Fuel 241 (2019) 372–381

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Full Length Article

Gasification performance of Spirulina microalgae – A thermodynamic study T

with tar formation
Muflih A. Adnana,c,1, Qingang Xiongb,1, Arif Hidayata, Mohammad M. Hossainc,d,
⁎

a
Department of Chemical Engineering, Islamic University of Indonesia, Sleman, Daerah Istimewa Yogyakarta 55584, Indonesia
b
IT Innovation Center, General Motors, Warren, MI 48092, USA
c
Department of Chemical Engineering, King Fahd University of Petroleum & Minerals, Dhahran 31261, Saudi Arabia
d
Center of Research Excellence in Nanotechnology, King Fahd University of Petroleum & Minerals, Dhahran 31261, Saudi Arabia

ARTICLE INFO ABSTRACT

Keywords: In this work, the performance of a novel configuration for Spirulina microalgae gasification was investigated
Biomass gasification through an improved thermodynamic model using Aspen Plus. Compared with existing thermodynamic models,
Spirulina microalgae tar formation is included in the improved counterpart. The proposed novel gasification process consists of four
Tar formation primary zones: (i) pyrolysis, (ii) combustion, (iii) gasification, and (iv) optimization. First, the modeling results
Thermodynamic analysis
were compared against experimental values, where a good agreement (relative error < 10%) was obtained
Optimization
under identical operating conditions. Then, performance of the novel gasification configuration was studied
using the developed improved thermodynamic model at various operating conditions. Metrics such as gasifi-
cation system efficiency, syngas composition and cold gas efficiency were used to measure the performance. It
was found that incorporation of the optimization zone improves the concentration of CO and H2 at the controlled
use of gasifying agents. Moreover, injection of suitable amount of gasifying agents enhances the gasification
performance. Finally, the effects of O2 equivalence ratio and steam injection on the system performance were
investigated.

1. Introduction (i.e., O2, CO2) [3,4]. Indeed, production cost of microalgae is a major
consideration for commercialization of microalgae for biofuels. The
In recent years, besides traditional agricultural biomass, a special selection of proper nutrients, water and CO2 could potentially cut the
type of biomass, microalgae, has received considerable attention as a production cost by > 50% [5]. Furthermore, the production cost can be
clean energy source to substitute fossil fuels due to the increased con- reduced by taking suitable land for cultivation of microalgae [6] and
cern on energy security as well as environmental sustainability [1]. the harvesting method [7]. Among various approaches to convert mi-
Biomass from different sources including terrestrial biomass and marine croalgae into biofuels, gasification through which a mixture of incon-
biomass is considered as a potential candidate to substitute the fossil densable gas such as H2, CO, CH4 and CO2 is produced, has been widely
fuels given its advantages over fossil fuels in term of environment issue viewed as a promising way due to its relatively high energy conversion
(e.g., carbon neutral cycle). Recently, on purpose marine biomass such efficiency [2].
as microalgae has received a growing attention as a clean energy source However, at industrial scale, effective gasification of microalgae is
attributable to its advantages over terrestrial biomass including its still limited largely due to the existence of tar, a complex mixture of
ability to recover CO2 through photosynthesis way during their growing aromatic hydrocarbons [8]. Because of the existence of tar which comes
period, tolerance with nutrients in the water, higher photosynthesis out along with the produced incondensable gas, gasification efficiency
efficiency and shorter growth cycle [2]. The use of microalgae emits can be significantly diminished [9]. Therefore, tar concentration during
notably low SOx emission due to its minimum concentration of sulfur. the gasification of microalgae should be kept as minimum as possible.
In addition, even microalgae consists of high-protein, indicating con- In most instances, tar concentration can be reduced using separation
siderable amount of nitrogen element, the NOx formation during gasi- either by dry treatment (i.e., cyclone, filters, etc.) or wet treatment (i.e.,
fication process could be minimized by selecting proper gasifying agent spray towers, wet cyclones, etc.). Although separation has been

⁎
Corresponding author at: Department of Chemical Engineering, King Fahd University of Petroleum & Minerals, Dhahran 31261, Saudi Arabia.
E-mail address: [email protected] (M.M. Hossain).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.fuel.2018.12.061
Received 1 September 2018; Received in revised form 10 December 2018; Accepted 11 December 2018
0016-2361/ © 2018 Elsevier Ltd. All rights reserved.
M.A. Adnan et al. Fuel 241 (2019) 372–381

Fig. 1. Schematic diagram of the proposed gasification process for Spirulina.

demonstrated as an effective way to remove tar from the produced consuming work, especially for a large-scale microalgae gasification
incondensable gas, it is not able to fully preserve the high gasification [21]. Thermodynamic modeling, where steady-state equilibrium phy-
efficiency given tar is wasted instead of being converted to incon- sicochemical principles are applied to predict the overall reactor out-
densable gas [10]. Moreover, post-processing the separated tar requires come, has been widely viewed as a promising way to quickly estimate
additional energy, which will further decrease the overall gasification the overall performance of biomass gasification with reasonable accu-
efficiency [1,11]. Thus, it is more feasible to directly convert tar into racy [22–25]. For this reason, thermodynamic modeling has also been
incondensable combustible gas. largely employed to simulate biomass gasification and evaluate the
During microalgae gasification, tar is primarily formed in the pyr- performance of novel gasifier designs [26,27]. This is also the case to
olysis step which occurs at relatively low temperature. In principle, microalgae gasification [22,23]. However, most thermodynamic mod-
direct conversion of tar into incondensable combustible gas can be eling of microalgae gasification uses relatively simplified reactions to
achieved through three approaches, i.e., (i) increasing the gasification model the tar formation and conversion. This will definitely lower the
temperature, (ii) employment of tar cracking catalysts, and (iii) novel overall prediction accuracy for thermodynamic modeling of microalgae
gasifier design. However, thermal cracking of tar at high temperature is gasification. Due to the high nitrogenated content in microalgae, many
costly as this is an energy intensive process [1,12]. In general, using studies have revealed that it is reasonable to approximate tar as ni-
catalysts should be a proper way to increase tar conversion at relatively trogenated aromatic hydrocarbon to preserve engineering accuracy
low temperature [1,13]. However, it is highly possible for catalysts to [28,29]. Therefore, such tar approximation is adopted in our current
suffer from the problems of deactivation due to pore blockage by coke thermodynamic modeling of microalgae gasification [30].
and degradation of mechanical strengths [14–16]. For design of novel In this work, a comprehensive thermodynamic modeling of the
gasifiers, in recent years many investigations have shown that it is an foregoing mentioned new configuration for microalgae gasification was
efficient way to increase tar conversion and gasification efficiency. For conducted using Aspen Plus. The single-species microalgae, Spirulina,
example, Susanto and Beenackers [17] proposed a new design on a was selected as the feedstock and tar was modeled as a mixture of ni-
continuous downdraft gasifier for woody biomass, in which an internal trogenated aromatic hydrocarbons. Spirulina contains high concentra-
cycle is introduced. With such novel design, tar produced from the tion of protein, which is favorable for production of oil during pyrolysis
pyrolysis zone is cracked in the combustion zone, through which the stage [31]. Furthermore, the vaporized oil is converted into syngas as
final collected tar concentration decreases by 97% (from the major gasification product. First, the thermodynamic modeling was
1410 mg·Nm−3 to 48 mg·Nm−3). Similarly, Brandt et al. [18] success- validated against experimental results to prove its accuracy. Then,
fully reduced tar content below 15 mg·Nm−3 using the design of two- performance of the new Spirulina gasification system was analyzed with
stage gasifier with a dry wood as the feedstock. Therefore, it could be respect to gasification system efficiency, syngas composition and cold
anticipated that novel design of gasifier could significantly increase the gas efficiency. Finally, the flow rates of oxygen and steam were varied
efficiency of microalgae gasification. to investigate their effects on gasification performance for optimal op-
In our previous work [19], a gasification system including a CO2- eration of the new design.
absorber to upgrade the syngas quality by removing CO2 from the
syngas stream was proposed and assessed. It was proved to be very 2. Description of the novel design
efficient for microalgae gasification. In this study, such novel gasifica-
tion design is further enhanced by realizing the in-situ utilization of The proposed novel design of microalgae gasification process is
pure CO2 as the side product through facilitating the Bouduard reaction shown in Fig. 1, where four major zones are involved, i.e., pyrolysis
to enhance the char and CO2 conversion into CO, which is usually used zone, combustion zone, gasification zone, and optimization zone. The
in a direct carbon solid oxide fuel cell (SOFC) [20]. The improved gasifying agents are steam and high-purity oxygen. The ultimate and
configuration consists of pyrolysis, combustion, gasification, and opti- proximate analysis of the feedstock Spirulina including its heating value
mization stages, respectively, with a number of advantages such as are summarized in Table 1. The Spirulina feedstock including its prop-
production of clean syngas due to an effective tar conversion and in-situ erties (i.e., ultimate, proximate and high heating value) for simulation
utilization of CO2. is adapted from the one used by Hong et al. [31]. The actual operation
Assessing the performance of a novel design for microalgae gasifi- of Spirulina gasification in this novel configuration can be majorly de-
cation is critical to its subsequent optimization and scale-up processes. scribed as follows. At the inlet, Spirulina is continuously fed at constant
However, it is rather difficult, even if possible, to use the traditional flow rate of 100 kg/h. The feedstock first enters the pyrolysis zone (Z-
experimental approach to conduct such laborious, high-cost and time- 1). In Z-1, moisture content in Spirulina evaporates first due to high

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M.A. Adnan et al. Fuel 241 (2019) 372–381

Table 1
Properties of Spirulina [31]. Methane formation C + 2H2 ↔ CH4 (13)
Proximate, % mass

Moisture 6.7
3. Model development
Volatile matters 73.5
Fixed carbon 13.2
Ash 6.6 Performance of the proposed novel gasification process for Spirulina
Ultimate, % mass
is modeled using AspenPlus®, primarily based on the minimization of
C 49.8 Gibbs free energy [23,32]. In the simulation, the feedstock Spirulina is
H 6.6 classified as a nonconventional element while the gasifying agents are
O 31.9 categorized as conventional elements. Regarding the solid products,
N 11.0
carbon and ash are modeled as cisolid and nonconventional elements,
S 0.7
respectively. The gaseous products including H2, H2O, CO, CO2, CH4,
HHV, MJ/kg 15.1
C2H6 and tar are considered as conventional elements. It is worth
noting that the tar in this simulation is represented by a mixture of
indole, benzyl nitrile, benzonitrile, quinolone, p-cresol, phenol and
temperature. Then, Spirulina is decomposed into solid (i.e., char) and
naphthalene. The Peng-Robinson equation of state is chosen as the
gaseous products including water vapor, permanent gases (CO, H2, CH4
thermodynamic model due to its good accuracy for simulation of ga-
and CO2) and tars. These pyrolysis products are sent to the cyclone 1
sification process [23,30,33]. The following assumptions are made: (i)
(CL-1) to separate the solid products from the gaseous products. The
ash is inert; (ii) mass transfer limitation is minimum; and (iii) pressure
solid products are further split into two streams: one to the gasification
drop along the equipment is trivial. Operating parameters of the pro-
zone (Z-3) and the other to the optimization zone (Z-4). At the same
posed novel gasification process for Spirulina are listed in Table 2. The
time, the gaseous products are directed to the combustion zone (Z-2). In
efficiency of the rotating equipment is adapted from the previous lit-
Z-2, the gaseous products contact with the gasifying agents and the tar
erature [19]. In the following, detailed information on the thermo-
concentration decays due to its conversion to permanent gases. After
dynamic modeling of zones from pyrolysis to optimization is described.
that, the products from Z-2 are sent to Z-3, where they interact with a
portion of char obtained from CL-1. The gasification products are then
directed to cyclone-2 (CL-2) to remove the unconverted char. Later, the 3.1. Pyrolysis zone (Z-1)
solid products are directed to Z-4 while the gaseous products are cooled
in the cooler-1 (CR-1). The condensed water from CR-1 is separated in Spirulina enters Z-1 with constant mass flow rate of 100 kg/h. In Z-1,
the flash-1 (FL-1) before it is fed to the CO2-absorber (AS) unit, where the feedstock is thermally decomposed into (a) gaseous products
the CO2 is removed from the cooled dry gaseous gasification products. (conventional elements) including H2, H2O, CO, CO2, CH4, C2H6 and
The high-purity CO2 is directed to Z-4 while other gaseous gasification tar, (b) carbon (ci-solid element), and (c) ash (nonconventional ele-
products are sent to the cooler-2 (CR-2), along with the gas from the ment). For the thermodynamic modeling of Z-1, the following as-
cyclone-3 (CL-3). In Z-4, the high-purity CO2 reacts with a portion of sumptions are made:
char received from CL-1 and part of gasifying agents (i.e., O2 and
steam). The condensed water from CR-2 is removed in the flash-2 (FL-2) (i) The char only consists of carbon and ash. This has been confirmed
before distributing the syngas to the users. The overall gasification through experiment by Fagbemi et al. [34], reporting that a large
process as described above except the pyrolysis phase majorly contains content of carbon (> 88 wt%) is observed on the char from pyr-
the following reactions [30]: olysis at 773 K.
1 (ii) The amount of char is calculated based on the experimental value
Partial oxidation C+ O2 CO
(1) suggested by Hong et al. [31], showing the char yield from pyr-
2
olysis at 973 K.
(iii) The tar is limited to indole, benzyl nitrile, benzonitrile, quinolone,
Boudouard reaction C + CO2 ↔ 2CO (2) p-cresol, phenol and naphthalene. This is based on the experi-
mental results from Hong et al. [31], where tar was found to be
Steam reforming C + H2O ↔ CO + H2 (3)
almost composed of nitrogenated compounds, phenols, and poly-
Water-gas shift reaction CO + H2O ↔ CO2 + H2 (4) cyclic aromatic hydrocarbons during pyrolysis at 973 K.
(iv) Due to the extreme complexity of the nitrogenated compounds,
Methane reforming CH4 + H2O ↔ CO + 3H2 (5) their thermochemical properties are obtained using the empirical
CO2 reforming CH4 + CO2 ↔ 2CO + 2H2 (6) relationship proposed by Benson et al. [35].

1 1
Steam reforming of aromatic C x Hy Nz + x H2 O x CO + (y + 2x )H2 + z N2 The quantity of products as well as heat needed are predicted by
2 2
(7)
Table 2
Operating conditions of the proposed novel gasification process for Spirulina in
p-Cresol steam reforming C7H8O + 6H2O ↔ 7CO + 10H2 (8) the simulation.
Inlet temperature of Spirulina, boiler feed water and O2 298 K
Phenol steam reforming C6H5OH + 5H2O ↔ 6CO + 8H2 (9) Temperature of steam entering gasification zone 623 K
Temperature of pyrolysis zone (Z-1) 973 K
Naphthalene steam reforming C10H8 + 10H2O ↔ 10CO + 14H2 (10)
Temperature of combustion zone (Z-2) 1523 K
1 Temperature of gasification zone (Z-3) 1423 K
Alkane combustion Cn H2n + 2 + (3n + 1)O2 nCO2 + (n + 1)H2 O Temperature of optimization zone (Z-4) 873 K
2
Efficiency of BFW pump 0.80
(11) O2 compressor
Isentropic efficiency 0.85
1 Mechanical efficiency 0.96
CO combustion CO + O2 CO2
2 (12)

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solving the elemental and heat balances simultaneously in the RYield. Table 3
Gas composition of the experimental work [38] and the model.
3.2. Combustion zone (Z-2) Compound Hong et al. [31] This work Error (%)

The gaseous products obtained from Z-1 then pass CL-1 and contact Gaseous product, mol%
H2 32.6% 33.4% 2.4%
with the gasifying agents in Z-2, undergoing exothermic reactions
CO 40.5% 37.8% 6.6%
which implies to high operating temperature (1523 K). Due to the high CH4 13.8% 15.1% 9.0%
temperature in Z-2, reactions in this zone are assumed to reach equi- CO2 7.9% 6.7% 15.4%
librium very fast. Therefore, the RGibss block is taken to represent Z-2 C2H6 3.0% 3.7% 24.2%
in the simulation. RGibss is the only Aspen Plus block which operates Tar 1.2% 1.5% 24.2%

according to the minimization of Gibbs free energy method. The pro- Solid product, wt%
ducts obtained from Z-2 are sent to Z-3 for further processing. Char 10.0% 10.9% 9.4%

3.3. Gasification zone (Z-3)

comparing the predicted solid and gaseous pyrolysis products with
those of the experimental data reported by Hong et al. [31]. Simulation
In Z-3, the hot gases received from Z-2 react with the solid pyrolysis
conditions were set the same as those in the corresponding experiment
products from CL-1, resulting in a set of endothermic reactions.
[31]. The product yields after the pyrolysis stage are summarized
Consequently, the temperature of Z-3 is slightly lower than its coun-
Table 3. It can be clearly seen that the proposed thermodynamic model
terpart in Z-2, as shown in Table 2. However, the temperature in Z-3 is
satisfactorily predicts the yield of each product. It is worth noting that
still considered to be adequate to achieve equilibrium. Therefore, the
the formation of tar is also predicted in this model. As mentioned
RGibbs block can still be properly used to model Z-3. The products from
earlier, tar consists of complex compounds when compared with other
Z-3 are sent to the gas separation process to remove CO2 from the
specific gaseous products. In addition, the concentration of tar in the
syngas stream.
syngas is considerably smaller than other species. Therefore, the dif-
ference of tar concentration between experiment and this model is
3.4. Optimization zone (Z-4)
reasonable if the above two factors are taken into account.
The CO2 from the CO2-absorber (AS) unit reacts with the un-
converted char received from CL-2. In addition, part of char obtained 6. Results and discussion
from CL-1 and part of gasifying agents is directed to Z-4. The en-
dothermic reactions in Z-4 lead to the decrease of the operating tem- The proposed novel gasification configuration is first evaluated by
perature. Again, an equilibrium condition is assumed to occur at this the foregoing developed thermodynamic model, at a constant feedstock
temperature, where the RGibbs block is employed to model Z-4. feed rate of 100 kg/h. The temperatures of the pyrolysis zone (Z-1),
combustion zone (Z-2), gasification zone (Z-3), and optimization zone
4. Performance evaluation (Z-4) are maintained constant at 973 K, 1523 K, 1423 K and 873 K, re-
spectively. Then, the effects of O2 equivalence ratio and steam injection
Performance of a gasification process is usually assessed based on on process performance are investigated.
the following aspects: (i) concentration of the targeted syngas products
(i.e., primarily H2 and CO), (ii) cold gas efficiency (CGE), and (iii) ga- 6.1. Process description
sification system efficiency (GSE). Composition of the syngas is ex-
pressed in terms of dry gas basis. The CGE designates the ratio of ser- As mentioned above, the overall gasification process consists of four
viceable energy in the syngas to the reserved energy in the feedstock primary steps, in which the pyrolysis step converts the Spirulina feed-
and steam, which can be expressed as stock into char and pyrolysis gas products, the combustion step reforms
tar into the desired permanent gases, the gasification step converts char
msgs ·LHVsgs
CGE ( ) = , into syngas and the optimization step transforms unconverted char into
mms · LHVms + Hsm·msm (14) valuable gases with the help of the recycled CO2. Pure oxygen and
where m H, and LHV are the mass flow rate, enthalpy and the lower steam are fed into the system with an oxygen equivalence ratio (O2 ER
heating value, respectively. The subscript sgs, ms and sm represent the ratio) of 0.3 and steam to carbon (S/C) ratio of 1.0. The O2 ER ratio
syngas, Spirulina and steam, respectively. defined as the ratio of actual oxygen to biomass ratio to the stoichio-
GSE accounts for the efficiency of the whole gasification system, metric oxygen to biomass ratio. The S/C ratio is the molar ratio of steam
which is expressed as to carbon in the biomass. Before entering the gasifier, the steam flow is
split into two streams. One stream, containing 80% of the fed steam,
msgs × LHVsgs + Qcr 1 + Qcr 2
GSE = , enters the combustion zone (Z-2) and the other stream (20%) goes to
mms × LHVms + Qz + Qz + Qz + Qz + Qbr + Ec + Eox + Eas
the optimization zone (Z-4). On the other hand, oxygen is directly in-
1 2 3 4 1

(15) troduced to the combustion zone (Z-2). The char from the cyclone-1
where Q and E are the heat rate and energy rate, respectively. The use (CL-1) is split into two streams and sent to gasification zone (Z-3) and
of relatively purified O2 (95% O2) for gasification is favorable due to its optimization zone (Z-4). In this regard, the optimization zone (Z-4) is
ability to provide a higher gasification temperature which leads to a selected as a reference for quantifying the char split in term of mass
higher conversion of tar reforming, compared with air [17,30]. Con- fraction, called C to Z-4. Thus, when the entire char stream is directed
sequently, additional energy of 305 kWh per ton of O2 is required for to the gasification zone (Z-3), the condition is referred as C to Z-4 of 0.0.
the gasification process [36]. An extra energy consumption of 3 MJ/kg Fig. 2 shows the molar flow rates of the major constituents of the
of CO2 absorbed is also involved to run the amine-based CO2 absorber feed and the products streams of each primary zone. It is clearly seen in
with the CO2 removal efficiency of 90% [37]. Fig. 2a that the product streams contains tar, carbon and light gases
including H2, CO, CO2, CH4, C2H6, O2, N2 and H2O. This result indicates
5. Model validation that in the pyrolysis stage, the Spirulina biomass is completely decom-
posed into gaseous products and tar. The low temperature of the pyr-
The proposed thermodynamic model was first validated by olysis stage (973 K) favors the conversion of Spirulina biomass into tar

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M.A. Adnan et al. Fuel 241 (2019) 372–381

Fig. 2. Mole flow of the feed and product of (a) pyrolysis zone, (b) combustion zone, (c) gasification zone, and (d) optimization zone. (Feed: grey; product: black).

[38–40]. Following the pyrolysis step, the mixed product stream is sent increase of CO flow rates in the product stream (Fig. 2d). Interesting to
to cyclone-1 (CL-1) in order to separate solids from the rest of the see (in Fig. 2d) that the overall CO2 flow slightly increases, despite its
products. The separated solid products is sent to the splitter for splitting consumption in reaction Eq. (2). This increase of CO2 can be explained
the char to: (1) the gasification zone (Z-3) and (2) the optimization zone by comparing CO2 and H2 production via water-gas shift reaction (Eq.
(Z-4), while the gaseous products including tar are sent to the com- (4)), which results in a higher flow rate of H2. The slight increase of H2
bustion zone (Z-2) for further processing. flow rate is due to hydrogen consumption in methanation reaction (Eq.
In the combustion zone (Z-2), the gaseous pyrolysis products react (13)) to give CH4.
with the gasifying agents (O2 and steam) to permanent gases. As a re-
sult, the molar flow rates of CH4, C2H6 and O2 in the product stream 6.2. The effects of O2 equivalence ratio
significantly decrease, while the flow rates of H2O and CO2 increase
(Fig. 2b). The exothermic alkane combustion reactions also increase the The effect of O2 equivalence ratio (ER) (varied from 0.00 to 1.00) on
combustion zone temperature up to 1523 K. This high temperature fa- the gasification performance is investigated at a constant S/C ratio of
cilitates the tar reforming reactions (Eqs. (7)–(10)) and converts tar into 1.0. The char supplied to Z-4 is varied between 0 and 0.6 (as a fraction
the permanent gases. This is confirmed by the absence of tar in the of total char flow) to study the effect of char split configuration at
product stream. The tar reforming reactions also contribute to the various O2 split fractions (O2 to Z-4 is varied between 0.0 and 0.4).
production of H2 and CO [30]. The combustion zone (Z-2) products The dry basis concentrations of the primary constituents (H2, CO
flows to the gasification zone (Z-3) for further reactions. and CO2) in the syngas at various splits of char and oxygen for the O2
In gasification zone (Z-3), the combustion products react with char ER from 0.00 to 1.00 are shown in Fig. 3. It can be clearly seen that
received from the cyclone-1 (CL-1). Consequently, the carbon feed rates increasing O2 ER at a certain value favors CO2 production and decreases
of the product stream decreases, while the reform products (H2 and CO) the concentrations of H2 and CO. Further increase in O2 ER after the
increase, as shown in Fig. 2c. This observation indicates that the steam optimal point has minimum influence on the syngas composition. In-
reforming reaction (Eq. (3)) dominates in the gasification stage. The deed, the production of CO and H2 is dominated by partial oxidation
flow rate of CO2 in the product stream is slightly higher than its reaction (Eq. (1)) and steam reforming reaction (Eq. (3)). However, the
counterpart in the feed stream. This suggests the participation of the presence of excessive O2 in the gasification system promotes CO oxi-
water-gas shift reaction (Eq. (4)), which is also confirmed by the de- dation reaction (Eq. (12)), resulting in CO2 formation and restrain the
crease flow rate of H2O. The gasification products from Z-3 is sent to the concentrations of CO and H2. The reason for the plateau (Figs. 3a and
gas treatment process including Cyclone-2 (CL-2) and CO2-absorber 4a) of syngas composition at high O2 ER can be explained by the ab-
(AS) to remove the unconverted char and CO2 from the main syngas sence of CO due to the lack of carbon source from char. The CO con-
stream, respectively. centration is near to zero, where a complete carbon conversion is
In the optimization zone (Z-4), char received from the cyclone-2 reached at very high O2 ER (O2 ER > 0.92 when the C to Z-4 equals 0).
(CL-2) and cyclone-1 (CL-1), reacts with pure CO2 and steam, received Similar result is observed on the other char split fractions. These results
from the CO2-absorber (AS) and the boiler (BR), respectively. In Z-4, indicate that higher amount of O2 in the gasification process is re-
char reacts with the oxidizing agents converting C and CO2 into CO sponsible for the CO oxidation to CO2 (Eq. (12)), leading to minimum
(Eqs. (2) and (4)). This is confirmed by disappearance of carbon and CO production. Billdaud et al. [41] also reported similar conclusion

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M.A. Adnan et al. Fuel 241 (2019) 372–381

Fig. 4. The effect of O2 ER ratio on carbon conversion at different O2 to Z-4

fractions: (a) O2 to Z-4 of 0.0, (b) O2 to Z-4 of 0.2 and (c) O2 to Z-4 of 0.4.
Fig. 3. The effect of O2 equivalence ratio on the composition of syngas at dif-
ferent O2 to Z-4 fractions: (a) O2 to Z-4 of 0.0, (b) O2 to Z-4 of 0.2 and (c) O2 to
concentration that facilitate the char conversion through the steam
Z-4 of 0.4. (Red: CO, black: H2 and brown: CO2). (For interpretation of the
references to colour in this figure legend, the reader is referred to the web reforming reaction (Eq. (3)). At minimum char flow to the optimization
version of this article.) zone (Z-4), the char is mainly fed to the gasification zone (Z-3), and
converted into CO. It is worth noting that higher char fraction to op-
timization zone (Z-4) has a positive influence on CO concentration,
with a set of gasification experiments using beech wood as the feed-
while a negative effect is found on CO2 concentration, especially at high
stock. In their experiments, the highest CO concentration (24 mol/kg
O2 ER ratio. The reason of this lays on the fact that the increase of char
feedstock) was observed when O2 ER is around 0.42. CO concentration
split to the optimization zone (Z-4) retards carbon conversion, which
decreased from 24 to 11 mol/kg feedstock with the increase of O2 ER
leads to low activity of CO combustion reaction (Eq. (12)) due to the
from 0.42 to 0.60.
limited CO concentration.
The variation of char fed (as fraction) to Z-4 has a significant impact
As mentioned above, O2 is split into the combustion zone (Z-2) and
on the syngas composition (Fig. 4a). At high char flow and low O2 ER,
the optimization zone (Z-4). The split fraction of O2 to the optimization
the concentrations of CO2 and H2 slightly increase while the con-
zone (Z-4) has a considerable influence on the syngas composition, by
centration of CO decreases. However, the influence of char on the
comparing Fig. 3a–c. The increase of O2 split fraction to optimization
syngas composition fades as the O2 ER is elevated up to a certain value.
zone (Z-4) minimizes the effect of O2 ER ratio on the syngas composi-
When the O2 ER exceeds this threshold, the effect of char split becomes
tion. For example, as it can be seen in Fig. 3a that the concentration of
more prominent. The reason for this behavior comes from the fact that
H2 drastically decreases from 0.58 to 0.29 with increase of O2 ER ratio
at this configuration O2 is primarily sent to Z-2, which contributes to
from 0.0 to 0.5 at the C to Z-4 and the O2 to Z-4 of 0.6 and 0.0. Under
the combustion and provides high temperature and high steam H2O
similar situation, a slower reduction rate of H2 concentration

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M.A. Adnan et al. Fuel 241 (2019) 372–381

(0.58–0.40) is observed when the O2 to Z-4 is elevates from 0.0 to 0.4.

This result indicates that the formation of syngas constituents primarily
determines in the combustion zone (Z-2) and gasification zone (Z-3)
due to its opportunity to receive a rich mixture of products from the
pyrolysis stage (Z-1). Consequently, the presence of O2 at higher level in
the combustion zone (Z-2) has stronger control to the syngas compo-
sition given it affects the product of the gasification zone (Z-3) when
compared to its counterpart in the optimization zone (Z-4), which
handles a smaller number of feed compounds (mainly only char and
CO2). The identical fashion is found on the concentration of CO and
CO2.
In line with the syngas composition, the split fraction of O2 to op-
timization zone (Z-4) also has a strong effect on the carbon conversions
(Fig. 4). The addition of O2 to the optimization zone (Z-4) with the O2
to Z-4 of 0.4 slightly reduces the O2 requirement (O2 ER ratio of 0.08) to
achieve a complete carbon conversion. This result can be explained by
the fewer number of species that is involved in the optimization zone
(Z-4) as compared to the species in the gasification zone (Z-2). There-
fore, in the optimization zone (Z-4) the O2 supply is exclusively reacted
with char through the partial oxidation reaction (Eq. (1)). In addition,
the presence of pure CO2 from the CO2-absorber (AS) facilitates char
conversion by Bouduard reaction (Eq. (2)).
The significant influence of O2 is also observed on the CGE, as
shown in Fig. 5. It can be clearly seen in Fig. 5a that the CGE con-
tinuously decreases with the increase of O2 ER ratio up to a certain
condition in the gasification with the O2 to Z-4 of 0.0. Further increase
of O2 supply above that O2 ER ratio value has a negligible influence on
the CGE. This result indicates that the CGE is strongly influenced by the
syngas composition. The lower concentration of combustible species in
the syngas due to the increase of O2 ER ratio leads to a lower CGE. In
addition, the sustained CGE with the increase of O2 ER ratio can be
related to the constant syngas composition at high O2 ER ratio. This is
confirmed by the CGE with the O2 to Z-4 of 0.2 and 0.4 as depicted in
Fig. 5b and c, respectively. Similar conclusion is previous drawn by
Adnan et al. [19], reporting an adverse influence of the increase of O2
injection to the gasification of various feedstock on the CGE.
The O2 also has a considerable effect on the GSE, as depicted in
Fig. 5. One can see in Fig. 5a that the increase of O2 ER ratio has an
adverse effect on the GSE to the minimum GSE value. Further increase
of O2 ER ratio has a negligible influence on the GSE. Again, this finding
indicates that the syngas composition has a strong influence on the GSE.
The similar conclusion is reported in the previous studies [19,30].

6.3. The effects of steam injection

The parametric study on the effect of steam is carried out by in-

troducing a various boiler feed water with the S/C ratio of 0.0–2.0 at a
constant Spirulina flow rate of 100 kg/h. In this S/C ratio parametric Fig. 5. The effect of equivalence ratio on GSE (red) and CGE (black) at different
study, O2 is added to the combustion zone (Z-2) at O2 ER ratio of 0.25. O2 to Z-4 fractions: (a) O2 to Z-4 of 0.0, (b) O2 to Z-4 of 0.2 and (c) O2 to Z-4 of
The char split fraction to the optimization zone (Z-4) is varied between 0.4. (For interpretation of the references to colour in this figure legend, the
the C to Z-4 of 0.0 to 0.6 in order to study the effect of char at various reader is referred to the web version of this article.)
steam split fractions to the optimization zone (Z-4) with the steam to Z-
4 from 0.0 to 0.4. previous experimental investigation by Li et al. [42] on the gasification
Fig. 6 plots the effect of S/C ratio on dry basis syngas composition at using a corn stalk as the feedstock. In addition, steam contributes a
various char and steam split fraction into the optimization zone (Z-4). It considerable amount of hydrogen source for reforming reaction [43].
can be clearly seen from this figure that the S/C ratio significantly af- Similar trend is also found in the gasification with the steam to Z-4 of
fects the syngas composition. The addition, steam has a positive influ- 0.2 and 0.4 with slight different values, as depicted in Fig. 6b and c,
ence on the concentration of H2 and CO2, while an adverse effect is respectively. The char split ratio to the optimization zone (Z-4) has a
found on CO concentration. This can be explained by the fact that the minimum influence of the syngas composition. At the low S/C ratio, the
increase of H2O amount in the gasification process facilitates water-gas concentration of CO and H2 diminish while the CO2 concentration
shift reaction (Eq. (4)), consuming CO and H2O to produce CO2 and H2. elevates when the C to Z-4 is increased from 0.0 to 0.6. At high S/C
As per CO species, it is worth noting that the CO as a reactant of water- ratio the opposite trend is found on the CO concentration. For instance,
gas shift reaction (Eq. (4)) is produced from the conversion of carbon the CO2 concentration slightly augments from 0.04 to 0.07 while the
with the steam through reforming reaction (Eq. (3)). This is confirmed concentration of CO and H2 slightly decreases from 0.41 to 0.40 and
by the increase of carbon conversion with increasing S/C ratio as de- 0.49 to 0.46, respectively, when the C to Z-4 was increased from 0.0 to
picted in Fig. 7a. The present result found a good agreement with the

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M.A. Adnan et al. Fuel 241 (2019) 372–381

Fig. 7. The effect of S/C ratio on carbon conversion at different steam to Z-4
fractions: (a) steam to Z-4 of 0.0, (b) steam to Z-4 of 0.2 and (c) steam to Z-4 of
Fig. 6. The effect of S/C ratio on the composition of syngas at different steam to
0.4.
Z-4 fractions: (a) steam to Z-4 of 0.0, (b) steam to Z-4 of 0.2 and (c) steam to Z-4
of 0.4. (Red: CO, black: H2 and brown: CO2). (For interpretation of the refer-
ences to colour in this figure legend, the reader is referred to the web version of Fig. 6a–c. This can be explained by the fact that the steam reforming
this article.) reaction (Eq. (3)), which is promoted by steam injection, facilitates
conversion of carbon and steam into CO and H2. It is worth noting that
0.6 on the gasification with the steam to Z-4 and the S/C ratio of 0.0 at higher steam to Z-4, the domination of the water-gas shift (Eq. (4))
and 0.31, respectively. Under the similar conditions with higher S/C reaction increases due to the excess amount of steam, converting CO
ratio (2.00), the concentration of CO slightly raises from 0.26 to 0.27 and steam into CO2 and H2.
while the concentration of H2 declined from 0.50 to 0.49 and the CO2 The considerable effect of steam at various char split fraction to the
concentration remains constant at 0.19. The explanation of this lays on optimization zone (Z-4) is also found on the CGE, as depicted in Fig. 8.
the fact that the steam reforming reaction (Eq. (3)) has a minor influ- The CGE slightly mitigates with the increase of S/C ratio from 0.0 to 2.0
ence on the syngas composition due to the small amount of char from at the C to Z-4 of 0.0. These results can be explained by the fact that the
the pyrolysis product (i.e., 10 wt%). The limited CO concentration leads increase of heating value due to the slight increase of H2 concentration
to the minimum effect of the water-gas shift reaction (Eq. (4)). This is is counterbalanced by the significant decrease of CO concentration,
confirmed by the significant increase of carbon conversion that is not in resulting a decline of net syngas heating value. This is an indication of
line with the increase of CO concentration in the syngas as depicted in strong influence of syngas composition on the CGE. The similar fashion
Figs. 7 and 6, respectively. is observed on the gasification with the steam to Z-4 of 0.2 and 0.4, as
The influence of the char split fraction the optimization zone (Z-4) shown in Fig. 8b and c, respectively. The identical conclusion is re-
on the syngas concentration is higher when the steam split fraction to ported in the previous published literature [19]. The char split fraction
the optimization zone (Z-4) is increased from 0.0 to 0.4, as shown in to the optimization zone (Z-4) has a negative effect on the CGE at low

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CO. This is confirmed by the increase of CO2 concentration as the S/C

ratio is elevated, as depicted in Fig. 6.

7. Conclusions

A new biomass gasification configuration is developed using Aspen

Plus software, considering the formation of tar during the pyrolysis
stage. The Spirulina microalgae is considered as the biomass feedstock.
Following are the conclusion of this study:

i. The performances (syngas composition, cold gas efficiency and ga-

sification system efficiency) of gasification process vary with dif-
ferent char, O2 and steam split fraction to the optimization zone (Z-
4).
ii. The use of suitable amount of oxygen (O2 ER) as a gasifying agent
enables a complete reforming of tar into syngas in the combustion
zone (Z-2).
iii. The use of steam as a gasifying agent facilitates H2 production. The
highest H2 concentration (0.58) is observed on the gasification at O2
ER ratio and S/C ratio of 0.0 and 1.0, respectively, for char to Z-4
and O2 to Z-4 of 0.6 and 0.0, respectively.
iv. The highest CGE (1.04) and GSE (0.52) is found in gasification at
the O2 ER ratio, the S/C ratio and C to Z-4 of 0.0, 1.0, 0.0, re-
spectively for all studied O2 to Z-4 (0.0, 0.2, and 0.4).
v. The inclusion of the optimization zone (Z-4) promotes the con-
centration of CO and H2 at the controlled use of gasifying agents.

Acknowledgements

The author(s) would like to acknowledge the financial support

provided by the Deanship of Scientific Research (DSR) at King Fahd
University of Petroleum & Minerals (KFUPM) for funding this work
through project No. IN161022. We also would like to acknowledge the
supports from the directorate of research and community services at
Islamic University of Indonesia (DPPM-UII).

References

[1] de Lasa H, Salaices E, Mazumder J, Lucky R. Catalytic steam gasification of biomass:

catalysts, thermodynamics and kinetics. Chem Rev 2011;111:5404.
[2] Nautiyal P, Subramanian KA, Dastidar MG. Production and characterization of
biodiesel from algae. Fuel Process Technol 2014;120:79.
[3] Adnan MA, Hossain MM. CO2 gasification of microalgae (N. Oculata) – a thermo-
dynamic study. MATEC Web Conf 2018;154:01002.
[4] Adnan MA, Hossain MM. Co-gasification of Indonesian coal and microalgae – a
thermodynamic study and performance evaluation. Chem Eng Process - Process
Intensif 2018;128:1.
[5] Slade R, Bauen A. Micro-algae cultivation for biofuels: cost, energy balance, en-
Fig. 8. The effect of S/C ratio on GSE (red lines) and CGE (blak lines) at dif- vironmental impacts and future prospects. Biomass Bioenergy 2013;53:29.
ferent steam to Z-4 fractions: (a) steam to Z-4 of 0.0, (b) steam to Z-4 of 0.2 and [6] Park H, Lee C-G. Theoretical calculations on the feasibility of microalgal biofuels:
(c) steam to Z-4 of 0.4. utilization of marine resources could help realizing the potential of microalgae.
Biotechnol J 2016;11:1461.
[7] Richardson JW, Johnson MD, Lacey R, Oyler J, Capareda S. Harvesting and ex-
S/C ratio. The influence of the char split fraction diminishes at higher traction technology contributions to algae biofuels economic viability. Algal Res
2014;5:70.
S/C ratios. This indicates that lower carbon conversion results in lower [8] Valderrama Rios ML, González AM, Lora EES, Almazán del Olmo OA. Reduction of
CGE due to the reduction of syngas flow rate. This is confirmed by the tar generated during biomass gasification: a review. Biomass Bioenergy
decrease of carbon conversion at higher C to Z-4, as depicted in Fig. 7. 2018;108:345.
[9] Jia S, Ning S, Ying H, Sun Y, Xu W, Yin H. High quality syngas production from
The steam also has a positive influence on the GSE, as shown in
catalytic gasification of woodchip char. Energy Convers Manage 2017;151:457.
Fig. 7. One can see from this figure that the GSE slightly increases from [10] Anis S, Zainal ZA. Tar reduction in biomass producer gas via mechanical, catalytic
0.47 to 0.48 with the increase of S/C ratio from 0.0 to 2.0 for the ga- and thermal methods: a review. Renew Sust Energ Rev 2011;15:2355.
[11] Guan G, Kaewpanha M, Hao X, Abudula A. Catalytic steam reforming of biomass
sification with C to Z-4 and C to Z-4 of 0.0 and 0.0, respectively
tar: Prospects and challenges. Renew Sust Energy Rev 2016;58:450.
(Fig. 7a). The higher increase of GSE is observed on higher char split [12] Fagbemi L, Khezami L, Capart R. Pyrolysis products from different biomasses: ap-
fraction to the optimization zone (Z-4). For instance, on the gasification plication to the thermal cracking of tar. Appl Energy 2001;69:293.
at the C to Z-4 of 0.6, the GSE significantly elevates from 0.40 to 0.45 [13] Jiang L, Liu C, Hu S, Wang Y, Xu K, Su S, et al. Catalytic behaviors of alkali metal
salt involved in homogeneous volatile and heterogeneous char reforming in steam
with the increase of S/C ratio from 0.0 to 2.0 for steam to Z-4 of 0.0. gasification of cellulose. Energy Convers Manage 2018;158:147.
The identical fashion is observed on the steam to Z-4 of 0.2 and 0.4 as [14] Abu El-Rub Z, Bramer EA, Brem G. Review of catalysts for tar elimination in bio-
depicted in Fig. 7b and c, respectively. This indicates that the addition mass gasification processes. Ind Eng Chem Res 2004;43:6911.
[15] Mazumder J, De Lasa H. Fluidizable Ni/La2O3-γAl2O3 catalyst for steam gasifi-
of steam facilitates an exothermic CO combustion reaction (12) given cation of a cellulosic biomass surrogate. Appl Catal B 2014;160–161:67.
the steam promotes steam reforming reactions (Eq. (3)) which produce [16] Adnan MA, Muraza O, Razzak SA, Hossain MM, de Lasa HI. Iron oxide over silica-

380
M.A. Adnan et al. Fuel 241 (2019) 372–381

doped alumina catalyst for catalytic steam reforming of toluene as a surrogate tar study by including tar. Int J Hydrogen Energy 2017;42:10971.
biomass species. Energy Fuels 2017;31(7):7471–81. [31] Hong Y, Chen W, Luo X, Pang C, Lester E, Wu T. Microwave-enhanced pyrolysis of
[17] Susanto H, Beenackers AACM. A moving-bed gasifier with internal recycle of pyr- macroalgae and microalgae for syngas production. Bioresour Technol 2017;237:47.
olysis gas. Fuel 1996;75:1339. [32] Renganathan T, Yadav MV, Pushpavanam S, Voolapalli RK, Cho YS. CO2 utilization
[18] Brandt P, Larsen E, Henriksen U. High tar reduction in a two-stage gasifier. Energy for gasification of carbonaceous feedstocks: a thermodynamic analysis. Chem Eng
Fuels 2000;14:816. Sci 2012;83:159.
[19] Adnan MA, Hossain MM. Gasification performance of various microalgae biomass – [33] Yan L, He B. On a clean power generation system with the co-gasification of bio-
a thermodynamic study by considering tar formation using Aspen plus. Energy mass and coal in a quadruple fluidized bed gasifier. Bioresour Technol
Convers Manage 2018;165:783. 2017;235:113.
[20] Tang Y, Liu J. Effect of anode and Boudouard reaction catalysts on the performance [34] Fagbemi L, Khezami L, Capart R. Pyrolysis products from different biomasses. Appl
of direct carbon solid oxide fuel cells. Int J Hydrogen Energy 2010;35:11188. Energy 2001;69:293.
[21] Masmoudi MA, Halouani K, Sahraoui M. Comprehensive experimental investigation [35] Benson SW, Cruickshank FR, Golden DM, Haugen GR, O'Neal HE, Rodgers AS, et al.
and numerical modeling of the combined partial oxidation-gasification zone in a Additivity rules for the estimation of thermochemical properties. Chem Rev
pilot downdraft air-blown gasifier. Energy Convers Manage 2017;144:34. 1969;69:279.
[22] Adnan MA, Hossain MM. Gasification of various biomasses including microalgae [36] Tijmensen MJA, Faaij APC, Hamelinck CN, van Hardeveld MRM. Exploration of the
using CO2 – a thermodynamic study. Renew Energy 2018;119:598. possibilities for production of Fischer Tropsch liquids and power via biomass ga-
[23] Adnan MA, Susanto H, Binous H, Muraza O, Hossain MM. Feed compositions and sification. Biomass Bioenergy 2002;23:129.
gasification potential of several biomasses including a microalgae: a thermo- [37] Peters L, Hussain A, Follmann M, Melin T, Hägg MB. CO2 removal from natural gas
dynamic modeling approach. Int J Hydrogen Energy 2017;42:17009. by employing amine absorption and membrane technology—a technical and eco-
[24] Fortunato B, Brunetti G, Camporeale SM, Torresi M, Fornarelli F. Thermodynamic nomical analysis. Chem Eng J 2011;172:952.
model of a downdraft gasifier. Energy Convers Manage 2017;140:281. [38] Duman G, Uddin MA, Yanik J. Hydrogen production from algal biomass via steam
[25] Han J, Liang Y, Hu J, Qin L, Street J, Lu Y, et al. Modeling downdraft biomass gasification. Bioresour Technol 2014;166:24.
gasification process by restricting chemical reaction equilibrium with Aspen Plus. [39] Stark AK, Bates RB, Zhao Z, Ghoniem AF. Prediction and validation of major gas
Energy Convers Manage 2017;153:641. and tar species from a reactor network model of air-blown fluidized bed biomass
[26] Xiang X, Gong G, Shi Y, Cai Y, Wang C. Thermodynamic modeling and analysis of a gasification. Energy Fuels 2015;29:2437.
serial composite process for biomass and coal co-gasification. Renew Sust Energ Rev [40] Stark AK, Ghoniem AF. Quantification of the influence of particle diameter on
2018;82:2768. Polycyclic Aromatic Hydrocarbon (PAH) formation in fluidized bed biomass pyr-
[27] Zhang X, Li H, Liu L, Bai C, Wang S, Zeng J, et al. Thermodynamic and economic olysis. Fuel 2017;206:276.
analysis of biomass partial gasification process. Appl Therm Eng 2018;129:410. [41] Billaud J, Valin S, Peyrot M, Salvador S. Influence of H2O, CO2 and O2 addition on
[28] Gopaul SG, Dutta A, Clemmer R. Chemical looping gasification for hydrogen pro- biomass gasification in entrained flow reactor conditions: experiments and mod-
duction: a comparison of two unique processes simulated using ASPEN Plus. Int J elling. Fuel 2016;166:166.
Hydrogen Energy 2014;39:5804. [42] Li B, Yang H, Wei L, Shao J, Wang X, Chen H. Hydrogen production from agri-
[29] Mostafavi E, Pauls JH, Lim CJ, Mahinpey N. Simulation of high-temperature steam- cultural biomass wastes gasification in a fluidized bed with calcium oxide enhan-
only gasification of woody biomass with dry-sorption CO2 capture. Can J Chem Eng cing. Int J Hydrogen Energy 2017;42:4832.
2016;94:1648. [43] Shayan E, Zare V, Mirzaee I. Hydrogen production from biomass gasification; a
[30] Adnan MA, Susanto H, Binous H, Muraza O, Hossain MM. Enhancement of hy- theoretical comparison of using different gasification agents. Energy Convers
drogen production in a modified moving bed downdraft gasifier – a thermodynamic Manage 2018;159:30.

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