i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 5 0 ( 2 0 2 4 ) 2 1 1 e2 2 5

Available online at www.sciencedirect.com

ScienceDirect

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

Model development for biogas generation,

purification and hydrogen production via steam
methane reforming

R. Tamilselvan, A Immanuel Selwynraj*

School of Mechanical Engineering, Vellore Institute of Technology, Vellore, India

highlights graphical abstract

Biogas production, purification,

and hydrogen production model
developed.

Biogas potential of biomasses pre-
dicted from ultimate and proxi-
mate values.

The model was validated with ex-
periments, theory, and simula-
tions models.

article info abstract

Article history: Biogas, a renewable energy source produced by the anaerobic digestion of organic matter,
Received 23 May 2023 can reduce greenhouse gas emissions. The purification and hydrogen conversion of biogas
Received in revised form enhance its versatility as an energy carrier and reduce dependency on fossil fuels. This
25 July 2023 sustainable process fosters a cleaner future. In this study, simulation models were used to
Accepted 7 August 2023 optimize the process conditions and assess the technical feasibility of the biogas-to-
Available online 23 August 2023 hydrogen production. In addition to the anaerobic digestion process, simulation models
were also developed for biogas purification via water scrubbing and hydrogen production
Keywords: via steam methane reforming (SMR) using Aspen Plus simulation software. Simulation
Aspen plus results demonstrated that the maximum methane yield of 520 mL/gVS was achieved at an
Anaerobic digestion organic loading rate of 20 g/L, while the minimum yield of 230 mL/gVS was observed below
Bio-methane 10 g/L. Optimal anaerobic digestion temperature for maximum gas yield (548 mL/gVS) was
Hydrogen found to be 30  C, with a decrease in biogas production above 40  C. In the water scrubbing
Steam methane reforming model, maximum CO2 absorption occurred at 15 bar pressure, whereas reducing the
pressure to 5 bar significantly lowered the absorption rate. The SMR model yielded the
highest hydrogen production rate of 10.15 kg/h using purified methane (99%) as feed, but
the methane content was affected by the biogas composition.
© 2023 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

* Corresponding author.
E-mail addresses: immanuel.selwynraj@vit.ac.in, aisraj1979@gmail.com (A.I. Selwynraj).
https://doi.org/10.1016/j.ijhydene.2023.08.096
0360-3199/© 2023 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
212 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 5 0 ( 2 0 2 4 ) 2 1 1 e2 2 5
1. Introduction
The index of energy consumption measures a country's in-
dustrial economy and people's wealth. Because of rising en-
ergy consumption and demand in the household and
industrial sectors, renewable energy supply is a crucial pri-
ority in the future world. Currently, over 80% of the world's
energy needs are met by fossil fuels. In developed and
emerging nations, the annual growth rates of energy con-
sumption are 1% and 5%, respectively [1]. Crude price fluctu-
ations put pressure on the global economy. Hence, the nations
are accelerating their efforts to explore clean energy sources
to meet the Sustainable Development Goals (SDGs) of the
United Nations (UN) [2,3]. India has set a Net Zero emissions
target for 2070, driven by the ongoing expansion of its econ-
omy which has led to an increasing demand for resources,
notably energy. India currently purchases over 40% of its pri-
mary energy requirements, resulting in an expenditure
exceeding $90 billion annually [4]. Therefore, India intends to
raise the goals for renewable energy to approximately 175 and
275 GW (GW) by 2022 and 2027 respectively. The use of biogas,
a renewable fuel, has increased significantly in recent years.
In 2012, global biogas usage was 14.5 GW. By 2022, this figure
had more than doubled to 29.5 GW. This increase is due in part
to the growing demand for renewable energy sources and the
desire to reduce greenhouse gas emissions [5]. Biogas is a
sustainable energy source that usually consists of approxi-
mately 55% vol methane and 45% vol carbon dioxide. It has
multiple applications, including the generation of heat and
electricity. Additionally, it can be purified and converted into
compressed natural gas (CNG) and hydrogen (H2) [6].
The AD entails four steps of biochemical processes, namely
hydrolysis (polymers to monomers), acidogenesis (CO2, H2 and
short-chain fatty acids), acetogenesis (CO2, H2, and acetic acid)
and methanogenesis (CH4 and CO2). The efficiency of AD relies
on the operational aspects, including reactor temperature,
rate of organic loading, blending, solid retention period, sub-
strate type, reactor design, pH and environmental conditions.
Models serve as valuable tools for enhancing understanding of
bioprocesses, exploring their responses to parameter varia-
tions, and predicting overall performance. Process simulation
models are highly valued by industries and researchers due to
their ability to provide accurate predictions and conduct
sensitivity analyses more efficiently and cost-effectively
compared to real plant scenarios. Aspen Plus® is a robust
process simulator with integrated functionality for steady-
state and dynamic-process simulations, including AD. It of-
fers equipment-design tools, rigorous property methods and
thermodynamic calculations [7].
The majority of kinetic-based simulation models rely on the
well-known AD Model No. 1 (ADM1), created by a team of re-
searchers with funding from the International Water Associa-
tion (IWA) and the AD mechanism is grouped into
physiochemical and biochemical reactions [8]. Several in-
vestigators attempted to simulate the AD system by incorpo-
rating the complex kinetics and reaction coefficients from
ADM1. Compared to other process simulation tools, Aspen Plus
offers robust frameworks for simulation and sensitivity anal-
ysis, conceptual design, optimization and economic
assessments. Despite these benefits, minimal research has
been done on creating process simulations for AD in the Aspen
context [9]. Rajendran et al. (2014) Created a process simulation
model (PSM) based on the ADM1 in Aspen plus environment to
estimate the biogas generation from any feedstock at known
process parameters [10]. The Non-Random Two-Liquid (NRTL)
property method was chosen for PSM and a series of 46
biochemical reactions was used, which included a volume of a
digester, hydraulic retention time, pH, inhibitions and kinetics.
The hydrolysis process was based on the reaction's extent,
whereas the acidogenic, acetogenic and methanogenic pro-
cesses were based on kinetics. The variation in biomethane
production between the Aspen simulation and experimental
results was 0.3% (minimum) and 12.4%, according to their
findings (maximum). Aguilar et al. (2017) developed the model
to study the potential of biogas generation using anaerobic co-
digestion (ACOD) of vegetable market wastes (VW) and primary
sludge (PS) under 35  C and 55  C at different mixing ratios
(2:1,1:1,1:2) with volatile solid (VS) concentration of 89.6%,
84.53% and 86.99%, respectively. The hydraulic retention time
(HRT) was fixed at 21 days and an organic loading rate (OLR) of
3.34, 2.49 and 2.08 gVS/day were used. Their results indicated
that the VW: PS ratio of 1:2 at 35  C produces 25% higher
methane content than the same ratio at 55  C. However, this
study could not explain why methane content was lower under
thermophilic (55  C) than under mesophilic (35  C) circum-
stances [11]. Batstone and Keller (2003) claimed that the
methane predictions are accurate enough, though the ADM1
did not represent catalyzed reactions by microorganisms [8].
The ADM1 requires numerous data (compositions of cel-
lulose, hemicellulose and lignin) to define the fractional con-
version of organic matters [10]. In addition, 46 chemical
reactions with complex kinetics are considered for the
degradation of substrates by microorganisms. To address this
issue, a process simulation model for anaerobic digestion was
developed, based on stoichiometry equations. The model
utilizes the elemental composition of the biomass, thereby
eliminating the need for complicated and detailed informa-
tion on its composition. This approach ensures the reliability
and accessibility of the model, especially for researchers and
practitioners who are looking for a cost-effective and efficient
solution for simulating AD. In addition, a simulation model for
biogas purification was developed, utilizing pressurized water
as a fundamental technique for CO2 removal. This process
plays a crucial role in enhancing the purity of biogas,
rendering it suitable for use as a fuel. Biogas, a renewable fuel
with chemical potential, can be converted into syngas and
used to produce hydrogen after a clean-up process [12]. This
advancement in fuel cell technology and spark ignition en-
gines opens up possibilities for applications in power gener-
ation, transportation, and industrial processes [13,14].
Regarding it, a simulation model for hydrogen production
from methane was created, employing steam methane
reforming. These simulation models for anaerobic digestion,
biogas purification, and hydrogen production have the po-
tential to contribute significantly to the advancement of sus-
tainable and efficient biogas production processes. The
practical implications of this research are significant. Relying
on readily available ultimate analysis data, the approach en-
ables swift evaluations of biogas yield potential for diverse
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 5 0 ( 2 0 2 4 ) 2 1 1 e2 2 5
biomass sources. This aids in selecting and optimizing feed-
stocks for biogas plants, facilitating efficient and informed
decision-making. Additionally, the model's simplified nature
broadens possibilities for optimizing processes, designing
systems, and making informed choices in the realm of biogas
production. The novelty of stoichiometry-based model is uti-
lizing ultimate analysis values, represents a pioneering
advancement in the field of biogas yield prediction. This
ground-breaking approach holds tremendous promise for the
biogas industry, enabling more empowers researchers and
practitioners to make informed choices and contributing to
the sustainable utilization of biomass resources for renewable
energy production.
1.1. Proximate and ultimate analysis of biomass
The composition of ash, volatile solids (VS) and moisture (M) is
calculated using proximity analysis (PA) with ASTM E1755-01,
ASTM E872-82, and ASTM D4442-16 standards, respectively
[15e17]. The FC content in the biomass is calculated using
Equation (1).
Fixed carbon ¼ 100- (%M biomass þ %ash biomass þ
% VS biomass)
The elemental composition of organic matter impacts the
energy output and effective usage of biomass resources for
biofuel production. The ultimate analysis (UA) is used to
calculate the elemental composition of biomasses, including
Carbon (C), Hydrogen (H2), Oxygen (O2), Chlorine (Cl2), Sulphur
(S) and Nitrogen (N2). However, the UA needs very costly in-
struments and experts with extensive training. The PA needs
common laboratory tools and may be carried out by any
qualified technician. The correlations with an absolute error
of 3.21% (C), 4.79% (H), and 3.40% (N) and a bias error of 0.21%
(C), 0.15% (H), and 0.41% (N) proved to be the most accurate in
determining the elemental composition of any biomass
resource via proximity analysis [18]. The correlations are
represented in equations (2)e(4), where C, H, O, VS and FC are
represented in mass % on a dry basis.
Carbon ¼ 0.634 FC þ 0.455 VS (wt. %)
Hydrogen ¼ 0.052 FC þ 0.062 VS (wt. %)
Oxygen ¼ 0.304 FC þ 0.476 VS (wt. %)
This correlation could be extremely useful in situations
where much more expensive and sophisticated experimental
setups are not available to find the elemental composition.
However, a prior understanding of N and S is required for the
most effective and accurate forecast.
2. Materials and methods
2.1. Feed stock preparation and characterization
Dried rice straw (RS) and fresh cow dung were collected from a
local farm, and the RS was washed in running water and
213
ground into small pieces (0.5 mm) using a 2 hp electric grinder.
Then, the RS was dried at 80  C for 4 h in an oven to remove
excess moisture. The elemental analysis of RS was performed
using a PerkinElmer analyzer (2400 CHNS/O Series). From the
elemental analysis, it was observed that in RS, the composi-
tion was C: 38.2%, O: 51.5%, H: 7.94%, S: 0.92%, and N: 0.72%.
For cow dung, the composition was found to be C: 34.4%, O:
57.14%, H: 5.2%, S: 6.04%, and N:1.7%, based on the elemental
analysis. Consequently, the proximate analysis (PA) of RS
showed Moisture (M): 10.3%, volatile matter (VS): 60.85%, fixed
carbon (FC): 21.2%, and ash: 6.1%. On the other hand, for cow
dung, the PA revealed M: 6.45%, VS: 55.4%, FC: 13.4%, and ash:
26.3% [16]. Rice straw (RS) on its own has a high carbon-to-
nitrogen (C/N) ratio of 53, making it unsuitable for anaerobic
digestion. Methanogenic bacteria need a sufficient amount of
nitrogen to produce biogas effectively. However, when RS is
combined with cow dung, the nitrogen content of the mixture
increases, allowing the bacteria to function properly and
produce biogas. Additionally, the different degradation rates
of the two materials prevent overloading of the biogas digester
[19,20].
2.2. Anaerobic digestion process
(1)
The rice straw and cow dung mixture is placed in three 2L
airtight customized anaerobic batch reactors, with a hydraulic
retention time set to be 12 days at atmospheric temperature
(32  C±2  C). To achieve organic loadings of 8 g/L, 15 g/L, and
18 g/L in the digesters, the cow dung and rice straw are mixed
in the proportions of CD:RS at 10.9:7.1, 22.2:12.8, and
33.4:16.6 g, respectively. The biogas produced from the
digester is measured using the water displacement method.
Each day, the pH values are monitored, and NaOH (0.01 N) and
HCl (0.01 N) solutions are added to the digester to control the
desired pH level (6e7.5) [21]. The digesters are agitated for
15 min per day using a mechanical agitator to ensure proper
mixing of substrates and to prevent the accumulation of
organic content under the digester.
2.3. Description of the process simulation model
(2) The proposed simulation model is divided into three process
flowsheets: (i) Biogas generation from biomass in AD, (ii) Up-
(3) grade of the biogas into purified methane (Water scrubbing),
(iii) Hydrogen production from biogas through steam methane
(4) reforming.
2.3.1. Anaerobic digestion
The AD is a biological decomposition process to produce
biogas in an oxygen-free environment by a variety of micro-
organisms. The biochemical reaction involved in the AD pro-
cess is illustrated in Fig. 1. AD has four sequential stages:
hydrolysis, acidogenesis, acetogenesis and methanogenesis,
where the macromolecular biomass such as carbohydrates,
protein and lipids are split into monomers at the hydrolysis
step. Therefore, carbohydrates are consequently converted
into simple sugars; proteins break down into amino acids and
lipids into long-chain fatty acids [22]. The bacterial group
involved in hydrolysis releases exoenzyme to catalyze the
degradation process.
214 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 5 0 ( 2 0 2 4 ) 2 1 1 e2 2 5

Fig. 1 e Bio-Chemical reactions involved in AD.

2.3.2. Water scrubbing CH4þH2O / 3H2þCO; DHo ¼ 206 kJ/mol (5)

The technique of removing CO2 and H2S from biogas streams
is crucial for the sequestration of greenhouse gas emissions. A
CH4 content of more than 95% is often necessary for gas grid or
vehicle use. To accomplish this, a significant portion of CO2
emissions from biogas must be reduced. Cryogenic, mem-
brane separation, pressure swing absorption (PSA) and
chemical absorption approaches are currently used to pro-
duce purified methane. Due to its effectiveness in the removal
rate of CO2 from biogas and its environmentally friendly
process, the water scrubbing method is adopted [23]. In the
water scrubbing (WS) process, CO2 and H2S present in the
biogas will be physically adsorbed by highly pressurized water
since these gases have a high rate of solubility than CH4 in
water. The resulting scrubbing will take place due to contra-
flow. As a result, the WS approach requires less water [24].
Since the SMR is endothermic, a constant heat source is
required. The rate of H2 generation is further boosted by the
water gas shift (WGS) process, where the portion of CO com-
bines with water to form H2 and CO2 (Equation (6)) [25].
CO þ H2O / CO2 þ H2; DHo ¼ 41.1 kJ/mol (6)
2.3.4. Theoretical prediction of biogas yield
The Buswell's equation (7) is used to calculate the biogas po-
tential of a substrate and CH4 yield from a fully decomposable
organic feedstock with their chemical (CaHbOcNd) composition
[26].

4a  b  2c þ 3d 4a þ b  2c  3d 4a  b þ 2c þ 3d
Ca Hb Oc Nd þ H2 O / CH4 þ CO2 þ dNH3 (7)
4 8 8

2.3.3. Steam methane reforming

Methane reacts with pressurized steam to create H2 enriched
syngas. To break down the long-chain (H and C atoms) hy-
drocarbons into CH4 and syngas, the feedstock must be pre-
treated to desulfurize and pre-reformed with steam. CH4 is
transformed into H2 and CO (equation (5)) in the primary
reactor.
The requirements of organic material for cell development
and metabolic functions are not taken into account in this
equation. The total volume of biogas generated from a mole of
degradable organic material is the sum of methane and car-
bon dioxide. Methane yield per gram of organic material is %
of CH4 in biogas at vol/vol or mole/mole (equation (8)).
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 5 0 ( 2 0 2 4 ) 2 1 1 e2 2 5 215

3. N2 þ 3H2 / 2 NH3
4aþb2c3d
 22:4 4. C þ O2 / CO2
CH4 yield ¼ 8
(8) 5. C þ 2H2 / CH4
12a þ b þ 16c þ 14d
6. 2C þ 2H2O / CH4 þ CO2

3. Simulation results and discussion
3.1. Process simulation model of AD
The PSM of AD is shown in Fig. 2. The AD is modelled by
means of two distinct reactors, namely the RYIELD reactor (B1)
and RSTOIC (B2). The B1 block allows the substrate to be
broken down into its constituent elements, whereas block B2
transforms the elemental components into the different
gaseous compounds found in the biogas. The input parame-
ters of these blocks and their roles in plant AD are present in
Table 1. Since the plant AD handles solids, the SOLIDS prop-
erty method is used to create the PSM. The conventional and
non-conventional (C) stream classes are used in the model.
The inlet feedstock is considered an NC stream because the
biomass's physical properties are not present in the aspen
standard library. Other elements such as C, H2, N2, CH4, CO,
H2O, S and NH3 are represented as conventional streams.
Furthermore, fixed carbon (FC) and ash content in the biomass
are also defined as NC streams.
The present PSM does not include biological activities that
are known to occur during AD when compared to ADM1 used
by Ref. [10]. However, the function of the yield reactor and the
hydrolysis stage is similar. The RYIELD (B1) reactor de-
composes the complex physical structure of biomass, which
ASPEN defines as NC, into conventional elemental compo-
nents (C, H, and O) and NC components (FC and Ash). The
stoichiometric reaction of volatile matter is defined in the
RSTOIC reactor to produce biogas. Non-reacted ash and FC
content, along with excessive water leave the reactor as
digestate. The AD modelling is made easier by the following
stoichiometric reactions.
1. 2H2 þ O2 / 2H2O
2. S þ H2 / H2S
Based on the feed material, the reaction's limiting reactant
varies. The limiting reactants of reactions 2,3 and 6 are S, N2
and C, respectively. The limiting reactant for reaction 1 is O2
when the hydrogen and oxygen mass ratio (H2/O2) is greater
than 0.25 because of low degradability. Generally, forest resi-
dues (wood) fall under this category. On the other hand, sub-
strates with an H2/O2 ratio of less than 0.25 often use H2 as a
limiting reactant. Since ASPEN is insensitive to atom
balancing, careful consideration of atom balance and mass
balance was made when making yield computations for the
RYIELD reactor. The data from the UA are used to determine
the yield distribution. The following formulas are used to
determine the yield distribution, where X-is the ultimate
analysis value and m-mass.
Mass of H2 ¼ (1 e XMoisture)*XH*mFeed
Mass of O2 ¼ (1 e XMoisture)*XO*mFeed
Mass N2 ¼ (1 e XMoisture)*XN*mFeed
Mass of H2O ¼ XMoisture*mFeed
Mass of S ¼ (1 e XMoisture)*XS*mFeed
Mass of C ¼ (1 e XMoisture)*XC*mFeed
Mass of ASH ¼ (1 e XMoisture)*XASH*mFeed
3.1.1. Model validation
The volume of methane generated from different biodegrad-
able waste is validated against the theoretical approaches and
different experimental results. Prediction methods tend to

Fig. 2 e Flow sheet of Anaerobic Digestion.

216 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 5 0 ( 2 0 2 4 ) 2 1 1 e2 2 5
Table 1 e Components and their functions in the PSM flow sheet.
Block Name Pressure (bar) & Temperature (o C)
B1 Decomposition 1 & 25
B2 Anaerobic Digester 1 & 25
B3 Splitter 1 & 25
B4 Flash column 1 & 37
B5 Separator 1 & 37
B6 Mixer 1 & 25
underestimate or overestimate the amount of biogas gener-
ated from a substrate, assuming that the complete trans-
formation of volatile materials results in theoretical biogas.
Although the precise methane yield value is nearly impossible
to predict because AD involves complex biochemical and
biological processes. The main objective of the present PSM is
to prevent a significant overestimation of the methane yield.
Table 2 lists the various organic materials and managed
data scenarios that were used to create PSM to compute the
discrepancies between other experimental data and PSM.
Following are descriptions of each case:
CASE I: The substrate used was cow dung, and the organic
loading rate was 0.33 L/day. The produced biogas yield was
353.5 L/kgvs/day [27]. The UA analysis of the substrates was
based on Fajobi et al. (2022) [28].
CASE II: The substrate used was municipal solid waste
(MSW), and the organic loading rate was 3gvs/L/day. The pro-
duced biogas yield was 0.54 m3/kgvs/day [29]. The UA analysis
of the substrates was based on Salwa Khamis et al. (2019) [30].
CASE III: The substrate used was pig manure (PM) and the
organic loading rate was 230.4gvs/day. The produced biogas
yield was 0.269 m3/kgvs/day [31]. The UA analysis of the sub-
strates was based on Smith, Ekpo, and Ross (2020) [32].
CASE 1V: Anaerobic co-digestion, the substrates were pig
manure (PM) and rice straw (RS). The organic loading rate was
100g/day (53%-PM and 47%-RS). The produced biogas yield
was 342.35 mL/gvs [33].
Table 2 presents the validation of different case studies
with experimental and theoretical results from Rajendran
et al. (2014) Aspen PSM. The lowest and highest differences
found using the various PSM validations were 0.32% for case 3
and 6.6% for case 4. In case I, the current PSM predicts biogas
production of 0.348 m3/kgvs/day, which is much closer to the
experimental results Fajobi et al. (2022) when compared to the
PSM model developed by Rajendran et al. (2014). Also, the PSM
doesn't consider how much organic matter is lost because
microorganisms consume it.
3.2. Sensitivity analysis
Fig. 3 shows the comparison of bio-methane potential (BMP) of
experimental, theoretical and ADM1-based PSM with the
present model. The present model exhibits good consistency
with experimental results. The chemical composition of the
Phase Function
Vapor-liquid Decompose and separate the elemental composition
from biomass (C,H,O,N,S,FC and Ash)
Vapor-liquid Convert decomposed products into biogas and
digestate
Vapor-liquid Separate the gaseous components and water content
present in the gas.
Vapor-liquid Remove the moisture content in the biogas.
Vapor-liquid Separate the H2S from the biogas for reducing the
toxicity of gas.
Liquid Mix the excess water from the RSTOIC reactor and
moisture from the flash column separator to make
digestate
feed and the extent of the stoichiometric reaction are the two
most important aspects of PSM that influence simulated re-
sults. However, the elemental composition of the substrates
cannot be modified when using a single-feed AD system.
Nonetheless, the selection of substrates for anaerobic co-
digestion for biogas enhancement can be based on the ratio
of carbon to nitrogen (C: N). The optimum C: N ratio for AD is
between 20:1 and 30:1 [34]. The inclusion of carbon-rich co-
digestion materials in animal manure could enhance the C: N
ratio and methane generation. For instance, the C: N ratio of
swine (6:1) and dairy manures (9:1) can be increased by
incorporating food processing leftovers or crop residues such
as rice and oat straw (C: N ratio 48: 1).
In this study, anaerobic co-digestion of pig manure and rice
straw were simulated using PA and UA analysis (case 4). The
utilization of pig manure as a feedstock material in anaerobic
digestion (AD) technology has seen significant development.
Previous studies have indicated that the mesophilic condi-
tioned AD process of pig manure can achieve a biogas pro-
duction rate of up to 5 m3/(m3$d). Nevertheless, pig manure
possesses distinctive attributes such as elevated nitrogen (N)
content, lower carbon (C) content, and an imbalanced C/N
ratio, which hinder its potential as a valuable feed source for
biogas production [33,35,36]. When pig manure is used as the
sole substrate for AD, it can lead to ammonia suppression,
which negatively affects biogas production and reduces
decomposition efficiency. However, the concept of anaerobic
co-digestion has recently emerged as a promising solution to
improve the efficiency and effectiveness of AD. On the other
hand, rice straw contains a significant amount of carbohy-
drates and has a high carbon-to-nitrogen (C/N) ratio, which
can also hinder the growth and metabolism of methanogens
responsible for biogas production due to acid accumulation.
Therefore, by adjusting the quantities of straw and pig
manure during co-fermentation, an appropriate C/N ratio can
be achieved [37,38]. Moreover, in India, rice production yields
about 110 million metric tons annually, generating approxi-
mately 170 million metric tons of rice straw [39]. With their
elemental composition, the C:N ratio is attained at about 28:1
and the rate of methane yield was 471.5 mL/gvs, when the
molar fraction of CH4 and CO2 is about 54% and 39%, respec-
tively. Dennehy et al. (2018) also investigated the effect of co-
digestion with pig manure and food waste in AD and found
that the maximum methane yield was 333 mL/gvs. The
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 5 0 ( 2 0 2 4 ) 2 1 1 e2 2 5 217

% of differencea
1.4%
5.4%
0.3%
6.6%
Present study (PS) results
348.369 L/kgvs/day

0.270 m3/kgvs/day
0.57 m3/kgvs/day

320.25 mL/gvs

Fig. 3 e Comparison of simulation BMP with experimental

[10] PSM results

0.473 m3/kgvs/day
0.268 m3/kgvs/day
365.83L/kgvs/day

and theoretical BMP values.

e

difference between case 4 and the experimental result was

34% [36] Therefore, it is understood that dairy or pig manure
Theoretical yield
393.4783L/kgvs/day

0.450 m3/kgvs/day
0.53 m3/kgvs/day

co-digested with straw materials containing a high C:N ratio

could increase the BMP in AD. The change in the extent of the
471.5 mL/gvs

stoichiometric reactions also played an important role in PSM.

Hence, a sensitivity study was carried out by varying the re-
action extent in the order of 1, 0.8, 0.6 and 0.5 for all the cases.
Fig. 4 shows the sensitivity analysis of PSM and the results
revealed that 1.5%e5.25% CH4 yield enhancement is attained
Experimental results

while changing the reaction extent to 0.6. However, when the

0.269 m3/kgvs/day
0.54 m3/kgvs/day
353.5 L/kgvs/day

rate of extent is less than or equal to 0.5, the rate of CH4 yield
342.35 mL/gvs

was gradually reduced and the concentration of CO2 increased

significantly. Therefore, PSM reaction extent should be 0.6e1
for better bioconversion. Nonetheless, the simulation model
includes the kinetics of biodegradability and the rate of
catabolism by microbes may change their reaction extent
below 0.5 [40].
Loading rate

230.4 gvs/day
3gvs/L/day
0.33 L/day

100 g/day

Difference between experimental and current PSM results.

3.2.1. Influence of organic loading rate on biogas production

The process simulation model was configured to run with
different volumes of anaerobic reactors, namely 1L, 3L, and 5L.
Each reactor was set to have an organic loading rate (OLR) of
5g, 10g, and 20g, respectively. In Case I (1 L volume), the
Municipal solid waste (MSW)

highest gas production of 476 mL/gVS is achieved with an OLR

Table 2 e Model validation of PSM.

of 10g. The smaller volume facilitates better mixing and

Substrate

improved mass transfer, enhancing substrate conversion and

promoting higher gas production. The shorter retention time
Pig manure (PM)
PM þ Rice straw

in the reactor allows for faster organic matter degradation,

Cow dung

resulting in increased biogas generation. In Case II (3 L vol-

ume), the maximum yield of 520 mL/gVS is obtained with an
OLR of 20g. The larger volume provides increased substrate
availability, enabling enhanced gas production. The longer
retention time in the reactor allows for more thorough organic
Case study

matter degradation, leading to higher biogas yields. In Case III

(5 L volume), the maximum gas yield of 480 mL/gVS is
observed at an OLR of 10g. The larger volume offers increased
IV
III
II

a
I

substrate availability and longer retention time, improving

218 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 5 0 ( 2 0 2 4 ) 2 1 1 e2 2 5
Fig. 4 e Sensitivity analysis of PSM.
degradation and gas production. However, the OLR of 10g
maintains an optimal balance between substrate supply and
system efficiency, ensuring efficient substrate utilization and
promoting higher gas yields. These factors, including volume,
retention time, substrate availability, and organic loading
rate, play crucial roles in influencing gas production and
optimizing biogas systems. According to the experimental
findings of Zhang et al. [41], it was observed that biogas pro-
duction is considerably low when the OLR falls below 10 g/L.
Additionally, the cumulative biogas production rate at an OLR
of 25 g/L was found to be significantly lower compared to an
OLR of 20 g/L. Likewise, the simulation model demonstrated
that the highest biogas yield was achieved at an OLR of 20 g/L,
while the minimum gas yield was observed when the OLR was
maintained below 10 g/L. The results obtained from the Aspen
simulation closely align with the experimental findings,
revealing a high degree of agreement between the two. An
illustration of effect of OLR on gas yield shown in Fig. 8S (a)
(Supplementary material).
3.2.2. Effect of temperature on biogas production
In the study of impact of temperature on biogas production
using a simulation model, a 3 L volume with an organic loading
rate of 20 g was examined at different temperature levels: 25  C,
30  C, 40  C, and 50  C, resulting in methane production mea-
surements of 520 mL/gVS, 548 mL/gVS, 510 mL/gVS, and 515
mL/gVS, respectively (30  C > 25  C > 40  C > 50  C). Increasing
the temperature from 25  C to 30  C led to higher biogas pro-
duction, likely due to temperature-driven changes in reaction
rates and increased molecular collision frequency. However,
further increasing the temperature from 30  C to 40  C resulted
in a decrease in biogas production, possibly influenced by fac-
tors such as vapor pressure and reduced gas solubility.
Comparing temperatures of 40  C and 50  C showed a slight
increase in biogas production, potentially related to the solu-
bility characteristics of gas components. Controlling tempera-
ture within an optimal range is critical for maximizing biogas
production efficiency in the simulation model, as factors such
as reaction rates and gas solubility can impact biogas
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 5 0 ( 2 0 2 4 ) 2 1 1 e2 2 5
generation. Similarly, Membere et al. [42] conducted a study on
the influence of temperature on biogas production using four
temperature levels: 25  C, 35  C, 45  C, and 55  C. The results
showed that the highest gas yield of 639 mL/gVS was achieved
at 35  C, while the lowest gas yield of 501 mL/gVS was observed
at 55  C. This study confirmed that temperatures within the
range of 30e35  C enhance biogas production compared to
higher or lower temperatures. The rate of a chemical reaction is
determined by its activation energy, while temperature in-
fluences the average kinetic energy of molecules. Higher tem-
peratures increase the reaction rate as more molecules gain
sufficient energy to react. The equilibrium composition of a
reaction depends on its Gibbs free energy, which decreases
with rising temperature, shifting the equilibrium towards
products with lower Gibbs free energy. In biogas production,
increasing temperature favors methane over carbon dioxide,
leading to a higher methane content in the biogas [43]. An
illustration of effect of temperature on gas yield shown in
Fig. 8S (b) (Supplementary material).
3.3. Water scrubbing
The water scrubbing is an absorption process since CO2 has a
high solubility in pressurized water (10e25 bar) than CH4 [44].
The flow sheet of biogas purification by pressurized water is
shown in Fig. 5. This study examines the absorbance of CO2 in
water and the enhancement of the absorbance process using
ASPEN plus. The process chemistry behind the water scrub-
bing process was described in equations (9) and (10).
CO2 þ H2O / H2CO3
H2S þ H2O / H2SO3
equation (9) describes the reaction of carbon dioxide with
water to form carbonic acid. Carbonic acid is a weak acid that
can dissociate into bicarbonate and hydrogen ions, which can
further react with water to form more bicarbonate and
Fig. 5 e Flowsheet of biogas purification by water scrubbing method.
219
hydronium ions. This reaction is important in the context of
biogas purification because carbon dioxide is a common im-
purity in biogas and must be removed to increase the energy
content of the gas. equation (10) shows the reaction of
hydrogen sulfide with water to form sulfurous acid. Sulfurous
acid is another weak acid that can dissociate into bisulfite and
hydrogen ions, which can further react with water to form
more bisulfite and hydronium ions. Like carbon dioxide,
hydrogen sulfide is a common impurity in biogas that must be
removed to prevent corrosion and fouling of equipment and to
reduce harmful emissions.
As the majority of the components employed in this
simulation environment are a polar mixture of pressure up to
15 bars, the NRTL thermodynamic model is chosen that in-
fluence the results. The major component blocks employed in
the simulation process and inlet feeds are described as
follows:
Pump (B1): Used to increase the pressure of water up to
15 bar for better contra flow between water and biogas. The
discharge pressure from block B1 is 15 bar and pump effi-
ciency is assumed as 75%.
Multistage compressor (B2): The three-stage compressor with
an intercooler is employed to increase the biogas pressure to
15 bar from the atmospheric condition. The temperature of
the outlet stream from block B2 is set to be 50  C.
CO2 separation column (B3): This block allows biogas and
pressurized water in contraflow to dissolve CO2. This is a
two-stage process, where bioCH4 is produced in stage 1 (top)
and regenerated water in stage 2 (bottom). The calculation
mode is rate-based and the internal structure of a column
(9) (Dimensions: 7 m height and 0.35 m diameter) is packed
type.
(10)
3.3.1. Inlet streams
Biogas (50% CH4þ 50% CO2) at 1 bar and 25  C and the feed rate
is 1 cum/hr (case IV).
Water supply: 1 bar and 25  C and the feed rate (0.25e0.75
cum/hr)
220 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 5 0 ( 2 0 2 4 ) 2 1 1 e2 2 5

3.3.2. Sensitivity analysis physical and chemical adsorption techniques could enhance
In order to attain the maximum CO2 absorbance, the water biogas purification [45]. They suggested that the calcium hy-
pressure (3e30 bar), feed rate (0.25e0.75 cum/hr) and biogas droxide (Ca (OH)2) solution could be the best option for
composition are varied. According to the simulation results, removing CO2 from biogas. However, using chemical agents is
while maintaining the biogas composition of 50:50 (CH4: CO2) not economically feasible, and the byproducts of these pro-
and water pressure at 15 bar at 0.50 cum/hr, the rate of CO2 cesses may be harmful to the environment.
absorption is about 99%. Furthermore, for the same inlet In addition, the biogas composition with higher methane
condition, by varying the pressure to 10 bar and 5 bars, the rate concentration (65% CH4 and 35% CO2) showed better CO2 ab-
of CO2 absorption was 98 and 89%, respectively (Fig. 6(a)). sorption in water scrubbing even at low pressure (3 bar)
To find the influence of water addition in the process, the (Fig. 6(d)). Nowadays, modern pretreatment techniques are
flow rate of water increased by about 0.75cum/hr for the same employed to produce biogas with higher methane concen-
biogas composition and flow rate. There is no significant tration through AD [46,47]. All the process stream specifica-
improvement in CO2 absorption by increasing the flow rate of tions and output results are shown in Table 3.
water from 0.5 cum/hr (Fig. 6(b)). Nonetheless, there is a 2%
decrement in absorption when the water flow rate is reduced 3.3.3. Model validation
to 0.25cum/hr. The simulation model is validated with experimental data
While varying the biogas composition as 30% CH4 and 70% from a pilot-scale water scrubbing plant, located at “The
CO2 at 15 bar pressure, only 40e50% of CO2 is absorbed, and a Centre for Rural Development and Technology”, IIT, Delhi [23].
change in pressure does not result in a significant improve- The pilot scale plant was operated with the following pa-
ment. It is concluded that the biogas containing a low con- rameters: Column height: 3 m, diameter: 0.15 m, biogas flow
centration of (<50%) CH4 cannot be effectively purified in the rate: 20 m3/h, solvent flowrate: 4.4 m3/h, Biogas feed: 60% CH4
water scrubbing method (Fig. 6(c)). For such conditions, the and 40% CO2 and pressure:10 bar. The output of the stream

Fig. 6 e Variation in CO2 absorption based on the composition of biogas and pressure change, (a) CH4/CO2/H2O: 0.474/0.474/
499 kg/h; (b) CH4/CO2/H2O: 0.474/0.474/748.5 kg/h; (c) CH4/CO2/H2O: 0.418/0.627/0.249 kg/h; (d) CH4/CO2/H2O: 0.540/0.291/
0.748.5 kg/h.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 5 0 ( 2 0 2 4 ) 2 1 1 e2 2 5 221

Table 3 e Process stream specifications of water scrubbing.

S.No Pressure Biogas composition (%) Mass flows (Inlet) Mass fraction (Outlet) Mole fraction (Outlet) % of CO2
(bar) (kg/hr) absorption
CH4 CO2 CH4 CO2 H2O CH4 CO2 H2O CH4 CO2 H2O
1 15 0.50 0.50 0.474 0.474 499 0.979 0.017 0.002 0.99 0.006 0.002 99
2 10 0.50 0.50 0.474 0.474 499 0.961 0.035 0.003 0.98 0.013 0.003 98
3 5 0.50 0.50 0.474 0.474 499 0.88 0.10 0.003 0.95 0.040 0.006 89
4 15 0.50 0.50 0.474 0.474 748.5 0.98 0.008 0.002 0.99 0.003 0.002 99
5 15 0.50 0.50 0.474 0.474 249.5 0.93 0.057 0.002 0.97 0.02 0.002 97
6 15 0.3 0.7 0.418 0.627 249.5 0.32 0.671 e 0.57 0.42 e 40
7 30 0.3 0.7 0.418 0.627 249.5 0.25 0.74 0.48 0.51 e 50
8 3 0.65 0.35 0.540 0.291 748.5 0.91 0.075 0.008 0.96 0.028 0.007 88
9 10 0.65 0.35 0.540 0.291 748.5 0.98 0.01 0.003 0.99 0.004 0.003 99
10 15 0.65 0.35 0.540 0.291 748.5 0.99 0.005 0.002 0.99 0.002 0.002 99

from the plant contains 95% CH4 and 5% CO2. The present
model was set to simulate the same operating conditions. The
results show that the volume of CH4 and CO2 at the outlet
stream was 95.6% and 4.08%, respectively. The difference be-
tween the simulation and experimental results was 0.6%.
3.4. Steam methane reforming
In this study, the Gibbs free energy minimization method is
used to determine the equilibrium composition and temper-
ature under distinct thermodynamic conditions. For the
simulation model of steam methane reforming (SMR), the
following elements were considered: H2O, carbon monoxide
(CO), carbon dioxide (CO2), CH4 (99% purified from biogas), and
air (N2/O2:79/21). In this simulation study, the Peng-Robinson
equation of state with modified Huron-vidal mixing rules
(PRMHV2) property method is chosen. It is applicable for polar
and non-polar components and processes operating at high
pressure and temperature. The Aspen Plus flow sheet of SMR
for H2 production is shown in Fig. 7 and unit blocks, stream
input and specifications are shown in Table 4.
The SMR simulation process consists of four main stages:
The Reformer Unit, High Temperature Water Gas Shift (HT-
WGS) Unit, Low Temperature Water Gas Shift (LT-WGS) Unit,
and Tailgas Combustion Unit.
Reformer Unit: High-pressure steam (3e25 bar) is mixed
with biogas at temperatures ranging from 700 to 1000  C in the
RSTOIC (B6) reactor. This reaction produces H2, CO, and a
small amount CO2. Some CH4 escapes, but it is captured and
converted into an inert element in the RGibbs (B7) reactor. The
RGibbs reactor acts as a filter, removing excess CH4 from the
process.
High Temperature Water gas shift Unit (HT-WGS): The HT-
WGS unit utilizes the Rstoic reactor as its gas shift reactor.
Operating at high temperatures (350e450  C) and pressure
(16e20 bar), its main purpose is to convert CO and H2O into
CO2 and H2. By adjusting temperature, pressure, and biogas
properties, the HT-WGS unit ensures efficient conversion of
CO and H2O into CO2 and H2 within the Rstoic reactor.
Low Temperature Water Gas Shift Unit (LT-WGS): The reason
for employing the LT-WGS step after HT-WGS in the SMR
process is to enhance the overall CO conversion and reduce
CO levels to meet the desired specifications. The HT-WGS
reaction alone may not achieve sufficient CO conversion,
and the LT-WGS step helps to further drive the conversion
towards CO2 and H2. By cascading the HT-WGS and LT-WGS
units, the overall efficiency of CO removal is improved, lead-
ing to higher purity hydrogen production.
Tail Gas Combustion Unit: The outlet stream from the LT-WGS
unit, mixed with water vapor, is transferred to the flash column

Fig. 7 e The Aspen Plus flow sheet of SMR for H2 production.

222 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 5 0 ( 2 0 2 4 ) 2 1 1 e2 2 5

(B13) to remove excess moisture and maintain a temperature of

FC and Component
38  C. The moisture-free gases then pass through the pressure
swing absorber (PSA) to separate H2 from other gases, forming

0.75 and CO
0.75 and CO
0.8 and CH4

1 and CH4

1 and CO
the tail gas. The tail gas, containing trace amounts of CH4 and

1 and H2
other gases, is burned in the tailgas combustion unit with excess
air or oxygen. This minimizes the release of unreacted CH4 and

e
e
e
CO, potent greenhouse gases, into the atmosphere. The com-
bustion of the tail gas generates heat energy that can be recov-
ered and utilized within the SMR process, improving overall

CH4þ2O2/CO2þ2H2O
energy efficiency and sustainability.
CH4þH2O/3CH2þCO

CO þ H2O/ H2þCO2
CO þ H2O/ H2þCO2

The water and purified methane flow rates of 45 and 40 kg/h,

Reactions

COþ0.5O2/CO2
H2þ0.5O2/H2O
respectively, at 1 bar and 25  C, are fed to the model. The mixture
of CH4 and H2O at 16 bar and 909  C is maintained before entering
the mainstream reformer unit. The CH4 reacts with water
(fractional conversion of 0.8) and produces H2 and CO. The
produced syngas is fed to HT-WGS (413  C), where CO reacts with
e

e
e
e

water (fractional conversion of 0.75) and produces H2 and CO2.

Furthermore, the water gas shifting process is executed at a
simulate tail gas burning for additional energy generation

reduced temperature (210  C). The outlet from the LT-WGS unit
is mixed with CH4, CO, H2O, CO2 and H2 at different molar con-
centrations at high pressure (16 bar). To separate H2 from the
syngas, Pressure swing adsorption (PSA) unit is used. When the
split fraction is set as 79%, the H2 yield is 10.16 kg/h. The tail gas
from the PAS unit contains volatile gases, including CH4 (0.128%)
and H2 (0.35%). Since CH4 is a greenhouse gas, further treatment
is required before it leaves the atmosphere. The tail gas could be
To model the reforming of biogas
Role

combusted with atmospheric air to reduce the molar concen-

Maintain optimum temperature

tration. The chemical reaction involved in the combustion pro-

Maintain optimum pressure
model separation of H2

cess and the entire stream specification employed in the

model WGS process
model WGS process

simulation model are shown in Table 5.

Pressure change

3.4.1. Sensitivity analysis

To conduct a sensitivity analysis of hydrogen production from
biogas, several parameters were varied, including pressure,
temperature, and the composition of the biogas. The composi-
Table 4 e Units and module used in Aspen Plus simulation flow Sheet.

To
To
To
To

tion of the inlet stream was initially adjusted to three different

ratios: 75% CH4 and 25% CO2, 50% CH4 and 50% CO2, and 40% CH4
and 60% CO2. The pressure and temperature were kept constant
T:210  C; P:15.7 bar
T:38  C; P:15.7 bar
Stream inputs
T:909  C; P:16 bar

T:350  C; P:16 bar

based on the previous simulation study. The corresponding

T:250  C; P:1 bar

T:25  C; P:16 bar

T:85  C; P:1 bar

hydrogen production rates were found to be approximately

T:25e909  C

7.04 kg/h, 4.23 kg/h, and 1.24 kg/h, respectively. These results
highlight the significant impact of the biogas composition on
hydrogen conversion, suggesting that purified methane is
crucial for achieving optimal hydrogen conversion. Addition-
ally, the pressure was varied to 5 bar, 10 bar, and 20 bar, resulting
Aspen Module

in hydrogen production rates of approximately 3.2 kg/h, 5.42 kg/

Compressor

h, and 10.94 kg/h, respectively. Furthermore, the temperature

was adjusted to 500  C, 700  C, 800  C, and 1000  C, leading to
RSTOIC

RSTOIC
RSTOIC

RSTOIC
RGIBBS

Heater
FLASH

Valve

hydrogen production rates of 4.26 kg/h, 6.92 kg/h, 8.4 kg/h, and
10.64 kg/h, respectively. This sensitivity analysis demonstrates
the importance of considering various factors in hydrogen pro-
duction from biogas. The composition of the biogas feed, as well
Tail gas combustion unit

as the pressure and temperature conditions, have significant

effects on the rate of hydrogen conversion. These findings
emphasize the need for high-quality, purified methane to ach-
ieve optimal hydrogen production. Additionally, varying the
H-1 to H-7

pressure and temperature can also impact the efficiency of

Reformer

HTWGS
LTWGS

hydrogen generation. Therefore, understanding the sensitivity

Units

PSA

of these parameters is crucial for designing and optimizing

V1
C1

hydrogen production processes.

 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 5 0 ( 2 0 2 4 ) 2 1 1 e2 2 5 223

Table 5 e Stream specification of SMR flow sheet.

Streams Pressure and Mass flow rate Molar flow rate Molar fraction
Temperature (oC/Bar) (kg/hr) (kmol/hr)
CH4 CO2 CO H2O H2 N2 O2
Biogas 25/1 40 2.45 0.99 0.01 e e e e
water 25/1 45 2.49 e e e 1 e e
REF-I 909/16 85 4.94 0.04 0.004 e 0.504 e e
REF-O 909/16 85 8.83 0.05 0.012 0.209 0.053 0.669 e
HTWGAS-I 350/16 85 8.83 0.05 0.012 0.209 0.053 0.669
HTWGAS-O 413/16 85 8.83 0.05 0.065 0.156 0 0.722 0
HTWGAS-O 210/16 85 8.83 0.05 0.068 0.056 0 0.822 0
H2 38/16 10.15 5.03 e e e e 1 e
Tail gas 38/16 74.84 3.79 0.12 0.15 0.365 0 0.35 e
AIR 25/1 92.14 3.19 e e e e e 0.79 0.21
COMP-I 250/1 167 6.98 0.06 0.082 0.198 0.19 0.36 0.09
COMP-O 1468/1 166.9 6.59 0.05 0.169 0.149 0.10 0.144 0.38 0
Flue Gas 200/1 166.9 6.59 0.05 0.169 1.149 0.10 0.144 0.38 0

3.5. Comparison of experimental and simulation results
To evaluate the efficiency of the process simulation model,
the results from the simulation were compared with those
obtained from a laboratory-scale batch anaerobic digester
with a 2L volume. The gas yield from the simulation model
was determined for organic loading rates of 8g, 15g, and 18g,
resulting in yields of 242 mL/gVS, 436 mL/gVS, and 492 mL/
gVS, respectively. Conversely, the experimental gas yields at
the same organic loading rates were recorded as 212 mL/gVS,
396 mL/gVS, and 458 mL/gVS. Based on the comparison of
simulation and experimental results, it was observed that the
maximum difference between the two was 12%, while the
minimum difference was 7%. This indicates the reliability of
the developed simulation model. Additionally, the uncer-
tainty between simulation and experimental data was found
to be highest when the organic loading rate was set to be less
than 10%. This might be attributed to the poor organic loading
rate, which leads to insufficient nutrient supply to microor-
ganisms responsible for biogas production. Nonetheless, In
the simulation model, it is challenging to fully represent the
natural variability and complexity of microbial activities that
occur during anaerobic digestion. However, continuous ef-
forts should be made to refine the model to better replicate the
real-world anaerobic digestion process and improve its accu-
racy in predicting biogas production.
occurred at 10 g/L. The optimal temperature range for gas
production was 30e35  C, with a yield of 548 mL/gVS,
decreasing significantly beyond 40  C. Biogas purification
involved pressure ranging from 3 to 15 bar and varying biogas
compositions (50% CH4:50% CO2, 65% CH4:35% CO2, and 30%
CH4:70% CO2), with 99% CO2 absorption at 15 bar and 50%
CH4:50% CO2 composition. Notably, 10 bar pressure achieved
99% CO2 absorption with a 65% CH4:35% CO2 composition. In
hydrogen production from biogas, using feed streams with 99%,
75%, 50%, and 40% methane yielded hydrogen production rates
of 10.15 kg/h, 7.04 kg/h, 4.23 kg/h, and 1.24 kg/h, respectively.
The highest hydrogen production of 10.94 kg/h occurred at
20 bar and 1000  C, and beyond 900  C and 16 bars, the hydrogen
yield was not significant. Simulation and experimental results
showed a maximum difference of 12% and a minimum differ-
ence of 7%. The simulation results provide a base model for
studying anaerobic digestion in a simulated environment,
exploring biogas production rates, organic loading rate effects,
and temperature influences. Additionally, the model identifies
optimal conditions for biogas purification and hydrogen pro-
duction via steam methane reforming. These insights are
valuable for further research and process optimization in
renewable energy production.
Data availability

No data was used for the research described in the article.

4. Conclusion

Anaerobic digestion of animal manure, municipal solid waste, Funding

and rice straw was simulated with Aspen Plus software,
including optimization analysis for the anaerobic reactor. The
simulation process comprised three steps: biogas production
via anaerobic digestion, conversion of biogas to biomethane
(99% purity), and further conversion of biogas to hydrogen
through steam methane reforming. Three anaerobic batch re-
actors (1L, 3L, and 5L) with organic loading rates of 5g, 10g, and
15g were simulated at temperatures of 25  C, 30  C, 40  C, and
50  C. Maximum gas yield of 520 mL/gVS was achieved at 20 g/L
organic loading rate, and minimum yield of 230 mL/gVS
This research did not receive any specific grant from funding
agencies in the public, commercial, or not-for-profit sectors.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
224 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 5 0 ( 2 0 2 4 ) 2 1 1 e2 2 5
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.ijhydene.2023.08.096.
Abbreviations:
AD: Anaerobic Digestion
ADM1: Anaerobic digestion model No.1
HRT: Hydraulic retention time
PA: Proximity analysis
PS: Present study
PSM: Process simulation model
UA: Ultimate analysis
VS: Volatile solids
VW: Vegetable wastes
OLR: Organic Loading Rate
mL/gVS/: Milli litter/ gram of volatile solids
references
[1] Abu-Rumman G, Khdair AI, Khdair SI. Current status and
future investment potential in renewable energy in Jordan:
an overview. Heliyon 2020;6(2):e03346. https://doi.org/
10.1016/j.heliyon.2020.e03346.
[2] Sajad Hashemi S, Karimi K, Majid Karimi A. Ethanolic
ammonia pretreatment for efficient biogas production from
sugarcane bagasse. Fuel 2019;248(November 2018):196e204.
https://doi.org/10.1016/j.fuel.2019.03.080.
[3] Voituriez T, Morita K, Giordano T, Bakkour N, Shimizu N.
Financing the 2030 agenda for sustainable development.
Governing Through Goals: Sustainable Development Goals as
Governance Innovation 2017;16301(October):259e73. https://
doi.org/10.1057/978-1-137-45443-0_24.
[4] Harichandan S, Kar SK, Rai PK. A systematic and critical
review of green hydrogen economy in India. Int J Hydrogen
Energy May 2023. https://doi.org/10.1016/
J.IJHYDENE.2023.04.316.
[5] Thiruselvi D, et al. A critical review on global trends in biogas
scenario with its up-gradation techniques for fuel cell and
future perspectives. Int J Hydrogen Energy May
2021;46(31):16734e50. https://doi.org/10.1016/
J.IJHYDENE.2020.10.023.
[6] Jackson SA, Kang X, O'Shea R, O'Leary N, Murphy JD,
Dobson ADW. Anaerobic digestion performance and
microbial community structures in biogas production from
whiskey distillers organic by-products. Bioresour Technol
Rep 2020;12(May):100565. https://doi.org/10.1016/
j.biteb.2020.100565.


[7] Bravo D, Alvarez-Hornos FJ, Penya-roja JM, San-Valero P,
Gabaldo
n C. Aspen Plus process-simulation model:
producing biogas from VOC emissions in an anaerobic
bioscrubber. J Environ Manag May 2018;213:530e40. https://
doi.org/10.1016/J.JENVMAN.2018.02.040.
[8] Batstone DJ, Keller J. Industrial applications of the IWA
anaerobic digestion model No. 1 (ADM1). Water Sci Technol
2003;47(12):199e206. https://doi.org/10.2166/wst.2003.0647.
[9] Al-Rubaye H, Karambelkar S, Shivashankaraiah MM,
Smith JD. Process simulation of two-stage anaerobic
digestion for methane production. Biofuels
2019;10(2):181e91. https://doi.org/10.1080/
17597269.2017.1309854.
[10] Rajendran K, Kankanala HR, Lundin M, Taherzadeh MJ. A
novel process simulation model (PSM) for anaerobic
digestion using Aspen Plus. Bioresour Technol
2014;168:7e13. https://doi.org/10.1016/j.biortech.2014.01.051.
[11] Aguilar MC, Wang YD, Roskilly T, Pathare PB, Lamidi RO.
Biogas from anaerobic co-digestion of food waste and
primary sludge for cogeneration of power and heat. Energy
Proc 2017;142:70e6. https://doi.org/10.1016/
j.egypro.2017.12.012.
[12] Galvagno A, Chiodo V, Urbani F, Freni F. Biogas as hydrogen
source for fuel cell applications. Int J Hydrogen Energy Apr.
2013;38(10):3913e20. https://doi.org/10.1016/
J.IJHYDENE.2013.01.083.
[13] Heck JD, Vaz WS, Koylu UO, Leu MC. Decoupling pressure
and distribution effects of flow fields on polymer electrolyte
fuel cell system performance. Sustain Energy Technol
Assessments Dec. 2019;36:100551. https://doi.org/10.1016/
J.SETA.2019.100551.
[14] Jabbr AI, Gaja H, Koylu UO. Multi-objective optimization of
operating parameters for a H2/Diesel dual-fuel compression-
ignition engine. Int J Hydrogen Energy 2020;45(38):19965e75.
https://doi.org/10.1016/J.IJHYDENE.2020.05.071. Jul.
[15] Standard test method for ash in biomass, “ASTM E1755-01,”.
2010.
[16] Standard test method for volatile matter in the analysis of
particulate wood fuels, “ASTM E872-82(2019),”. 2019 [Online].
Available: https://www.astm.org/e0872-82r19.html.
[17] Standard test methods for direct moisture content
measurement of wood and wood-based materials, “ASTM
d4442-16,”. 2020 [Online]. Available: https://www.astm.org/
d4442-16.html.
[18] Parikh J, Channiwala SA, Ghosal GK. A correlation for
calculating elemental composition from proximate analysis
of biomass materials. Fuel 2007;86(12e13):1710e9. https://
doi.org/10.1016/j.fuel.2006.12.029.
[19] Yan L, Liu C, Zhang Y, Liu S, Zhang Y. Effects of C/N ratio
variation in swine biogas slurry on soil dissolved organic
matter: content and fluorescence characteristics. Ecotoxicol
Environ Saf Feb. 2021;209:111804. https://doi.org/10.1016/
J.ECOENV.2020.111804.
[20] Dai X, Li X, Zhang D, Chen Y, Dai L. Simultaneous
enhancement of methane production and methane content
in biogas from waste activated sludge and perennial ryegrass
anaerobic co-digestion: the effects of pH and C/N ratio.
Bioresour Technol Sep. 2016;216:323e30. https://doi.org/
10.1016/J.BIORTECH.2016.05.100.
[21] Tian G, et al. The effect of temperature on the microbial
communities of peak biogas production in batch biogas
reactors. Renew Energy Aug. 2018;123:15e25. https://doi.org/
10.1016/J.RENENE.2018.01.119.
[22] Hoang AT, et al. Production of biochar from crop residues
and its application for anaerobic digestion. Bioresour
Technol 2022;363(September):127970. https://doi.org/10.1016/
j.biortech.2022.127970.
[23] Nock WJ, Walker M, Kapoor R, Heaven S. Modeling the water
scrubbing process and energy requirements for CO 2 capture
to upgrade biogas to biomethane. Ind Eng Chem Res
2014;53(32):12783e92. https://doi.org/10.1021/ie501280p.
[24] Gantina TM, Iriani P, Maridjo, Wachjoe CK. Biogas
purification using water scrubber with variations of water
flow rate and biogas pressure. J Phys Conf Ser 2020;1450(1).
https://doi.org/10.1088/1742-6596/1450/1/012011.
[25] Antonini C, Treyer K, Streb A, van der Spek M, Bauer C,
Mazzotti M. Hydrogen production from natural gas and
biomethane with carbon capture and storage - a techno-
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 5 0 ( 2 0 2 4 ) 2 1 1 e2 2 5
environmental analysis. Sustain Energy Fuels
2020;4(6):2967e86. https://doi.org/10.1039/d0se00222d.
[26] Achinas S, Euverink GJW. Theoretical analysis of biogas
potential prediction from agricultural waste. Resource-
Efficient Technologies 2016;2(3):143e7. https://doi.org/
10.1016/j.reffit.2016.08.001.
[27] Kaparaju P, Ellegaard L, Angelidaki I. Optimisation of biogas
production from manure through serial digestion: lab-scale
and pilot-scale studies. Bioresour Technol 2009;100(2):701e9.
https://doi.org/10.1016/j.biortech.2008.07.023.
[28] Fajobi MO, Lasode OA, Adeleke AA, Ikubanni PP, Balogun AO.
Investigation of physicochemical characteristics of selected
lignocellulose biomass. Sci Rep 2022;12(1):1e14. https://
doi.org/10.1038/s41598-022-07061-2.
[29] Forga
cs G, Pourbafrani M, Niklasson C, Taherzadeh MJ,
Hova
th IS. Methane production from citrus wastes: process
development and cost estimation. J Chem Tech Biotechnol
Feb. 2012;87(2):250e5. https://doi.org/10.1002/JCTB.2707.
[30] Salwa Khamis S, Purwanto H, Naili Rozhan A, Abd
Rahman M, Mohd Salleh H. Characterization of municipal
solid waste in Malaysia for energy recovery. IOP Conf Ser
Earth Environ Sci 2019;264(1). https://doi.org/10.1088/1755-
1315/264/1/012003.
[31] Fujita M, Scharer JM, Moo-Young M. Effect of corn stover
addition on the anaerobic digestion of swine manure. Agric
Wastes 1980;2(3):177e84. https://doi.org/10.1016/0141-
4607(80)90014-1. Jul.
[32] Smith AM, Ekpo U, Ross AB. The influence of pH on the
combustion properties of bio-coal following hydrothermal
treatment of swine manure. Energies 2020;13(2):1e20.
https://doi.org/10.3390/en13020331.
[33] Zhong B, An X, Shen F, An W, Zhang Q. Anaerobic Co-
digestion of rice straw and pig manure pretreated with a
cellulolytic microflora: methane yield evaluation and
kinetics analysis. Front Bioeng Biotechnol 2021;8:1e13.
https://doi.org/10.3389/fbioe.2020.579405. February.
[34] Increasing anaerobic digestion performance with
codigestion- United States environmental protection agency
(EPA) 2012
[35] Nasir IM, Mohd Ghazi TI, Omar R. Anaerobic digestion
technology in livestock manure treatment for biogas
production: a review. Eng Life Sci Jun. 2012;12(3):258e69.
https://doi.org/10.1002/ELSC.201100150.
[36] Dennehy C, et al. Anaerobic co-digestion of pig manure and
food waste; effects on digestate biosafety, dewaterability,
and microbial community dynamics. Waste Manag
2018;71:532e41. https://doi.org/10.1016/
j.wasman.2017.10.047.
[37] Shen F, Li H, Wu X, Wang Y, Zhang Q. Effect of organic
loading rate on anaerobic co-digestion of rice straw and pig
manure with or without biological pretreatment. Bioresour
225
Technol Feb. 2018;250:155e62. https://doi.org/10.1016/
J.BIORTECH.2017.11.037.
[38] Ji JL, Chen F, Liu S, Yang Y, Hou C, Wang YZ. Co-production of
biogas and humic acid using rice straw and pig manure as
substrates through solid-state anaerobic fermentation and
subsequent aerobic composting. J Environ Manag Oct.
2022;320:115860. https://doi.org/10.1016/
J.JENVMAN.2022.115860.
[39] Pal DB, et al. Enhanced biogas production potential analysis
of rice straw: biomass characterization, kinetics and
anaerobic co-digestion investigations. Bioresour Technol
2022;358:127391. https://doi.org/10.1016/
J.BIORTECH.2022.127391. Aug.
[40] Anaya Menacho W, Mazid AM, Das N. Modelling and analysis
for biogas production process simulation of food waste using
Aspen Plus. Fuel 2022;309(September 2021):122058. https://
doi.org/10.1016/j.fuel.2021.122058.
[41] Zhang C, Sun Y, Cao T, Wang W, Huo S, Liu ZH. Influence of
organic load on biogas production and response of microbial
community in anaerobic digestion of food waste. Int J
Hydrogen Energy Sep. 2022;47(77):32849e60. https://doi.org/
10.1016/J.IJHYDENE.2022.07.187.
[42] Membere E, Sallis P. Effect of temperature on kinetics of
biogas production from macroalgae. Bioresour Technol Sep.
2018;263:410e7. https://doi.org/10.1016/
J.BIORTECH.2018.05.023.
[43] Zhang Y, Li J, Liu F, Yan H, Li J, Zhang X. Reduction of Gibbs
free energy and enhancement of Methanosaeta by
bicarbonate to promote anaerobic syntrophic butyrate
oxidation. Bioresour Technol Nov. 2018;267:209e17. https://
doi.org/10.1016/J.BIORTECH.2018.06.098.
[44] Sugiharto A, Hidayat M. Sensitivity analysis of water
scrubbing process for biogas purification sensitivity analysis
of water scrubbing process for biogas purification. 2016.
October 2015. p. 35e9. https://doi.org/10.13140/RG.2.1.3142.
9206.
[45] Al Mamun MR, Torii S. Enhancement of methane
concentration by removing contaminants from biogas
mixtures using combined method of absorption and
adsorption. Int J Chem Eng 2017;2017. https://doi.org/10.1155/
2017/7906859.
[46] Garcia-Aguirre J, Aymerich E, Gonza
lez-Mtnez J, de Gon
~ i,
Esteban-Gutie
rrez M. Selective VFA production potential
from organic waste streams: assessing temperature and pH
influence. Bioresour Technol 2017;244(July):1081e8. https://
doi.org/10.1016/j.biortech.2017.07.187.
[47] Frigon JC, Mehta P, Guiot SR. Impact of mechanical, chemical
and enzymatic pre-treatments on the methane yield from
the anaerobic digestion of switchgrass. Biomass Bioenergy
Jan. 2012;36:1e11. https://doi.org/10.1016/
J.BIOMBIOE.2011.02.013.