Relative Enrichment index (REI) reects the change in concentration
of trace metals in combustion products. REI is also used to distinguish
the different classes of elements. REI was calculated using the following
formula [37].
REI Concentration of element in ash  Ash percentage in the feed fuel
Concentration of element in feed fuel  100
REI of trace metals in y ash is shown in Table 5. During glycol
gasication, there were very less particles in syngas and almost all the
trace metals were distributed into gaseous form, thus REI values were
signicantly lower and are not comparable to that in glycol slurry gasi-
cation. Hence, the data is not presented here. All the trace metals were
more enriched in y ash from slurry gasication compared to glycol y
ash. The REI of V, Se, Cr, Ni, Cd, and Hg in y ash were lower than 1, im-
plies that these metals tend to volatilize in reducing gasication
environment. Mercury is highly volatile and was almost distributed in
syngas with least REI value (0.01) in y ash. REI of As, Be, and Pb in y
ash were 0.01 in glycol gasication, whereas more than 1.2 in slurry
gasication. This reveals that availability of particle and carbon content
in syngas has strong inuence in determining the distribution behavior
of As, Be, Pb. However, the inuence of particle and carbon content in
syngas was not strong for V, Se, Cr, Ni, Cd and Hg. Depending on volatil-
ization and REI, trace elements in coal ashes are classied into three
classes [38,39]. Non-volatile elements are mainly collected with y
ash or bottom ash. Whereas volatile elements like Hg and an intermedi-
ate volatile metals for example As and Se are emitted to the atmosphere.
Ni, Pb, Cd, and Cr fall in class II, which are distributed into particles and
mostly removed in the APCDs.
3.6. Morphology of y ash particles
Fig. 3 (a) shows the morphology of straw char particles before
gasication showing irregular shape particles, those are rich in carbon
content as shown in elemental analysis. Fig. 3 (b) shows the morpholo-
gy of particles in syngas emitted from slurry gasication. Particles with
heterogeneous size and shapes were observed. No ash agglomeration
was observed. The irregular shaped particles are dominant, which are
unburned char particles and mineral substances. The minerals present
in particle surface in different samples are almost the same. Basically,
two types of particles existed in y ash from gasication (i) irregular
mostly unburned carbon (char) particles and mineral substances, and
(ii) spherical particlesformed by volatilization and condensation.
Mostly, the spherical particles were lesser than 10 m in geometric
diameter. This implies that melting might have occurred only in a very
limited region, e.g. on the surface of burning char [40] and feeding of
ne milled straw char in the gasier.
Fig. 3 (c) shows the magnied view of the spherical particle. Spher-
ical particles are formed by nucleation and condensation. Micro-spheres
Table 5
REI of trace metals in y ash from slurry
gasication.
Metals REI
V 0.1
As 1.4
Be 1.5
Se 0.3
Pb 1.2
Cr 0.3
Ni 0.3
Cd 0.1
Hg 0.1
 D. Pudasainee et al. / Fuel Processing Technology 120 (2014) 5460 59

Fig. 3. SEM photograph of y ash particles in syngas emitted from slurry (straw char 10 wt.%) gasication. (a) Char particles before gasication (b) Overall view of particles at
2000 magnication, (c) Spherical particles at 10,000 magnication (d) Char particles at 5000 magnication.

were not seen to cluster each other. Fig. 3 (d) shows the closer view of
the char particles. The char particles appear spongy and hole-like struc-
tures appears in the surface due to release of volatiles from char parti-
cles. Some ne spherical particles are seen trapped in char particles. It
is also evident from quantitative analyses that syngas contained signif-
icantly higher levels of unburned carbon in slurry compared to glycol
gasication. The unburned carbon has some oxidant/adsorption sites
similar to activated carbon. The occurrence of more number of char
particles in syngas is favorable for reducing the emission of mercury
into the atmosphere [38,41]. It can therefore be anticipated to have
more reduction of trace metals emission from gasication system than
the similar combustion system.
4. Limitations and uncertainties
We are not aware of standard method for sampling and analysis of
metals in syngas. In the absence of validated method for measuring
metals in syngas from gasication, the sampling methods developed
for metals measurement in ue gas from combustion system has been
used [9]. However, this has certain limitations such as lack of informa-
tion about inuence of y ash cake particle, inuence of syngas compo-
nents etc. As presented in Section 3.3 syngas from slurry gasication
contained higher y ash particles and carbon content in it. Fly ash parti-
cles collected in the lter (lter cake layer) during sampling might inu-
ence the adsorption of metals in the cake layer affecting the distribution
of metals into particle and gas phase. In general, this effect is anticipated
to be more for Be, Pb, Cr, and Hg. The effects of lter cake on adsorption
behavior of metals in gasication environment are to be quantied in
the future.
Due to variation in operating conditions, syngas chemistry, paramet-
ric uncertainties (such as measurement, sampling and systematic
errors) etc. emission measurement is subjected to uncertainty. All the
efforts were made to ensure that the data collected during this study
are of higher quality. Equipments and analyzers were calibrated and
operated according to the manufacturer's specication. Sampling, han-
dling, storage, recovery, analysis were done as per standard operating
procedure. Sampling, tests and analysis, at the identical condition,
were carried out three times to ensure reliability.
5. Conclusions
The physico-chemical characteristics: elemental composition, heat-
ing value, chlorine content, and selected trace metals in straw char
and glycol used in the gasication process were analyzed. Trace metals
emission concentrations, distribution into particle and gas phase were
measured, and particle morphology was observed. The following con-
clusions can be drawn from the present study.
1. Concentrations of all the metals (As, Be, Cd, Cr, V, Ni, Pb, Se, Hg) stud-
ied were very low in glycol. However, emission concentrations of
60 D. Pudasainee et al. / Fuel Processing Technology 120 (2014) 5460
metals in syngas from glycol gasication were detected. During glycol
gasication, metals concentration in syngas ranged from 0.1 g/Nm3
(V) to 4.6 g/Nm3 (Cr). In slurry gasication, metals concentration
ranged from 2.4 g/Nm3 (Hg) to 53.2 g/Nm3 (Ni). Considering
their contribution in catalyst deactivation, efforts are required to
control trace metals as minimum as possible.
2. In general, metals distribution into gas phase in syngas was higher
than combustion ue gas. Tendency of metals to speciate into parti-
cle phase increased in slurry gasication than glycol gasication
due to increase of y ash particles and carbon content in it.
3. Mercury emission concentrations in syngas ranged from 2.2 to
2.4 g/Nm3. Mercury in syngas was speciated predominantly into
elemental form followed by oxidized form whereas share of particle
bond mercury was the least.
4. The REI values showed the tendency of trace metals to volatilize
more in reducing gasication environment. Availability of particle
and carbon content in syngas had strong inuence in distribution
behavior of As, Be, and Pb than other metals studied.
Study on relation of trace metals emission and speciation with oper-
ational variables (temperature and gas composition) are to be carried
out.
Acknowledgments
Dr. Deepak Pudasainee acknowledges his postdoctoral research
fellowship from Alexander von Humboldt Foundation, Germany.
Authors thank Dr. Britta Bergfeldt, Dr. Gnter Beuchle from Institute of
Technical Chemistry, KIT for their help during experiment and sample
analysis.
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