Bioresource Technology 245 (2017) 925–932

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Process simulation of ethanol production from biomass gasification and T

syngas fermentation
⁎
Oscar Pardo-Planasa, Hasan K. Atiyeha, , John R. Phillipsa, Clint P. Aicheleb, Sayeed Mohammadb
a
Department of Biosystems and Agricultural Engineering, Oklahoma State University, Stillwater, OK, USA
b
School of Chemical Engineering, Oklahoma State University, Stillwater, OK, USA

A R T I C L E I N F O A B S T R A C T

Keywords: The hybrid gasification-syngas fermentation platform can produce more bioethanol utilizing all biomass com-
Syngas fermentation ponents compared to the biochemical conversion technology. Syngas fermentation operates at mild temperatures
Process simulation and pressures and avoids using expensive pretreatment processes and enzymes. This study presents a new
Aspen Plus process simulation model developed with Aspen Plus® of a biorefinery based on a hybrid conversion technology
Ethanol
for the production of anhydrous ethanol using 1200 tons per day (wb) of switchgrass. The simulation model
Gasification
consists of three modules: gasification, fermentation, and product recovery. The results revealed a potential
production of about 36.5 million gallons of anhydrous ethanol per year. Sensitivity analyses were also performed
to investigate the effects of gasification and fermentation parameters that are keys for the development of an
efficient process in terms of energy conservation and ethanol production.

1. Introduction
The Energy Independence and Security Act targeted a production of
ethanol of 36 billion gallons by 2022 (Schnepf, 2011), and expects
cellulosic materials to be used as a sustainable feedstock for renewable
ethanol. The biochemical platform of ethanol production ferments su-
gars obtained from hydrolyzates of pretreated biomass. However, this
platform is unable to degrade lignin, which is a major portion of bio-
mass. Therefore, the potential ethanol yield is reduced significantly. In
addition, the biochemical platform requires expensive pretreatment
processes to make the polymeric sugars in the biomass amenable to
enzymes. These problems can be avoided by first gasifying the lig-
nocellulosic biomass to synthesis gas (syngas), containing primarily CO
and H2 along with some CO2. The syngas is converted to alcohols and
organic acids by acetogenic microorganisms via the Wood-Ljungdahl
metabolic pathway (Henstra et al., 2007; Liew et al., 2016; Phillips
et al., 2017). Different acetogenic microorganisms have the ability to
produce different alcohols, including ethanol, butanol, propanol, and
hexanol, and their corresponding organic acids. However, most aceto-
genic microorganisms produce ethanol and acetic acid, which are the
focus of the present study. The stoichiometric equations for the pro-
duction of ethanol and acetic acid are displayed below:
4CO + 2H2O →CH3 COOH + 2CO2
2CO2 + 4H2 →CH3 COOH + 2H2O
6CO + 3H2O →C2 H5OH + 4CO2 (3)
2CO2 + 6H2 →C2 H5OH + 3H2O (4)
Clostridium ljungdahlii (Tanner et al., 1993), Clostridium carbox-
idivorans (Phillips et al., 2015; Ukpong et al., 2012), Clostridium rags-
dalei (Devarapalli et al., 2017; Saxena and Tanner, 2011), and Alkali-
baculum bacchi (Liu et al., 2012) are examples of microbes that produce
alcohols and organic acids via syngas fermentation. The main ad-
vantages of syngas fermentation include potential of high product yield
due to utilization of all biomass fractions, including lignin, as well as
operation at mild pressures and temperatures. However, there are
challenges in syngas fermentation, such as low gas-liquid mass transfer
rates and the cost of medium. These issues have been partially ad-
dressed in the literature (Devarapalli et al., 2017; Gao et al., 2013;
Orgill et al., 2013; Phillips et al., 2017).
To date, little efforts have been directed to process simulation of the
hybrid gasification-syngas fermentation. To our knowledge, there are
few published studies on process simulation of syngas fermentation.
One of these studies was focused on the production of poly-
hydroxylalkanoate and hydrogen rather than ethanol (Choi et al.,
2010). Another study used process simulation for modeling the pro-
duction of ethanol via syngas fermentation, although it was based on a
(1) small-scale process (Rao, 2005). Piccolo and Bezzo (2009) presented
techno-economic analyses for two ethanol production processes. One
(2)

⁎
Corresponding author at: Department of Biosystems and Agricultural Engineering, 214 Ag Hall, Oklahoma State University, Stillwater, OK 74078, USA.
E-mail address: hasan.atiyeh@okstate.edu (H.K. Atiyeh).

http://dx.doi.org/10.1016/j.biortech.2017.08.193
Received 6 July 2017; Received in revised form 28 August 2017; Accepted 29 August 2017
Available online 01 September 2017
0960-8524/ © 2017 Elsevier Ltd. All rights reserved.
O. Pardo-Planas et al.
Fig. 1. Process flow diagram (PFD) depicts flow of material through the simplified equipment for gasification of switchgrass and syngas fermentation to produce ethanol. BFW: boiler
feedwater system; STM: steam; Syngas: synthesis gas; CWS: circulating water system.).
Adapted from Phillips et al. (2017
process was the conventional hydrolysis of biomass followed by fer-
mentation, and the other process was gasification followed by syngas
fermentation. Martín and Grossmann (2011) optimized energy use for
gasification of biomass and compared conversion of syngas to alcohols
using catalytic and fermentation processes. Ardila et al. (2014) pre-
sented a simulation model for gasification of sugarcane bagasse fol-
lowed by syngas fermentation without including the amount of feed-
stock used, ethanol yield or separation process. In addition, none of the
previous studies examined effects of critical syngas fermentation
parameters such as specific gas uptake rate, ethanol concentration and
substrate gas conversion efficiencies on required reactor volume and
energy requirement. As evident from the above, there is a need for
developing detailed simulation models for investigating the hybrid
gasification-syngas fermentation process. This study aims to fulfill that
need in the existing literature.
Modeling and simulation of the biomass gasification-syngas fer-
mentation process can provide a powerful tool for evaluation of this
technology at a commercial scale. Process simulation software
packages, such as Aspen Plus®, or Aspen Hysys®, SimSci™ Pro/II, have
been used in the chemical industry for performing techno-economic
analysis of multiple types of processes. The objective of the present
study was to design a new model in Aspen Plus® of an integrated ga-
sification-syngas fermentation plant for ethanol production from
switchgrass as a model lignocellulosic biomass. This study should thus
provide a framework for defining the gasification, fermentation, and
product recovery units to support equipment specification, and will be
the basis for a future comprehensive techno-economic analysis.
2. Model description
2.1. Simulation software
The model describing the various unit operations used for gasifi-
cation fermentation and product separation was developed in Aspen
Plus® version 8.2 (AspenTech, Inc.). For the purpose of designing the
gasification and fermentation stages of the process, both Aspen Plus
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Bioresource Technology 245 (2017) 925–932
blocks and user-defined calculator blocks were integrated. These two
types of calculation tools exchanged data until the mass and energy
balances converged.
Aspen Plus® provides different thermodynamic packages to calcu-
late the phase equilibria throughout the simulation. The non-random-
two-liquid (NRTL) model was the main thermodynamic model used for
this study (Renon and Prausnitz, 1969). The thermodynamic package
chosen should be capable of accurately describing the phase equili-
brium between different components in the mixture, including a water-
ethanol azeotrope that exists in these systems. Further the gasification
process requires an equation of state approach. In this study, the Red-
lich-Kwong-Soave equation of state (Soave, 1972) with Boston Mathias
alpha function (RKS-BM) was used to calculate the phase equilibria
during gasification, and the ASME steam table correlations were used
for calculating steam properties.
2.2. The hybrid gasification-syngas fermentation process
A process flow diagram depicts the gasification of biomass, fer-
mentation of CO and H2 into ethanol and recovery of ethanol by dis-
tillation and drying (Fig. 1). This simplified depiction of the equipment
and material flows is represented mathematically within the Aspen
Plus® model. Switchgrass is fed into a gasifier and converted by partial
combustion to syngas containing mainly CO and H2 along with some
CO2. The syngas is converted into ethanol and acetic acid in the fer-
menter by acetogenic microorganism like Clostridium ragsdalei. Ethanol
produced is removed from the fermentation broth or beer by distillation
and dried in packed beds of molecular sieves with a recovery of water
and ethanol.
2.3. Biomass feedstock
Switchgrass (Panicum virgatum) is a herbaceous species that has
been identified as a good candidate for being used as a sustainable
energy crop for biofuel production because of its high yield and effi-
cient use of water and nutrients (Sanderson et al., 1996). The available
O. Pardo-Planas et al.
hectares of switchgrass have the potential to produce 95 billion L of
ethanol at low feedstock prices (Morrow et al., 2006), ranging $55 to
$87 per metric ton (Haque et al., 2014). Different studies have focused
on modeling and optimization of harvesting and logistics for an effi-
cient delivery of switchgrass to biorefineries, particularly in the
southern plains of US (Haque and Epplin, 2012; Hwang et al., 2009).
Switchgrass was identified as a species that can be simultaneously used
as a bioenergy feedstock and for feeding cattle (Mosali et al., 2013).
Although Aspen Plus® offers a comprehensive library of chemical
compounds for modeling, switchgrass or other biomass are not part of
the library. The biomass was defined in the model as a nonconventional
solid compound. The switchgrass contained 14.63% (wb) moisture,
81.59% (db) volatile matter, 4.72% (db) ash, 13.69% (db) fixed carbon
(Sharma et al., 2014). Switchgrass ultimate analysis showed that it
contained on a dry basis (db) 0.24% nitrogen, 5.91% hydrogen, 52.74%
carbon, 41.05% oxygen and 0.06% sulfur (Sharma et al., 2014). The
chemical formula of CH1.344O0.584N0.004 was calculated based on the
ultimate analysis (dry basis and ash free, daf) of switchgrass harvested
in Oklahoma and reported in the literature (Sharma et al., 2014). The
formula was necessary for stoichiometric calculations during gasifica-
tion. The total inlet stream of biomass entering the process was set to
1200 tons/day (wet basis), which represent a medium size bioethanol
facility. Although switchgrass was the feedstock chosen for the present
study, the model presented is flexible to utilize any kind of feedstock as
long as the composition (proximate and ultimate analysis) is known.
2.4. Description of the Aspen Plus model
2.4.1. Overview of the model
The Aspen Plus® model of the plant consists of three modules: ga-
sification, fermentation, and product recovery. The proposed plant is
able to process 1200 metric tons of switchgrass per day (wb) to obtain
pure ethanol. The gasification, fermentation and distillation are as-
sumed to operate at atmospheric pressure. Fig. 2 shows the Aspen Plus®
flowsheet with labeled streams and blocks. Prior to entering the pro-
cess, preparation of the biomass solids will require transport, storage
and conveying of the raw feedstock, and likely will require grinding,
drying and metering to achieve a controlled feed rate.
First, the biomass (stream SWITCHGR) enters the process through
the gasifier (units DECOMP and RGIBBS), and is converted to synthesis
gas in presence of oxygen. The gas is then cleaned and cooled (units
SEPARAT and COOLER) and sent to the fermenter (BIOREAC). The
microorganisms grow in liquid media added to the fermenter and
convert the carbon monoxide and hydrogen into ethanol and acetic
acid. The gas and liquid phases are separated and the beer is sent to a
distillation column (DISTILL) where concentration near the ethanol/
water azeotrope is obtained. Dry ethanol can then be achieved by
Fig. 2. Aspen Plus® flowsheet with labeled streams and units.
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Bioresource Technology 245 (2017) 925–932
pressure swing adsorption of water from the ethanol vapor in beds of
molecular sieves (M-SIEVES).
2.4.2. Gasification module
Biomass is converted by thermal decomposition and partial oxida-
tion to synthesis gas (or syngas), a mixture mainly composed of CO and
H2 with some CO2. Syngas also contains water, N2, CH4, and smaller
amounts of other compounds such as tars, H2S, or NH3 (Cheng, 2010).
Gasification takes place at high temperatures (600–1000 °C) and re-
quires an energy input for the decomposition of biomass into gases in a
sequence of drying, pyrolysis and combustion. The energy required to
drive drying and pyrolysis can be provided externally or by partial
combustion of the biomass. Different oxidizing agents can be used, for
example oxygen, air, steam, or a combination of them (Kumar et al.,
2009b). Several reactor configurations have been proposed and re-
viewed for gasification of biomass (Bridgwater, 1995; Warnecke, 2000)
although fluidized bed reactors are considered more suitable for scale-
up purposes. In a fluidized bed, drying, pyrolysis and combustion will
occur together in a well-mixed bed of solids. In order to obtain a flexible
module, the gasifier in our Aspen Plus® model is a general gasification
model where energy is obtained by partially combusting the feedstock,
and steam, and/or oxygen or air can be used as gasification agents. The
gasifier depicted in the process flow diagram in Fig. 1 was modeled
after the ICM Auger gasifier, which has zones of drying, pyrolysis and
combustion so that carbon remaining in the char may be controlled.
Aspen Plus® lacks a block describing gasification, so the gasification
step was modeled by using different operation units available in the
software, as previously proposed in the literature (Kumar et al., 2009a).
In addition, calculator blocks were integrated in the process flowsheet
to perform calculations with the results fed into the simulation soft-
ware.
The biomass was decomposed in a yield reactor unit (RYIELD).
However, as previously proposed in the literature (Kumar et al., 2009a),
the biomass does not decompose into the pure elemental composition,
but into the main possible products of gasification reported in the lit-
erature. Among these possible products, tar was disregarded in order to
simplify the simulation and due to the low production yield reported by
experimental studies (0.02–0.05 g tar per g biomass) (Kumar et al.,
2009a). Although syngas contains small amount of tar and was not used
in the model simulation, it should be noted that tar can lead to poor
fermentation. Therefore, the syngas should be cleaned to remove the tar
and other impurities before feeding the gas to the microorganism. The
calculator blocks (DECOM2 and ER blocks) receive the feed rate and
composition of switchgrass from selections in ASPEN Plus. The oxi-
dizing agent, equivalence ratio, the steam-to-biomass ratio, and the
carbon conversion efficiency are inputs to these calculator blocks. The
equivalence ratio is defined as the actual oxygen-to-biomass ratio
O. Pardo-Planas et al.
Table 1
Main gasification and fermentation parameters used in the simulation. Values in parenthesis were the base case scenario, while ranges represent sensitivity analyses.
Gasification parameters
Equivalence Ratio 0.35–0.45
Steam to Biomass Ratio 0–0.5
Biomass feed (wb), ton/d 1200
Pressure, atm 1 Acetic acid concentration, g L−1
Carbon conversion efficiency, % 95
wb: wet basis; HHV: Higher heating value.
gx: grams of cells.
divided by the stoichiometric oxygen-to-biomass ratio (Turn et al.,
1998), as described by Eq. (5).
Actual oxygen to biomass ratio
Equivalence Ratio (ER) =
Stoichiometric oxygen to biomass ratio
Similarly, the steam-to-biomass ratio (SBR) is defined as the steam
mass flow rate used as oxidizing agent divided by the mass flow rate of
biomass (Turn et al., 1998), as shown in Eq. (6).
Steam mass flow rate
Steam-to-biomass ratio (SBR) =
Biomass mass flow rate
The carbon conversion efficiency is defined as the amount of carbon
from the feedstock that is transferred to the synthesis gas. The rest of
the carbon, from the fixed carbon fraction of the biomass, remains as
solid on the ash. The physical design and the operation of the gasifier
determine this distribution.
Decomposition of the solid biomass is modeled as conversion to
gaseous products (CO, CO2, N2, H2, water) and a solid residual char/
ash. The key aspect of this calculation was the distribution of oxygen
atoms from the biomass and from the gasification agents to form carbon
monoxide, water, and carbon dioxide molecules, in this order of pre-
ference. The composition of the resulting gas stream was calculated and
entered in ASPEN Plus to determine the equilibrium composition and
temperature.
The product of the RYield reactor was then sent to an equilibrium
reactor (RGIBBS), where the composition of the synthesis gas was cal-
culated by minimization of Gibbs energy. The hypothesis was that the
reactor reaches chemical and physical equilibrium at the specified
conditions. Given the possible products and the input streams, the si-
mulator solves the unit for minimization of the Gibbs free energy. The
selected possible products of the reactions were CO, CO2, H2, H2O, CH4,
N2, C2H2, C2H2, NO, NO2, N2O, NH3, and HNO3, based on experimental
data published in the literature. The gasification module also calculated
the temperature of the syngas exiting the gasifier, based on the enthalpy
of all input streams. The heat losses during gasification can be specified
in the model and were chosen as 1% of the higher heating value (HHV)
of the biomass (Jin et al., 2009).
Finally, the clean-up of the synthesis gas was modeled with a se-
parator block (SEPARAT) that simulated the removal of ash and char
(solids) from the gas, which would be typically achieved by cyclonic
separation. The syngas was subsequently cooled down to the fermen-
tation temperature (37 °C) and sent to the bioreactor. Condensed water
(WATER-SY) was separated out, and was reused in the fermentation
process although certain treatment may be required. Cooling of syngas
to bioreactor temperature would be physically conducted in a heat re-
covery steam generator followed by a cooler as depicted in the process
flow diagram (Fig. 1). Steam produced in gasification may be used in
process heating, particularly in distillation and drying to recover
ethanol. Ash and char may be a saleable byproduct; however, carbon
residual on the ash represents energy lost from the syngas product.
Table 1 summarizes the main parameters used for the simulation of the
Bioresource Technology 245 (2017) 925–932
Fermentation parameters
Specific gas uptake, mol (CO + H2) gx−1 h−1 0.02–0.20 (0.10)
Cell retention time, h 100
Ethanol concentration, g L−1 20–70 (30)
3
Cell concentration, gx L−1 10
CO conversion efficiency, % 70–95 (90)
H2 conversion efficiency, % 10–95 (90)
gasification process. A sensitivity analysis on equivalence ratio and
steam to biomass ratio was performed in order to select the optimal
conditions for the subsequent fermentation process.
(5)
2.4.3. Fermentation module
The fermenter was modeled using a stoichiometric reactor
(BIOREACT) in Aspen Plus® combined with a calculator block at at-
mospheric pressure and 37 °C. This temperature was chosen because it
is the optimal temperature for growth of most ethanol-producing
acetogenic microorganisms. However, operating at lower temperatures
(6)
can be beneficial because the solubility of the substrate gases increases
at lower temperature, therefore decreasing the mass transfer demand of
the fermentation. The bioreactor containing cells of the acetogenic
bacteria (cell broth or beer) is a vessel designed to promote transfer of
CO and H2 into the cells in the beer. CO and H2 are transformed to
ethanol via reactions mediated by enzymes inside the cells. The pro-
ductivity of the fermenter (mol ethanol L−1 h−1) is proportional to the
product of the cell concentration (gx L−1) and the specific uptake by the
bacteria (mol CO + H2 gx−1 h−1); and that rate of gas uptake is equal
to the product of the gas feed rate (mol CO + H2 h−1) and the fraction
of gas converted. CO and H2 are sparingly soluble in the aqueous
medium and must be continuously replenished to sustain production.
An inventory of active cells must be maintained that is sufficient to
convert the syngas fed to the fermentation. Cells retained by filtering
the beer sent to distillation can be returned to the fermenter to attain a
high cell concentration. Growing cells demand energy derived from
production of ethanol and a purge of cells is required to keep the cell
inventory active. The process flow diagram (Fig. 1) shows the fermenter
as a continuously stirred tank reactor (CSTR). However, any fermenter
type can potentially be used with similar amount of cells to convert the
equivalent quantity of syngas.
Synthesis gas (SYNGAS3) at the fermentation temperature enters
the reactor from the gasification unit. Liquid medium required for cell
growth is also fed into the fermenter, part of it as fresh concentrated
nutrients (MEDIUM-F). The product stream is a combination of liquid
and gas that must be separated. A series of cooler and flash units were
used to model this separation, minimizing the ethanol lost in the ex-
haust gas (SPENTGAS). The fermenter was assumed to have a cell re-
cycle system that facilitated a high cell concentration. Therefore, a
purge stream (CELLPURG) was necessary to model the purge of cells
that would take place in a commercial plant in order to avoid accu-
mulation of cell mass in the system. To reduce the ethanol loss in this
purge, the cells were concentrated ten times and separated out as a cell
cake (CELLCAKE) while the rest of the broth was recovered back to the
process. Finally, the liquid broth (BEERCOLD) was sent to the product
recovery unit. The water with acetic acid from the recovery module was
recycled back to the fermentation module to minimize the water re-
quirement, nutrient and product loss of the process although a purge
stream (PURGE) was needed for mass balance convergence. Heat in-
tegration was also used by preheating the beer entering the distillation
column using the hot bottoms stream from the column. Acetic acid
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O. Pardo-Planas et al. Bioresource Technology 245 (2017) 925–932

concentration was considered to remain stable in the process as it is 0.60 1100

CO&H2, SBR=0 CO&H2, SBR=0.2 CO&H2, SBR=0.5
known to be converted to ethanol by the microorganisms (Liu et al., Temp, SBR=0 Temp, SBR=0.2 Temp, SBR=0.5
2012). The acetate-acetic acid system is also used as a pH buffer. 1000

CO + H2 produced (kmol/s)
The reactor stoichiometry was calculated using a calculator block
0.55
based on stream compositions and flow rates from Aspen Plus and

Gas temperature (°C)

900
performance and kinetic assumptions shown in Table 1. These as-
sumptions were based on the laboratory scale data from our research
group, and the current state of the technology. 0.50 800
In addition to the required stoichiometry, the calculator block cal-
culates the necessary fresh medium and purge to close the cell and
700
product mass balance. Sensitivity analysis was performed on certain
fermentation parameters (specific gas uptake, ethanol concentration, 0.45
and CO and H2 conversion efficiencies) to investigate how these para- 600
meters affect equipment design and overall results of the process.
0.40 500
2.4.4. Ethanol recovery module 0.35 0.37 0.39 0.41 0.43 0.45
The use of ethanol as a biofuel requires a high purity product.
Equivalence ratio
However, water and ethanol form an atmospheric azeotrope at 96.5%
wt, thus it is not possible to achieve the desired product via distillation Fig. 3. Influence of equivalence ratio on CO and H2 production and syngas temperature at
alone. In this model, a combination of distillation and molecular sieves different steam-to-biomass ratios (SBR).

was used. In the first step, the beer from the fermenter was distilled
until an ethanol purity of 92.4%wt was obtained in the distillate. This
concentration was identified as a typical concentration achieved in
biorefineries (Huang et al., 2008). Then, the remaining water was re-
moved using molecular sieves. This is a vapor dehydration process that
is based on the adsorption of the water molecules on the sieve micro-
pores (Teo and Ruthven, 1986).
A rigorous distillation unit (Radfrac) was used to model the first step
of the ethanol recovery. Based on preliminary shortcut calculations, the
number of stages of the column was set to 25, with the feed entering at
stage number 11. The design specs feature in Aspen Plus was used to
design a column capable of obtaining a product purity of 92.4%, while
minimizing the loss of ethanol in the bottoms (recovery of ethanol in
distillate was set to 99.5%). Based on these design specifications, the
mass distillate to feed ratio and the reflux ratio were calculated. Heat
integration was performed by preheating the beer feed to 90 °C using
the hot bottoms stream. The molecular sieves unit was modeled using a
Separator block that generates a pure ethanol stream as the final pro-
duct of the simulated plant.
3. Results and discussion
3.1. Gasification
The gasification module was used to establish the best conditions for
the subsequent fermentation process. For the purpose of this simulation
study, a good quality syngas was defined as a gas rich in carbon mon-
oxide and hydrogen; the two main syngas constituents that can be
ERs reported in the literature. Typically, ERs between 0.1 and 0.3 are
investigated in gasification research (Lv et al., 2007). This can be ex-
plained based on the type of gasification modeled. The gasification in
the present study used direct heating, requiring oxygen to partially
combust the biomass in order to obtain the necessary heat for the en-
dothermic reactions, avoid diluting the syngas with N2 and producing
lower concentration of hydrocarbon compared to indirect gasification
(Martín and Grossmann, 2011). For indirectly-heated gasifiers the heat
is provided externally, therefore less oxygen is consumed.
The model predicts the composition of syngas at each operating
condition. At the optimal condition (ER = 0.405 and no steam), the
syngas (after condensed water was removed) was comprised of 32.68%
CO, 35.52% H2, 26.67% CO2, and balance of moisture in a molar basis.
It should be noted that the approach used for the present model is a
thermodynamic equilibrium model. This approach has the advantage of
being flexible and simple: the simulation does not require complex re-
action mechanisms or intermediate species. The assumptions for this
approach include perfect reactor mixing with uniform temperature, and
long enough residence times and fast enough reaction rates to achieve
thermodynamic equilibrium (Puig-Arnavat et al., 2010) through a
simple set of reactions. These assumptions may cause underestimation
of CO2, CH4 (Puig-Arnavat et al., 2010), and other hydrocarbons, which
led several authors to develop corrected thermodynamic models. In the
present study, the thermodynamic approach was improved by including
0.35 0.93
CO H2 CO2 CH4 Water Total

metabolized by acetogens. Carbon dioxide can also be metabolized by 0.30

Flow rate of syngas components (kmol/s)

acetogenic bacteria. However, with the syngas produced in the pro- 0.91
Total syngas flow rate (kmol/s)

posed model, there is net production of CO2. Therefore, the primary 0.25
objective of the sensitivity analyses was to determine the best operating
conditions in terms of equivalence ratio (ER) and steam-to-biomass 0.89
0.20
ratio (SBR) to maximize the production of CO and H2. This objective
maximizes the energy conservation of the process, so the maximum 0.15
amount of energy contained in the switchgrass is available in the 0.87
synthesis gas generated and little energy is lost in the exhaust gas.
0.10
Fig. 3 shows the influence of the equivalence ratio on CO and H2
production and syngas temperature. The total amount of CO and H2 in 0.85
0.05
the synthesis gas (on a molar basis) reached a maximum at an ER of
0.405. The temperature of the syngas at this point at a SBR of 0 (no
0.00 0.83
steam added) was about 730 °C. The addition of steam as a gasifying
0.35 0.37 0.39 0.41 0.43 0.45
agent decreased the gasification temperature, but an increase of Equivalence ratio
equivalence ratio led to higher temperatures, as the availability of
oxygen for combustion increased. Fig. 4. Effect of equivalence ratio on molar flow rates of syngas constituents for a steam-
to-biomass ratio of zero.
It can be noted that the optimal ER ratio of 0.405 is higher than the

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O. Pardo-Planas et al. Bioresource Technology 245 (2017) 925–932

heat loss and carbon conversion efficiency assumptions (Table 1), to 10000

Required reactor volume (m3)

better describe realistic scenarios. The present model can be used to A
8000
simulate different operating conditions and understand how these
conditions affect the gasification performance. As an example, Fig. 4
6000
shows the influence of ER on individual and total syngas molar flow
rates at SBR = 0. The results are in agreement with the reactions that 4000
take place during gasification shown below (Zhou et al., 2009).
Boudouard: C(s) + CO2 ↔ 2CO ΔH∘ = +162 kJ/mol (7) 2000

Steam reforming: CH 4 + H2 O(g) ↔ CO + 3H2 ΔH∘ = +206 kJ/mo 0

0.00 0.05 0.10 0.15 0.20 0.25
(8) Specific gas uptake (mol CO+H2/gx h)
Water gas: C(s) + H2 O(g) ↔ CO + H2 ΔH∘ = +131 kJ/mol (9)
100

Distillation reboiler duty (MW)

Water–gas shift: CO + H2 O(g) ↔ CO2 + H2 ΔH∘ = −41 kJ/mol B
(10) 80

Oxidation: C(s) + O2 ↔ CO2 ΔH∘ = −408.8 kJ/mol (11) 60

Higher temperatures (caused by higher heat release at increased 40

ERs) do not favor exothermic reactions (Eqs. (10) and (11), leading to
decreasing CO2 flow rates. On the other hand, higher temperatures 20
favor endothermic reactions (Eqs. (7)–(9)) causing higher CO produc-
0
tion. Specifically, the Bouduard reaction (Eq. (7)) requires contacting
0 20 40 60 80
solid carbon with CO2 to release two molecules of CO. H2 production Ethanol concentration in beer (g/L)
was favored by increasing temperatures (Eqs. (7)–(9)), until it reached a
maximum and then decreased, probably when the substrates for reac- Fig. 5. (A) Effect of specific gas uptake on required reactor volume with 10 gx/L cell mass
tions (7)–(9) (e.g. carbon and methane) were consumed (Fig. 4). In (B) Effect of ethanol concentration in beer on energy required for distillation.

terms of energy efficiency, the Higher Heating Value (HHV) of the

synthesis gas produced accounted for 66.0% of the HHV present in the 100%
Energy output distribution, % HHV

A
switchgrass.
75%
3.2. Fermentation and product recovery

The fermentation module was analyzed based on the synthesis gas 50%
produced with the gasification parameters that were identified as most
appropriate in section 3.1 (ER = 0.405, SBR = 0). For the base con-
25%
ditions with 30 g/L ethanol listed in Table 1, the plant produced
36.5 million gallons of anhydrous ethanol per year (97.7 gallons per dry
ton of switchgrass). Under these conditions, a fermentation plant with 0%
1751 m3 working volume was required. In order to fulfill the product 70 80 90 95
recovery and purity, the distillation column operated at a reflux ratio of CO conversion, %
7.70 while the distillate-to-feed ratio was 3.1% in a mass basis. It was Energy in ethanol Energy in exhaust gas
observed that preheating the beer entering the column to 95 °C using
100%
the hot bottoms stream decreased the reboiler duty in the distillation
Energy output distribution, % HHV

B
column by approximately 20%. The required reboiler duty after heat
integration was 33.91 MWth. 75%
Several parameters have a high impact on the design and operation
of a syngas fermentation reactor. The present model was used to ana-
lyze the influence of three of these parameters; particularly the specific 50%
gas uptake, the ethanol concentration achieved in the fermenter, and
the gas conversion efficiencies. The specific gas uptake is the rate of gas 25%
substrate per mass of cells, and is dependent on the strain used and the
enzymatic activity of the cells. Fig. 5A shows the impact of the specific
gas uptake on the reactor volume required. It is important to note that a 0%
high cell density in the reactor is not enough to minimize capital costs 10 30 50 70 90 95
H2 conversion, %
associated with the reactor requirements. The culture in the fermenter
must be active (which is associated with specific gas uptake) in order to Fig. 6. (A) Effect of CO conversion on the output energy distribution (HHV basis) with H2
achieve the goal of minimizing reactor sizing. conversion fixed at 90% (B) Effect of H2 conversion on the output energy distribution
The ethanol concentration achieved in the fermenter has a great (HHV basis) with CO conversion fixed at 90%.
impact on the economics of the process. Product recovery has been
identified as an important portion of the energy requirements of a overall economics of the process as already highlighted in the literature
biorefinery (Huang et al., 2008). More specifically, the concentration of (Vane, 2008).
ethanol in the beer affects the energy cost of the separation process. Another parameter that is critical during syngas fermentation is the
Fig. 5B shows the effect of the ethanol concentration on the reboiler percentage of gas converted in the bioreactor. Both hydrogen and
duty. Concentrations lower than 30 g L−1 would require significantly carbon monoxide are known to be substrates for ethanol production
higher amount of energy for product recovery, which would affect the

930
O. Pardo-Planas et al.
Table 2
Material balance and energy duties of hybrid thermochemical gasification-syngas fermentation plant (for base case scenario in Table 1).
Inputs
Material, kg d−1
Switchgrass 1,200,000
O2 609,292
Medium (water & nutrients) 420,275
Energy Duties, MWth
Oxygen heater/AIRHEAT 0.16
Fermenter/BIOREACT 19.89
Distillation–Reboiler/not labeled 33.91
using acetogens (Phillips et al., 1994). An efficient hybrid thermo-
chemical-syngas fermentation plant needs to have active cells that
utilize both gases to a high extent. Fig. 6 shows the importance of gas
conversions in terms of the energy efficiency of the fermentation pro-
cess in a Higher Heating Value (HHV) basis. The objective of a suc-
cessful fermentation step should be maximizing the energy conserva-
tion from the syngas into the ethanol produced. Although a high H2
conversion is not essential for ethanol production with syngas fer-
mentation, it is important to maintain a high conversion of both gases
in order to develop an energy efficient process. For example, when both
CO and H2 conversions were 90% only 13.6% of the energy (in HHV
basis) from the syngas was lost in the exhaust gas (Fig. 6). The energy
efficiency of the conversion of syngas to ethanol was 63.5% (HHV
basis). The rest of the energy contained in the synthesis gas was lost in
the exhaust gas, in the acetic acid produced, and in the purge.
3.3. Summary of the overall process
The designed process in the present study generated 36.5 million
gallons of anhydrous ethanol per year from 1200 tons per day (wb) of
switchgrass under the base conditions. Table 2 presents an overall
material balance of the process and the energy duties of the main units
in the flowsheet. These results were generated by Aspen Plus®. Besides
ethanol as a product, the process produced more than 74 tons of char/
ash per day. Char is generally burned or disposed of (Qian et al., 2013),
although there are potential uses for this material that would result in a
more economical process. Some of these applications are soil re-
mediation (Chen et al., 2012), water and sewage treatment (Oleszczuk
et al., 2012), synthesis of activated carbon (Azargohar and Dalai, 2006)
and cleanup and conditioning of synthesis gas (Wang et al., 2011). Use
of the exhaust gas containing unconverted H2 and CO will maximize the
recovery of energy. CO2 release to the atmosphere is a concern due to
its greenhouse effect, so it may be captured for reuse in other industrial
processes including further biofuel production (Ramachandriya et al.,
2013).
The base case scenario for gasification and fermentation parameters
in Tables 1 and 2 resulted in a yield of 97.7 gallons per dry ton of
switchgrass. Recent experimental studies using the biochemical plat-
form reported a production of 45 gallons ethanol per dry ton of biomass
using SO2-steam pretreatment (Ewanick and Bura, 2011) and 64 gallons
ethanol per dry ton of switchgrass using microwave-based alkali pre-
treatment (Keshwani and Cheng, 2010). This showed that the hybrid
process proposed in the present study has the potential to achieve
higher ethanol yield than the biochemical platform. Syngas fermenta-
tion has the potential to produce 30% more ethanol from the same
amount of biomass including lignin compared to the biochemical
platform as previously reported (Tanner, 2008). In addition, the
931
Bioresource Technology 245 (2017) 925–932
Outputs
Char and ash 74,131
Exhaust gas 1,765,995
CO2 1,689,253
H2 4902
CO 62,683
Cell cake 49,032
Purge 34,084
Ethanol 298,771
Syngas cooler/COOLER −28.33
Reactor condensation system/CONDINS −1.76
Distillation–Condenser/not labled −31.27
Bottoms cooler/not labeled below preheat −1.97
proposed process does not require complex pretreatments or use of
enzymes for sugar release. Two companies developing hybrid thermo-
chemical-syngas fermentation processes have claimed to achieve yields
of up to 100 gallons per dry ton of biomass (Daniell et al., 2012). These
claims are in agreement with the results presented in this paper.
The most energy intensive step of the process was the distillation of
the fermentation beer (33.91 MWth). On the other hand, the gasification
module proved to be energy self-sufficient, as it produced excess energy
during cooling of syngas (28.33 MWth) that may be reused in other
parts of the process through steam generation. The present model
achieved an energy conservation efficiency of 66.0% (HHV basis)
during the gasification and 63.5% during fermentation. Therefore, the
overall energy conservation efficiency from switchgrass to ethanol was
41.95% in a HHV basis.
4. Conclusions
The proposed process model for the hybrid gasification-syngas fer-
mentation plant estimated a production capacity of 36.5 million gallons
of ethanol per year from 1200 tons (wb) of switchgrass per day. The
process yielded 97.7 gallons of ethanol per dry ton of biomass, which is
higher than the yields currently achieved by the biochemical platform.
Distillation was the most energy intensive step in the process. An in-
crease in specific CO and H2 uptake rate by the microorganism resulted
in lower reactor volume. This work will be the basis of a detailed
techno-economic analysis of the proposed technology.
Acknowledgements
This research was supported by the Sun Grant Program – South
Center No. DOTS59-07-G-00053, USDA–NIFA Project No. OKL03005
and the Oklahoma Agricultural Experiment Station.
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