Article

pubs.acs.org/IECR

Equilibrium Modeling of Sorption-Enhanced Cogasification of

Sewage Sludge and Wood for Hydrogen-Rich Gas Production with in
Situ Carbon Dioxide Capture
Vineet S. Sikarwar,†,# Guozhao Ji,†,# Ming Zhao,*,†,‡ and Yujue Wang*,†
†
School of Environment, Tsinghua University, Beijing 100084, China
‡
Key Laboratory for Solid Waste Management and Environment Safety, Ministry of Education, Beijing, 100084, China
*
S Supporting Information

ABSTRACT: Sewage sludge disposal is troublesome because of the presence of microbes, toxins, and heavy metals in it. Co-
gasification of sewage sludge with wood is a promising pathway to dispose of sewage sludge and generate usable syngas,
simultaneously. By using a sorbent for in situ sorption of CO2, H2 fraction in the generated syngas can be enhanced considerably.
An equilibrium model was developed taking wood and sewage sludge as the model compounds and CaO as the sorbent. This
evaluation was performed by employing ASPEN PLUS (V 8.8) software. Principle of Gibbs free-energy minimization was
adopted to predict the outlet gas composition and gas yield. The impact of reactor temperature (600 to 900 °C) and sludge
content (0 to 100 wt % at 700 °C) in the feedstock on syngas yield and constituents were assessed. With 30 wt % sludge,
maximum gas yield was observed as 0.526 kg h−1 at 900 °C while minimum CO2 fraction was achieved at 700 °C. At 700 °C, the
highest gas yield of 0.251 kg h−1 was recorded at 50 wt % sludge, whereas minimum CO2 concentration was observed at 30 wt %
sludge. The model predictions were in good agreement with the experimental findings. The study reflects that CO2-sorption
enhanced gasification of sewage sludge with other biomass such as wood is an attractive option to dispose of sewage sludge in an
environmental friendly manner and to generate hydrogen-rich fuel gas.

1. INTRODUCTION resources. Biomass has been researched for decades to extract

Climate change because of the rise in temperature due to the
greenhouse gas (GHG) effect is a constant source of concern
for all countries. GHG emissions occur mainly because of fossil
fuel combustion coupled with other anthropogenic activities.1,2
Fossil fuels are the primary source of power generation around
the globe and therefore suffer from the threat of extinction.
More importantly, they are the cardinal source of CO2 emission
(∼41%), which is the key GHG responsible for global
warming.3 This calls for a shift from conventional petro-fuels
to renewable energy resources such as solar photovoltaic,
hydroelectric generation, wind, biomass, etc. 1 Biomass
exploitation for power generation has an edge over other
renewables as its transportation (for example, Bioliq concept)
and storage is easier.1 Moreover, it is less reliant upon climate
and location, and amply available unlike other nonconventional
usable energy and chemicals via numerous processes.
Gasification offers an efficient and feasible route to valorize
the biomass waste by usable energy production in an
environment friendly manner. Biomass is inherently a carbon-
neutral source. Deployment of a sorbent such as calcium oxide
(CaO) to capture CO2 in situ results in an enhancement in H2
production.4 In addition, it makes the biomass a carbon
negative resource.5 The basic idea is the removal of CO2 from
the reaction system (R2, R3, R4, and R6 in Table 1) as soon as
it is formed, which in turn shifts the equilibrium according to
Special Issue: Tapio Salmi Festschrift
Received: January 21, 2017
Revised: April 19, 2017
Accepted: April 26, 2017
Published: April 26, 2017

© XXXX American Chemical Society A DOI: 10.1021/acs.iecr.7b00306

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Industrial & Engineering Chemistry Research Article

Table 1. Significant Chemical Reactions in CO2-Sorption as fertilizer or disposed in land-fills. It is also treated by
Enhanced Biomass Gasification1,6 combustion and incineration.12
Lately, cogasification of SS and biomass has gained much
equation reaction ΔHo25
number name/type chemical equation (kJ mol−1) attention on account of some inherent benefits.3,13,14 Sludge
R1 water gas-I C + H2O ⇌ CO + H2 +131.0
contains high moisture and ash content, whereas biomass (such
R2 water gas-II C + 2H2O ⇌ CO2 + +90.1
as wood) contains high volatiles with low ash and water
2H2 content. Therefore, cogasifying them compensates each other’s
R3 water gas shift CO + H2O ⇌ CO2 + H2 −41.2 weaknesses.15 Furthermore, SS moisture can be utilized as the
R4 methane CH4 + 2H2O ⇌ CO2 + +206.0 gasifying agent. In addition, increase in syngas yield and
reforming 4H2 reduction in undesirable gases are other advantages of
R5 Boudouard C + CO2 ⇌ 2CO +172.0 cogasification.16 Therefore, it can be assumed that cogasifica-
R6 oxidation-I C + O2 ⇌ CO2 −394.0 tion of biomass and sludge followed by syngas cleaning and
R7 oxidation-II 2C + O2 ⇌ 2CO −111.0 conditioning would deliver syngas which may be suitable for
R8 methanation-I C + 2H2 ⇌ CH4 −72.8 basic applications such as heat and electricity generation and
R9 carbonation CaO + CO2 ⇌ CaCO3 −178.9 advanced applications such as IC (internal combustion)
R10 calcination CaCO3 ⇌ CaO + CO2 +178.9
engines, gas turbines, and fuel cells. However, further research
R11 methanation-II 2CO + 2H2 → CH4 + −247.0
CO2 is required in this direction.
Operational variables such as temperature, pressure, flow, etc.
should be adjusted inside the gasification vessel to get the most
Le Chatelier’s principle, resulting in an increase in H2 yield.1 efficient performance. Optimal conditions are assessed by
Carbonation (R9 in Table 1) takes place at lower temperatures experimental work which requires time and money. Mathe-
(600 to 750 °C) and captures CO2 to form CaCO3 with heat matical modeling has emerged as a partial solution to this
release. This heat is utilized to drive many endothermic problem.17 Models can be developed to gauge a diverse range
chemical interactions during gasification. At higher temper- of operating conditions in a cost and time effective manner and
atures, calcination (R10 in Table 1) takes place to regenerate provides quantitative and qualitative data for real-life
the sorbent along with a release of concentrated stream of processes.18−20 Moreover, it is a vital aid in testing several
CO2.6 Captured CO2 may be sequestered or may be employed feedstock materials and their behavior in different types of
as raw material for further chemical synthesis. The conventional reactors without actually building them.
biomass gasification process and the advantages of CO2- Generally, gasification modeling is carried out via two
sorption enhanced gasification over the former are explored approaches, namely, thermodynamic (equilibrium) or kinetic
amply and can be found elsewhere.1,2,5,6 (rate based).21 Thermodynamic models help in computing
Sewage sludge (SS) is the solid waste generated from syngas characteristics for given operating conditions for a
municipal and industrial wastewater treatment plants. The rise specific gasifier. While developing an equilibrium model, it is
in population coupled with urbanization has resulted in a supposed that chemical interactions are taking place for an
drastic increase in SS generation. The composition of SS is infinite time.22 Practically, it has been found that while the
complex due to the presence of microorganisms, biodegradable results reflect the system potential, they can vary considerably
and nonbiodegradable organics, heavy metals, etc.7,8 Appro- from real-life scenarios, thus necessitating a more accurate
priate disposal of SS is necessary to prevent soil, air, and water approach.1 Although kinetic models are more accurate vis-à-vis
pollution at varied levels. Suitable pretreatment followed by thermodynamic models, equilibrium models convey a quick
available cost-effective disposal is paramount to ensure minimal idea of the limits of operation and are less computationally
environmental impact.9−11 Usually, sewage sludge is either used intensive in nature. Stoichiometric and nonstoichiometric are

Figure 1. Concept of CO2-sorption enhanced cogasification of wood and sludge.

B DOI: 10.1021/acs.iecr.7b00306
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Table 2. Analysis of Wood and Sludge14
wood
proximate ultimate
matter (wt %) element dry basis (wt %)
fixed carbon 15.8 C 49.97
volatile matter 83.1 H 7.91
moisture 8.6 O 40.6
ash 1.1 N 0.36
S 0.06
Figure 2. Flowsheet depicting the simulation in Aspen Plus (V8.8).
the two pathways to generate an equilibrium model.23 The
former employs selected independent reactions and equilibrium
relations between them. On the other hand, the latter considers
the selected species as a system and minimizes the total Gibbs
free energy of the system. Literature reflects that both the
pathways yield the same results.21 In the present work, the
Gibbs free energy minimization approach is employed to
develop the equilibrium model.
Till date, no work to our knowledge has been reported in the
literature to evaluate cogasification of woody biomass and
sewage sludge in the presence of sorbent for in situ CO2 capture
via equilibrium modeling. In this article, we develop a simple
but rigorous equilibrium model for CO2-sorption enhanced
cogasification of sludge and wood to assess the influence of
temperature and sludge mixing ratio on the gas yield and gas
composition in a fixed bed reactor.
A cartoon of the proposed process is depicted in Figure 1,
which reflects that wood and sewage sludge are used as
cofeedstock for syngas production. Sewage sludge contains
water which acts as a gasifying agent inside the gasifier, and
therefore no gasifying agent is supplied from outside. Char and
tar coupled with gases are produced in the process for which
the main gases are H2, CO, CO2, CH4, and steam. CaO is
present in the system as a sorbent and it captures CO2 to form
CaCO3 at lower temperatures, which in turn shifts the
equilibrium of WGS resulting in more H2 production.
Moreover, tar cracking also leads to increased H2 and lighter
hydrocarbons generation. At elevated temperatures, CaCO3
undergoes calcination to produce CaO and CO2. The
generated syngas is employed for end gas applications, whereas
released CO2 postcalcination is sequestered. Co-gasification of
sludge with wood in the presence of CaO for in situ CO2
capture, therefore, results in higher gas yield with increased H2
content.
2. MODELING METHODOLOGY
A nonstoichiometric thermodynamic modeling approach
employing the Gibbs free energy minimization approach was
adopted to formulate the model taking wood and sewage sludge
C DOI: 10.1021/acs.iecr.7b00306
Article
sludge
proximate ultimate
matter (wt %) element dry basis (wt %)
fixed carbon 15.9 C 12.99
volatile matter 15.6 H 2.54
moisture 76 O 16.3
ash 68.5 N 2.37
S <0.05
as the feedstocks in the presence of CaO as the sorbent. The
proximate and ultimate analyses, taken from the work done by
other authors,14 are shown in Table 2.
2.1. Assumptions in Model Formulation. The following
assumptions were adopted to develop the modeling framework:
(i) all the state variables including temperature and pressure
were uniform inside the gasifier; (ii) the particle size of
feedstocks, sorbent and bed materials had no effect on the
performance of the gasifier;5 (iii) gasifier was operated at 1 bar
pressure and under isothermal conditions; (iv) pyrolysis took
place instantaneously and major gases produced are H2, CO,
CO2, and CH4.2,17 Lower heating value (LHV) calculations
were done taking these four gases into account; (v) char
produced during pyrolysis was considered as pure carbon; (vi)
catalytic activity of CaO was not considered; (vii) pyrolysis
occurred prior to the reforming reactions and char gasification
(R1, R2, R5).
2.2. Model Development. Gasification of biomass consists
of many overlapping steps, namely, drying, pyrolysis, partial
oxidation, and gasification. Devolatization of biomass feedstock
takes place followed by heterogeneous partial oxidation of char
coupled with gas phase reactions and tar cracking. Tar cracking
can be represented in a simple manner as depicted in eq 1.1
pCn Hx ↔ qCmHy + r H 2 (1)
where CnHx represents tar, which is the combination of
numerous organic compounds, and CmHy represents a lighter
hydrocarbon as compared to CnHx.
When SS and wood blend was fed to the gasifier, drying took
place which resulted in the production of in situ steam.
Pyrolysis followed by reforming and char gasification (R1, R2,
R5), and tar cracking (1) occurred creating a complex network
of chemical interactions as depicted in Table 1. The final molar
compositions of major syngas constituents were the function of
these chemical reactions.
As fresh CaO was fed into the gasifier with a feed rate of 0.5
kg h−1 from outside, the carbonation reaction (R9 in Table 1)
took place to produce CaCO3. In the absence of a loop, CaO
was not regenerated postcarbonation reaction. The conden-
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Table 3. Description of Aspen Plus Flowsheeta

name of the block/stream
employed type objective basic condition (blocks)
WOOD stream one of the feedstock (lignocellulosic)
SLUDGE stream second feedstock
FEED stream mixed feed of wood and sludge
FEEDPYRO stream feed to pyrolyzer
PRODPYRO stream product from pyrolyzer
CAO stream CaO (sorbent) feed to gasifier
FEEDGASI stream feed to gasifier
PRODGASI stream product from gasifier
FEEDCYC stream feed to cyclone
GASES stream product gases (mainly H2, CO, CO2 and CH4)
SOLIDS stream residual solids (mainly char and ash)
MIXER1 block mixes wood and sludge
HEATER block preheat the feed which is sent to pyrolyzer T = 600 to 900 °C, P = 1 bar
PYRO block RYIELD reactor for pyrolysis (breaks down the feed into respective components) T = 600 to 900 °C, P = 1 bar
MIXER2 block mixes the pyrolysis products with CaO sorbent
GASI block RGIBBS reactor for gasification (employs Gibbs free energy minimization T = 600 to 900 °C, P = 1 bar
approach)
STRMCHNG block stream changer to change the material streamflow
CYCLONE block cyclone to separate product gases and solids P drop = 0.015 bar
a
T = temperature, P = pressure.

sable hydrocarbons “commonly known as tars” were also
produced in the pyrolysis along with the gases and char. To
make the model rigorous, several aromatics were considered to
represent tar as a whole, which can be found with other
components in the Supporting Information (Table S1).
The different steps considered in formulating the model in
Aspen Plus (V8.8) in order to depict the real gasification
process were the decomposition of feed (biomass and sludge),
volatile reactions, and gasification (Table 1) followed by solid
gas separation, as shown in the Aspen Plus flowsheet in Figure
2. Total feed (wood + sludge) flow rate was 1.2 kg h−1. In the
first case, wood and wet sewage sludge were taken as mixed
feedstock with a blending ratio of 70 wt % of wood and 30 wt %
of sewage sludge to evaluate the impact of temperature (600 to
900 °C) on syngas yield and composition. On the other hand,
to assess the influence of sludge mixing ratio on the outlet gas,
sludge was mixed with wood in different ratios (0, 30, 50, 70,
and 100 by wt %) at 700 °C. No external steam was supplied to
the gasifier, and hence the steam participating in the reactions
was derived from the moisture content of the wet sewage
sludge and wood.
Description of the flowsheet can be found in Table 3.
Referring to the flowsheet, wood and sludge were mixed in the
mixer (MIXER1) and heated in the heater (HEATER) prior to
feeding into the pyrolyzer (PYRO), which was working at the 1
bar pressure. RYIELD was employed as pyrolyzer on account of
its ability to break down the complex feedstock such as biomass
based on the defined yields. The following reaction supposedly
occurred in the pyrolyzer.1
Cx HyOz → H 2 + CO + CO2(g) + HC(g) + Tar(l)
+ Char(s)
where CxHyOz represents biomass and HC represents hydro-
carbons.
A calculator block was used to calculate the yields of main
gases as a function of temperature (600 to 900 °C) based on
the empirical equations (Table S3 in the Supporting
Information) developed by Puig-Arnavat et al.24 and Fagbemi
et al.25 for pyrolysis in fixed bed. These quadratic equations
were the functions of temperature and they closely computed
the values of different components of syngas, tar, and char
generated post-devolatization.
The products generated after the pyrolyzer were fed to the
gasifier (GASI) after mixing them with CaO in the mixer
(MIXER2). It should be noted that the temperature of the
gasifier feedstock was the same as the temperature of its
productsbecause of the same working temperatures of pyrolyzer
and gasifier. RGIBBS was employed as gasifier which worked
on the principle of Gibbs free energy minimization theory of
thermodynamics to calculate the equilibrium yield and
composition. This was the most appropriate reactor to be
used for gasification in Aspen Plus because of its ability to
perform phase and equilibrium calculations involving multiple
phases. All the reactions depicted in Table 1 possibly took place
in the gasifier. Finally, products from the gasifier were sent to
the cyclone to separate solids and gases.
2.3. Model Validation. The validation of the proposed
model was carried out employing the experimental data
obtained by other authors14 for the cogasification of wet
sewage sludge with forestry waste with in situ steam in a lab-
scale fixed bed gasifier. Peng et al.14 investigated the influence
of sewage sludge content and reactor temperature on the
product gas yields and gas composition. The LHV (kJ Nm−3)
of the product gas was computed based on the following
equation:
LHV = (CO × 126.36 + H 2 × 107.98 + CH4 × 358.18)
(3)
where CO, H2, and CH4 reflect the product gas components in
(2) molar percentages.
The dry gas fractions predicted by the model for H2, CO,
CO2, and CH4 were quite close to the experimental values.
Figure 3 compares the modeling and experimental results for
the changes in gas composition with temperature (700 to 900
°C), whereas Figure 4 depicts the alterations in gas
composition with increasing sludge content (0 to 70 wt % at
D DOI: 10.1021/acs.iecr.7b00306
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Figure 3. Experimental results vs modeling predictions for the
variation in gas composition with the temperature.
Figure 4. Experimental results vs modeling predictions for the
variation in gas composition with the changes in sewage sludge ratio.
800 °C) in the feedstock. These figures emphatically show that
the modeling predictions are in good agreement with the
experimental results and the deviations are well within the
reasonable limits.
3. MODEL PREDICTIONS AND DISCUSSIONS
3.1. Impact of Temperature. To compare the impact of
CO2-sorbent, molar compositions of main syngas constituents
were evaluated with and without CaO over a temperature range
of 600 to 900 °C at atmospheric pressure. Figure 5a depicts the
alterations in gas composition for the cogasification of SS and
wood in the presence of CaO with rising temperature, whereas
Figure 5b shows the variation in syngas components in the
absence of CaO. The feedstock feeding rate was 1.2 kg h−1
while CaO was fed at a rate of 0.5 kg h−1. The ratio of sludge to
wood was taken as 30 to 70 by wt %.
E DOI: 10.1021/acs.iecr.7b00306
Article
In the absence of the sorbent, as expected, H2 and CO
increased with rising temperature until 850 and 900 °C
respectively, while CH4 decreased continuously for the entire
temperature range (Figure 5b). Overall gas yield was reduced
from 600 to 800 °C and then increased slightly. Maximum gas
yield at 800 °C was on account of the increased water gas, char
gasification (R1, R2, R5), and tar cracking (1) reactions. Water
gas reactions (R1 and R2) and Boudouard reaction (R5) are
endothermic in nature and therefore, they were favored at
elevated temperatures. It resulted in higher H2 and CO
concentrations from 4.4 to 44.6 vol % and 6.4 to 35.3 vol %,
respectively, when the temperature was raised from 600 to 900
°C. In addition, the methanation reaction (R8) was favored at
lower temperature resulting in higher CH4 molar concentration
at lower temperatures. On the other hand, methane reforming
(R4) was strengthened at a higher temperature and
consequently, for the same temperature range, CH4 decreased
from 40.1 to 0.3 vol %. CO2 concentration was continuously
reduced from 48.9 to 19.6 vol % reflecting the importance of
the water gas shift (R3) in the reverse direction as the
temperature was raised. It also contributed to an increase in the
water content of the reacting system (Figure 5b). In addition,
Boudouard reaction (R5) was also strengthened at higher
temperature resulting in a decrease in CO2 and increase in CO.
It can be noted that water gas reactions (R1, R2) were also
active at higher temperature which consumed H2O and char,
and produced CO and CO2. Previous studies6,26 have also
found the same trend in the generation of main gases during
sludge gasification in the presence of steam.
The influence of CO2-sorbent on the variation of syngas
constituents for the cogasification of SS and wood is depicted in
Figure 5a. It is clearly seen that the molar concentration of H2
was considerably increased from 600 to 850 °C with maximum
H2 concentration of 45.7 vol % at 850 °C. The rise over this
temperature range was due to the synergistic effect of
carbonation (R9), enhanced char gasification (R1, R2, R5)
and slightly due to increased tar cracking (1). It should be
noted that the carbonation reaction (R9) is exothermic in
nature, thus the heat released aids in strengthening
endothermic gasification and reforming reactions (R1, R2,
R4, and R5). Furthermore, CO2 capture by CaO shifts the
equilibrium of the water gas shift (R3) on the right side
according to Le Chatelier’s principle resulting in enhanced H2
production. This was proven by reduced CO molar
concentrations in this system (Figure 5a) as compared to the
reacting system without CaO (Figure 5b). H2 reduction (from
850 to 900 °C) was due to the reverse water gas shift reaction,
since water gas shift reaction (R3) is exothermic and the
thermodynamic equilibrium favors the reverse direction at
elevated temperatures, which reduces H2 yield and enhances
CO yield. Meanwhile, CO increment from 30.5 to 33.4 vol %
with temperature rise from 850 to 900 °C was observed to
prove the possibility of reverse water gas shift. In addition, CO2
sorption at lower temperatures resulted in higher CH4 due to
the exothermic methanation reaction II (R11). On the other
hand, a decrease in CH4 was observed as the temperature was
increased on account of the strengthening of methane
reforming (R4) reaction. The increment of vapor was ascribed
to the reverse water gas shift at higher temperature.
Table 4 displays the flow rates (kg h−1) of main syngas
constituents for CO2-sorption enhanced cogasification of SS
and wood, along with the gas yield and LHV for the
temperature range of 600 to 900 °C. Gas yield was enhanced
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Figure 5. (a) Variation in the major constituents of syngas with rising temperature (a) with the sorbent (CaO) and (b) without the sorbent (CaO).

Table 4. Impact of the Temperature on Major Gas Constituents of Syngas, Gas Yield, and LHV for CO2-Sorption Enhanced Co-
gasification of Sludge and Wooda
600 °C 650 °C 700 °C 750 °C 800 °C 850 °C 900 °C
(kg h−1)
H2 0.0013 0.0027 0.0042 0.0122 0.0202 0.0228 0.0239
CO 0.0103 0.0191 0.0309 0.0821 0.1803 0.2138 0.2502
CO2 0.0644 0.0399 0.0253 0.1096 0.2565 0.2475 0.2508
CH4 0.1320 0.1306 0.0933 0.0537 0.0166 0.0044 0.0012
H2O 0.0002 0.0003 0.0004 0.0043 0.0131 0.0194 0.0263
gas yield 0.21 (0.60) 0.19 (0.60) 0.15 (0.53) 0.25 (0.50) 0.47 (0.48) 0.48 (0.50) 0.53 (0.53)
LHV (MJ Nm−3) 28.60 (15.70) 28.40 (15.90) 25.50 (14.20) 15.00 (11.60) 9.70 (9.80) 9.20 (9.40) 9.10 (9.40)
CaO 0 0 0.043 0.214 0.500 0.500 0.500
CaCO3 0.892 0.892 0.814 0.509 0 0 0
a
Values in parentheses are taken from the same simulation without employing CaO.

from 0.21 to 0.53 kg h−1 when the temperature was increased
from 600 to 900 °C. Maximum value of LHV was achieved at
600 °C as 28.60 MJ Nm−3. It was on account of the higher CH4
molar concentration at that temperature as LHV is more
dependent upon CH4 content than other constituents (such as
H2 or CO) due to its higher heating value. In addition,
comparatively lower CO2 concentration at 600 °C is also
responsible for the highest LHV. The values mentioned in
parentheses in Table 4 for LHV and gas yield were from the
simulation without employing CaO, for comparison. It was
seen that gas yield was reduced for the sorption case as
compared to the nonsorption case, on account of CO2 sorption.
However, LHVs were found to be higher when the sorbent was
employed. The probable reason is higher H2 and CH4
concentrations in the sorption case which contributed toward
higher heating value. These predictions clearly reveal the
potential of enhancing H2 concentrations in SS-wood
cogasification especially in the CO2-sorption temperature
range (600 to 750 °C), by using a sorbent such as CaO. In
addition, it provides an opportunity to reduce the carbon
emissions on one hand and get a concentrated stream of CO2
on the other hand, which may further be employed as the raw
material for chemical synthesis or can be sequestered.
3.2. Impact of Sludge Mixing Ratio. The feedstock blend
comprised sewage sludge and wood. The influence of a variable
F DOI: 10.1021/acs.iecr.7b00306
mixing ratio of input raw material on syngas constituents was
also assessed at 700 °C. For this purpose, SS content was varied
from 0 to 100 wt %. Figure 6 panels a and b depict the changes
in syngas components in the presence and absence of CaO,
respectively at 800 °C, whereas Figure 6 panels c and d display
the changes in syngas components in the presence and absence
of CaO, respectively at 700 °C. As the model validation for
varying sludge content was performed at 800 °C, Figure 6
panels a and b were shown. However, 800 °C is not an optimal
temperature for CO2 sorption, therefore, assessment for the
influence of varying sludge content was carried out at 700 °C
(Figure 6c,d).
Figure 6d clearly shows an increase in H2 fraction from 12.7
to 59.0 vol % when SS content was increased from 0 to 100%
without the use of the sorbent. The opposite trend was
observed for CO which reduced from 29.1 to 2.4 vol % for the
same SS fraction range due to WGS (R3). Moreover, variation
in CO2 is slight from 37.5 vol % at 0 wt % sludge content to
33.5 vol % at 100 wt % sludge. Water gas (R1) was responsible
for the enhancement in H2 molar fractions. Also, H2 rise was on
account of water gas-II (R2), water gas shift (R3), and methane
reforming (R4) reactions. These reactions varied CO2 content
as well although to a small extent. Water was seen to rise
continuously with increasing sludge content due to the rich
moisture content in sewage sludge (Table 2). CH4 continu-
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Figure 6. (a) Variation in the major constituents of syngas with variable sewage sludge ratio (a) with the sorbent (CaO) at 800 °C; (b) without the
sorbent (CaO) at 800 °C; (c) with the sorbent (CaO) at 700 °C; (d) without the sorbent (CaO) at 700 °C.

Table 5. Impact of the Sludge Ratio (wt %) on Major Gas Constituents of Syngas, Gas Yield, and LHV for CO2-Sorption
Enhanced Co-gasification of Sludge and Wooda
0 wt % 30 wt % 50 wt % 70 wt % 100 wt %
(kg h−1)
H2 0.0029 0.0042 0.0122 0.0338 0.0329
CO 0.0222 0.0309 0.0339 0.0138 0.0013
CO2 0.0179 0.0253 0.0823 0.1204 0.0728
CH4 0.0651 0.0933 0.1225 0.0484 0.0004
H2O 0.0003 0.0004 0.004 0.0407 0.2519
gas yield 0.11 (0.36) 0.15 (0.53) 0.25 (0.64) 0.22 (0.59) 0.11 (0.35)
LHV (MJ Nm‑3) 25.50 (12.40) 25.50 (14.20) 21.10 (13.40) 12.80 (9.50) 9.80 (8.40)
CaO 0.143 0.044 0 0 0.128
CaCO3 0.637 0.815 0.892 0.892 0.664
a
Values in parentheses are taken from the same simulation without employing CaO.

ously decreased from 20.6 to 4.9 vol % when SS fraction in the The influence of varying sludge ratio on syngas constituents
blend was raised from 0 to 100% because of the higher vapor in the presence of CaO is depicted in Figure 6c. It reflects that
fraction enhancing methane steam reforming R4. H2 molar concentrations was enhanced from 21.8 to 90.5 vol %,
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when SS content was increased from 0 to 100% by mass, which
nearly reached twice to the case without deploying CaO
(Figure 6d). Meanwhile there was a fall in CO2 fraction from
6.1 to 5.9 vol % when sewage sludge content was enhanced
from 0 to 30 wt %. Enhancement in water gas, water gas shift,
and reforming reactions (R1, R2, R3, and R4) in the presence
of steam coupled with the strengthening of Boudouard reaction
(R5) were responsible for the hikes in H2 molar fractions. The
same findings were evidenced by Zhang and coauthors27 for
wet sewage sludge pyrolysis. When the SS fraction was
increased from 0 to 100 wt %, there was a marked decrease
in CO from 11.7 to 0.2 vol %. On the other hand, CO2 was
increased from 5.9 to 9.1 vol % when SS was enhanced from 30
to 100 wt %. These observations were on account of the
reduction in organic and fixed carbon content in the feedstock
blend with the increasing SS fraction. When sludge content was
enhanced in the feedstock, the amount of H2O was increased
and the fraction of C element was reduced. It is evident in
Table 2 that C was low, whereas H2O was high in sludge. The
increase in H2O was considerable when the sludge fraction was
increased from 30 to 100 wt %. Therefore, the decrease in CO
was due to increased H2O from sludge as it consumed CO in
water gas shift reaction (R3). Also, reduced C in the feedstock
was partially liable for decrease in CO. In addition, the moisture
amount increased with the increasing SS and hence, water gas
shift (R3) converted more CO into CO2. The methane fraction
reduction was attributed to the same reason for CO decline.
Table 5 displays the flow rate (kg h−1) of major syngas
products along with LHV and gas yield with varying sludge
fraction (0 to 100 wt %) at 700 °C. In the cogasification of
sludge and wood, the highest gas yield was found as 0.25 kg h−1
at 50 wt % sludge and it reduced to 0.11 kg h−1 for 100% sludge
gasification. Maximum LHV of 25.5 MJ Nm−3 was recorded at
0 and 30 wt % SS content which was due to the higher CH4 and
CO molar fractions. The values mentioned in parentheses in
Table 5 for LHV and gas yield were from the simulation
without employing CaO, for comparative purposes. The trend
found in the predictions reasonably matched with the previous
studies qualitatively.14 Gas yield was reduced on account of
CO2 sorption whereas LHV was enhanced due to higher H2
and CH4 fractions in generated syngas, for the sorption
enhanced case vis-à-vis the nonsorption case.
4. CONCLUSIONS
In this work, an equilibrium model was developed using Aspen
Plus (V8.8) simulator, with an objective to evaluate the viability
of CO2-sorption enhanced cogasification of wood and sewage
sludge in the presence of CaO as sorbent. Simulation results of
the effects of both the reactor temperature and the sludge
mixing ratio in the feedstock blend, on gas composition, yield,
and LHV for the cogasification of wet sewage sludge and
woody biomass in the presence of CaO were presented. Several
Aspen Plus unit operation blocks were joined and empirical
equations were used to make the model rigorous and deduce
precise predictions. The predictions were compared against the
experimental work published by other authors and both showed
reasonable accuracy.
Minimum CO2 fraction was achieved at 700 °C with a gas
yield of 0.154 kg h−1. Maximum gas yield was observed as 0.526
kg h−1 at 900 °C with LHV of 9.1 MJ Nm−3. On the other
hand, the highest LHV of 28.6 MJ Nm−3 was achieved at 600
°C. At 700 °C with 30 wt % sludge in the feedstock, minimum
CO2 concentration was obtained with a gas yield of 0.154 kg
H DOI: 10.1021/acs.iecr.7b00306
Article
h−1. Maximum gas yield was observed as 0.251 kg h−1 with a
LHV of 21.1 MJ Nm−3 when 50 wt % sludge was present,
whereas highest LHV of 25.5 MJ Nm−3 was achieved at 0 and
30 wt % sludge. These findings reflect that CO2-sorption
enhanced gasification of sewage sludge with other biomass such
as wood is an attractive option to dispose sewage sludge in an
environmental friendly way along with the generation of
hydrogen rich fuel gas.
Future Work. Model predictions and experimental data
were found to be in good agreement qualitatively. However,
some modifications are required to improve the simulation
results. Improvement in the predictions can be obtained by
incorporating the reaction kinetics in the process. Thermody-
namic results and kinetic studies along with the solid residue
analysis for this process are currently in progress in our
laboratory (Lab for Biomass and CCUS Technologies) and the
results will soon be communicated.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.iecr.7b00306.
Components considered in the equilibrium model for
CO2-sorption enhanced cogasification (Table S1);
characterization of nonconventional material in Aspen
Plus (Table S2); empirical correlations to calculate H2,
CO, CO2, and CH4 yields in fixed bed gasification (Table
S3) (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
*Phone: +86 10 6278 4701. E-mail: ming.zhao@tsinghua.edu.
cn.
*E-mail: wangyujue@tsinghua.edu.cn.
ORCID
Guozhao Ji: 0000-0003-4556-2675
Ming Zhao: 0000-0002-5801-5593
Author Contributions
#
V.S.S. and G.J. contributed equally.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This contribution was identified by Prof. Maobing Tu
(University of Cincinnati) as the Best Presentation in the
session “Chemistry of Biomass Waste Conversion to Energy &
Chemicals” in the Division of Environmental Chemistry of the
2016 ACS Fall National Meeting in Philadelphia, PA. This work
was supported by the Tsinghua University Initiative Scientific
Research Program (Grant No. 20161080094).
■
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I DOI: 10.1021/acs.iecr.7b00306
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX