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Renewable and Sustainable Energy Reviews (xxxx) xxxx–xxxx

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews


journal homepage: www.elsevier.com/locate/rser

Design of an organic waste power plant coupling anaerobic digestion and


solid oxide fuel cell technologies

Addison J. Rayner , Johnathan Briggs1, Reed Tremback2, Ryan M.C. Clemmer
School of Engineering, University of Guelph, 50 Stone Road East, Guelph, Ontario, Canada, N1G2W1

A R T I C L E I N F O A BS T RAC T

Keywords: The preliminary design of an organic waste power plant utilizing both anaerobic digestion and solid oxide fuel
Waste management cell (SOFC) technologies is presented along with a review of these technologies. Food waste and sewage sludge
Organic waste from a mid-sized Canadian municipality were modeled as feedstock for anaerobic digestion. The biogas quality
Anaerobic digestion and quantity produced from the digestion process were determined by modeling the municipal waste’s chemical
Biogas
composition and chemical oxygen demand (COD) content. Overall, between 480 kW and 1410 kW of electrical
Solid oxide fuel cell
power can be produced from the SOFC system fueled by the biogas. The compatibility of these two technologies
is evident and the major challenges and benefits associated with implementing this concept are discussed. This
work demonstrates that an organic waste power plant is a sustainable solution to waste management and power
production.

1. Introduction landfill life and decrease health and environmental impact through
reduction of harmful leachate and emissions [3,4].
Energy production and waste management are growing issues in A number of cities, such as Guelph, Ontario, Canada, have adopted
modern society [1,2]. Traditional energy production relies heavily on source separation methods for diverting organic wastes from landfill
non-renewable resources which are damaging to the environment [3]. However, many of these municipalities do not take full advantage
while the majority of waste management practices do not use the of the biogas production that could be achieved through anaerobic
potential energy stored in organic wastes. It is therefore desirable to digestion of organic waste material. This is especially true of municipal
develop a sewage and municipal waste disposal process that can cleanly waste water treatment plants (WWTPs). In the United States, less than
harness the energy contained in organic wastes. Coupling existing 10% of municipal WWTPs produce biogas for beneficial use, yet 6.5
anaerobic digestion technology with solid oxide fuel cells (SOFCs) is a million tonnes of energy dense sewage sludge are generated by the
unique approach to solving these problems. By creating an organic country annually [7,8]. There are currently very few options for
waste fueled power plant using these two technologies, electricity, heat, disposal of sewage sludge and those methods are both costly and
and compost can be produced from organic wastes while reducing the strictly regulated due to the potential for contamination and pollution
emission of greenhouse gases and avoiding the release of harmful [9]. One alternative method for disposal would be to use anaerobic
pollutants such as methane, nitrous oxides, and sulphur oxides. digestion, which converts the municipal waste to biogas. This disposal
Organic wastes can create a number of environmental and health method has the added benefit of destroying pathogens contained in the
hazards when contained in landfill. Leachate from organic materials waste material, leaving nutrient rich compost which can be safely used
can cause problems such as ground water contamination while landfill as fertilizer.
gasses created by organics decomposing contribute to greenhouse gas Biogas produced through an anaerobic digestion process is primar-
(GHG) emissions. In the literature [3,4], diversion of organic materials ily methane. This hydrocarbon fuel, alongside coal and oil, is often
from landfill sites is commonly proposed as a solution to these health combusted to produce electricity or flared [10]. In 2008, the electrical
and environmental impacts. However, in 2012, over 65% of municipal power generation sector was the largest GHG contributor in Canada,
solid wastes in Canada and the United States were disposed of in a producing 16% of all Canadian GHG emissions [11]. In the United
landfill [5,6]. Diverting organic wastes from landfill sites will extend States, the electrical power requirements of waste water treatment


Correspondence to: Dalhousie University, 1360 Barrington Street, Box 15000, Halifax, Nova Scotia, Canada, B3H4R2.
E-mail address: Addison.rayner@dal.ca (A.J. Rayner).
1
Present affiliation: Queen’s University, Kingston, Ontario, Canada.
2
Present address: Engineering Services Canada, Calgary, Alberta, Canada.

http://dx.doi.org/10.1016/j.rser.2016.12.084
Received 31 March 2016; Received in revised form 7 December 2016; Accepted 12 December 2016
1364-0321/ Crown Copyright © 2016 Published by Elsevier Ltd. All rights reserved.

Please cite this article as: Rayner, A., Renewable and Sustainable Energy Reviews (2016), http://dx.doi.org/10.1016/j.rser.2016.12.084
A.J. Rayner et al. Renewable and Sustainable Energy Reviews (xxxx) xxxx–xxxx

alone contribute 21 million tonnes of GHG emissions annually [10]. is needed to optimally couple these two technologies together in a
Instead of combusting the obtained biogas from digestion of organic system such as the one investigated by Papurello et al. [16].
wastes, the raw biogas can be refined into fuel for an SOFC system. Having reviewed the literature, the authors believe this is the first
SOFCs can efficiently produce electricity and heat from the electro- known presentation of a simplified ADFC system model which cumu-
chemical combination of biogas and oxidant, effectively offsetting the latively explains the diverse breadth of the technology (organic waste
GHG emissions associated with WWTPs [12]. processing, anaerobic digestion, biogas production, and SOFC perfor-
Provided any contaminants in the biogas, such as hydrogen mance) to demonstrate the benefits and feasibility of the entire ADFC
sulphide, are removed, an SOFC system could continuously provide process. Literature review of these topics is used to provide a mean-
clean electricity from anaerobic digestion of municipal wastes. Other ingful commentary on the design and implications of ADFC systems.
systems that couple anaerobic digestion with hydrogen fuel cells, such
as the proton exchange membrane (PEM) fuel cell, require hydrogen 1.1. Anaerobic digestion
fuel to be derived from the produced biogas through a complex process
[13]. It is also necessary to remove carbon monoxide from the biogas to Anaerobic digestion is the process of microorganisms decomposing
prevent poisoning of PEM fuel cell systems [14]. These fuel processing organic compounds in the absence of oxygen [9]. The products of
steps require additional infrastructure and energy, making the SOFC a anaerobic digestion are biogas, which primarily consists of methane,
more efficient and cost effective option for pairing anaerobic digestion carbon dioxide, and digestate [26]. The digestate from the anaerobic
and fuel cell technology. SOFCs can also operate using the variable digestion process can be used as fertilizer for the agriculture industry
composition of the biogas, whereas internal combustion engines [26]. The quality of the biogas and digestate depend on the type of
require a significantly higher amount of tuning to run effectively with material being digested, the pre-processing of that material, and the
varying fuels. conditions in which the digestion is taking place. Inorganic material
An anaerobic digestion/fuel cell (ADFC) system fueled by municipal remains effectively undigested if included in the process [27].
sewage and organic wastes provides both waste management and The anaerobic digestion process consists of three main stages:
energy solutions simultaneously while remaining environmentally hydrolysis; fermentation; and methanogenesis. During hydrolysis,
friendly. An ADFC can be considered a carbon neutral power source insoluble organic matter is broken down to make soluble organic
because the biogas produced from waste streams is naturally occurring; substances such as amino acids, fatty acids, and sugars [28,29].
anaerobic digesters in this context are simply used to speed up the Fermentation consists of two sub-processes, acidogenesis and aceto-
digestion process of the bacteria. For this reason it can be assumed the genesis, which break down the products of hydrolosis into alcohols,
energy produced by an ADFC system would directly offset any green- acetic acid, and gas containing H2 and CO2 [29–31]. Two main
house emissions incurred on a traditional power plant in its place. methanogenic bacteria groups produce methane during methanogen-
The concept of an anaerobic digestion-solid oxide fuel cell (ADFC) esis. One group of bacteria splits two acetate molecules to form
system has only been evaluated a few times in literature [12,15–17]. methane and carbon dioxide [29–31] while the remaining group uses
Previous work by Van Herle et al. [17] present data on multiple biogas hydrogen as an electron donor and carbon dioxide as an electron
sources, such as landfills, and provide a case study of a small scale acceptor to produce methane [29]. The acetate reaction is the primary
SOFC co-generation system running on biogas. In their study, model- reaction that produces methane due to the low hydrogen production
ing software (BELSIM) is used to model the fuel reforming reactions rate in the fermentation process [27].
and SOFC thermodynamics involved in utilizing different biogas
sources. The results demonstrate that the concept is applicable on 1.2. Solid oxide fuel cells
scales from individual farms with 10 kW systems to landfill sites with
1 MW systems. But despite providing a lengthy discussion on design Fuels cells are energy conversion devices that convert the chemical
and performance parameters of the model SOFC system, Van Herle potential energy of a fuel into electricity without the need for combus-
et al. do not discuss the equally important design aspects of anaerobic tion. They can achieve overall efficiencies exceeding 60% in combined
digestion. This theme continues in the literature [12,15] where heat and power systems and they do not emit the harmful GHGs, such
anaerobic digestion is not manipulated or controlled to produce an as nitrous and sulphur oxides, that combustion does [14,32]. There are
optimal biogas for use in SOFC applications. Instead, the more multiple types of fuel cells, most of which rely on pure hydrogen for
common approach to researching ADFC technologies is to start with fuel. SOFCs are superior to other designs in the way that they can
an approximate biogas composition and then model or test biogas handle a wide range of hydrocarbon fuels, such as methane and carbon
reforming and model SOFC thermodynamics from there [15,18–21]. monoxide without the use of expensive catalysts such as platinum.
In contrast, Papurello et al. [16] recently completed a pilot scale The electrochemical combination of the fuel with an oxidant
study of a waste-to-energy system which successfully couples anaerobic produces electrical current (We), waste heat (Q), and water. There
digestion of organic wastes from municipal sources and SOFC tech- are significantly less pollutants released in the process compared to
nologies. In their work, they cite three years of anaerobic digestion traditional combustion reactions used to drive electrical generators
development to obtain a high methane concentration in the biogas. [33]. By connecting multiple cells in series, the overall voltage can be
However, their system achieved a digester efficiency of 20% and had a increased and SOFC stacks can be built for different scale applications.
retention time of 40 days. In addition, their system achieved an overall The heat rejection from the fuel cell yields opportunity for co-
electrical efficiency of 17%. Their experimental research suggests that generation which would further increase the overall efficiency of the
coupling AD and SOFC technologies is feasible, but points to the need system.
for optimization of the fuel cell system [16].
More recent work on coupling these two technologies by Lackey 1.3. Coupling anaerobic digestion and SOFC technology
et al. [15] focuses on UniSIM modeling and experimental operation of
an SOFC operating with biogas from waste water treatment plants but The process of converting organic waste into biogas can be
does not include a discussion of waste processing or anaerobic controlled through the use of an anaerobic digester under specific
digestion technologies as developed in Papurello et al’s pilot scale operating conditions. The inputs to the digester are heat, water, and
system. The contribution by Lackey et al. helps optimize the SOFC pre-processed organic waste. During the digestion process appreciable
performance side of ADFC technologies which is also intensively quantities of biogas are produced. The process provides an effective
studied in the literature [12,15,17–25]. To fully develop the combined solution for organic waste management while the biogas can be
ADFC system, unification of both anaerobic digestion and SOFC fields captured and used as fuel and the digestate can be used as a nutrient

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rich fertilizer [8,27]. The intense use of biogas from multiple sources destroying the necessary bacteria for sustained digester operation.
such as landfills and sewage wastes can also help suppress methane The refined biogas is utilized as fuel for a 774 kW SOFC system. The
emissions, which is a potent greenhouse gas [17]. primary reactions occurring within the cell are the overall oxidation of
Biogas produced in WWTPs is either flared or utilized in an methane, fuel reforming reactions, and oxidation of hydrogen shown in
electrical generation process such as a gas turbine or a combined heat Eqs. (1)–(4) [22,33]:
and power unit (CHP). The achievable electrical efficiency of these CH4 + 2O2 → 2H2 O + CO2 + We + Q (Overall) (1)
processes typically falls within 20–40% [17,34,35] for large scale
systems. Fuel cells can achieve much higher efficiencies in the range CH4 + H2 O → 3H2 + CO (Steam reforming) (2)
of 50–60% without the need for combustion [14]. Since SOFCs have
high efficiency, a solid state design, and the ability to process a wide
CO + H2 O → H2 + CO2 (Water gas shift) (3)
variety of carbon-based fuels, they are a suitable candidate for many H2 + O 2 − → H2 O + 2e− (Oxidation of hydrogen) (4)
applications, such as integration with an anaerobic digester [17,32,36].
Coupling an anaerobic digester with an SOFC system is an efficient Here, carbon dioxide, water, waste heat (Q), and electrical work
alternative to traditional energy production and waste management (We) are the products of the process. In PEM fuel cell systems, the
methods. production of carbon monoxide via the water gas shift reaction can
cause cell poisoning which requires further hydrogen gas purification
1.4. ADFC system overview [14,33]. Conversely, methane, carbon monoxide, and hydrogen can be
used directly as fuels in an SOFC. The fuel and oxidant streams must
An anaerobic digestion/fuel cell system to process municipal pass through a pre-heating stage before entering the SOFC in order to
sewage sludge and source separated organic wastes to form methane prevent thermal shock of the stack. The electricity produced from the
that is fed into an SOFC to generate electricity is presented. This simple SOFC can be sold back to the electrical grid. The excess heat generated
model highlights the feasibility of this concept and helps link the by the SOFC (107 kW) is used to pre-heat the digester slurry feed, fuel,
various processes together in a refined manner. A schematic of the and oxidant. The excess heat can also be used to provide temperature
process flow diagram for the ADFC system is presented in Fig. 1. control over the digester or be passed to a combined heat and power
Once on site, waste feed stocks are mixed into a slurry with 60–80% (CHP) unit to produce additional electrical power.
moisture content. The slurry is then pumped through a pre-heating
stage to raise its temperature to approximately 55 °C prior to entering 2. Modeling and results
the anaerobic digester. The digestion process is designed to operate
using thermophilic bacteria at 50–55 °C to achieve a lower retention 2.1. Anaerobic digestion and methane production modeling
time and more continuous flow of biogas production [29,31]. A
continuous plug flow reactor is used to digest the high solids slurry To model the anaerobic digester, a system that will predict the
over a 15 day retention time. An effluent loop is utilized to ensure equal composition and quantity of the biogas produced given known
spread of bacteria to the input slurry feed and maintain adequate characteristics of the input waste is needed. Two methods were used
retention time, increasing digester efficiency [36]. Biogas is continu- to model the digestion process. The Buswell and Boruff Method
ously drawn off of the digester vessel and is subject to a bio-trickling enabled the determination of the quality of the biogas produced while
filter, primarily targeting H2S gas [37]. The refined biogas is then sent the chemical oxygen demand (COD) model was used to determine the
to the SOFC or to storage. quantity of biogas produced from the given feedstock [31].
The solid digestate exiting the reactor is controlled by a screw
conveyor. This conveyor moves the digestate material through the de- 2.1.1. Buswell and Boruff method
watering process. The excess water enters the effluent loop and the The Buswell and Boruff Method [31], presented in Eq. (5), requires
solids are dried to be sent for further composting. The effluent drawn the ultimate analysis of the carbon (v), hydrogen (w), oxygen (x),
off must be scrubbed of contaminants such as absorbed H2S without nitrogen (y), and sulphur content (z), of the specific organic waste

Fig. 1. Schematic process flow diagram of the ADFC system with gas turbine co-generation.

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(CvHwOxNySz). The model outputs the estimated molar quantity of Table 2


methane (CH4), carbon dioxide (CO2), ammonia (NH3), and hydrogen Ultimate analysis of food waste.
sulphide (H2S) that will be produced under anaerobic conditions.
Source Ash (%wt) Ultimate analysis (%wt) COD (g/L)
⎛ w x 3y z⎞
Cv Hw Ox Ny Sz + ⎜v − + + + ⎟ H2 O C H O N S
⎝ 4 2 4 2⎠
⎛ v w x 3y z ⎞ [35,52,64,65] 5 48 6.4 37.6 2.6 0.4 277–360
→ ⎜ + + + + ⎟ CH4 + yNH3 + zH2 S
⎝2 8 4 8 4⎠ (5)
The expected mass of each gas can be approximated by multiplying
there is 30,700 kg COD/day, 9600 kg COD/day, and 16,500 kg COD/
the mole fraction by the given number of moles of the input fuel and
day in the sewage sludge derived from waste water in the high, low, and
the molar weight of the associated gas.
average cases respectively.

2.1.2. COD of methane


The COD of methane is the amount of oxygen required to oxidize 2.2.2. COD from solid waste
methane into carbon dioxide as given in Eq. (6): The City of Guelph’s composting facility received 17,300 tonnes of
organic waste in 2012 [42]. Of this waste, approximately 15,000 tonnes
CH4 + 2O2 → CO2 + H2 O (6) were mixed organic materials consisting primarily of food waste, which
The COD per mole of methane then becomes Eq. (7): is well suited for anaerobic digestion. Therefore, 15 million kg/year, or
just over 41,000 kg/day, of organic food waste is available for feed-
2 mol O2 33 g O2 64 g COD
× = . stock. High, low, and average cases for the COD contained in this waste
1 mol CH 4 1 mol O2 1 mol CH 4 (7) stream are taken from literature as 360 g/L, 277 g/L, and 318.5 g/L,
Using the ideal gas law, the volume of methane produced from respectively. This translates into 14,800 kg COD/day, 11,400 kg COD/
anaerobic digestion at 55 °C (328 K) and 1 atm becomes 0.421 m3 of day, 13,100 kg COD/day in the high, low, and average cases, respec-
CH4 per kilogram of COD. From literature it is generally accepted that tively, when the density of the food waste is taken as that of water.
0.35 m3 of methane can be produced per kilogram of COD [31]. Ultimate analysis results for food waste are also presented in Table 2.

2.2. Waste water and solid waste feedstock 2.2.3. Total COD input
The total COD in the feedstock for the ADFC system is the
The anaerobic digester feedstock is a combination of sewage sludge summation of both the waste water sewage sludge and solid organic
derived from municipal waste water and organic food waste from waste CODs. The feedstock characteristics in each of the three model
source separated municipal solid waste. To determine the potential cases are summarized in Table 3.
biogas production through anaerobic digestion, data on the quantity The Buswell and Boruff Method was evaluated using the average of
and composition of municipal organic waste and sewage sludge in the ultimate analysis data taken from a variety of sources and
terms of the ultimate analysis and COD is required. The City of Guelph, presented in Tables 1 and 2 for sewage sludge and solid organic waste
in Ontario, Canada, having a population of over 120,000 [38], was [9,34,52,59–65]. The results of this analysis are summarized in Table 4
selected to estimate the volume of organic waste available as it is a mid- and show that the biogas stream will consist of approximately 62%
sized Canadian municipality with the required data [39]. From the methane. This is in agreement with the measured biogas compositions
literature, the expected quality, including the ultimate analysis and presented in literature [12]. The H2S content of the biogas is 4000 ppm
expected COD of sewage sludge waste from municipal waste water and which is too high for SOFC operation and will need to be removed from
food waste is presented in Tables 1 and 2, respectively. the biogas stream along with other fuel contaminants such as siloxanes
[12,20].
2.2.1. COD from waste water The ideal daily methane production volumes were determined from
The City of Guelph produces approximately 64,000 m3 of waste- the Buswell and Boruff Method for high, low, and average cases as
water per day [40]. High, low, and average cases for the COD contained presented in Table 5. Digester efficiency and biogas compositional
in this waste stream are taken from literature as 800 mg/L, 250 mg/L, fluctuations were taken into account by applying a 70%, 80%, and 90%
and 430 mg/L, respectively [31] however, only 60% of the COD present generation efficiency to determine a range of potential methane
in wastewater is expected to be retained in the sewage sludge being fed production outputs which is typical for anaerobic digesters [43–45].
into the anaerobic digester [41]. Converting these units into kg COD/ The relation between COD in the daily input stream (kg) and modeled
day, and accounting for the 60% remaining COD in the sewage sludge, methane output (m3) is presented in Fig. 2. From Table 5, the expected

Table 1
Characteristics of waste water sludge samples.

Source Sample Proximate Analysis (%wt) Ultimate analysis (%wt)

Moisture Volatile matter Ash Fixed carbon C H N S O

[9] 1 5.2 60.7 29.5 9.8 35.7 5.2 3.5 0.7 25.4
[59] 2 5.0 72.5 16.0 11.5 45.9 6.3 5.1 0.6 26.9
[60] 3 11.8 60.6 26.6 12.8 39.5 6.2 3.9 1.5 25.5
[61] 4 4.3 59.3 31.0 9.7 38.1 5.2 4.5 0.9 20.3
5 3.9 58.5 30.8 10.7 38.3 5.1 3.7 0.7 21.4
6 8.5 50.8 43.3 5.9 30.1 4.1 3.8 0.9 17.8
[62] 7 78.1 60.7 36.9 2.4 37.3 5.8 5.5 0.8 13.7
[63] 8 – 55.9 40.3 3.8 29.0 4.4 3.2 0.5 22.6
9 – 49.6 44.0 6.4 25.5 3.7 2.4 0.6 23.8
10 – 71.0 21.2 7.8 40.0 6.0 7.0 0.7 25.1
Average 16.7 60 32 8.08 35.94 5.2 4.26 0.72 22.25

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Table 3 1
H2 (g) + O2 (g) → H2 O(g)
COD input to ADFC in the mixed feedstock. 2 (11)

Case Sewage Sludge (kg Organic Food Waste Total in Feedstock (kg Water, as a product of this reaction, will react with the supplied
COD/day) (kg COD/day) COD/day) methane to continue this reforming process while the electrons can
conduct through an external electric circuit from the anode to the
High 30,700 14,800 45,500
Low 9600 11,400 21,000 cathode. Once in steady state operating conditions, each mole of
Average 16,500 13,100 29,600 methane produces 4 moles of H2 fuel within the anode of the cell.
Dry reforming reactions can also occur within the anode due to the
large concentration of CO2. Although often referred to as an effective
Table 4 alternative to steam reforming, dry reforming is generally less desirable
Predicted chemical composition of biogas.
as it produces less hydrogen per mole of methane fuel. In addition, the
Gas Species Molar Fraction reverse water gas shift (RWGS) reaction (Eq. (12)), which consumes
hydrogen, is highly endothermic and can lead to thermal shock of the
CH4 0.621 anode material [46]:
CO2 0.324
NH3 0.052 H2 (g) + CO2 (g) → CO(g) + H2 O(g) (12)
H2S 0.004
The RWGS reaction also gives rise to the Bouduard reaction (BD),
which can lead to catalyst damage due to carbon deposition as shown in
Table 5 Eq. (13):
Calculated methane production volumes for each model case.
2CO(g) → C(g) + CO2 (g) (13)
Case Ideal Volume CH4 (m3/day) Actual CH4 Yield (m3/day)
Steam reforming then, becomes the desired reaction as it provides
High 15,900 14,300 more hydrogen fuel without compromising cell reliability [18,47,48].
Low 7300 5100
The quality of the biogas will have a significant impact on cell
Average 10,400 8300
performance. From the Buswell Boruff model, the biogas composition
becomes 66% CH4 and 34% CO2 once other gas species (i.e., NH3 and
H2S) are removed through fuel refinement. The presence of CO2 dilutes
the concentration of methane, and ultimately hydrogen within the fuel
stream, hindering performance. SOFCs are commonly naturally aspi-
rated, meaning that the cathode reaction will only contain 0.21 molar
fraction of oxygen to represent atmospheric air.

2.4. Fuel cell efficiency

Thermodynamic irreversibilities, known as polarization losses,


result in a reduced cell performance compared with the theoretical
power output. The polarization losses for an SOFC are difficult to
model and are commonly determined experimentally. For this paper,
literature values for the actual cell potential for nickel based, anode-
supported, SOFCs operating on biogas were substituted to evaluate
system performance. Table 6 presents the most common values of
actual cell potential for SOFCs operating using methane and biogas
Fig. 2. Methane production per day based on COD flow rate for different digester
efficiencies.
while Table 7 presents the values used to characterize the SOFC output
in the ADFC system.
case will produce about 8300 m3 of methane based on the COD of the From the experimental operation of SOFCs in the literature, an
waste water and solid waste and an 80% digester efficiency (29,600 kg actual cell potential, E*, of 0.8 V, at a current density of approximately
COD/day from Table 3). 0.2 A/cm2, was selected as an average case. The reversible cell
efficiency was determined to be 76% when operating on pure hydrogen
fuel at 800 °C. The reversible cell potential, Er, for a fuel cell operating
2.3. Fuel reforming and SOFC reactions at a given temperature and pressure can be determined from the

During continuous operation, methane gas will not be directly Table 6


oxidized in the SOFC anode due to a number of internal reforming Literature values for cell potential of nickel based, anode-supported, SOFCs operating at
reactions (Eqs. (9)–(11)) which are more thermodynamically favour- 800 °C with different current densities and methane contents.
able. However, during initial start-up, methane may oxidize to produce
E (V) J (A/ Operating Temp. (° Fuel Composition Source
carbon dioxide and water as given in Eq. (8): cm2) C)
CH4 (g) + 2O2 (g) = CO2 (g) + 2H2 O(g) (8) 1.10 0.20 800 75% CH4, CH4:CO2=3 [46]
1.00 0.20 800 97% CH4, 3% H2O [46]
Once water is present within the anode, methane will preferentially 0.65 0.05 800 Raw Biogas, CH4:CO2=1.5 [21]
cause fuel reforming reactions to occur: 0.81 0.20 800 Desulfurized Biogas, [21]
CH4:CO2=1.5
CH4 (g) + H2 O(g) → 3H2 (g) + CO(g) (9) 0.80 0.20 800 Desulfurized Biogas, [20]
CH4:CO2=1
CO(g) + H2 O(g) → H2 (g) + CO2 (g) (10) 0.63 0.50 800 Desulfurized Biogas, [20]
CH4:CO2=1
Hydrogen then becomes the fuel for the electrochemical reaction:

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Table 7 Table 8
Actual cell performance characteristics applied to ADFC system models. Fuel volume, molar amount, and energy potential for each model case.

E (V) J (A/ Operating Temp. (° Fuel Composition Source Case Utilized CH4 (m3/ Moles of H2 (mol/ Chemical Potential Energy
cm2) C) day) day) (kW)

0.80 0.20 800 Desulfurized Biogas, [20,21] High 11,500 7.23×105 2400
CH4:CO2=1.5 Low 4100 2.59×105 860
Average 6600 4.18×105 1380

change in Gibbs free energy, Δg, the number of moles of electrons


transferred in the reaction, n, and Faraday’s constant, F using Eq. (14): the SOFC. The utilized volumes of methane are shown in Table 8, based
−∆g (T , P ) on 80% of the methane produced in Table 5.
Er (T , P ) = . The fuel is pre-heated to 500 °C (773 K) to prevent thermal shock of
nF (14)
the SOFC from introduction of cold fuel. The number of moles of
The reversible cell potential for an SOFC operating with pure methane is determined from the ideal gas law. Four moles of hydrogen
hydrogen fuel at 800 °C and 1 atm was determined to be 0.976 V. are derived from each mole of methane through the internal reforming
The concentration losses associated with the modeled biogas fuel reactions (Eqs. (9) and (10)). The molar amounts of hydrogen are
stream at a particular temperature, T, can be taken into account using presented in Table 8.
the Nernst equation (Eq. (15)): The energy potential of the utilized amount of fuel is calculated by
RT multiplying the number of moles of hydrogen by the higher heating
E (T , Pi ) = Er (T , P ) − lnK
nF (15) value of hydrogen gas (HHV of H2=286 kJ/mol fuel). Since the utilized
quantity of fuel is produced on a daily scale, the energy potential was
where K is written as Eq. (16):
then converted into kilowatts by dividing by the number of seconds in a
⎡ Pc ⎤ twenty-four hour period. The chemical potential energy of each volume
K = ⎢ aC b ⎥
⎣ PA PB ⎦ (16) of fuel is shown in Table 8.

and Pxy
in Eq. (16) is the partial pressure of each gas species. The terms
a, b, and c are the stoichiometric coefficients of the reactants A (H2) 2.7. SOFC performance
and B (O2) and products C (H2O) respectively in the electrochemical
reaction. The reversible cell potential for the modeled biogas, deter- The calculated molar fraction of methane gas species within the fuel
mined via the Nernst equation is 0.925 V based on a hydrogen molar stream was 0.621 mol CH4 per mole of fuel. The molar fraction of CO2
fraction of 0.725 and oxygen molar fraction of 0.21. Leveraging this was 0.324 mol CO2 per mole fuel while a molar fraction of 0.21 was
information, the cell efficiency can be calculated from the operating used for oxygen to represent standard atmospheric air as the oxidant.
potential, E*, and the reversible potential, Er via Eq. (17): Once reformed, the fuel contains 2.64 mol H2 and 1 mol CO2. The fuel
E* is reacted with 0.21 mol of O2 present in the cathode. The resulting cell
ηE = . potential from the Nernst equation is 0.925 V. Considering the
Er (17)
inefficiencies of the fuel cell and auxiliary equipment, the overall
The overall energy conversion efficiency of the cell, ηFC, can be SOFC energy conversion efficiency becomes 56%.
determined via the product of the cell and reversible cell efficiencies. From the literature, operating nickel based, anode-supported,
Applying an approximate efficiency of 85% to account for auxiliary SOFCs at a current density of 0.2 A/cm2 and 800 °C produced a cell
equipment, the overall SOFC system efficiency is 56%. voltage of 0.8 V. A state-of-the-art Ni-YSZ anode supported SOFC
could be utilized to produce the modeled power requirements.
2.5. Heat generation Assuming each cell is a 10 cm by 10 cm planar design, the power per
cell is 16 W and the power density is 0.16 W/cm2. This is well below
At the operating temperature, T, heat, q, is generated as a result of the maximum accepted operating power density for planar SOFCs
the change in entropy, Δs, and the entropy production, Ps, associated which is 0.48 W/cm2 [14].
with polarization losses (ηpol) and can be calculated from Eqs. (18)– Using the calculated cell efficiency of 56%, the SOFC system will be
(20): able to produce 774 kW of electrical power based on the available
q = T ∆s − TPs (18) potential energy in the average case. Overall, the electrical power
output ranges from 480 to 1340 kW. The heat generated by the system
where was calculated to be 84.3 kJ/mol of hydrogen fuel. Utilizing the ideal
TPs = nFηpol (19) gas law, the heat power generated was calculated for each biogas
production case. The energy required to drive the endothermic internal
and fuel reforming reactions is 247.3 kJ/mol of CH4 [33]. The heat power
Er = E* + ηpol . released by the SOFC is the difference between the generated heat
(20)
power and the heat consumed in the reforming reactions. The results
The sum of the cell’s irreversible losses, ηpol, can be determined by are outlined in Table 9.
rearranging Eq. (20). The total losses can then be substituted into Eqs.
(18) and (19) to solve for the heat generated by the system which is Table 9
84.3 kJ/mol of hydrogen fuel for the ADFC system. Energy performance of the overall system based on different biogas production scenarios
using the potential energy stored in the reformed fuel (H2 at 773 K and 1 atm).

2.6. Fuel utilization Case Power Output (kW) Electrical Power (kW) Power in Heat (kW)

To ensure reactions within the SOFC do not starve, excess fuel High 2400 1340 190
Low 860 480 67
should be supplied. Therefore, the expectation is that 80% of the fuel
Average 1380 770 110
will be consumed (utilized) and the 20% excess will be exhausted from

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A.J. Rayner et al. Renewable and Sustainable Energy Reviews (xxxx) xxxx–xxxx

3. Discussion far less than the modeled result of 4000 ppm. This suggests that a large
portion of H2S gas will be removed from the biogas through absorption
3.1. System performance into the effluent stream, however, an H2S stripping process is required
before the biogas can be used by an SOFC. A bio-trickling filter is one
Under the average case conditions it is predicted that the SOFC effective method of achieving this because of its minimal waste and
system will produce 774 kW of DC electricity and 107 kW of excess high H2S removal efficiency of up to 99% [37]. For industrial scale
heat. The SOFC system model obtained an energy conversion efficiency applications, sulphur compounds can be eliminated from the fuel
of 56%. The performance of the system agrees with the literature where stream via hydrogenation to H2S and subsequent absorption using
SOFCs have been shown to exceed 60% efficiency [12,14,33]. Papurello zinc oxide [33].
et al. recently verified the feasibility of a similar pilot scale system, Other contaminants such as siloxanes and halocarbons can also be
although with reduced efficiency due the method of fuel reforming and produced by the digestion process. Previous research has shown that
limitations of scale [16]. such contaminants, in particular siloxanes, can be detrimental to SOFC
System performance in the presented model can be improved performance in small concentrations [50]. Although outside of the
further by reducing the concentration of carbon dioxide in the fuel scope of the presented model, the sensitivity of SOFCs to fuel
stream. To accomplish this, a CO2 absorption process [49] may be used contaminants highlights the need to consider effective biogas cleaning
to refine the fuel before entering the SOFC system. Although incurring steps when coupling these two technologies.
larger capital and operational costs, this method will provide fuel with It has recently been demonstrated that an activated carbon bed
minimal levels of CO2 and in turn, better performance. could effectively clean biogas produced from a dry digestion process to
sustain operation of a pilot scale SOFC system. The biogas utilized in
3.2. Fuel processing of biogas for SOFCs those studies contained 52 ppm of H2S gas, of which 98% was removed
in the worst case, while other contaminants were removed to accep-
The biogas produced through anaerobic digestion will have fluctu- table levels for SOFC operation [16].
ating concentrations of methane, carbon dioxide, and contaminants.
From the literature it has been observed that SOFCs can be operated 3.3. Cogeneration opportunities
stably with CH4 as a fuel source [20,21,46]. The modeled biogas
composition was 62% CH4 and 32% CO2 [23,31,46]. CO2 concentra- The exhaust of the SOFC stacks will contain 20% of the fuel that was
tions of greater than 25% in the fuel stream are tolerable [46], not utilized in the SOFC. In addition, high quality heat is generated by
indicating that the modeled ratio of methane to carbon dioxide in the SOFC stacks. These two sources of energy can be utilized in a co-
biogas is acceptable for SOFC operation. However, lower concentra- generation system to increase the overall efficiency of the ADFC. There
tions of CO2 are desired to minimize the impact on system perfor- a number of different methods for recovering the heat and chemical
mance. energy exhausted by the SOFC. These include technologies such as
The concentration of CO2 within the produced biogas will dilute the steam or gas turbines and combined heat and power units. The
fuel, decreasing performance. The addition of carbon dioxide to electrical efficiencies and power generation potential of different power
methane fuels has been observed to increase the stable operating generation technologies are presented in Table 10.
range of SOFCs while suppressing coking. Additions of air into the fuel The 20% of fuel exhausted by the SOFC has 248 kW of chemical
stream have also been shown to increase the stability of cell operation potential power. If a CHP system with an electrical efficiency of 30% is
while suppressing coking but increase the risk of oxidation of the anode implemented [51], about 74 kW of additional electrical power can be
structure [23,46]. obtained. Based on these results, 850 kW of total electrical power can
At higher concentrations of CO2, dry internal reforming reactions be produced by the SOFC using the anaerobic digester biogas and a
can occur alongside steam reforming. These reactions are more CHP co-generation system in the average case. The overall efficiency of
endothermic and can result in thermal shock of the anode layer when the SOFC system with a CHP co-gen is 61%, which agrees with the
uncontrolled. This can cause the cell to crack, sacrificing gas sealing, literature [14,32,33,51].
electrical conductivity, mechanical strength, and overall functionality
[14,33,46]. For this reason, there must be an upper limit for the 3.4. Optimization and modeling
allowable CO2 content within the fuel stream unless the internal
reforming reactions are properly controlled. It should be highlighted The presented model demonstrates that although AD and SOFC
that lower concentrations of CO2 will result in better, more reliable, cell technologies can be feasibly coupled, they both involve numerous
performance and additions of steam can help promote the more design variables which must be optimized. Papurello et al’s pilot scale
desirable steam reforming reactions [47,48]. system [16] echoes the need to optimize ADFC technologies. Computer
There are a number of contaminants within the biogas drawn off of modeling and simulation methods for both anaerobic digestion [52],
anaerobic digestion processes. These contaminants include ammonia and fuel reforming for SOFC performance [24,25,53–56] have been
(NH3) and hydrogen sulphide (H2S) gases. The decomposition of presented in the literature, but simulations of the entire ADFC process
ammonia makes it a potential fuel source on its own and may enhance incorporating these models should be carried out in future optimiza-
the performance of SOFCs running on biogas [33]. tion work. Further evaluation of economics [57], scalability, and
Hydrogen sulphide is a poisonous gas that poses a threat to the inclusion of better waste data and digestion models could all improve
functionality of SOFCs. The H2S content in biogas is typically in the the presented model further.
200 ppm range however SOFCs can only tolerate H2S concentrations
within the ppb range. The results of an SOFC exposure to 1 ppm of H2S Table 10
vary in the literature [14,20,33]. For this reason, it is recommended Comparison of different power generation technologies in the context of ADFC system
co-generation.
that H2S levels be constrained to 100 ppb within the processed biogas
fuel stream. Technology Electrical Efficiency (%) Power Gen. in ADFC (kW) Source
H2S is readily absorbed into water. Since there is 60–80% moisture
content within the digester, a large portion of the H2S gas will be Steam Turbine 7 17 [51,66]
Gas Turbine 25 62 [51,67]
absorbed into the slurry. The effluent stream will then carry this
CHP 30 74 [51]
absorbed portion of the produced H2S. The average H2S content in Sterling Cycle 40 99 [51]
biogas produced by Ontario, Canada, WWTPs is 78 ppm [12], which is

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