i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 8 ) 1 e9

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Hydrogen enriched syngas production via

gasification of biofuels pellets/powders blended
from olive mill solid wastes and pine sawdust
under different water steam/nitrogen atmospheres

M. Zribi a, M. Lajili a,*, F.J. Escudero-Sanz b

a
UR: EMIR (Etude des Milieux Ionises et Reactifs), 15 Avenue Ibn Eljazzar IPEIM, Monastir, 5019, Tunisia
b
RAPSODEE (UMR CNRS 5302)IMT Mines-AlbiCampus Jarlard, 81013, Albi CT Cedex9, France

article info abstract

Article history: In this work, we study the gasification of pellets produced, after densification, by blending olive
Received 30 July 2018 mill solid wastes, impregnated or not by olive mill waste water, and pine sawdust under different
Received in revised form steam/nitrogen atmospheres. The charcoals necessary for the gasification tests were prepared
15 September 2018 by pyrolysis using a fixed bed reactor. The gasification technique using steam was chosen in
Accepted 3 October 2018 order to produce a hydrogen-enriched syngas. Gasification tests were performed using macro-
Available online xxx thermogravimetric equipment. Tests were carried out at different temperatures (750
C,
800
C, 820
C, 850
C and 900
C), and at different atmospheres composed by nitrogen and steam
Keywords: at different percentages (10%, 20% and 30%). Results show that the mass variation profiles is
Biomass similar to the usual lingo-cellulosic gasification process. Moreover, the increase of temperatures
Pyrolysis or water steam partial pressures affects positively the rate of conversion and the char reactivity
Gasification by accelerating the gasification process. The increase of the gasification yields demonstrates the
Syngas promise of using olive mill by-products as alternative biofuels (H2 enriched syngas).
Rate of conversion © 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Char reactivity

can be utilized through three routes: physicochemical (e.g. the

Introduction production of vegetable oils from seeds of oil plants using two/
three phases trituration), biochemical (e.g. fermentation and
Energy supply represents a major challenge facing our planet hydrolysis of sugar plants, anaerobic digestion of wet biomass,
today. In particular, the transition from fossil resources into etc.) and thermochemical (e.g. torrefaction, pyrolysis, com-
sustainable and renewable ones becomes is becoming a bustion and gasification) [7,8]. Pyrolysis and gasification pro-
pressing issue [1e4]. This transition is justified by greenhouse cesses have emerged as suitable paths for producing alternative
gas and other pollutants emissions which affect seriously solid, liquid and gaseous biofuels. Especially, alternative
human health and climate change [5]. For this reason biomass gaseous biofuels, called syngas, can be obtained through
feedstocks have emerged in last decade as a promising biomass gasification with steam and/or carbon dioxide [9e12].
renewable energy source and, thereby, received a particular This trend was accelerated by huge demands on hydrogen and
attention due to their high availability worldwide [6]. Biomass

* Corresponding author.
E-mail address: marzouk.lajili@ipeim.rnu.tn (M. Lajili).
https://doi.org/10.1016/j.ijhydene.2018.10.021
0360-3199/© 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article in press as: Zribi M, et al., Hydrogen enriched syngas production via gasification of biofuels pellets/powders
blended from olive mill solid wastes and pine sawdust under different water steam/nitrogen atmospheres, International Journal of
Hydrogen Energy (2018), https://doi.org/10.1016/j.ijhydene.2018.10.021
2 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 8 ) 1 e9

syngas in new industriel applications. In fact, syngas has  EOMSW-OMWW: composed of 50% exhausted olive mill
proved to be a promising route in chemical, oil and energy due solid waste and 50% olive mill wastewater.
to its wide applications. This gas can be used as a feedstock for  EOMSW100: composed of 100% olive mill solid waste.
the production of hydrogen, ammonia, methanol and Ficher-
Tropsch products [13]. Moreover, it can be considered as a fuel In order to study the influence of particle sizing during
for gas turbine plants used for electricity generation [14], or as a gasification, the charcoals obtained after the slow pyrolysis
fuel cell for mobile sources (e.g. cars) [15]. It can also play the process were crushed and then sieved for obtaining a powder
role of an electricity supplier through solid oxide fuel cells [13]. composed by particles of less than 100 mm size.
Finally it can be exploited as a primary fuel [16].
All this richness of the syngas comes from its composition. Samples characterization
Indeed, recent investigations on biomass show that syngas
includes H2, CO, CO2, CH4, H2O in different proportions The moisture content of the different samples was deter-
depending on the biomass, and also on the conditions in which mined using a stove at 105
C during a period of 24 h according
the syngas is produced, such as temperature, pressure, resi- to the EN 14774 standard, and by using a scale precisa XT220A
dence time and the gasifier agent [17e19]. H2 and CO are the for weighing the mass of sample before and after moisture
major components of interest here since they could be con- evaporation. The ash content was determined using a muffle
verted to alternative synthetic biofuel through various pro- furnace in which the temperature is fixed at 900
C during
cesses such as the Ficher-Tropsch reaction [20]. Moreover, the 1.5 h according to the DIN 51719 standard.
combustion of the syngas is relatively clean by comparison to The high heating value (HHV) was determined using a
fossil fuels. Hence, this combustion is presents many advan- calometric bomb calorimeter IKAC200 according to the EN
tages such as the decrease of particulate matter (PMs) which 14918 standard. Then, the low heating value (LHV) is deduced
can be deposed easely on human airways causing serious res- from the HHV according to:
piratory problems as is was modelled and simulated in Ref. [21].    
%H %Hu %Hu
Several investigations have studied the char gasification under LHV ¼ HHV  LV 9  1 þ (1)
100 100 100
different atmospheres [22e25]. Also, it was reported in the
literature that the char textural properties are clearly correlated Both LHV and HHV are expressed in (MJ.kg1), LV is the latent
to gasification rate [26]. Moreover, it was reported that the heat of vaporization (approximately 2502 kJ kg1), %H is the
calorific value of the produced gas depends on the gasifier hydrogen percentage and %Hu is the moisture ratio.
agent. Indeed, it is well known that air gasification produces a The bulk densities of the different samples were also
poor quality of syngas in terms of heating value (a higher determined by calculating the ratio of the mass and the vol-
heating value, HHV, of around 4e7 MJ/Nm3); whereas, using ume of the container conformingly to the CENTS15103 stan-
pure oxygen or water steam as gasifier agent leads to a higher dard method. The energy density is a crucial parameter
quality of syngas (around 10e18 MJ/Nm3, HHV) [5,14,27,28]. characterizing the solid biofuels. It is obtained by multiplying
In this study, the charcoal was prepared using slow pyrolysis the LHV and the bulk density [29].
under an inert atmosphere in a horizontal fixed bed furnace. The mineral analysis shows that the potassium (K), the
After that, we carried out gasification tests using a macro-TG at calcium (Ca) and the sodium (Na) are the main elements
various atmospheres composed of a mixture of N2 and water present in the different prepared samples.
steam with a given partial pressure and under a given
isothermal temperature. We focused on the effect of the partial Experimental device
pressure variation and temperature variation on the conver-
sion; the rate of conversion and the char reactivity respectively. Gasification, as an intricate process, makes impossible to
control and optimize its several overlapping steps separately.
Hence, to improve the gasification efficiency and the char
Experimental device transformation rate, gasification should be performed in the
absence of the volatiles [30]. For this reason, a preliminary
Samples and preparation slow pyrolysis process was investigated under inert atmo-
spheres using a horizontal fixed bed reactor in order to pro-
The olive mill wastes used in this work were collected from duce the char. Then, the gasification tests of prepared samples
the Zouila oil Press Company situated in Mahdia in Tunisia, (pellets and powders) were assessed in a Macro-
while, the pine sawdust was provided from a wood factory thermogravimetric (M-TG) reactor which was previously
situated in Tunisia. Samples were prepared as it was reported described with precision [4]. Indeed, the M-TG device is mainly
in our previous work [29]. First we carry out a densification of formed by three parts: (1) the heating system composed by a
the raw materials (olive mill solid waste (OMSW) with and liquid water evaporator, a gas pre-heater and an alumina cy-
without impregnation by olive mill wastewater (OMWW), and lindrical reactor heated electrically, (2) a gas flow control
with and without mixing with pine sawdust (PS)) to obtain the system allowing gas mixture for varying the gasification at-
pellets. Hence, 4 samples types were prepared: mosphere composition, (3) a weighing system including an
electronic balance (±0.1 mg) and a stand with a platinum
 PS100: composed of 100% pine sawdust. basket. The cylindrical reactor is 2 m long and 0.75 m internal
 PS-OMWW: composed of 50% pine sawdust and 50% olive diameter. Before injection into the reaction zones, the
mill wastewater. different mixtures of gas should be pre-heated to the chosen

Please cite this article in press as: Zribi M, et al., Hydrogen enriched syngas production via gasification of biofuels pellets/powders
blended from olive mill solid wastes and pine sawdust under different water steam/nitrogen atmospheres, International Journal of
Hydrogen Energy (2018), https://doi.org/10.1016/j.ijhydene.2018.10.021
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 8 ) 1 e9 3

reaction temperature. The metallic stand placed over the Comparison with other available biomasses reported in the
electronic scale is equipped with three ceramic hollow tubes literature is carried out. This comparison shows that the
with 1 m length and 2.4 mm external diameter. These tubes prepared samples follow typical compositions [1,2]. Indeed,
end with a platinum basket of 50 mm diameter, a solid bottom we notice that the OW is characterised by its relatively high
and a side wall made from a 0.5 mm grid in order to allow the ash content (5.20%); whereas, the PS ash content is relatively
gas to pass through it. The totality of the weighing system can small (<0.30%). Moreover, the prepared pellets generate a high
be moved in the vertical direction using a crank handle. A percentage of volatiles. More precisely, the PS pellets are
special attention should be paid to introduce the sample in- richer of volatiles than the OW pellets (73.95% for OW versus
side the reactor hot zone within 13e15 s. Hence, these con- 84.20% for PS). Finally, both OW and PS samples present
ditions of very fast heating (about 100
C/s) are close to the considerable contents of fixed carbon; 17.62% and 15.40%
fluidized bed rectors' conditions. The average speed of the respectively.
fluid inside the reactor was approximately 0.2 m/s in order to Consigned results in Table 1 show that the OW pellets have
avoid any turbulent regime and the nitrogen volume flow rate more carbon content than the PS pellets. However, the oxygen
was fixed at 6 NL/min. The mass loss was recorded using a content of the PS pellets is higher than that of the OW pellets.
MSE524S scale and an in-house Lab-View code. The related The nitrogen content is significant only for OW pellets; while,
data to the sample entrance in the furnace were rejected in the sulphur contents can be neglected for both pellets types.
order to avoid the buoyancy forces’ effect via a preliminary Hence, a non-negligible amounts of NOx (NO þ NO2) can be
blank test. For achieving our study, some parameters char- expected during the combustion of the OW pellets. In
acterizing the gasification process were defined: contrast, given the very small sulphur contents (<0.1) SOx
emissions are expected to be insignificant [29].
 The characteristic time of gasification tG corresponding to Table 2 shows that inorganic elements (Na, K and Ca) are
the needed time to reach 97% of char conversion according highly concentrated in the EOMSW, EOMSW-OMWW and PS-
to the following expression: OMWW samples. This elevated concentration is not only
due to the initial amount of Na, K and Ca in raw material
tG ¼ tX¼97%  tX¼0% (2) EOMSW but also due to impregnation process when using
OMWW (rich of these minerals) [30,31]. It is worth noting that
 The char reactivity which represents the rate of char con- these higher inorganic contents are very interesting of point of
sumption divided by an extensive properly, namely the view catalytic effect during gasification process [31e33].
char mass. This parameter is expressed by:
Effects of the variation of the H2O partial pressure and the
Rt ¼ ½1=ð1  Xt Þ  ½dXt =dt (3) temperature on the conversion

where, X is the conversion of char during the gasification: The gasification is a thermochemical conversion process
occurring at relatively elevated temperature, up to 1400
C in
Xt ¼ ðm0  mt Þ=ðm0  mash Þ (4) some cases [32e34]. Materials which are subject to this pro-
cess are solid carbonaceous fuels such as coal and biomasses
m0, mt and mash are the initial mass of char, the mass at a time in the presence of a gasifier agent such as air, oxygen, steam
t and the mass of the residual ash respectively. and/or carbon dioxide. This gasifier agent is injected in small
concentrations with an inert gas such as nitrogen (N2). The
 The rate of conversion defined as: gasification yields consist of a biogas, tars (liquids from con-
densable vapours) and remaining biochar (solid). The main
yG ¼ dXt =dt (5) product of gasification is a mixture of gases, called syngas
which is mainly composed of CO, H2, CO2, CH4 and volatile
organic compounds C2-4Hx and tars.
Results and discussions After studying the gasification of the 4 different samples at
different temperatures and for different percentages of steam,
Samples characterization results show that the conversion curves X ¼ f(t) follow the
usual behaviour during the thermal degradation of lingo-
The energy contents, the ultimate and the proximate analyses cellulosic materials as it is illustrated on Fig. 1 and Fig. 2.
of the different samples are summarized in Table 1. A Moreover, we found that, when increasing the partial pressure

Table 1 e Proximate analysis and ultimate analysis for the tasted samples.
Samples Proximate analysis LHV BD ED Ultimate analysis
%Hu (W.b.) %VM (d.b.) %FC (d.b.) %Ash (d.b.) %C %H %O %N %S
OW100 38.34 73.95 17.62 8.43 19.23 920 17.69 49.50 5.33 43.81 1.27 0.09
PS100 7.90 84.20 15.40 0.40 17.80 693 12.33 47.17 6.10 46.27 <0.1 <0.01

BD: The bulk density (kg.m3); ED: The energy density (GJ.m3); d.b.: on dry basis; w.b.: on wet basis.

Please cite this article in press as: Zribi M, et al., Hydrogen enriched syngas production via gasification of biofuels pellets/powders
blended from olive mill solid wastes and pine sawdust under different water steam/nitrogen atmospheres, International Journal of
Hydrogen Energy (2018), https://doi.org/10.1016/j.ijhydene.2018.10.021
4 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 8 ) 1 e9

0.025
Table 2 e Concentration of inorganic elements (g/kg d.b. EOMSW-
OMWW
basis).
EOMSW100
0.02
Parameter EOMSW EOMSW-OMWW PS PS-OMWW
PS-OMWW

Na 0.78 1.79 0.01 1.15 0.015

dX/dt (%/s)
PS100
K 3.67 7.53 0.36 3.40
Ca 1.13 1.45 0.36 0.87
0.01

0.005
1
0.9
0
0.8
0 0.2 0.4 0.6 0.8 1
0.7 Conversion X
Conversion X

0.6 20%

0.5 15%

0.4 10% Fig. 3 e Rate of Conversion evolution as a function of the

0.3 conversion of the different samples at 900
C and under
0.2 20% H2Ov.
0.1
0
0 100 200 300 400 500
Time (s)

is discrepancy is expected since the chars are different (beech

wood chips for Guizani et al. [4]) and also the techniques with
Fig. 1 e Influence of the H2O partial pressure on the
which the char were prepared were different (high-heating
temporal variation of the conversion of PS-OMWW100
rate chars for them and low-heating rate for us).
under 850
C.

Influence of the samples types on the rate of conversion and

the char reactivity

of the steam, the reaction rate increases as shown in Fig. 1 in The rate of conversion dX/dt is a gasification characteristic
agreement with what was reported in the literature [4,35]. which is always considered as a preliminary indicator of the
Moreover, Fig. 2 shows the char conversion evolution as a material reactivity. Fig. 3 shows the conversion rate dX/dt, as
function of elapsed time at 20% H2Ov and for five different functions of X for different samples. The results show that
temperatures; 750
C, 800
C, 820
C, 850
C and 900
C rates of conversion evolving as function of the conversion (X)
respectively. It can be seen that an increase in temperature depend strongly on the samples type. Indeed, we observe that
from 750 to 900
C yields an increase in the rate of char con- at 900
C and at 20% H2Ov conditions, the EOMSW100 exhibits
version and consequently to a decrease of the characteristic a greater reactivity than PS100. Moreover, the addition of the
time of gasification [4]. More precisely, in Fig. 1 a conversion OMWW for each sample enhances its reactivity, perhaps due
level of 90% was reached respectively after 90, 130 and 150 s to its richness in inorganic matter (K, Ca and Na) [36]. Thus,
with steam concentrations of 20%, 15% and 10% respectively. the maximum rate of mass loss corresponds to EOMSW-
These values of the characteristic time of gasification are OMWW; while the lowest value is attributed to 100PS (Figs.
different to values obtained by Guizani et al. [4] which are 3, and Fig. 4).
higher (330s and 580 s for 20% and 10% H2O respectively). This

1 0.07
0.9
0.06 EOMSW-OMWW
0.8
EOMSW100
Reactivity with H2O (s-1)

0.7 0.05
PS-OMWW
0.6
Conversion X

900°C
0.04 PS100
0.5 850°C
0.4 820°C 0.03
0.3 800°C
0.02
0.2 750°C

0.1 0.01
0 0
0 100 200 300 400 500 600 0 0.2 0.4 0.6 0.8 1
Time (s)
Conversion X

Fig. 2 e Influence of the variation of the temperature on the Fig. 4 e The char reactivity variation as a function of the
temporal variation of the conversion of EOMSW-OMWW conversion of the different samples realized at 900
C and
under 20% H2Ov. under 20% H2Ov.

Please cite this article in press as: Zribi M, et al., Hydrogen enriched syngas production via gasification of biofuels pellets/powders
blended from olive mill solid wastes and pine sawdust under different water steam/nitrogen atmospheres, International Journal of
Hydrogen Energy (2018), https://doi.org/10.1016/j.ijhydene.2018.10.021
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 8 ) 1 e9 5

0.02 0.025 900°C

20%
0.018 15%
850°C

0.016 10% 0.02 800°C

750°C
0.014

dX/dt (%/s)
0.012 0.015
dX/dt (%/s)

0.01
0.008 0.01
0.006
0.004 0.005
0.002
0 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
Conversion X Conversion X

Fig. 5 e Influence of the partial pressure water steam on Fig. 7 e Influence of the variation of temperature on the
the rate of conversion as function of the conversion at rate of conversion. under 20% H2O for EOMSW-OMWW.
850
C for PS-OMWW sample.

higher for 10% water steam than for 15% water steam and this
Influence of the variation of the steam water partial for X > 0.6.
pressure and the temperature on the rate of conversion and Fig. 7 and Fig. 8 show the evolution of the rate of conversion
the char reactivity and the char gasification reactivity as a function of X, and for 5
fixed temperatures (750, 800, 820, 850 and 900
C). We conclude
Fig. 5 and Fig. 6 show respectively, the influence of the partial that the samples become more reactive with higher temper-
pressure of the water steam on the rate of conversion and ature in agreement with what was reported in the literature
also, on the char reactivity as a function of the conversion (X) [37,38].
at 850
C for the PS-OMWW sample. We observed that the char
reactivity increases with a higher percentage of steam from 10 Influence of the samples’ properties on the gasification
to 20% in agreement with results stated by Guizani et al. [37]. reactivity
Moreover, we notice that each curve presents two stages: in
the left side zone corresponding to X < 0.5 the rate of con- Table 3 shows the characteristic times of gasification and
version increases slightly; whereas, in the right side zone for rates during the gasification stage for the four samples when
X > 0.5 the rate of conversion presents a quite decrease. This working at the same temperature 850
C and under the same
result is may be due to the kinetic of the reactions which is steam percentage 20%. The characteristic time tG corresponds
affected not only by the nature of the gasifier agent and its to the time needed to reach 97% of char conversion is calcu-
partial pressure, but also, by the heat flux interaction between lated using the following expression:
the gas flow and the sample, and perhaps by the degree level
tG ¼ tX¼97%  tX¼0% (6)
of the conversion (X). These observations are consolidated by
Fig. 6, but in this case, the char gasification reactivity is in a Moreover, Fig. 9 displays the influence of the samples’
continuous increase. However, as we can see, the rate of types on the gasification reactivity as a function of elapsed
conversion and the char gasification reactivity become quite time.

0.06 0.07

0.05
20% 0.06 900°C
15% 820°C
0.05
Reactivity with H2O (s-1)
Reacttivity with H2O (s-1)

10% 800°C
0.04
750°C
0.04
0.03
0.03
0.02
0.02

0.01 0.01

0 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
Conversion X Conversion X

Fig. 6 e Influence of the partial pressure water steam on Fig. 8 e Influence of the temperature on the char
the char gasification reactivity as a function of the gasification reactivity as a function of the conversion under
conversion at 850
C for PS-OMWW sample. 20% H2O for the EOMSW-OMWW sample.

Please cite this article in press as: Zribi M, et al., Hydrogen enriched syngas production via gasification of biofuels pellets/powders
blended from olive mill solid wastes and pine sawdust under different water steam/nitrogen atmospheres, International Journal of
Hydrogen Energy (2018), https://doi.org/10.1016/j.ijhydene.2018.10.021
6 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 8 ) 1 e9

Table 3 e Determination of the time characteristic and the Table 4 e The characteristic time and the gasification rate
rate of gasification of the 4 samples, at the same of the EOMSW-OMWW at different temperatures.
temperature 850
C and the same water steam percentage Temperature H2O percentage tG (s) yG(103 s1)
20%.
800
C 10% 202 4.80
Sample EOMSW EOMSW- PS-OMWW PS100
15% 182 5.33
100 OMWW
20% 172 5.64
tG(s) 103 99 197 197 820
C 10% 195 4.97
yG (103 s1) 9.42 9.80 7.89 4.92 20% 162 5.99
850
C 10% 115 8.43
15% 113 8.58
The conversion function X, and more precisely in the 20% 99 9.80

region presenting the highest gradient of variation, is usu-

ally considered as a preliminary indicator of the material
reactivity. At 850
C, the lowest rate of conversion is 9
y = 0,076x - 56,48
exhibited by the PS100 sample as it is illustrated in Fig. 9 and 8

The average gasification rate (10-3 s -1)

R² = 0,871

confirmed in Table 3 (the characteristic time is approxi- 7

mately 4.92 103 s1), while the highest one is obtained by 6

EOMSW-OMWW powder (approximately 9.80 103s1). 5

However, we notice that these values are higher than those 4

reported in the literature under the same experimental 3

conditions [39]. Indeed, in agreement with many published 2

results in the literature, the blended and impregnated 1

samples experience the highest gasification rates thanks to 0

790 800 810 820 830 840 850 860
the mineral contents supplied by the OMWW as it is shown Temperature (°C)
in Table 2 [4,11,26,32,39e41].

Fig. 10 e Evolution of the average gasification rate of

Influence of temperature and steam molar fraction on the
EOMSW-OMWW as a function of the temperature.
characteristic time and gasification rate of EOMSW-OMWW

The gasification of the char of EOMSW-OMWW under the

powder state (particles sizes are less than 100 mm) was studied
at three different temperatures; 800
C, 820
C and 850
C, and
Indeed, at 800
C the characteristic times are 202 s, 182 s,
under different steam molar fraction; 10%, 15% and 20%
172 s at 10%, 15% and 20% respectively. Note that under
respectively. Table 4 summarizes the characteristic gasifica-
similar experimental conditions, Guizani et al. [10] show that
tion times and the gasification rates for the different tem-
for a conversion (X) of 90%, and at a temperature of 900
C, the
peratures and steam percentages.
gasification rate of beech wood chips is approximately 15 103
We observe in Table 4 that the characteristic times of the
s1. However, our obtained values are lower than those found
EOMSW-OMWW gasification are 202 s, 195 s, 115 s at 800
C,
by Guizani et al. [10], but higher than those reported by Lajili
820
C, and 850
C respectively when the steam percentage is
et al. [39].
10%. Therefore, as indicated earlier, the reactivity increases
The average gasification rate is defined as the mean gasi-
with an increased temperature. We also note that the steam
fication rate. More precisely it is calculated as the average
partial pressures affect positively the samples’ reactivity.

1 6
The average gasification rate (10-3 s-1)

0.9 5 y = 0,084x + 3,996

0.8 R² = 0,977
Conversion X

0.7 4

0.6 EOMSW-OMWW 3
0.5 EOMSW100

0.4 PS-OMWW 2
PS100
0.3 1
0.2
0.1 0
0 5 10 15 20 25
0
H2O (%)
0 100 200 300 400
Time (s)

Fig. 11 e Evolution of the average gasification rate of

Fig. 9 e Comparison between the temporal evolutions of
EOMSW-OMWW as a function of the steam partial
the conversion of the four samples under 20% water steam
pressure.
composition and at 850
C.

Please cite this article in press as: Zribi M, et al., Hydrogen enriched syngas production via gasification of biofuels pellets/powders
blended from olive mill solid wastes and pine sawdust under different water steam/nitrogen atmospheres, International Journal of
Hydrogen Energy (2018), https://doi.org/10.1016/j.ijhydene.2018.10.021
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 8 ) 1 e9 7

Table 5 e The characteristic times and the gasification rates of the different samples in powder and pellet states at 850
C
and under 20% water steam molar fraction.
Powder form Pellets form
EOMSW100 EOMSW-OMWW PS-OMWW EOMSW100 EOMSW-OMWW PS-OMWW
tG(s) 103 99 123 tG(s) 830 755 666
yG(103 s1) 9.42 9.80 7.89 yG(103 s1) 1.21 1.33 1.50

value of the conversion rate through the char conversion gasification performance. They concluded that when
range (X ¼ 0% - X ¼ 95%). Fig. 10 and Fig. 11 show the average increasing the particle size from 0.125 to 0.250 mm, the CO and
gasification rate evolution as a function of temperature and H2 concentrations were decreased, while the contents of CO2
steam molar fraction respectively. and CH4 were increased. This result can be explained by the
Fig. 10 shows that the average gasification rate increases fact that when the particle size decreased, the reactions are
from 4.80.103 s1 to 8.43.103 s1 for a steam fraction of 10% mainly controlled by pyrolysis and gasification, whereas when
when we increase the temperature from 800
C to 850
C. At the particle size increased the reactions are mainly governed
850
C and 10% H2Ov, our values are about twice higher than by the diffusion process. Consequently, the size of particle
those performed by Nilsson et al. [42]. Fig. 11 shows that the influences seriously the gas diffusion speed. Finally, the
mean gasification rate increases from 4.80.103 s1 to smaller particle size is expected to be more advantageous to
5.64.103 s1 at 800
C when we increase the steam molar produce high quality gas. Moreover, we observe that for the
fraction from 10% to 20%. However, according to Lajili et al. powder form the highest rate of gasification is exhibited by
[39], the average gasification rate is four times lower than EOMSW-OMWW (9.80 103s1) with a characteristic time of
what we find in this work, while the characteristic time of 99 s followed by EOMSW100 (9.42 103s1), PS-OMWW (7.89
gasification is much higher (755 s at 850
C and 20% H2O for the 103s1) and PS100 (4.92 103s1) respectively. Such behaviour
pellets of impregnated exhausted olive mill solid waste). We can be attributed to the richness of the impregnated samples
can conclude that the powder form enhances the sample's in inorganic matter provided by the OMWW, and especially in
gasification reactivity. potassium (K) which is known by its high catalytic effect [4,39].
Indeed, the Schmidt's team, when working on the effects of
Comparison between the pellets and the powder during biomass inorganics using rhodium as catalyst, concluded that
gasification the role of the sodium and potassium, which are the main
inorganic compounds in our case, was to decrease the
In this section, we focus on the comparison of the gasification methane conversion by 9% and 16% respectively. Further-
of the powder samples and the pellets samples when they are more, the potassium decreased the H2 and CO selectivity by
treated under the same experimental conditions of 20% steam 5% and 7% respectively [46].
molar fraction and 850
C. In contrast, we also observe that the PS-OMWW pellet pre-
Table 5 shows the characteristic times and the gasification sents the highest gasification rate followed by EOMSW-OMWW
rates for the different samples in powder and pellet states and EOMSW100 respectively. Accordingly, the characteristic
respectively. time for pellets exhibits the opposite trend to that of the gasi-
We can see that for all samples, the characteristic time of fication rate i.e. it decreases from EOMSW100 to EOMSW-
gasification is shorter and the gasification rate is higher for OMWW and then to PS-OMWW. These observations are in
powders than for pellets. Also, the rate of gasification is higher accordance with recent results reported by Lajili et al. [39]. In
for powders than for pellets. Indeed, as it was stated by S. Luo addition to the catalytic effect due the impregnation process,
et al. [43], this effect can be explained by the increase of the the high reactivity of the powder, by comparison to the pellets,
surface area of the small particles interacting with the gasifier during gasification also can be related to the low mass the high
agent (steam) and by the formation of volatile products that surface exchange and to the heat transfer limitation. Measured
leave the sample without undergoing secondary cracking re- kinetics may be considered as intrinsic kinetics. Therefore, the
actions. At the contrary, for the larger particles, this phe- powder form strengthens the samples’ reactivity.
nomenon could be dominant, leading to a more char and tar
formation. Hence, mass and heat limitations are more sig-
nificant for larger particles. In our case these physical phe- Conclusion
nomena are more accentuated due the big difference in size
between pellets and powder. Moreover, it was reported by Slow pyrolysis experiments were carried out in order to pre-
Inayat et al. [44] that smaller particle size of blended biomass pare 4 chars from Tunisian (OMSW, OMWW and PS) bio-
prepared from wood chips (acacia mangium) and coconut masses. These chars were crushed and sieved in powder form
shells (Cocos nucifera L) leads to higher hydrogen, carbon in order to obtain gasification tests under different isothermal
monoxide and methane concentrations in syngas. High peak temperatures and steam molar fractions mixed with nitrogen
concentrations were clearly observed with the 5e10 mm (N2).
particles; whereas the concentrations decrease with the big The results show that the conversion, the rate of conver-
particle size (25e50 mm). Besides, Y. Feng et al. [45] have sion and the char reactivity are enhanced by the steam partial
studied the influence of particle size and temperature on pressure for a given temperature. Moreover, we found that the

Please cite this article in press as: Zribi M, et al., Hydrogen enriched syngas production via gasification of biofuels pellets/powders
blended from olive mill solid wastes and pine sawdust under different water steam/nitrogen atmospheres, International Journal of
Hydrogen Energy (2018), https://doi.org/10.1016/j.ijhydene.2018.10.021
8 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 8 ) 1 e9

same three gasification variables increase with temperature mixture: evolution of chemical, textural and structural
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Hydrogen Energy (2018), https://doi.org/10.1016/j.ijhydene.2018.10.021
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Please cite this article in press as: Zribi M, et al., Hydrogen enriched syngas production via gasification of biofuels pellets/powders
blended from olive mill solid wastes and pine sawdust under different water steam/nitrogen atmospheres, International Journal of
Hydrogen Energy (2018), https://doi.org/10.1016/j.ijhydene.2018.10.021