Science of the Total Environment 664 (2019) 567–575

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Science of the Total Environment

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

Potential of tri-reforming process and membrane technology for

improving ammonia production and CO2 reduction
Ahmad Taghizade Damanabi a, Morteza Servatan a, Saeed Mazinani a,⁎, Abdul Ghani Olabi b,c, Zhien Zhang d,⁎
a
Process Engineering for Sustainable Systems, Department of Chemical Engineering, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium
b
Sustainable and Renewable Energy Engineering, University of Sharjah, Sharjah, United Arab Emirates
c
Mechanical Engineering and Design, School of Engineering and Applied Science, Aston University, Aston Triangle, Birmingham B4 7ET, UK
d
William G. Lowrie Department of Chemical and Biomolecular Engineering, The Ohio State University, Columbus, OH 43210, USA

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• A tri-reforming process was coupled

with a membrane separation unit to en-
hance the ammonia synthesis process
efficiency.
• Increasing temperature and decreasing
pressure improved the hydrocarbons
conversion and H2/CO ratio.
• The proposed strategy increased NH3
production and reduced CO2 emission
simultaneously.

a r t i c l e i n f o a b s t r a c t

Article history: In this work, a tri-reforming process was coupled with a membrane separation unit to enhance efficiency of am-
Received 7 December 2018 monia (NH3) synthesis process in terms of CO2 emission, NH3 production, and NOx emission. Primary and sec-
Received in revised form 28 January 2019 ondary reformers were replaced by a tri-reforming process, while a Perovskite membrane was applied to
Accepted 29 January 2019
separate nitrogen (N2) from oxygen (O2). A conventional NH3 synthesis process and the proposed process
Available online 30 January 2019
were simulated by Aspen-Hysys and compared in order to investigate the performance of the proposed sterategy.
Editor: Damia Barcelo The simulation results indicated that when temperature increased and pressure decreased, conversion of
hydrocarbons and H2/CO ratio were improved from 1.73 to 2.54, which resulted in an increase in NH3 production
Keywords: by 27 %, and a decrease in CO2 emission rate from 1192 kg/h to approximately 1 kg/h. The proposed sterategy was
CO2 emission optimized in terms of different parameters e.g., temperature and pressure. Optimum reaction pressure and tem-
NH3 synthesis process perature were determined to be between 1 and 10 bar and 500–800 °C, respectively. The results of the study re-
Tri-reforming process vealed that the proposed strategy not only removed amine and methanol sweeteners which reduce the
Perovskite membrane operational costs of the process, but also decreased the NOx content from 8220 ppm to almost 10 ppm.
© 2019 Elsevier B.V. All rights reserved.

⁎ Corresponding authors.
E-mail addresses: saeed.mazinani@kuleuven.be (S. Mazinani), zhang.4528@osu.edu (Z. Zhang).

https://doi.org/10.1016/j.scitotenv.2019.01.391
0048-9697/© 2019 Elsevier B.V. All rights reserved.
568 A.T. Damanabi et al. / Science of the Total Environment 664 (2019) 567–575
1. Introduction
Ammonia (NH3) significantly contributes to nutritional needs of ter-
restrial organisms by serving as a precursor to food and fertilizers. NH3,
either directly or indirectly, is used as a building block for synthesis of
many pharmaceutical or commercial cleaning products (Lam et al.,
2018; Arora et al., 2018; Jeremiaš et al., 2014). Additionally, NH3 can
be used for chemical processes in which an energy carrier is needed
(Bicer et al., 2017; Bicer and Dincer, 2018a; Jain et al., 2017). According
to annual energy report (Bicer and Dincer, 2018a), approximately 2 % of
the world's commercial energy (as fossil fuels) is consumed for NH3
synthesis. It was also reported that 245 million tons of CO2 was released
by the NH3 industry in 2010 (Bicer and Dincer, 2018b). Thus, it is essen-
tial to improve the NH3 synthesis process in order to significantly reduce
CO2 emissions, as the most important cause of greenhouse effect
(Mazinani et al., 2018; Mazinani et al., 2015; Pan et al., 2018). NH3 is
produced by the Haber process in a synthesis reactor at pressure of
200–300 bar and temperature of 400–600 °C. The hydrogen (H2) re-
quired for the process is produced by methane (CH4) reforming using
a mixture of steam and air (Bicer et al., 2017). The CO2 produced during
the CH4 steam reforming reaction is removed by an amine absorp-
tion unit, while the required N2 is provided through air injection
into the reformer reactors. The efficiency of the process depends sig-
nificantly upon the H 2 production rate (Bicer et al., 2017). Tri-
reforming process is a new technology that has recently been used
to increase H2 production and recycle produced CO2. In this process,
steam, oxygen (O2), and CO2 are used for CH4 reforming and gener-
ating synthesis gas. The use of tri-reforming actually increases pro-
duced H2 and consequently, enhances NH 3 production along with
reduction in production costs (Damanabi and Bahadori, 2017;
Dwivedi et al., 2018; Sadeghi et al., 2018). Recent studies showed
that the use of tri-reforming process can reduce energy consumption
and increases the efficienty of process (Sadeghi et al., 2018;
Katarzyna et al., 2017; Song and Pan, 2004).
Much research has been done on optimizing and improving the NH3
production process. The research can be divided into four aspects: 1-
source of feed, 2- reduction of CO2 emissions, 3- decreasing the required
energy for the process, and 4- using other systems such as membrane
systems (Bicer and Dincer, 2018a). The main feed for NH3 production
is N2 and H2 produced from water (H2O) electrolysis (Jain et al.,
2017); however, the other resources including natural gas (Lu et al.,
2015; Frattini et al., 2016; Amin et al., 2013) and biomass (Arora et al.,
2017; Zhao et al., 2011; Andersson and Lundgren, 2014) have been in-
vestigated recently. The second aspect is related to reducing CO2 emis-
sions to the atmosphere. Several methods have been proposed for
reduction of CO2 production such as injection of produced CO2 into oil
reservoirs for secondary oil recovery as an enhanced oil recovery
(EOR) method (Bicer and Dincer, 2018b), implementing biomass as
feed (Gilbert et al., 2014; Zhang et al., 2018a; Zhang et al., 2018b), and
enhancing the efficiency of the process (Bicer et al., 2016). Energy con-
sumption of the process needs to be improved and optimized (Bicer and
Dincer, 2017). Finally, the last aspect is application of membranes for in-
creasing the efficiency of NH3 production and decreasing the required
energy. Separation of some materials from reaction zone increases the
equilibrium reactions' efficiency (Orrego and Junior, 2016; Damanabi
and Bahadori, 2018; Psara et al., 2015).
The application of membranes in chemical reaction processes is now
largely concentrated in H2 and O2-containing reaction systems. Differ-
ent types of ceramic membranes could be used for air separation to its
components such as O2. Recently, perovskite membranes have attracted
much attention due to excellent O2 permeability and good stability at
high temperatures and pressures. Actually, the resistance of perovskite
membranes versus thermo-mechanical and chemical decomposition
at high temperatures is decisive to use it (Ghadimi et al., 2011; Hu
et al., 2018; Lu et al., 2018). The parameters that influence the O2 per-
meation in the perovskite membranes include operating temperature
and pressure, membrane thickness, feed flow rate, and purity of the
feed (Ghadimi et al., 2011).
In this work, a tri-reforming process was associated with a mem-
brane separation unit in NH3 synthesis process in order to reduce CO2
emissions and increase NH3 production, simultaneously. A perovskite
membrane was eomployed to separate N2 from O2. The conventional
and proposed processes were simulated and compared in terms of
CO2 emission, NH3 production and NOx emission to evaluate the perfor-
mance of the proposed process. Additionally, in order to optimize the
proposed process, the effects of different parameters e.g., temperature
and pressure have been evaluated.
2. Methodology
2.1. Assumption
The main assumptions for this model are listed below:
• The simulation was peformed in steady state condition.
• Pressure drop along the NH3 synthesis reactor was considered to be
ignorable. However, in other reactors, pressure was computed from
Ergun equation.
• All the reactors were simulated in shell and tube form.
2.2. Process description
One of the most commonly used methods for producing synthesis
gas is reforming of natural gas or naphtha with steam (Dincer, 2012).
Generally, the NH3 production stages can be summarized in Fig. 1.
Catalysts used in the NH3 synthesis are sensitive to sulfur, so the first
step is to remove sulfur compounds, mostly hydrogen sulfide (H2S) and
thiol, from natural gas. The sulfur compounds are removed by passing
the natural gas through an active carbon or zinc oxide substrate. H2S
can be removed at different temperatures, in this simulation it was re-
moved at temperatures between 370 and 400 °C (highest efficiency of
removal).
Steam reforming reactions are carried out in two steps. In the pri-
mary reformer, the catalysts are placed in tubes with a diameter of
0.1 cm, which are heated in a furnace. Steam and feed (with 3 to 1
ratio) are introduced into the reformer, at a pressure of 30 atm and
370 °C, where reforming reactions are carried out. The residence time
in the reformer is not long enough so the reforming reactions are not
complete. Therefore, the outlet contain significant amounts of hydrocar-
bons along with H2, CO, CO2 and steam.
CH 4 þ H2 O→CO þ 3 H 2 ð1Þ
CH 4 þ 2 H 2 O→CO2 þ 4 H2 ð2Þ
Hot gases emitted from the primary reformer along with air are
injected to the catalyst bed of the secondary reformer. The gas from
the secondary reformer consists of N2, H2, CO, CO2, steam and a small
amount of CH4. CO2 poisons the synthesized catalysts and thus should
be completely removed from the synthesis gas.
CH 4 þ 0:5O2 →CO þ 2H 2 ð3Þ
CH 4 þ O2 →CO2 þ 2H 2 ΔH ¼ −880 kJ=mol ð4Þ
After the reformer reactors, the synthesis gas is introduced into
water-gas shift (WGS) reactors. The goal here is to convert carbon mon-
oxide (CO) into CO2 through a WGS reaction:
H 2 O þ CO↔H 2 þ CO2 ð5Þ
 A.T. Damanabi et al. / Science of the Total Environment 664 (2019) 567–575 569

Fig. 1. A schematic of conventional NH3 production unit.

The reaction would be desirable at lower temperatures, however, In Eq. (8), kj is pre-coefficient exponential, Ej is activation coefficient
with decreasing temperature the reaction rate will be decreased. Thus, and R is gas constant. The feed enters the NH3 reactor after passing
in order to achieve an optimal temperature, the WGS reactions are usu- through the compressor and heat exchangers. In this reactor, an alumi-
ally take place in two steps at high temperatures and low temperatures. num oxide catalyst is used. The NH3 produced in accordance with
First, the reactions are carried out at a high temperature of about 400 °C Eq. (8) is separated off by a three phase separator and the unreactive
in the presence of an iron oxide catalyst, and then carried out at a low gases are returned to the reactor through a compressor. Table 2 and
temperature of 200 °C using a copper-zinc catalyst. Eq. (11) show Arrthenius kinetic parameters for Eq. (10).
The next step is to remove CO2, which is usually done using chemical
absoprtion by potassium carbonate solution or monoethanolamine N2 þ 3H 2 ↔2NH3 ð9Þ
(MEA). The last remaining COx is eliminated by methanation in accor- 0 !1−β !β 1
dance with relations (6) and (7) by passing gas through the bed of a P N2 P 3H2 P2NH3
nickel catalyst at 350 °C, the reforming reaction is diverted to the origi- RNH3 ¼ @K 1  −K 1  A ð10Þ
K eq 2 P2NH3 P 3H2
nal material and the carbon components are converted to CH4 and
steam:

E
−RTi
K i ¼ Ai  e ð11Þ
CO þ 3 H 2 →CH 4 þ H 2 O ð6Þ
In Eq. (10) and Eq. (11), β = 0.27 for the Al2O3 base catalyst is ob-
CO2 þ 4H 2 →CH4 þ 2 H2 O ΔH ¼ þ247 kJ=mol ð7Þ tained at 573–723 K (Araujo and Skogestad, 2008). Fig. 2 shows the sim-
ulation process of a conventional NH3 production.
The outlet gas is cooled and the condensed steam is used again to
produce the synthesis gas. Table 1 and Eq. (8) show Arrthenius kinetic 2.3. Process optimization
parameters for Eq. (1) to Eq. (3) and Eq. (5) to Eq. (6).
In the NH3 synthesis process, CH4 is firstly desulfurized by the zinc

E
 oxide adsorbents and then converted to synthesized gas by the re-
−RTj
K j ¼ kj  e ð8Þ
formers. Synthesis gas produced is sent to the amine unit to remove
CO2. The sweet stream is introduced into the methanator reactor for fur-
ther separation of CO2. The outlet from the methanator reactor is sent to

Table 1
Reaction Arrhenius kinetic parameters (Rahimpour et al., 2012).

Reaction no. kj (mol/(kgCat·s)) Ej (J/mol) Table 2

1 1187.55 240,100 Arrhenius kinetic parameters in the NH3 synthesis reaction (Araujo and Skogestad, 2008).
2 2872.45 243,900
Reaction no. kj (mol/(kgCat·s)) Ej (J/mol)
3 8231.65 86,000
5 114.17 58,826.3 1 1.79 × 104 87,090
6 39,638.3 83,423.9 2 2.75 × 1016 198,464
570 A.T. Damanabi et al. / Science of the Total Environment 664 (2019) 567–575

Fig. 2. Simulation of a conventional NH3 production unit (a) synthesis gas production section, (b) sweeting and methanator section, and (c) NH3 synthesis section.

the NH3 synthesis reactor. In order to improve the efficiency of this unit, of H2 and to complete the removal of CO2 and CO. To reduce the air pol-
a tri-reformer reactor was used instead of the reformers, and a palla- lutants, a perovskite membrane is used to separate N2 from O2 for NH3
dium silver (Pd/Ag) membrane was employed to enhance the purity synthesis. The schematic of the proposed process is shown in Fig. 3.
 A.T. Damanabi et al. / Science of the Total Environment 664 (2019) 567–575 571

Fig. 3. Schematic of the tri-reforming and membrane system proposed for NH3 process.

A tri-reforming reactor has been used to improve the efficiency of (contains CO), part of it, is transferred to the methanol unit, and the rest
the oxidation reactions (Eq. (1) to Eq. (5)). The reactions initiate sent to the other units (for instance to be used for production of Phos-
over the nickel-based catalyst as follow (Damanabi and Bahadori, gene). In NH3 synthesis, the air entering the second reformer is used
2017; Zhang et al., 2013): to supply N2 and O2 for synthesis gas production. This would lead to,
due to the high pressure and temperature operating in the NH3 produc-
CH4 þ H2 O→CO þ 3H2 ð12Þ tion unit, production of air pollutants such as NOx.
Perovskite membranes have high selectivity for O2 and can provide
CH4 þ 0:5O2 →CO þ 2H 2 ð13Þ
O2 and N2 needed to synthesize gas and NH3. For this purpose, after
compressing the air and increasing its temperature, it has been sent to
CH4 þ CO2 →2CO þ 2H 2 ð14Þ
the permeate side of the membrane. The N2 from the retentate is sent
CH 4 þ O2 →CO2 þ 2H 2 ΔH ¼ −880 kJ=mol ð15Þ to the NH3 synthesis reactor and its pressure increased. The O2 is
(from the permeate phase) is sent to the tri-reformimg reactor to be
CH 4 →C þ 2H 2 ΔH ¼ þ75 kJ=mol ð16Þ used for production of synthesis gas.

2CO↔CO2 þ C ΔH f ¼ −172 kJ=mol; ΔHrev ¼ þ172 kJ=mol ð17Þ 3. Results and discussion

C þ H 2 O→CO þ H2 ΔH ¼ þ131 kJ=mol ð18Þ 3.1. Optimization of syngas

C þ O2 →CO2 ΔH ¼ −394 kJ=mol
The products of tri-reforming reactors which consist of H2 and COx
components are delivered to the Pd/Ag membrane unit. As shown in
Fig. 4, the membrane, which has high selectivity for H2, separates H2
by about 99.99%. The purified H2 is sent to the NH3 synthesis reactor
(after pre-heating) by a compressor to produce NH3. The waste stream
ð19Þ The results of this section are divided in two categories including tri-
reforming reactor, and membrane process.
3.1.1. Tri-reforming reactor
As it was discussed before, reaction (5), and reactions (12) to (14)
are the main reactions inside the tri-reforming reactor. The reaction's
conversion is mostly related to the operating condition of the tri-

Fig. 4. Simulation of the proposed process for NH3 production using tri-reforming and membranes.
572 A.T. Damanabi et al. / Science of the Total Environment 664 (2019) 567–575

Fig. 5. Conversion of CH4, steam and CO2 in tri-reforming reactor as a function of pressure.

reforming reactor. Generally, in gas phase reactions, pressure plays an

important role in altering the overall conversion. Fig. 5 demonstrates
the effects of reactor pressure on the conversion of CH4, steam, and
CO2. It is observed that increasing the pressure decreases the conversion
of reaction (5) and reactions (12) to (14). Therefore, decreasing the
pressure to an amount as low as possible enhances the overall conver-
sion of the reactor.
The effect of pressure on selectivity of products in tri-reforming re-
actor is another issue which should be considered. Fig. 6 shows the
H2/CO ratios in tr–reforming reactor as a function of temperature, the
H2/CO ratios are 3.73 and 2.2 in 600 °C and 800 °C, respectively. As it
can be seen, in Fig. 6, increasing the reactor pressure detracts H2/CO
ratio. As CO can deactivate the catalyst, it is rational to keep the H2/CO
ratio in higher amounts. So, the low pressure is desired for high H2/CO
ratios. By raising the temperature, H2/CO ratio reduces moderately. In
fact, according to the Le Chatelier's principle at high temperatures, the
reverse reaction of WGS produces more CO (Damanabi and Bahadori,
2017). On the other hand, according to Eqs. (15) to (19), an increase
in temperature results in increase of coke production and thus the cata-
lyst will be deactivated.
Fig. 7(a), (b), and (c) displays flow rates of O2, CO2 and steam at tem-
peratures 500–800 °C along with their effects on the conversion of CH4.
It is seen that higher flow rates of O2 significantly alters the CH4 conver-
sion, i.e. increasing the O2 flow rate from 10 kmol/h to 100 kmol/h,

Fig. 7. Effects of different flow rates of (a) O2, (b) CO2, and (c) steam on conversion of CH4
at temperatures between 500–800 °C.

and conversion of CH4 from 48% to 95% at 600 °C. At temperatures

Fig. 6. Effects of pressure on H2/CO production ratio in tri-reforming reactor.
above 700 °C, difference between O2 injection rates (50 kmol/h and
100 kmol/h) seems to be negligible, so the O2 injection rate was set to
be 50 kmol/h. The effects of CO2 injection rate on CH4 conversion are
graphicaly shown in Fig. 7(b). It is clear that CO2 injection effect on
CH4 conversion is ignorable in comparison with O2, i.e. at 600 °C. In-
creasing the CO2 injection rate from 0 to 100 kmol/h, elevates the CH4
 A.T. Damanabi et al. / Science of the Total Environment 664 (2019) 567–575
Fig. 8. Conversion of CH4, CO2, and steam in tri-reforming reactor as a function of
temperature.
conversion only 9%. It should be mentioned that in this simulation, the
CO2 is only injected into the reactor by the feed line. The effects of
steam injection rate on the CH4 conversion are shown in Fig. 7(c). It
Fig. 9. Effects of temperature and air flow rate on O2 permeation flux through the BSCF
membranes. (a) thickness = 4.5 mm, He flow rate = 60 m3/min, air flow rate =
150 m3/min, (b) temperature = 800 °C, thickness = 4.5 mm, He flow rate = 60 m3/min.
573
can be seen that increasing the steam flow rate raised the conversion
of CH4. In fact, this is the reason why the injection rate of 150 kmol/h
was assumed for the steam.
The conversions of CH4, CO2, and steam in the tri-reforming reactor
for temperatures between 500 °C to 800 °C are displayed in Fig. 8. Ac-
cording to Fig. 8, it is clear that conversion of CH4, CO2 and steam at
500 °C is almost zero; although, by rising the reaction temperature, con-
version of CH4, CO2, and H2O were notably increased. As an example, ris-
ing the reaction temperature from 550 to 750 °C created a conversion
increase up to higher than 95% for CH4, 15% to 92% for steam and 13%
to 93% for CO2. The conversion reaches to its maximum value at 800
°C. CO2 conversion is lower than CH4 in each temperature due to its con-
sumption and production during the tri-reforming process as it was
discussed in Zhang et al. (Zhang et al., 2013) and Zhou et al. findings
(Zhou et al., 2011). Since increase in temperature is needed for higher
conversions of CH4 and CO2, it should be considered that the reactions
should take place at high temperatures; however, the coke formation
must be controlled.
3.1.2. Effect of different parameters on O2 diffusion
Fig. 9(a) shows the effect of temperature on the O2 permeation rate.
The increase in temperature leads to the rise of O2 permeation flux in
the perovskite membrane. Moreover, with the decrease in the bulk pen-
etration resistance, O2 permeation flux increases. The effect of air flow
rate on the rate of O2 diffusion from the BaxSr1-x Co0.8Fe0.2O0.3 (BSCF
as a provskite membrane) membranes is shown in Fig. 9(b). It can be
seen that the O2 permeation rate has been initially raised by increasing
the air flow rate until it reaches to 150 m3/min, then it remains almost
constant at flow rates over 150 m3/min. This could be related to the
Fig. 10. Comparison of (a) NOx emission rate, and (b) CO2 emission rate in conventional
and proposed processes.
574 A.T. Damanabi et al. / Science of the Total Environment 664 (2019) 567–575
Fig. 11. Comparison of NH3 production rate in conventional and proposed processes.
structural features of the membrane which would not affect the air flow
rate and the partial pressure of O2 in the upper side of the membrane.
Therefore, it is concluded that in the airflow rate investigation, espe-
cially in high flow rates of O2, diffusion portion can be ignored.
4. CO2 emission, NOx emission and NH3 production
Fig. 10(a) shows the net amount of NOx produced in the conven-
tional and proposed processes. The amount of NOx produced in the pro-
posed process reaches to almost zero. The required N2 for conventional
NH3 production process is supplied by air injection into the reactor. The
presence of O2 in the reactor is unfavorable because of its combination
with N2 which leads to NOx production. The required N2 in the proposed
process is provided by air separation using a perovskite membrane and
added to the H2 produced from the synthesis gas unit. This leads to a de-
crease in the production rate of NOx from 8220 ppm to 10 ppm.
Fig. 10(b) shows the net amount of CO2 released to the atmosphere
by the NH3 synthesis unit during the conventional and proposed pro-
cesses. The amount of CO2 emission released to the atmosphere in the
proposed process decreased from 1192 kg/h to approximately 1 kg/h.
In the conventional process, amine unit and methanol reactor are asso-
ciated with NH3 reactor to reuse CO2 from the synthesis gas stream,
which CO2 is released after the separation of the synthesis gas stream
into the atmosphere, but in the propsed process, the synthesis gas is
sent to the Pd/Ag membrane and CO2 is separated.
Fig. 11 shows the amount of NH3 produced in the conventional and
proposed processes. The production of NH3 increased from around
25,000 kg/h to 32,000 kg/h, about 27% increase compared to the con-
ventional process. The reason for this increase is due to the use of tri-
reforming reactor by utilizing produced CO2 which leads to increase in
the production of H2 and NH3.
5. Conclusion
In this paper, the efficiency of NH3 synthesis unit was improved by
associating a tri-reforming reactor with a membrane unit. In order to
enhance the NH3 production, three fluids of steam, O2, and CO2 were
injected into the tri-reforming reactor. The simulation results showed
that O2 and steam injection were more efficient than CO2 injection.
The optimum operating conditions obtained for tri-reforming reactor
were 1–2 bars and 750–800 °C. It was shown that increasing the tem-
perature from 500 °C to 750 °C increased the conversion of CH4 from
zero to 95 %. The H2/CO selectivity was entirely dependent on the
recycling value of separated CO2 in the reactor. The required N2 for
NH3 production was provided using a perovskite membrane as well as
the O2 required for the tri-reforming reactor. The future work could
involve using membrane reactors for NH3 production or thermally
coupled reactors in order to use synthesis gas.
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