Renewable Energy 115 (2018) 1e5

Contents lists available at ScienceDirect

Renewable Energy
journal homepage: www.elsevier.com/locate/renene

Effect of leaching pretreatment on the gasification of wine and vine

(residue) biomass
Siim Link b, *, Stelios Arvelakis a, Aadu Paist b, Truls Liliedahl c, Christer Rose

n c
a
Bioresource Technology Unit, Laboratory of Organic and Environment Technologies, Department of Chemical Engineering, National Technical University of
Athens, Zografou Campus, GR-15700, Athens, Greece
b
Department of Energy Technology, School of Engineering, Tallinn University of Technology, Ehitajate tee 5, 19086, Tallinn, Estonia
c
Division of Chemical Technology, KTH Royal Institute of Technology, Teknikringen 42, SE-100 44, Stockholm, Sweden

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

Article history: Utilization of biomass residues for energetic purposes increases the share of renewables in the total
Received 25 January 2017 energy balance. Gasification is one of the thermochemical processes that converts solid biomass to
Received in revised form valuable gaseous products. Prior to the gasification process, biomass material could be treated to improve
14 July 2017
the quality or composition of the product gas. Our focus is on fluidized bed gasification of untreated vine
Accepted 12 August 2017
Available online 13 August 2017
and pretreated vine residue and pretreated wine residue. Natural and artificial leaching were used as
pretreatment methods. Our results showed that CO and H2 content in the product gas are higher in
leached (16.9 and 10.0% respectively) vine residue than in untreated material (14.5 and 7.7% respectively).
Keywords:
Biomass
The naturally leached wine residue was found to have the highest CO content (18.1%) and relatively high
Pretreatment H2 content (9.7%) in the product gas, but lower CH4 (1.0%) and CO2 content (5.6%). The results of tar
Gasification measurements indicated that the leaching pre-treatment lowers the tar content in the evolved product
gas, e.g. by 36% in the case of vine residues. As a result, the controlled leaching pretreatment is rec-
ommended as an effective way of upgrading the composition of agricultural biomass.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction
In order to save fossil fuels and prevent global warming, biomass
fuels have been given increased attention [1]. Fossil fuels are the
primary feedstock for energy/fuels production in the world, but the
use of biomass for energetic purposes will decrease the consump-
tion of fossil fuels, and also helps to reduce the greenhouse gas
(GHG) emissions. Bioenergy is expected to become one of the major
energy resources in the future [2]. Among all thermochemical
conversion processes, gasification is one of the most promising
routes for the conversion of biomass to energy and fuels. Compared
to combustion, gasification exhibits improved energy efficiency in
combined cycle plants, reduced emissions, and lower operating
temperatures. The conversion of solid biomass to gaseous fuel
provides opportunities for retrofitting coal-fired boilers, replacing
natural gas in process heating, and developing distributed power
systems using biomass that are based on internal combustion en-
gines, gas turbines, or fuel cells [3]. The main reactor types used for
* Corresponding author.
E-mail address: siim.link@ttu.ee (S. Link).
biomass gasification are the fixed bed and the fluidized bed re-
actors. Fluidized beds exhibit excellent heat and mass transfer be-
tween the gas and the solid phase as well as temperature
distribution, high specific capacity and fast heat-up. They can
tolerate wide variations in fuel quality as well as a broad particle
size distribution. However, high dust content in the gas phase as
well as arising agglomeration/defluidization behaviour in the case
of biomass materials with low melting point ash (due to the pres-
ence of the constituents such as alkali metals and chlorine) pose a
serious problem for the fluidized bed reactors [4e7]. The distri-
bution of the gasification products could be influenced by different
kinds of biomasses and their mixtures under gasification conditions
and it is important to study the behaviour of different biomass
materials and their mixtures under gasification conditions in terms
of the optimization of process parameters and reactor design [8,9].
Many biomass feedstocks benefit from pretreatment to improve
physical and chemical properties for downstream energy conver-
sion, both thermochemical and biochemical [10]. One of them is a
leaching pretreatment method targeted on the removal of alkali
metals, sulphur and chlorine from the biomass material prior to
thermochemical conversion [11].
Wine and vine residue are the by-products of the wine industry

http://dx.doi.org/10.1016/j.renene.2017.08.028
0960-1481/© 2017 Elsevier Ltd. All rights reserved.
2 S. Link et al. / Renewable Energy 115 (2018) 1e5
in many countries in the Mediterranean region and their potential
as a source for energy production requires investigation. For
instance, in Greece, approximately 200 thousand tons of wine
residues and 560 thousand tons of vine residues are produced per
year [12].
This work studies the fluidized bed gasification of the untreated
as well as the pretreated (leached) vine residue, the naturally
leached wine residue, and the mixture of the naturally leached
wine and the untreated vine residue. Our analysis focuses on the
effect of the leaching pretreatment process under controlled as well
as under natural conditions on the product gas composition and tar
components on the wine and vine residue materials.
2. Materials and methods
2.1. Materials
We selected two parent fuel biomass materials, such as wine
and vine residues, for our study. Both of them originate from Greece
and come from Sitia prefecture in Crete. The used materials were
prepared and characterized in accordance with American Society
for Testing and Materials (ASTM) methods, such as D 2013-86
(Reapproved 1994), D 1102-84, D 3175-89a, D 5142-90, D 5373-93,
D 4208-88, D 2015-95 - proximate and ultimate analysis, gross
calorific value and ash analysis.
In gasification tests, next parent fuels and blends were used: a)
untreated vine residue (UVR), b) leached vine residue (LVR), c)
naturally leached wine residue (NLWR), and d) the blend of 50% of
untreated vine residue and 50% of naturally leached wine residue
(50UVR/50NLWR).
2.2. Leaching
The artificial leaching pretreatment procedure was applied on
the vine residue. Artificial leaching of the vine residue was carried
out according to the method developed by Arvelakis and Koukios
[13]. During the leaching process, the sample was put in a 200-
mesh plastic grid, tied up and submerged into tap water in a plastic
75 l volume barrel. The used mass/water ratio was 88.8 g/l and the
retention time was 12 h. At the end of the process, the sample was
left to air dry until constant weight under the sun of the Mediter-
ranean summer for a period of 5 days. During the drying process,
the bed thickness of the drying sample was kept below 15 cm to
guarantee the fast drying process without material loss due to
mold.
Wine residue was exposed to the natural leaching during the
winter period of 2006e2007. However, we were unaware of the
amount of precipitation received during that time.
2.3. Gasification set-up
The atmospheric fluidized bed gasifier was used in this study.
The gasification set-up coupled with a schema is described in detail
elsewhere [14]. However, we present here some essential data
regarding the experiment: the feeding rate of the screw feeder was
4 g/min; the gasification agent used: nitrogen with a flow rate of
9.5 l/min and oxygen with a flow rate of 0.85 l/min; the gasification
tests were performed with a reactor temperature of 800  C.
2.4. Evolved gas analysis
The components of the evolved product gas (CO, CO2, H2, CH4
and C2H6) were determined by gas chromatography (Shimadzu GC-
9AM), which comprises a thermal conductivity detector (TCD) and
a flame ionization detector (FID), as described elsewhere [14].
2.5. Tar sampling
The tar content of the evolved product gas was measured by the
solid-phase adsorption (SPA) method developed by Brage et al. [15],
as described in Ref. [14]. The advantages and disadvantages of this
method are discussed in Ref. [14].
2.6. Brief description of the gasification test procedure
The reactor was heated up to the desired temperature (800  C)
using external electrical heaters. After the reactor temperature was
stabilized, the fuel was fed in. The evolved product gas was led only
through the ceramic filter and the tar sampling was carried out.
During the experiment, the gas composition was determined after
every 10 min by the gas chromatograph. The tar sampling was
carried out right after the moment the gas chromatograph finished
the suction of the product gas for the analysis.
3. Results and discussion
3.1. Fuel characterization and composition
The leaching pretreatment decreases the ash content of the vine
residue (Table 1). The relatively high ash content of the naturally
leached wine residue is attributed to the occurrence of the soil
material in the sample due to its long stay outdoors during the
natural leaching process. In general, it was observed that the
amount of ash is reduced via the leaching pretreatment. In addition,
due to leaching, the chlorine content was reduced, but the volatile
matter content was increased. Previous research results from
Arvelakis [12] regarding wine residue verify these assumptions.
Also, previous studies have indicated increased volatile matter
content after leaching [14,16]. It is clear, that the naturally leached
wine residue exhibits extremely low gross calorific value for the
biofuel due to the high content of mineral matter, as discussed
above. The effect of the leaching pretreatment on the increase of
the gross calorific value of vine residue is low, amounting to 5%.
It can be seen from Table 2 that the naturally leached wine
sample has relatively high SiO2 content of 36.8% in ash, which
corresponds to 5.4% of Si content of the parent material. This
amount is assumed to be much higher than that in the untreated
wine residue (0.8% is Si content in the parent fuel), which is
attributed to the soil pollution of the leached material. At the same
time, the alkali metals (except Mg) and the chlorine content of the
leached wine residue were reduced moderately compared to the
untreated wine residue. The content of alkali and alkali earth
metals and chlorine is lower in the leached vine residue under the
controlled leaching conditions compared to the uncontrolled nat-
ural leaching of wine residue. This leads to the result that the
controlled leaching process produces better results than the natural
leaching process. The Si content of the parent material for the un-
treated and pretreated vine residue is 0.24%. The K2O content
calculated on the basis of the parent material is 8.3% or the K
content of 6.9% for the naturally leached wine residue. The K con-
tent of the untreated vine residue in the parent material is 0.38%
compared to that of 0.24% in the leached material. The Na content of
the untreated vine residue in the parent material is 0.078%
compared to that of 0.041% in the leached material. The reduction
of potassium is 37% after leaching and for sodium 47%. The chlorine
content is reduced after leaching from 0.0042% down to 0.00062%
(decreased by 85%), and the sulphur content is reduced after
leaching from 0.020% down to 0.014% (decrease by 30%) calculated
on the basis of the parent material in the case of the vine residue.
The CaO content in the naturally leached wine residue ash is quite
moderate, but due to the high ash content, the total amount of Ca
 S. Link et al. / Renewable Energy 115 (2018) 1e5 3

Table 1
Analysis and characterization of biomass samples.

Material Proximate analysis, dry basis (wt%) Ultimate analysis, dry basis (wt%) Gross Calorific value (MJ/kg)

Moisture Ash Volatile matter Fixed carbon N C H S Cl O

Untreated vine residue 8.5 4.2 81.3 14.5 0.8 52.0 5.8 0.0 0.1 37.1 21.6
Leached vine residue 11.9 3.1 81.6 15.3 1.0 53.5 6.2 0.0 0.0 36.2 22.8
Untreated wine residue 5.2 14.5 70.7 14.8 2.0 49.8 5.2 0.4 0.2 29.9 20.9
Naturally leached wine residue 7.9 31.7 48.6 19.7 2.3 48.8 6.8 0.3 <0.1 10.0 9.6

Table 2
Ash elemental analysis of the biomass samples, % ash basis.

Component Untreated vine residue Leached vine residue Untreated wine residue Naturally leached wine residue

K2O 10.9 9.5 60.3 26.1

Na2O 2.5 1.7 1.8 0.2
CaO 27.1 32.1 18.2 7.8
MgO 4.8 5.0 2.4 1.8
SiO2 12.5 16.8 11.3 36.8
Al2O3 4.0 3.8 2.3 9.0
Fe2O3 2.0 2.0 0.31 5.6
TiO2 <0.4 <0.4 0.1 <0.4
SO3 1.2 1.1 3.8 1.2
Cl 0.06 0.02 0.8 0.3

calculated on the parent material is 1.8%, compared to 0.81% for the b) The promoted CH4 reforming reaction with CO2 takes place
untreated and 0.71% for the leached vine residue. producing CO and H2.

3.2. Evolved product gas composition
Four different gasification tests were performed: a) untreated
vine residue (UVR), b) leached vine residue (LVR), c) naturally
leached wine residue (NLWR), and d) the blend of 50% of untreated
vine residue and 50% of naturally leached wine residue (50UVR/
50NLWR). The summary of product gas compositions together with
the calculated LHV value is presented in Table 3.
The product gas composition evolved after the gasification of
the artificially leached vine residue exhibited an upgraded
composition compared to the untreated sample. Due to the leach-
ing, the average values of CO and H2 concentrations increased by 17
and 30% respectively, which resulted in approximately 12% higher
LHV value of the product gas. Thus, the upgraded product gas
composition is caused by the higher moisture content of the
leached vine residue. It was observed in previous studies that the
higher moisture content favours the carbon conversion [17].
Thus, among the materials studied, the composition of the
product gas of the naturally leached wine residue is remarkably
different, composed of the highest CO content and the lowest
methane and carbon dioxide content. This could be explained by
the following two phenomena:
a) The carbon conversion to CO is enhanced due to higher ash
content, which is richer in alkali metals acting as catalysts
[18e20] compared to the two vine residue samples even after
the natural leaching process. The reason is that the alkali con-
tent of wine residues is much higher than that of vine residues
in the original untreated sample.
Table 3
Product gas composition and lower heating value (LHV).
Most probably, the methane reforming reaction is catalysed by
some chemical compound. It must be noted that the NLWR sample
contains much more mineral matter than other studied samples.
According to the literature, SiO2 and MgO available in biomass
mineral matter have been used as supports using Rh and Ni catalyst
to investigate the catalytic effect on reforming of CH4 with CO2. It
was found that at lower temperatures, the support materials such
as SiO2 and MgO are not alone active as catalysts up to tempera-
tures 550  C [21,22], but there are no data available for higher
temperatures, i.e. our gasification temperature was 800  C. Our
literature review failed to find studies on the catalytic activity of
some chemical compound (existent in biomass mineral matter) at
elevated temperature such as gasification temperature applied in
this study have been reported, further investigations are required.
In addition, it is believed that the high ash content, the low
amount of volatiles and the high amount of fixed carbon in the
naturally leached wine residues (remarkably different initial
composition compared to other studied materials) have a sub-
stantial impact on the gas composition of the product gas.
On the one hand, the reduced methane content lowers the
heating value of the product gas, on the other hand, the product gas
without methane is more suitable for Ficher-Tropsch synthesis, i.e.
less effort is needed to eliminate CH4. Therefore, the reason of
reduced methane content in the case of the NLWR is a topic for
further study.
The results of the test performed using the 50/50% mixture of
the UVR and the NLWR in Table 3 show that the composition of the
product gas is worse than that for both parent fuels separately.
Thus, all the different gas components with the exception of CO2 are
slightly higher now. This is attributed to gas sampling problems
encountered with the GC used for gas analysis.

Material CO H2 CO2 CH4 C2H6 LHV

Vol% Vol% Vol% Vol% Vol% MJ/m3 dry gas 3.3. Tar content of product gas
UVR 14.5 7.7 10.2 3.6 0.8 5.92
LVR 16.9 10.0 10.7 3.9 0.8 6.61 The tar content of the product gas before and after the catalyst of
NLWR 18.1 9.7 5.6 1.0 0.1 3.83 the studied samples is shown in Table 4. Untreated vine residue
50UVR/50NLWR 8.2 6.0 9.4 1.1 0.3 2.52
exhibits the highest tar content in the evolved product gas (269 mg/
4 S. Link et al. / Renewable Energy 115 (2018) 1e5
Table 4
Total tar content, mg/100 ml product gas.
Material Before catalyst After catalyst % Reduction
UVR 269 186 31
LVR 171 100 42
NLWR 90 41 55
50UVR/50NLWR 181 136 25
100 ml) and the naturally leached wine residue the lowest value (90
mg/100 ml). The tar content of the product gas of the leached vine
residue is 171 mg/100 ml, which is slightly lower than the mixture of
the naturally leached wine residue and the untreated vine residue
(181 mg/100 ml). Thus, the addition of the naturally leached wine
residue to the untreated vine residue lowers the tar content of the
product gas.
In the case of the LVR, it was observed that the tar yield is reduced
by 36% as compared with the UVR although the UVR sample con-
tains more alkali and alkali earth metals, which are considered to be
catalyst materials eliminating tars [23,24]. The impact of leaching on
the reduction of tar content in the product gas was detected also in
an earlier study [17]. Another study indicates that the leached
sample exhibits higher surface area accessible for the tar com-
pounds [14]. Therefore, a more active surface is available for tar
absorption on the surface of porous char particles prolonging the
residence time of the tar compound in the case of a leached sample.
After the tar compounds have been absorbed on the surface, they go
under pyrolysis, carbonization and are fixed on char particles,
resulting in the higher reduction rate of tar compounds in the
product gas [25]. Additionally, as can be seen from Table 1, there is
no Cl in the artificially leached vine residue. Usually, chlorine is
present in the mineral matter content of the fuel, such as KCl. KCl
melts already at relatively low temperatures (770  C) and tends to
react with silica and alkaline earth metals [26]. This reduces the
amount of alkali metals and alkaline earth metals (AAEM) available
as catalysts for carbon conversion, resulting in a higher tar content
of an unleached sample. Due to zero Cl content of the leached vine
residue, more alkali and alkaline earth metals are available, acting as
catalysts and the tar content of the product gas is lower compared
with an untreated sample. Nevertheless, the leached sample con-
tains less AAEM than an untreated sample.
The tar content of the product gas of the NLWR sample is seen to
have the lowest value. This could be imputed to the high potassium
content of the sample material in combination with the reduction
of chlorine that lowers substantially the agglomeration tendency in
the temperature segment (800e850  C) where our test took place.
The addition of NLWR to the UVR is seen to lower the tar content in
the product gas due to the higher amount of potassium compared
to the UVR sample.
Table 4 shows that the reduction of the tar content after the
catalyst is higher for the NLWR material with 55% reduction
observed, followed by the LVR material with 42% reduction
observed, while the lowest reduction is observed in the case of the
UVR material with only 31%. Similar to the case of the product gas
composition, the results from the test performed with the 50/50%
mixture of UVR and NLWR show an error after the catalyst most
likely due to some sampling problems, as compared to the results
from the tests performed with the 100% pure materials. On the
contrary, the results of the 50/50% mixture of UVR and NLWR
before the catalyst are seen to be consistent with the results derived
from the tests performed with the 100% biomass materials.
3.4. Comparison with other studies and fuels
Pine wood, Douglas fir, reed, untreated and leached olive
residue, etc. have been investigated as a feedstock under air-blown
atmospheric fluidized bed gasification conditions [14,27e30]. The
evolved product gas composition and tar content of product gas of
this study are in a good agreement with the results of previous
studies. However, there are deviations coming from the composi-
tion and properties of each fuel. In general, the results of this study
suggested that the wine and vine residues are suitable fuels for
gasification, and the yield of gasification could be improved via
leaching pre-treatment.
4. Conclusions
The artificial leaching pretreatment process of vine residues was
found to have an impact on the composition of the product gas and
the tar content. The result was a lower tar yield by 36% and a higher
yield of CO (by 17%) and H2 (by 30%) and a higher LHV value (by
12%) as compared with the untreated sample.
Naturally leached wine residue exhibited distinct gas composi-
tion compared to the vine residue materials, which was caused by
the different composition of the parent material. The inorganic
chemistry of the naturally leached wine residue under gasification
conditions needs further investigation.
Artificial/controlled leaching pretreatment produced better re-
sults than the natural leaching process in terms of ash content,
calorific value, volatiles as well as removal of inorganics. As a result,
the controlled leaching pretreatment is proposed as an effective
way of upgrading the composition of agricultural biomass.
Acknowledgement
Claes Brage and Yu Qizhuang are acknowledged for their assis-
tance in the tar analysis. Mikael Lundgren is acknowledged for his
technical assistance on the test rig. Thomas Nordgreen and Lars-
Peter Wiktorsson are acknowledged for their assistance in the ex-
periments. The work was financed by the SUSPOWER, a project
within the 6th Framework Program of the EU: Structuring the Eu-
ropean Research Area/Transnational Access. The research was
supported by the European Union, funded by European Regional
Development Fund.
References
[1] P. Piotrowska, M. Zevenhoven, K. Davidsson, M. Hupa, L.-E. Åmand, V. Barisi
c,
E. Coda Zabetta, Fate of alkali metals and phosphorus of rapeseed cake in
circulating fluidized bed boiler. Part 1: cocombustion with Wood, Energy Fuel
24 (2010) 333e345.
[2] P. Kaushal, R. Tyagi, Advanced simulation of biomass gasification in a fluidized
bed reactor using ASPEN PLUS, Renew. Energy 101 (2017) 629e636.
[3] K.R. Cummer, R.C. Brown, Ancillary equipment for biomass gasification,
Biomass Bioenergy 23 (2002) 113e128.
[4] B.M. Jenkins, R.R. Bakker, J.-B. Wei, On the properties of washed straw,
Biomass Bioenergy 10 (1996) 177e200.
[5] R. Warnecke, Gasification of biomass: comparison of fixed bed and fluidized
bed gasifier, Biomass Bioenergy 18 (2000) 489e497.
[6] P.A. Jensen, B. Sander, K. Dam-Johansen, Removal of K and Cl by leaching of
straw char, Biomass Bioenergy 20 (2001) 447e457.
[7] S. Arvelakis, H. Spliethoff, E.G. Koukios, Torrefaction and leaching: a novel pre-
treatment for the effective thermal conversion of agricultural residues, in:
15th European Biomass Conference & Exhibition, 2007, pp. 1384e1388
(Berlin, Germany).
[8] Z. Abu El-Rub, E.A. Bramer, G. Brem, Review of catalysts for tar elimination in
biomass gasification processes, Ind. Eng. Chem. Res. 43 (2004) 6911e6919.
[9] S. Monteiro Nunes, N. Paterson, A.A. Herod, D.R. Dugwell, R. Kandiyoti, Tar
formation and destruction in a fixed bed reactor simulating downdraft gasi-
fication: optimization of conditions, Energy Fuel 22 (2008) 1955e1964.
[10] C. Yu, P. Thy, L. Wang, S.N. Anderson, J.S. VanderGheynst, S.K. Upadhyaya,
B.M. Jenkins, Influence of leaching pretreatment on fuel properties of biomass,
Fuel Process. Technol. 128 (2014) 43e53.
[11] K.L. Chin, P.S. H'ng, M.T. Paridah, K. Szymona, M. Maminski, S.H. Lee,
W.C. Lum, M.Y. Nurliyana, M.J. Chow, W.Z. Go, Reducing ash related operation
problems of fast growing timber species and oil palm biomass for combustion
applications using leaching techniques, Energy 90 (2015) 622e630.
 S. Link et al. / Renewable Energy 115 (2018) 1e5
[12] S. Arvelakis, Improving the Biomass Gasification/combustion Technology via
Appropriate Physico-chemical Pre-treatments of the Raw Material, Doctoral
Thesis, National Technical University of Athens, 2001.
[13] S. Arvelakis, E.G. Koukios, Physicochemical upgrading of agroresidue as
feedstocks for energy production via thermochemical conversion methods,
Biomass Bioenergy 22 (2002) 331e348.
€ stro
[14] S. Link, S. Arvelakis, A. Paist, A. Martin, T. Liliedahl, K. Sjo € m, Atmospheric
fluidized bed gasification of untreated and leached olive residue, and co-
gasification of olive residue, reed, pine pellets and Douglas fir wood chips,
Appl. Energy 94 (2012) 89e97.
[15] C. Brage, Q. Yu, G. Chen, K. Sjo € stro
€ m, Use of amino phase adsorbent for
biomass tar sampling and separation, Fuel 76 (1997) 137e142.
[16] K. Raveendran, A. Ganesh, K.C. Khilar, Influence of mineral matter on biomass
pyrolysis characteristics, Fuel 74 (1995) 1812e1822.
[17] S. Arvelakis, J. Hurley, B. Folkedahl, E.G. Koukis, H. Spliethoff, Fluidized bed
gasification of high alkali and chlorine biomass: effect of pre-treatments on
the agglomeration behaviour, in: 33rd International Technical Conference on
Coal Utilization and Fuel Systems, 2008, pp. 591e602 (Clearwater, Florida,
USA).
[18] R.J. Ishak, Reaction Kinetics for Reduction of Manganese Ore with Carbon
Monoxide in the Presence of Carbon, Doctoral Thesis, The Norwegian Uni-
versity of Science and Technology, 2002.
[19] T. Lindstad, M. Syvertsen, R.J. Ishak, H.B. Arntzen, P.O. Grøntvedt, The influ-
ence of alkalis on the boudouard reaction, in: 10th International Ferroalloys
Congress, 2004, pp. 261e271 (Cape Town, South Africa).
[20] S. Link, S. Arvelakis, M. Hupa, P. Yrjas, I. Külaots, A. Paist, Reactivity of the
biomass chars originating from reed, Douglas fir, and pine, Energy Fuel. 24
(2010) 6533e6539.
[21] A. Erdo€helyi, J. Csere

nyi, F. Solymosi, Activation of CH4 and its reaction with
5
CO2 over supported Rh catalysts, J. Catal. 141 (1993) 287e299.
[22] M.C.J. Bradford, M.A. Vannice, Catalytic reforming of methane with carbon
dioxide over nickel catalysts. I. Catalyst characterization and activity, Appl.
Catal. A-Gen. 142 (1996) 73e96.
[23] D. Sutton, B. Kelleher, J.R.H. Ross, Review of literature on catalysts for biomass
gasification, Fuel Process, Technol. 73 (2001) 155e173.
[24] A. Pattiya, J. Titiloye, A.V. Bridgwater, Catalytic effect of char ash in fast py-
rolysis of cassaba rhizome, in: 15th European Biomass Conference & Exhibi-
tion, 2007, pp. 1374e1377 (Berlin, Germany).
[25] T. Namioka, K. Yoshikawa, H. Hatano, Y. Suzuki, High tar reduction with
porous particles for low temperature biomass gasification: effects of porous
particles on tar and gas yield during sawdust pyrolysis, J. Chem. Eng. Jpn. 36
(2003) 1440e1448.
[26] S. Arvelakis, H. Gehrmann, M. Beckmann, E.G. Koukios, Effect of leaching on
the ash behavior of olive residue during fluidized bed gasification, Biomass
Bioenergy 22 (2002) 55e69.
[27] I. Narv
aez, A. Orío, M.P. Aznar, J. Corella, Biomass gasification with air in an
atmospheric bubbling fluidized bed. Effect of six operational variables on the
quality of the produced raw gas, Ind. Eng. Chem. Res. 35 (1996) 2110e2120.
[28] J. Gil, J. Corella, M.P. Aznar, M.A. Caballero, Biomass gasification in atmo-
spheric and bubbling fluidized bed: effect of the type of gasifying agent on the
product distribution, Biomass Bioenergy 17 (1999) 389e3403.
[29] P. Carcía-Iban ~ ez, A. Cabanillas, J.M. Sa

nchez, Gasification of leached orujillo
(olive oil waste) in a pilot plant circulating fluidized bed reactor. Preliminary
results, Biomass Bioenergy 27 (2004) 183e194.
[30] L. Wang, C.L. Weller, D.D. Jones, M.A. Hanna, Contemporary issues in thermal
gasification of biomass and its application to electricity and fuel production,
Biomass Bioenergy 32 (2008) 573e581.