Journal of Cleaner Production 324 (2021) 129241

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Journal of Cleaner Production

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

Sustainable ammonia production from steam reforming of biomass-derived

glycerol in a heat-integrated intensified process: Modeling and
feasibility study
Mohammad Hasan Khademi a, *, Mohammad Lotfi-Varnoosfaderani b
a
Department of Chemical Engineering, College of Engineering, University of Isfahan, P.O. Box 81746-73441, Isfahan, Iran
b
Department of Chemical and Petroleum Engineering, Sharif University of Technology, P.O. Box 11155-9465, Tehran, Iran

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

Handling Editor: Kathleen Aviso Currently, ammonia, as a clean and sustainable energy carrier, is intensively synthesized from its elements during
the Haber-Bosch technology. This process requires a large amount of energy and emits numerous amounts of
Keywords: carbon dioxide, because hydrogen is dominantly produced from fossil fuels through reforming processes.
Sustainable ammonia production Biomass-derived glycerol steam reforming is an attractive alternative to traditional reforming for reducing the
Glycerol steam reforming
dependence on hydrocarbon resources and mitigating climate change. This research aims to intensify a heat-
Methane tri-reforming
integrated process for the co-production of ammonia and syngas from glycerol valorization. In this process,
Heat-integrated process
Synthesis gas glycerol reforming continuously provides hydrogen needed for ammonia synthesis, and the liquid glycerol is
simultaneously vaporized by heat generated from ammonia synthesis. Methane tri-reforming acts as a heat
source to drive glycerol reforming; at the same time, the effluent gas produced through glycerol reforming is
recycled to the tri-reforming side to reduce the greenhouse gas emissions. The role of different parameters on the
process performance is identified by a one-dimensional heterogeneous model. Numerical results show that by
adjusting the adequate operating conditions, glycerol and methane conversion >95%, nitrogen conversion
>25%, glycerol dryness fraction = 1.0, and syngas with hydrogen to carbon monoxide ratio above 2.0, suitable
for the Fischer-Tropsch and methanol synthesis processes, can be achieved. In addition, this heat-integrated
intensified process is promising in terms of energy saving, environmental pollution mitigation, feasibility and
effectiveness for industrial-scale application; however, experimental proof-of-concept is required to ensure the
safe operability of this process.

1. Introduction
Ammonia, as a potential hydrogen carrier and a carbon-free fuel, is
one of the essential chemicals in the petrochemical industry. It is mainly
used to produce fertilizers like ammonium nitrate, urea, and ammonium
phosphate, as well as many products such as explosives, fibers, plastics,
and polymers.
There are various pathways for ammonia production, such as Haber-
Bosch process, electro-catalysis (Soloveichik, 2019), photo-catalysis
(Medford and Hatzell, 2017), and chemical looping (Weng et al.,
2021) technologies. In the Haber-Bosch process, as the earliest tech­
nology, nitrogen and hydrogen in the gas phase react over magnetic iron
oxide catalyst at high temperatures and pressures. Recently,
electro-catalysis and photo-catalysis strategies have been actively
explored and investigated, but ammonia production rates are still far
from satisfactory (Soloveichik, 2019). To date, three unique approaches
to ammonia production via chemical looping technology have been re­
ported: (i) H2 chemical looping, a two-step process where metal nitrides
are directly reduced to a metallic state in the presence of H2 and back to
a metal nitride under pure N2 (Shan et al., 2018); (ii) H2O chemical
looping, a three-step process where a metal oxide precursor is reduced to
its metallic form before undergoing nitridation and subsequent hydro­
lysis to yield ammonia and restore the original oxide (Sarafraz and
Christo, 2021); and (iii) alkali or alkaline-earth metal hydride chemical
looping, a two-step process where N2 is reduced directly by the metal
hydride to form a metal imide that then undergoes disproportionation
under H2 to produce NH3 and restore the metal hydride (Gao et al.,
2018). In comparison with the conventional Haber-Bosch process, the

* Corresponding author.
E-mail address: m.khademi@eng.ui.ac.ir (M.H. Khademi).

https://doi.org/10.1016/j.jclepro.2021.129241
Received 12 July 2021; Received in revised form 30 September 2021; Accepted 2 October 2021
Available online 5 October 2021
0959-6526/© 2021 Elsevier Ltd. All rights reserved.
M.H. Khademi and M. Lotfi-Varnoosfaderani
chemical looping ammonia synthesis technology offers the following
advantages: 1) functioning at ambient pressure, minimizing cost and
safety concerns; 2) relying less on catalysts, reducing the costs of their
production and recycling; and 3) using water as a hydrogen source,
reducing energy consumption and associated CO2 emissions (Gálvez
et al., 2007). Despite the advantages of chemical looping technology,
approximately 90% of global ammonia is still produced commercially
through the Haber-Bosch process, as the most common route (Dincer
and Bicer, 2018), because there is no other economically viable for
synthesis of ammonia (Sarafraz and Christo, 2021).
Although hydrogen can be produced by different processes such as
steam reforming of fossil fuels, partial oxidation of heavy oil, water
electrolysis, and biomass gasification, this is one of the principal vital
challenges in the ammonia synthesis through Haber-Bosch process.
Steam reforming is the most common technology for producing
hydrogen from fossil fuels, most often natural gas. More than 72% of
ammonia is emanated from methane steam reforming, which releases
large amounts of CO2 to the atmosphere (about 2–3 tons of CO2 per each
ton of ammonia) (Anderson et al., 2008), leading to global warming and
environmental pollution. The use of biomass-based sources (Gilbert
et al., 2014), water electrolysis (Xu et al., 2018), injection of produced
CO2 into oil reservoirs for enhanced oil recovery (Bicer and Dincer,
2018), chemical looping combustion technology (Zhu et al., 2020),
carbon capture and storage (CCS) methods (Global Status Report -
Global CCS Institute), and improving the efficiency of the process (Bicer
et al., 2016) are promising alternatives to reduce CO2 emissions during
ammonia production.
From an environmental perspective, Gilbert et al. (2014) and Arora
et al. (2016) showed that using the biomass gasification approach for
ammonia production can reduce CO2 emissions by 54–68% compared to
the natural gas-based conventional ammonia synthesis process. Bicer
et al. (2016) compared life cycle assessment of various ammonia pro­
duction routes from hydrogen provided by water electrolysis, in which
electricity was supplied from municipal waste, biomass, nuclear, and
hydropower. They concluded that municipal waste- and
hydropower-based water electrolysis has the lowest environmental as­
pects. Chisalita et al. (2020) conducted an environmental assessment of
hydrogen production for ammonia synthesis through iron-based chem­
ical looping, water electrolysis, and methane steam reforming in com­
bination with CCS technology based on liquid-gas absorption by chilled
ammonia and amines. The analysis indicated that the chemical looping
hydrogen production and fossil sources-based electrolysis have the
lowest and highest overall emissions to soil, water, and air, respectively.
From a cost viewpoint, Zhang et al. (2019) carried out a comparative
techno-economic analysis of the Haber-Bosch process integrated with
methane steam reforming, water electrolysis, and biomass gasification.
They showed that biomass gasification and solid-oxide electrolysis have
the lowest and highest efficiencies, respectively, while water electrolysis
is the worst method in terms of economics and is not economically
feasible due to high electrical consumption. The coupling of CCS tech­
nology with fossil fuels-based ammonia production is more economical
than water electrolysis (Global Status Report - Global CCS Institute).
However, the high energy intensity of solvent regeneration and the
higher risk of fugitive emissions due to high solvent volatility are the
main drawbacks of solvents utilization in liquid-gas absorption-based
CCS technology (Mikulčić et al., 2019).
Even though methane steam reforming is currently the predominant
hydrogen production route for ammonia synthesis and the least energy
intensive technology among other methods, ammonia production costs
can increase with natural gas prices in parallel (Bicer et al., 2016). In
addition, fossil fuel depletion, global warming, and environmental
problems are the main drawbacks of this hydrogen production route,
which can be sufficient reasons to intensify and improve the ammonia
synthesis process and to use renewable biofuels as a suitable alternative
to fossil fuels.
One of the most important renewable fuels is biodiesel, whose annual
2
Journal of Cleaner Production 324 (2021) 129241
worldwide production is increasing recently; moreover, it is anticipated
to expand its global use continuously (U.S. Energy Information
Administration, International Energy Statistics, Biofuels Production).
Biodiesel decreases CO2 emissions by more than 52% (Okoye et al.,
2017); however, it is not competitive from the price viewpoint than
fossil fuels. Glycerol (nearly 10%), as the main by-product, is produced
by the conversion of animal fat or vegetable oils into biodiesel through
the catalytic trans-esterification process (Ma and Hanna, 1999). One
cost-effective way to reduce the price of biodiesel is to use glycerol to
produce hydrogen (Silva et al., 2015). Steam reforming of glycerol is the
most well-known and preferable technique for H2 production (Patch­
aravorachot et al., 2019) because it can theoretically make 7 mol of
hydrogen per mole of glycerol as follows:
C3 H8 O3 (g) + 3H2 O(g) ↔ 7H2 (g) + 3CO2 (g) (1)
Recently, from the mathematical modeling and simulation perspec­
tives, some researchers such as Khodabandehloo et al. (2020) and Unlu
and Hilmioglu (2020) have focused on glycerol’s potential to convert
hydrogen, and others like Saidi and Moradi (2020) and Macedo et al.
(2019) used a hydrogen perm-selective membrane reactor instead of a
conventional glycerol steam reformer to improve the glycerol conver­
sion and hydrogen yield. However, the main challenge in the glycerol
steam reforming process is the emissions of greenhouse gases, including
CH4, CO2, and H2O into the atmosphere. One way to meet this challenge
is to use the sorption-enhanced glycerol steam reforming process (Yang
et al., 2020), which involves the CO2 sorption along with the catalytic
reaction. Although this system reduces CO2 emissions, the major
disadvantage of this process is the regeneration of CO2 sorbents in
another reactor, which increases capital costs. An excellent solution to
diminish the CO2 emissions in the glycerol steam reformer is to use the
exiting gas stream, containing carbon dioxide and methane as a feed­
stock of methane tri-reforming reaction.
The methane tri-reforming consists of dry reforming, steam reform­
ing, and partial oxidation of methane, that combination of these re­
actions improves the reactor efficiency (Khademi and Alipour-Dehkordi,
2021). The advantages of this process are: 1) this is an autothermal re­
action, 2) carbon formation in this process is reduced due to the exis­
tence of steam and oxygen (Chein et al., 2017), 3) it does not require a
source of pure CO2 as a reactant, so CO2 produced by the glycerol steam
reforming process can be fed to this reaction, and 4) the synthesis gas
with proper H2/CO ratio for the downstream customary units can be
produced by adjusting the feed composition (Chein et al., 2017).
On the other hand, the heat required to drive the glycerol steam
reforming, as an endothermic reaction, can be provided by the methane
tri-reforming. Using a heat integration strategy for these two reactions
can significantly reduce energy consumption and greenhouse gas
emissions. Numerous theoretical studies have been performed on the
thermal integration of methane tri-reforming or glycerol reforming with
other reactions. For example, two thermally coupled reactors were
simulated, in which the methane tri-reforming reaction provided the
necessary heat for steam (Rahnama et al., 2014) and dry (Farniaei et al.,
2014) reforming of methane. These processes were able to produce
synthesis gas with different H2/CO ratios. Iliuta et al. (2012) suggested a
heat-integrated process for aqueous-phase glycerol reforming and
dimethyl ether synthesis reaction; in addition, Thirabunjongcharoen
et al. (2020) offered a shell and tube heat-exchanger reactor to integrate
methanol synthesis and aqueous-phase glycerol reforming reaction. In
these two cases, aqueous-phase glycerol reforming produced biosyngas
for dimethyl ether and methanol synthesis, which in return these syn­
thesis reactions supplied sufficient energy for the endothermic reaction.
Recently, Khazayialiabad et al. (2021) conducted a conceptual evalua­
tion of a thermally coupled reactor containing nitrobenzene hydroge­
nation and glycerol steam reforming for co-production of aniline and
hydrogen.
Since the ammonia synthesis reaction is highly exothermic,
removing the heat of the reaction is another critical issue in this reactor
M.H. Khademi and M. Lotfi-Varnoosfaderani Journal of Cleaner Production 324 (2021) 129241

Fig. 1. Flow diagram of the (a) conventional ammonia synthesis process and (b) heat-integrated intensified process.

Fig. 2. Conceptual diagram of three heat-integrated multi-tubular reactors for proposed process.

• According to the compressibility factor calculation based on the Peng-Robinson-Stryjek-Vera equation of state for ammonia synthesis (i.e., 1.0), glycerol steam
reforming (i.e., 0.982) and methane tri-reforming (i.e., 1.0), the behaviour of the gas can be considered ideal.
• Steady-state condition
• A uniform bed void fraction distribution is considered in both sides.
• The axial heat and mass diffusion can be disregarded compared to the bulk flow according to the large enough Peclet number (Pe > 100) (Weigand, 2004).
• Catalyst deactivation is ignored.
• The conduction resistance in the solid wall of tubes is ignored.
• The intra-particle mass and heat transfer restriction, defined as the effectiveness factor, is reported by De Groote and Froment (1996) and (Arab Aboosadi et al.,
2011) for methane tri-reforming. An empirical correlation for the effectiveness factor of catalyst size of 6–10 mm is developed by Dyson and Simon (1968) for
ammonia synthesis reaction as a function of conversion and temperature. This parameter is also assumed equal to one for glycerol steam reforming due to the small
diameter of the catalyst (i.e., 115 μm) and Thiele modulus <0.4.

to enhance the degree of conversion and prevent catalyst deactivation.
There are three cooling technologies to control the temperature of the
reactor, namely direct cooling (Carvalho et al., 2014), quench cooling
(Sadeghi and Kavianiboroujeni, 2008), and indirect cooling (Dashti
et al., 2006). A comparison between these cooling methods was per­
formed by Khademi and Sabbaghi (2017) and Azarhoosh et al. (2014).
They showed that direct cooling was the most efficient cooling
technology in terms of low-temperature level and ammonia production.
Recently, Iranshahi and co-authors suggested recuperative coupling
reactors as a direct cooling strategy for ammonia synthesis. They pre­
sented different configurations for thermally coupled reactors, in which
ammonia synthesis reaction was cooled by cyclohexane dehydrogena­
tion (Ghani et al., 2019), 2-butanol dehydrogenation (Ghani and Iran­
shahi, 2019), naphtha reforming (Shakeri et al., 2019), and methyl

3
M.H. Khademi and M. Lotfi-Varnoosfaderani Journal of Cleaner Production 324 (2021) 129241

formate (Nikzad and Iranshahi, 2021). 3. Methodology

In this work, a novel heat-integrated intensified process is proposed
for the sustainable ammonia production from steam reforming of 3.1. Mathematical model
biomass-derived glycerol to improve the NH3 synthesis process in order
to save energy and significantly reduce CO2 emissions, as the most Temperature and concentration changes along the reactor axis are
important cause of greenhouse effect. This process is also able to pro­ specified by a 1D heterogeneous model. A differential element is
duce synthesis gas, as a valuable product, through methane tri- considered along each reactor to derive the mass and energy balance
reforming reaction. In this regard, the effect of various parameters on equations for each side. The governing equations are simplified by the
the performance of the process, including ammonia production, dryness following assumptions:
fraction, methane and glycerol conversion, and H2/CO ratio in the
synthesis gas was evaluated using a heterogeneous one-dimensional 3.1.1. Mass balance for evaporation-side
model. Due to the existence of a two-phase flow in the evaporation-side of
reactor I and II, a mass balance equation for this side is expressed as:
2. Process description dx Ntube πdt TP ( b )
F0C3 H8 O3 + U1− 2 T2 − T1 = 0 for ​ x < 1 (2)
dz λ
2.1. Conventional ammonia synthesis process
at z = 0 x=0 (3)
A flow diagram of the conventional ammonia synthesis process is
shown in Fig. 1(a). Firstly, natural gas is desulfurized and then mixed where T2b = 625 K is the boiling point of glycerol, and dryness fraction,
with steam before entering the reformer. The carbon monoxide gener­ x, is defined as the ratio of the mass of vapor to the total mass of the
ated in the steam reformer is treated with water in a water-gas shift mixture.
converter to produce additional hydrogen. The steam changes to the
liquid phase in a condenser, and the discharged stream runs to the 3.1.2. Energy balance for evaporation-side
pressure swing adsorption (PSA). A pure hydrogen stream exits the PSA The two-phase flow can change to single-phase (vapor) due to the
unit, and the waste gases as well as methane makeup gas are combusted operating conditions, so to calculate the glycerol vapor temperature, the
with air to supply sufficient heat for the reformer. Finally, the hydrogen- sensible heat of the vapor must be taken into account for the single-
rich gas stream reacts with nitrogen to produce ammonia. phase. In this regard, an energy balance equation is given as:
( )
d Cp T2
F0C3 H8 O3 + Ntube πdt UTP
1− 2 (T2 − T1 ) = 0 for ​ x = 1 (4)
2.2. Heat-integrated intensified process dz

Fig. 1(b) indicates a flow diagram of the suggested process for the co- at z = z0 T2 = Tb2 (5)
production of ammonia and syngas. Glycerol in the liquid phase is first z0 is the position where the two-phase flow regime changes to a
evaporated in two equal-size heat-integrated multi-tubular reactors in single-phase flow. The two-phase heat transfer coefficient in the
series. After mixing the steam and glycerol vapor, if required, this stream evaporation-side was reported by Kandlikar (1990) as follows:
must be passed through a heat-exchanger to reach an adequate degree of
temperature for glycerol steam reforming reaction, and then entered hTP
= C1 CoC2 (25Frl )C5 + C3 BoC4 Ffl (6)
another heat-integrated multi-tubular reactor. A conceptual diagram of hl
these three heat-integrated multi-tubular reactors is shown in Fig. 2.
These reactors consist of a bundle of tubes placed in a shell. In reactors I hl = 0.023Re0.8 0.4
l Prl (Kl / dt ) (7)
and II, ammonia is synthesized in the tubes (also known as exothermic- ⎧
side), and glycerol is vaporized in the shell (also known as evaporation- ⎪
⎪
⎨
< 0.65 convective boiling region,
side). The heat required for the evaporation-side is continuously sup­ Co
C1 = 1.136, C2 = − 0.9, C3 = 667.2, C4 = 0.7, C5 = 0.3
(8)
⎪ > 0.65 nucleate boiling region
plied from the exothermic-side. In reactor III, glycerol steam reforming ⎪
⎩
C1 = 0.6683, C2 = − 0.2, C3 = 1, 058, C4 = 0.7, C5 = 0.3
takes place in the tubes (also known as endothermic-side), and methane
tri-reforming occurs in the shell (exothermic-side). The exothermic-side ( )0.8 ( )0.5
provides the heat required for the endothermic-side. As shown in Fig. 1 where Co = 1− x
x
ρg
ρl
q
is convection number, Bo = Gλ is boiling
(b), the outlet stream of the endothermic-side runs to the PSA. In order 2
to produce ammonia, pure hydrogen exited from the top of the PSA unit number, Frl = ρ2Ggdt is Froude number with all flow as liquid, and Ffl is a
l
is mixed with nitrogen, and recycled in parallel to the reactors I and II.

⎧
⎪
⎪ ρ υi ri in endothermic − side of reactor III
( ) ⎨ b
kc,i,k ak Ck ysi,k − ygi,k = ∑N
for solid − phase (9)
⎪
⎩ ρb
⎪ ηj υi,j rsj in exothermic − side of reactor I, II, III
j=1

Also, the waste gases (including: CH4, CO, CO2, and H2O) exited from fluid-dependent parameter which is calculated using the scheme sug­
the bottom of the PSA, as well as methane makeup gas and oxygen, are gested by Kandlikar (1990).
pressurized by a compressor, and fed to the entrance of the exothermic-
side of the reactor III to produce syngas. 3.1.3. Partial mass balances for component i

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M.H. Khademi and M. Lotfi-Varnoosfaderani Journal of Cleaner Production 324 (2021) 129241

( )
d us,k Ck ygi,k ( ) ( )
d Ck us,k Cp,k Tgk ( ) πdt
+ kc,i,k ak Ck ygi,k − ysi,k = 0 for ​ fluid − phase (10) + hk ak Tgk − Tsk + βγ U1− 2 (Tg2 − Tg1 ) = 0 for ​ fluid
dz dz Ac,k
− phase (15)
at z = 0 ygi,k = yg,0
i,k (11)

at z = 0 Tgk = Tg,0 (16)

where υi takes values of +1 and − 1, respectively, depending on whether k

component i is produced or consumed; and υi,j stands for stoichiometric In the above equations, the subscript k represents the side number of
coefficient of component i in reaction j. each reactor, so that k = 1 and 2 stands for tube- and shell-side,
respectively.
3.1.4. Total mass balance {
1 for ​ shell − side ​ of ​ reactor ​ III
( ) ( ) β= (17)
d us,k Ck ∑nk − 1 for ​ tube − side ​ of ​ reactor ​ I, II, III
+ a k Ck kc,i,k ygi,k − ysi,k = 0 (12)
dz i=1 {
1 for ​ tube − side
γ= (18)
at z = 0 us,k = u0s,k (13) Ntube for ​ shell − side

3.1.6. Momentum balance

3.1.5. Energy balances
{ }
dP (1 − εk )2 μk us,k (1 − εk )u2s,k ρk ρ us,k dus,k
εk k + 150 + 1.75 + k =0 (19)
dz ε2k d2p,k ε2k dp,k εk dz

⎧ ∑ n
⎪ ( )
⎪
⎪ ρb υi − ΔHf,i ri in ​ endothermic − side ​ of ​ reactor ​ III ​
⎪
⎨ i=1
( )
hk ak Tsk − Tgk = for ​ solid − phase (14)
⎪
⎪ ∑
N
⎪ ηj ( − ΔHr )j rsj
⎩ ρb
⎪ in ​ exothermic − side ​ of ​ reactor ​ I, II, III
j=1

Table 1
Auxiliary correlations.
Parameter Equation Ref.

Density of fluid mixture P ∑ n

g
ρ = y Mi
RT i=1 i
g
Viscosity of fluid mixture ∑n y μ Wilke (1950)
μ = ∑n i ig
i=1 j=1 yj φij [ ( )0.5 ( )−
[ ( )] 0.25 ]2
Mi − 0.5 μi Mi
φij = 8 1 + 1+
Mj μj μj
Gas viscosity μi = Ai + Bi T + Ci T2 Yaws (1999)
Molar heat capacity of fluid mixture n
∑
Cp = ygi Cp,i
i=1
Gas molar heat capacity Cp,i = Ai + Bi T + Ci T2 + Di T3 + Ei T4 Coker (2007)
Overall two-phase heat transfer coefficient for reactor I & II 1 1 1
= + TP
UTP hi h
Overall heat transfer coefficient for reactor III 1 1 1
= +
U hi ho
Heat transfer coefficient between the gas phase and tube wall Kg Cussler and Cussler (2009)
h = 0.023Re0.8 Pr0.3
( dt ) g
Heat transfer coefficient between the gas phase and packed-tube wall dp K Leva et al. (1948)
h = 3.5Re0.7 exp − 4.6 for ​ cooling ​ the ​ gas ​ phase
( dt ) dt
dp Kg Leva (1950)
h = 0.813Re0.9 exp − 6 for ​ heating ​ the ​ gas ​ phase
dt dt
g
Heat transfer coefficient between the gas phase and catalyst K McCabe et al. (1993)
h = 1.17Re0.585 Pr0.33
dp
1, 000Cp μ
Pr = g ∑n g
K i=1 yi Mi
Mass transfer coefficient between the catalyst and fluid phases − 2/3 g
kci = 1.17Re− 0.42 Sci u Cussler and Cussler (2009)
dp ug ρ
Re =
μ
μ
Sci =
ρDim
Molecular diffusion coefficient in a multi-component gas mixture 1− y Fairbanks and Wilke (1950)
Dim = ∑ yi
j
j∕
=i
Dij √̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
Binary diffusion coefficient 0.00143T1.75 1/Mi + 1/Mj Poling et al. (2001)
Dij = √̅̅̅ 1/3 1/3 2
2P[νci + νcj ]

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M.H. Khademi and M. Lotfi-Varnoosfaderani Journal of Cleaner Production 324 (2021) 129241

Table 2 Table 3
Kinetic parameters of the glycerol steam reforming reaction (Cheng et al., 2011). Base scenario for operating conditions of glycerol steam reforming,
Species A (mmol m− 2 − 1
s kPa− (a+b)
) E (kJ mol− 1) a b
methane tri-reforming, and ammonia synthesis reaction as well as the
geometry of reactors I, II, and III.
C3H8O3 3.81 59.8 0.48 0.34
H2 37.2 60.2 0.34 0.27 Parameter Value
CO2 11.6 61.8 0.39 0.41 Glycerol steam reforming reaction
CO 308.6 73.9 0.74 − 0.39
CH4 2,834.2 118.9 0.88 0.34 WHSV (h− 1) 20
H2O/C3H8O3 molar ratio 5
Inlet gas temperature (K) 740
Inlet gas pressure (atm) 5
at z = 0 Pk = P0k (20) Catalyst surface (m2/g)a 4.3
Catalyst diameter (m)a 1.15 × 10− 4

Catalyst density (kg m− 3)a 1,870

3.1.7. Auxiliary correlations
Methane tri-reforming reaction
A set of empirical correlations for estimating physical properties, CH4 molar flow rate (mol s− 1) 515
heat and mass transfer coefficients, and diffusion coefficient are listed in O2/CH4 molar ratio 0.6
Table 1. Inlet gas temperature (K) 1,000
Inlet gas pressure (atm) 20
Catalyst shape b 10-HOLE rings
Catalyst size (m)b 19 × 16
3.2. Kinetics model
Catalyst density (kg m− 3)b 1,870
Ammonia synthesis reaction
3.2.1. Ammonia synthesis
N2 molar flow rate (mol s− 1) 41.1
Nitrogen is converted to ammonia at high temperatures and pres­ N2/H2 molar ratio 1/3
sures through the magnetic iron oxide catalyst. Inlet gas temperature (K) 665
Inlet gas pressure (atm) 300
N2 + 3H2 ↔ 2NH3 ΔH298
r
​K
= − 92.4 ​ kJ ​ mol− 1
(21) Catalyst diameter (m)c 2.85 × 10− 3

Catalyst density (kg m− 3)c 1,870

The rate of this reaction was reported by Dyson and Simon (1968) as Number of tubes 250
follows: Tube diameter (m) 0.0254
Shell diameter (m) 0.5
( )[ ( )0.5 ( )0.5 ]
− E a3H a2NH3 Reactor length (m) 6
rNH3 = 2k0 exp K2a aN2 2 2 − (22) Bed porosity 0.4
RT aNH3 a3H2
Number of tubes 500
Tube diameter (m) 0.0254
log 10 Ka = − 2.691122log 10 T − 5.519265 × 10− 5 T + 1.848863 Shell diameter (m) 0.7
(23) Reactor length (m) 7
2, 001.6
× 10− 7 T2 + + 26, 899 Bed porosity 0.4
T
a
Cheng et al. (2011).
where k0 = 8.849 × 1014 , E = 170, 560 kJ mol− 1 , and Ka is equilibrium b
Rahimpour et al. (2012).
c
constant presented by Gillespie and Beattie (1930). Dyson and Simon (1968).

3.2.2. Glycerol steam reforming considered in this study, the carbon formation reactions including (30)–
The overall reaction (1) operates over the Ni/Al2O3 catalyst at at­ (32) have been neglected.
mospheric pressure and temperature of 723–823 K, which includes The rate of glycerol steam reforming was presented by Cheng et al.
glycerol decomposition and water-gas shift reactions as shown in Eqs. (2011) based on the power-law equation as follows:
(24) and (25) (Cheng et al., 2011): ( )
− Ei ai
ri = Ai exp P Pbi Acs (33)
C3 H8 O3 → 3CO + 4H2 ΔH298
r
​K
= 251 ​ kJ ​ mol− 1
(24) RT C3 H8 O3 H2 O

CO + H2 O ↔ CO2 + H2 ΔH298
r
​K
= − 41.1 ​ kJ ​ mol− 1
(25) where A and E denote the pre-exponential factor and activation energy,
respectively, and the reaction is also ath order concerning C3H8O3 and
However, reactions (24) and (25) may also be accompanied by re­ bth order concerning H2O. The kinetic parameters of glycerol steam
actions (26)–(32) as the side reactions (Cheng et al., 2011): reforming are tabulated in Table 2.
C3 H8 O3 + 5H2 ↔ 3CH4 + 3H2 O (26)
3.2.3. Tri-reforming of methane
CO + 3H2 ↔ CH4 + H2 O (27) The methane tri-reforming reactions, including methane steam
reforming, reverse CO2 methanation, water-gas shift, and complete
CO2 + 4H2 ↔ CH4 + 2H2 O (28) methane oxidation occur according to Eq. (34)‒(37) at 800–1,700 K and
10–30 bar over the Ni/MgO/CeZrO2/Al2O3 catalyst (Alipour-Dehkordi
CO2 + CH4 ↔ 2CO + 2H2 (29) and Khademi, 2019). It should be noted that since methane dry
reforming can be derived from reaction (34) minus reaction (36), so this
CH4 ↔ 2H2 + C (30) is not an independent reaction (Khademi et al., 2021). The accuracy of
these reactions was validated by Arab Aboosadi et al. (2011).
C + H2 O ↔ CO + H2 (31)
/
CH4 + H2 O ↔ CO + 3H2 ΔH298 r
​K
= 206 ​ kJ mol (34)
2CO ↔ C + CO2 (32)
/
The formation of CH4, as a by-product, must be taken into account CH4 + 2H2 O ↔ CO2 + 4H2 ΔH298
r
​K
= 164.9 ​ kJ mol (35)
according to reactions (26)–(29). On the other hand, from the findings of /
Wang et al. (2010), it can be prevented the carbon deposition at high CO + H2 O ↔ CO2 + H2 ΔH298
r
​K
= − 41.1 ​ kJ mol (36)
steam to glycerol ratios. Since the high steam to glycerol ratio is

6
M.H. Khademi and M. Lotfi-Varnoosfaderani Journal of Cleaner Production 324 (2021) 129241

/ /
CH4 + 2O2 ↔ CO2 + 2H2 O ΔH298 ​K
= − 802.7 ​ kJ mol (37) Fexo
(43)
r H2
H2 CO ​ ratio =
Xu and Froment (1989) reported a kinetic rate formula (Eq. 38–40) Fexo
CO

for methane steam reforming reactions (34)–(36), and De Smet et al.

F0N2 − Fexo
(2001) modified the kinetic rate proposed by Trimm and Lam (1980) for Nitrogen ​ conversion =
N2
(44)
methane complete oxidation (Eq. (41)) over the Ni-based catalyst. F0N2
( )
k1 P3H2 PCO 1 F0C3 H8 O3 − Fendo
r1 = 2.5 PCH4 PH2 O − × 2 (38) Glycerol ​ conversion =
C 3 H 8 O3
(45)
PH2 KI ∅ F0C3 H8 O3
( )
k2 P4H2 PCO2 1 F0CH4 − Fexo
r2 = 3.5 PCH4 P2H2 O − × (39) Methane ​ conversion =
CH4
(46)
PH2 KІІ ∅2 F0CH4
( )
k3 PH2 PCO2 1
r3 = PCO PH2 O − × (40)
PH2 KІІІ ∅2

k4a PCH4 PO2 k4b PCH4 PO2

r4 = ( )2 + (41)
1 + KCHC4 PCH4 + KOC2 PO2
1 + KCHC4 PCH4 + KOC2 PO2
3.4. Numerical solution

PH2 O
∅ = 1 + KCO PCO + KH2 PH2 + KCH4 PCH4 + KH2 O (42) The governing equations consist of algebraic and ordinary differen­
PH2 tial equations, in which the ordinary differential equations are dis­
The parameters of kinetic constants according to the Arrhenius law cretized into non-linear algebraic equations using the backward finite
difference method. In this regard, the length of the reactor is divided into

⎧
⎪ ṁNH3 LHVNH3 + ṁsyngas LHVsyngas
⎪
⎪ ∑3 i = steam, N2 , O2
⎪
⎪
⎪
⎪ ṁglycerol LHVglycerol + ṁCH4 LHVCH4 + ṁi hi
⎪
⎪ i=1
⎪
⎪
⎪
⎪
⎨ for heat − integrated intensified process
energy efficiency = (47)
⎪
⎪ ṁNH3 LHVNH3
⎪
⎪ i = steam, N2
⎪
⎪ ∑2
⎪
⎪ ṁ LHV CH4 + ṁi hi
⎪
⎪ CH 4 i=1
⎪
⎪
⎪
⎩
for methane steam reforming − based ammonia synthesis process

Table 4
Validation of model prediction with experimental data for glycerol steam reformer.
Molar ratio Temperature of feed stream

723 K 823 K

Experimental dataa Model prediction AE Experimental dataa Model prediction AE

H2/C3H8O3 1.0 0.8 0.2 3.3 2.8 0.5
CO2/C3H8O3 0.47 0.45 0.02 1.6 1.3 0.3
CO/C3H8O3 0.069 0.075 0.006 0.28 0.39 0.11
CH4/C3H8O3 0.017 0.009 0.008 0.23 0.17 0.06
a
Cheng et al. (2011).

and Van’t Hoff equation were reported by Alipour-Dehkordi and Kha­

demi (2020).
Table 5
3.3. Base-scenario definition Verification between model prediction and industrial data presented by Abashar
(2000) for ammonia synthesis reactor.
To characterize and simulate the reactor’s behaviour, the geometry Parameter Industrial data Model prediction RE
and operating conditions for evaporation-, exothermic-, and
Outlet composition (mol%)
endothermic-side are assigned as a base scenario in Table 3. Also, to N2 17.80 17.72 0.45
investigate the role of parameters affecting the performance of the re­ H2 53.90 53.69 0.39
actors, H2/CO ratio, nitrogen, glycerol, and methane conversion as well NH3 19.10 19.34 1.25
as energy efficiency of the process are defined as assessment criteria by CH4 6.30 6.31 0.16
Ar 2.90 2.94 1.38
equations 43–47. Outlet temperature (K) 728 737.52 1.30
N2 conversion 0.3091 0.3138 1.52

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M.H. Khademi and M. Lotfi-Varnoosfaderani Journal of Cleaner Production 324 (2021) 129241

Table 6 2,100 unequally-spaced points, and a numerical solution of all non-

Validation of model prediction with the experimental data for methane tri- linear and linear algebraic equations is found by the “fsolve” function
reformer. in MATLAB software (R2020a) based on the trust-region-dogleg method.
Feed temperature CO2 molar CH4
(K) fraction conversion 4. Results and discussion
1,023 Model prediction 13.2 98.7
Experimental 12.94 97.9 4.1. Model reliability analysis
dataa
RE 2.00% 0.81%
To validate the mathematical and kinetic models used for glycerol
1,123 Model prediction 10.9 99.9
Experimental 10.71 99.99 steam reforming, the molar ratio of products to reactant (glycerol) ob­
dataa tained by simulation at two feed temperatures of 723 and 823 K are
RE 1.77% 0.09% compared with the experimental data provided by Cheng et al. (2011)
a
Kang et al. (2007). under the geometry and operating conditions reported by them. Table 4
shows that the developed model can provide a convincing approxima­
tion of the experimental data with maximum absolute error (AE) of 0.5
for hydrogen to glycerol molar ratio at 823 K. Since the

Fig. 3. Variation of (a) glycerol and methane conversion, and (b) gas temperature in endothermic- and exothermic-side of reactor III under adiabatic and heat-
integrated conditions.

Fig. 4. Variation of dryness fraction, nitrogen conversion, and gas temperature in exothermic-side of reactor I and II.

8
M.H. Khademi and M. Lotfi-Varnoosfaderani Journal of Cleaner Production 324 (2021) 129241

Fig. 5. Effect of WHSV in endothermic-side of reactor III on (a) glycerol and methane conversion, ammonia production, H2/CO ratio, and (b) gas temperature in
exothermic-side of reactor II and III.

consumption/generation rate of steam was not presented in the kinetics
model and its concentration is predicted through the atomic balance, so
some notable error is observed in some cases.
As indicated in Table 5, a comparison between the model prediction
and industrial data presented by Abashar (2000), is done to confirm the
accuracy of the kinetic and mathematical models for ammonia synthesis
reaction. A good agreement between these results is recognized with
relative error (RE) for outlet composition not exceeding 1.5%.
Besides, the experimental data reported by Kang et al. (2007) at
equilibrium state is applied to validate the mathematical model and the
kinetic rate of methane tri-reforming reaction (see Table 6). There is a
good concordance between the experimental data and numerical
modeling results under the operating and geometry conditions
mentioned by Kang et al. (2007), due to the maximum relative error
(RE) of 2% for the molar fraction of carbon dioxide at 1,023 K.
Therefore, the given model can also be applied to simulate this heat-
integrated intensified process. However, experimental proof-of-concept
is required to validate the simulation results, get more certainty in the
model’s precision, and ensure the safe operability of this process.

Fig. 6. Effect of (a) O2/CH4, (b) O2/CH4, (c) H2O/glycerol, and (d) N2/H2 ratio on the performance of heat-integrated intensified process.

9
M.H. Khademi and M. Lotfi-Varnoosfaderani
4.2. Simulation results
A comparison between heat-integrated and adiabatic conditions for
reactor III, as shown in Fig. 3, is carried out in terms of glycerol and
methane conversion as well as gas temperature in exothermic- and
endothermic-side. In the adiabatic reactor (AR), no heat is transferred
from the solid wall of the exothermic-side into the endothermic-side. So,
the heat required for glycerol steam reforming is taken from feed gas
sensible heat, and temperature prfile reduces quickly to reach 565 K (see
Fig. 3(b)). This leads to a decrease in the reaction rate, and resulting in a
lower degree of glycerol conversion, i.e., 28% (see Fig. 3(a)). Instead,
the heat required for glycerol steam reforming in the heat-integrated
reactor is supplied by the other side; the gas temperature remains at a
higher level compared to the AR (see Fig. 3(b)), and consequently, the
glycerol conversion reaches 100% (see Fig. 3(a)).
At the first half of the heat-integrated reactor and AR, the methane
conversion increases rapidly (see Fig. 3(a)), due to temperature rise, and
after that approaches equilibrium conversion. Although the heat-
integrated reactor and AR almost have the same behaviour in terms of
methane conversion, the exothermic-side temperature in the heat-
integrated is much lower than that in the AR (see Fig. 3(b)), leading
to a delay in Ni/MgO/CeZrO2/Al2O3 catalyst deactivation. At the
entrance of the heat-integrated reactor, the temperature profile in the
exothermic-side increases to 1,440 K and then decreases rapidly to
1,140 K as a result of heat transferred from the solid wall; but in the AR,
which acts as a traditional autothermal tri-reformer, a hot spot tem­
perature (i.e., 1,540 K) is first observed at the dimensionless length of
0.2 and then gradually approaches 1,400 K due to fuel depletion.
Therefore, this heat-integrated process can also improve the conven­
tional autothermal tri-reformer in terms of catalyst lifetime by removing
heat from the solid wall.
The comparison between the heat-integrated reactor and AR in­
dicates that the methane tri-reforming reaction can provide the heat
required to drive the glycerol steam reforming, and coupling of these
two reactions can be feasible and beneficial for the following reasons: (i)
saving much energy by transferring 69.23 kW heat from the exothermic-
to endothermic-side in order to drive the glycerol steam reforming, (ii)
achieving the highest conversion of methane and glycerol, and (iii)
keeping the temperature of methane tri-reforming reaction lower than
normal to delay in catalyst deactivation.
Fig. 4 indicates the variations of the nitrogen conversion, dryness
fraction and gas temperature in the exothermic-side along the length of
Fig. 7. Effect of splitting factor on the performance of the reactor I and II.
10
Journal of Cleaner Production 324 (2021) 129241
reactors I and II. In the dimensionless length range of 0–0.1, the tem­
perature profile in both reactors rises to 695 K, which can be attributed
to rapid ammonia synthesis reaction rate as a result of high reactants
inlet concentration. After that, the molar fraction of nitrogen continu­
ously reduces, lowering the rate of nitrogen conversion, and conse­
quently the low heat generated through ammonia synthesis leads to a
decrease in temperature. At the entrance of reactor I, a breakingpoint in
the temperature profile is observed due to the shifting from convective
to nucleate boiling region in the evaporation-side. Nitrogen conversion
at the end of reactors I and II reaches 27% and 26%, respectively. The
dryness fraction in reactor I increases up to 0.5, two-phase flow gradu­
ally changes to vapor-phase flow at the end of reactor II, where the
dryness fraction will be equal to 1.0.
4.3. Effect of WHSV
The effect of weight hourly space velocity (WHSV) in glycerol steam
reforming reaction on the methane and glycerol conversion as well as
ammonia production and H2/CO ratio is indicated in Fig. 5(a). On the
endothermic-side, the gas residence time decreases due to an increase in
the WHSV, and this in turn, reduces the glycerol conversion. Simulta­
neously, the endothermic-side heat transfer coefficient is raised with
WHSV, leading to more heat transfer rate from the solid wall and
consequently decreasing the temperature in the exothermic-side (see
Fig. 5(b)). This causes a reduction in methane conversion. More
ammonia production and a higher H2/CO ratio are observed at higher
WHSV due to producing more hydrogen.
4.4. Effect of feed components molar ratio
The effect of the O2/CH4 ratio on the performance of reactor III is
illustrated in Fig. 6(a). Increasing the O2/CH4 ratio leads to more
available oxygen for the methane oxidation reaction, eventually
increasing the gas temperature and methane conversion. This causes
more heat transfer to the endothermic-side and increases the gas tem­
perature on this side, thereby increasing the glycerol conversion. It
should be noted that O2/CH4 ratio above 0.64 has no considerable effect
on both conversions. On the other hand, increasing the O2/CH4 ratio
decreases the H2/CO ratio due to more CO2 production, driving the
reverse water-gas shift reaction and producing more CO as a result of the
Le Chatelier’s principle.
The maximum gas temperature on the endothermic-side increases
from 750 to 1,050 K as a result of increasing the O2/CH4 ratio from 0.4 to
0.8. Although the higher temperature in endothermic-side benefits the
glycerol conversion, coke deposition is more likely to occur at higher
temperatures during reaction time, thereby leading to catalyst deacti­
vation. In this regard, Cheng et al. (2011) reported that coke was
deposited on Ni/Al2O3 catalyst at 823 K after 4 h, even under excess
steam/glycerol ratios. High temperatures also increase the cost of
reactor construction, energy consumption, and operational costs.
Therefore, in this study, 823 K is selected as the maximum allowable
temperature for glycerol steam reforming reaction to prevent coke
deposition. At this temperature, the O2/CH4 ratio equal to 0.59 is found,
and a synthesis gas with H2/CO ratio of 2.6 is produced. The results
show that the O2/CH4 = 0.59 is the best ratio to reach methane and
glycerol conversion above 90%.
The O2/CH4 ratio, as indicated in Fig. 6(b), affects the performance
of reactors I and II. More ammonia is produced with O2/CH4 ratio due to
increasing the glycerol conversion (see Fig. 6(a)) and more hydrogen. In
addition, the ammonia production rate remains constant for O2/CH4 >
0.64 according to reaching the highest degree of glycerol conversion, i.
e., 100%. The outlet dryness fraction of reactor II raises with O2/CH4
ratio, and eventually approaches 1.0 during the transition from two-
phase flow to pure vapor as a result of a higher heat transfer coeffi­
cient inside the tubes. Also, no change in the outlet temperature of the
evaporation-side of reactor II is observed and it remains at the boiling
M.H. Khademi and M. Lotfi-Varnoosfaderani Journal of Cleaner Production 324 (2021) 129241

Fig. 8. Effect of inlet gas temperature in (a) exothermic-side of reactor III, (b) exothermic-side of reactor III, (c) endothermic-side of reactor III, and (d) exothermic-
side of reactor I & II on the performance of heat-integrated intensified process.

Fig. 9. Effect of inlet gas pressure in (a) endothermic-side of reactor III, and (b) exothermic-side of reactor I and II on the performance of heat-integrated inten­
sified process.

point of glycerol. methane conversion. The ammonia production is diminished with

Fig. 6(c) shows the effect of steam/glycerol ratio, at a given WHSV (i.
e., 20 1/h), on the performance of the heat-integrated intensified pro­
cess. The glycerol conversion increases with steam/glycerol ratio up to
6.5 as a result of an increase in the reaction rate, and after that reaches
100% as a result of fuel depletion. The methane conversion also in­
creases because of lower heat transfer from the solid wall and higher
temperature levels on the exothermic-side. Although increasing the
steam/glycerol ratio from 3 to 12 leads to an increase in the glycerol
conversion up to 16%, it has a slight effect, lower than 4%, on the
steam/glycerol ratio due to less available hydrogen. Besides, an increase
in the outlet dryness fraction of reactor II is found by decreasing the
H2O/glycerol ratio from 12 to 5 due to the higher heat transfer coeffi­
cient in the exothermic-side of reactors I and II; and further reducing of
H2O/glycerol ratio causes complete evaporation of glycerol liquid phase
(dryness fraction = 1.0). On the other hand, it has been reported in the
literature (Silva et al., 2015) that an abundant amount of steam has a
positive effect on the performance of the catalyst in glycerol steam
reforming due to the lack of carbon deposition. Nevertheless, it seems

11
M.H. Khademi and M. Lotfi-Varnoosfaderani Journal of Cleaner Production 324 (2021) 129241

Fig. 10. Effect of number of tubes in reactor I and II on the (a) performance of heat-integrated intensified process and (b) temperature profile in exothermic-side of
reactor II.

4.6. Effect of gas temperature

Table 7
Comparison between conventional and heat-integrated intensified process.
The changes in the performance of the heat-integrated intensified
Parameter Value process with inlet gas temperature in the exothermic-side of reactor III
Proposed Conventional are presented in Fig. 8(a) and (b). Rising the temperature in the
process processa exothermic-side from 800 to 1,200 K makes the methane tri-reforming
The main source of fuel (kg /tNH3 ) 1,872 kg 756.29 kg Natural reaction at a faster rate, and increases the methane conversion by
Glycerol gas
Steam (kg /tNH3 ) 7,316.5 2,499.35
32%. In addition, glycerol conversion also increases due to more heat
Nitrogen (kg /tNH3 ) 824 914.67
transfer from the solid wall. Results indicate that maximum glycerol
conversion, i.e., 100%, is obtained at 1,000 K, where the H2/CO ratio is
Ammonia production (kg) 1,000 1,000
equal to 2.52. The H2/CO ratio reduces with temperature due to
Water for cooling of ammonia reactor – 400.71
(kg /tNH3 ) increasing the rate of reverse water-gas shift reaction, thereby resulting
Emissions to air (kg /tNH3 ) 0.0 5,500.36 in hydrogen consumption and CO production. Although higher con­
Energy efficiency 31% 40% versions are achieved at higher inlet temperatures, the gas temperature
a
in the endothermic-side of reactor III exceeds the maximum allowable
Chisalita et al. (2020).
temperature (i.e., 823 K) at inlet gas temperatures above 1,000 K (see
Fig. 8(a)). Therefore, due to the achievement of methane and glycerol
that H2O/glycerol ≅ 5 is the best ratio under the base scenario, but using conversion above 90% and exhibiting a longer Ni/Al2O3 catalyst life­
a stochastic optimization algorithm can help to find the correct ratio. As time, 950–1,000 K is the best inlet gas temperature in the exothermic-
indicated in Fig. 6(c), the H2/CO ratio in the synthesis gas increases with side of reactor III.
the steam to glycerol ratio due to the higher conversion of methane. As shown in Fig. 8(b), more ammonia is produced with inlet gas
Fig. 6(d) presents the variations of the performance of the reactors I temperature, due to higher glycerol conversion (see Fig. 8(a)) and
and II versus N2/H2 ratio. More ammonia is produced with an increase in consequently more hydrogen production; as such, dryness fraction in­
the N2/H2 ratio up to 0.8 due to increasing the feed molar flow rate, and creases from 0.7 to 1 as a result of greater heat transfer rate from the
then decreases due to reducing hydrogen conversion. Adding more heat solid wall. At inlet gas temperature above 1,000 K, no change in
to the evaporation-side can either change the glycerol phase from liquid ammonia production and dryness fraction is observed. However, the
to vapor or raise the temperature of the pure vapor. At the end of the dryness fraction more than 98% is also taken at 950–1,000 K.
evaporation-side of reactor II, the dryness fraction increases as the N2/ Although increasing inlet gas temperature in the endothermic-side of
H2 ratio increases from 0.25 to 0.37 at the glycerol boiling point tem­ reactor III from 723 to 823 K has no considerable effect on glycerol
perature. As such, at N2/H2 ratios above 0.37, sensible heat leads to an conversion, the maximum temperature in this side increases from 815 to
increase in the vapor phase temperature from 625 to 648 K. Therefore, 868 K (see Fig. 8(c)). As shown in this figure, to prevent the Ni/Al2O3
N2/H2 ratio ≅ 0.8 is recommended for this process in terms of more catalyst deactivation, 723–745 K is the appropriate inlet gas tempera­
ammonia production and higher glycerol temperature in the evapora­ ture for this side.
tion-side. The variations of the performance of the reactors I and II versus inlet
gas temperature in the exothermic-side of these reactors are indicated in
4.5. Effect of splitting factor Fig. 8(d). Higher inlet gas temperature is favored for the production of
ammonia and glycerol in the vapor-phase. The glycerol temperature
Although the change in the splitting factor (fraction of total feed, exiting from the evaporation-side rises to 730 K by increasing the inlet
containing H2 and N2 entering reactor I) has no significant effect on the temperature of exothermic-side, due to further heat transfer from the
dryness fraction, it has a noticeable influence on the nitrogen conversion solid wall. As a result, it is evident that increasing the temperature of
and ammonia production (see Fig. 7). Increasing splitting factor leads to glycerol vapor can be remarkably effective in reducing the size of the
lower residence time in reactor I, thereby decreasing nitrogen conver­ heat-exchanger, which is located between reactors II and III.
sion in this reactor. On the other hand, this term increases nitrogen
conversion in reactor II due to higher residence time. Therefore, the
highest ammonia production is obtained at the intersection of the ni­ 4.7. Effect of operating pressure
trogen conversion profiles, in which the splitting factor is equal to 0.52.
In other words, equally dividing the feed stream into two reactors in The reactor wall can be constructed of high-pressure resistant ma­
parallel leads to maximum ammonia production. terials to allow the reactor to operate at different pressures on both sides.

12
M.H. Khademi and M. Lotfi-Varnoosfaderani
Since the operating pressure of ammonia synthesis and glycerol steam
reforming reactions has a direct effect on ammonia production, the in­
fluence of this parameter on the performance of reactors is investigated
in Fig. 9. Increasing the gas pressure in the endothermic-side of reactor
III up to 5 atm increases the glycerol conversion, but a considerable
improvement in glycerol conversion is not found at higher pressures
more than 5 atm (see Fig. 9(a)). This trend can be attributed to this fact
that further enhancement in the pressure, from a certain point, does not
induce a dominant positive impact on the glycerol conversion with
respected to the thermodynamic limitation. On the other hand, the
ammonia production is not significantly affected by changes in pressure.
The influence of inlet gas pressure in the exothermic-side of reactor I
and II on ammonia production and dryness fraction (see Fig. 9(b)) shows
that the operating pressure is the most effective parameter during
ammonia synthesis, so that rising the pressure from 150 to 300 atm
increases the ammonia production more than two folds, due to the Le
Chatelier’s principle. In addition, the adequate dryness fraction (e.i.,
1.0) can be achieved at pressures above 300 atm.
4.8. Effect of tubes number
Fig. 10 illustrates the alterations of outlet temperature in
evaporation-side, dryness fraction, ammonia production, and tempera­
ture profile of ammonia synthesis in response to the number of tubes in
reactor I and II. At constant feed molar flow rate, increasing the number
of tubes reduces the molar flow rate of reactants in each tube, leading to
a severe reduction in temperature profile (see Fig. 10(b)) and a decrease
in ammonia production (see Fig. 10(a)). This can be attributed to slow
rate of glycerol reforming reaction as a result of low glycerol inlet
concentration. Although decreasing the number of tubes to less than 240
reduces the heat transfer surface area, more heat is transferred to the
evaporation-side as a result of higher operating temperature on the
exothermic-side. This concept increases the outlet temperature in the
evaporation-side of reactor II from 625 to 674 K and brings the dryness
fraction to 1.0 (see Fig. 10(a)).
4.9. Comparison between conventional and proposed process
Table 7 shows a comparison between ammonia production routes
through the heat-integrated intensified process and conventional
methane steam reforming data reported by Chisalita et al. (2020) in
terms of greenhouse gas emissions, energy efficiency, the amount of fuel
consumption, and cooling system for ammonia synthesis reactor.
Although the fuel consumption in the proposed process is higher than
the conventional, the main source of fuel for the proposed ammonia
production process is supplied from glycerol as a renewable carbon
resource which can reduce the price of biodiesel and make its production
process more economical. Correspondingly, more steam is also
consumed by the proposed process. In the conventional process, 400.71
kg of water per each tonne of ammonia is used to cool the ammonia
synthesis reactor, while in the proposed system, no external cooling
medium is required and the reactor is cooled by glycerol vaporization.
During the conventional process, large amounts of greenhouse gases
are released to the atmosphere through the furnace stack, but in the
proposed system, the greenhouse gases produced by glycerol steam
reforming are reused in the methane tri-reforming reaction to supply the
heat of reaction. Thus, this leads to a reduction in gas emissions to air
from 5,500.36 kg per tonne of NH3 to zero. Although ammonia pro­
duction via the conventional method yields a higher energy efficiency (i.
e., 40%) compared to the proposed method (i.e., 31%), it should be
noted that the energy of air and fuel for heating the furnace and elec­
tricity for gas compression in calculating energy efficiency of the con­
ventional process are not considered due to lack of information on this
issue. In addition, the proposed process produces synthesis gas, as a
valuable product for methanol and Fischer-Tropsch synthesis process,
13
Journal of Cleaner Production 324 (2021) 129241
with the lower heating value of 4,000 kJ/kg.
5. Conclusion
This study was focused on a heat-integrated intensified process to
produce ammonia and syngas as valuable products. In this process,
glycerol steam reforming continuously provided the hydrogen required
for ammonia synthesis, and the liquid glycerol was simultaneously
vaporized by heat generated from ammonia synthesis. Methane tri-
reforming was also used as a heat source to drive the glycerol reform­
ing, and at the same time, the effluent gas exiting from the glycerol
reforming side was consumed in the tri-reforming reaction. The
behaviour of the reactors was revealed through a 1D heterogeneous plug
flow model. The backward finite difference approach was applied to
discretize and solve the governing equations through the trust-region-
dogleg approach.
Based on detailed modeling and studying the impact of various pa­
rameters on the performance of this process, the acceptable range of
operating conditions for this system was found as follows: steam/glyc­
erol ratio ≅ 5.0, O2/CH4 ratio ≅ 0.6, N2/H2 ratio ≅ 0.8, splitting factor ≅
0.5, operating pressure of glycerol steam reforming ≅ 500 kPa, oper­
ating pressure of ammonia synthesis ≥ 300 atm, 950 < inlet gas tem­
perature of methane tri-reforming < 1,000 K, 723 < inlet gas
temperature of glycerol steam reforming <745 K, 670 < inlet gas tem­
perature of ammonia synthesis <750 K. Numerical results showed that
more than 90% of glycerol and methane, and more than 25% of nitrogen
can be converted to syngas and ammonia. In addition, glycerol dryness
fraction equal to 1.0, and a synthesis gas with H2/CO ratio above 2.0 was
obtained, which is compatible with the Fischer-Tropsch and methanol
synthesis processes.
In general, the advantages of this heat-integrated intensified process
compared to the conventional ammonia synthesis process are as follows:
(1) reducing the process capital cost due to the removal of the desul­
phuriser, steam reformer (furnace), water-gas shift converter, and
condenser; and elimination of the inter-stage cooler for ammonia syn­
thesis reactor, (2) simultaneous production of ammonia and synthesis
gas through glycerol valorization as a credible alternative to reforming
of natural gas, (3) providing the auto-thermality within the reactors by
coupling glycerol steam reforming and methane tri-reforming, as well as
ammonia synthesis reaction and evaporation of liquid glycerol, (4)
mitigation of the environmental pollution due to no flue gas emissions
into the atmosphere compared to the conventional process (i.e.,
5,500.36 kg/tNH3 ), and (5) use of greenhouse gases (CO2, CH4, and H2O)
produced via glycerol steam reforming as the feedstock of methane tri-
reforming.
CRediT authorship contribution statement
Mohammad Hasan Khademi: Conceptualization, Project adminis­
tration, Supervision, Writing – original draft, Writing – review & editing.
Mohammad Lotfi-Varnoosfaderani: Methodology, Software, Valida­
tion, Investigation, Writing – original draft.
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.
Acknowledgement
We thank Alireza Palizvan (Master’s student in chemical engineering
at University of Isfahan) for assistance with methodology, and for
comments that greatly improved the manuscript.
M.H. Khademi and M. Lotfi-Varnoosfaderani Journal of Cleaner Production 324 (2021) 129241

Nomenclature

a Catalyst specific surface area, m2 m− 3

Ac Cross-section area, m2
Acs Catalyst surface, m2 kgcat
− 1

Bo Boiling number
C Total concentration, mol m− 3
Co Convection number
Cp Molar heat capacity of the fluid, J mol− 1 K− 1
Dij Binary diffusion coefficient, m2 s− 1
Dim Diffusivity in a multicomponent gas mixture, m2 s− 1
dt Diameter of tube, m
dp Diameter of catalyst pelet, m
E Activation energy, kJ mol− 1
F Molar flow rate, mol s− 1
Frl Froude number with all flow in liquid
Ffl Fluid-dependent parameter
g gravitational acceleration, m s− 2
G Mass flux, kg m− 2 s− 1
h Heat transfer coefficient, W m− 2 K− 1
K Thermal conductivity, W m− 1 K− 1
Ka Equilibrium constant for ammonia synthesis reaction
1
Ki Adsorption equilibrium constant for methane tri-reforming (i = CH4, H2, CO, H2O, OC2 , CHC4 ), bar−
Kn Reaction equilibrium constant for methane tri-reforming (n = I, II, III)
kc Catalyst-fluid mass transfer coefficient, m s− 1
− 1 − 1
kj Rate constant for methane tri-reforming reaction (j = 1, 2, 3, 4a, 4b), mol kgcat s
M Molecular weight
N Total number of reactions
Ntube Number of tubes
n Total number of chemical components
P Pressure, Pa
Pr Prandtl number
Pi Partial pressure of species i, kPa
q Heat flux, W m− 2
R Universal gas constant, J mol− 1 K− 1
Re Reynolds number
− 1 − 1
r Rate of reaction, mol kgcat s
Sc Schmidt number
T Temperature, K
U Overall heat transfer coefficient, W m− 2 K− 1
us Superficial velocity, m s− 1
x Dryness fraction
y Molar fraction
z Axial coordinate, m

Greek letters
ΔHf Heat of formation, J mol− 1
ΔHr Heat of reaction, J mol− 1
μ Fluid viscosity, kg m− 1 s− 1
ε Bed porosity
η Effectiveness factor
λ Latent heat of vaporization, J mol− 1
ρ Fluid density, kg m− 3
ρb Catalytic bed density, kg m− 3
υ Stoichiometric coefficient
υc Molecular diffusion volume, cm3 mol− 1

Superscripts
0 Inlet condition
b Boiling point
endo Stands for the endothermic-side
exo Stands for the exothermic-side
g Gas-phase

14
M.H. Khademi and M. Lotfi-Varnoosfaderani Journal of Cleaner Production 324 (2021) 129241

s Catalyst-phase
TP Two-phase

Subscripts
i Chemical component
j Reaction No
k Side No. (1 = tube-side, 2 = shell-side)
l Liquid

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