International Journal of Greenhouse Gas Control 44 (2016) 4251

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International Journal of Greenhouse Gas Control

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

Urea synthesis using chemical looping process Techno-economic

evaluation of a novel plant conguration for a green production
Abdolaziz Edrisi a,b , Zohreh Mansoori b, , Bahram Dabir a,b
a
Chemical Engineering Department, Amirkabir University of Technology, Tehran, Iran
b
Energy Research Center, Amirkabir University of Technology, Tehran, Iran

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

Article history: Chemical looping is an attractive technology which can produce three pure streams of N2 , H2 and CO2 .
Received 24 February 2015 In this paper, for the rst time, a novel and green plant conguration is proposed for urea production
Received in revised form 20 October 2015 in which chemical looping process is used as primary stage to prepare feedstock of urea synthesis unit.
Accepted 27 October 2015
The proposed plant is intended by reduction in the number of operating units within heat and power
integration which provides signicant potential for investment cost reduction. Due to the reduction in
Keywords:
the number of plant units and also production of economically valuable intermediate streams of N2 ,
Urea
H2 , CO2 and NH3 , the proposed plant provides more technical exibility compared to the conventional
Chemical looping
Green plant
technologies. Economic evaluation of the proposed plant shows a considerable rate of return and nancial
Economic evaluation interest. In the different production rate, the proposed plant has a rate of return (IRR) above 28%, while the
CO2 utilization IRR of conventional plants is almost near 20%. Moreover, a combined process of novel and conventional
plants is presented which produces urea without any by-product.
2015 Elsevier Ltd. All rights reserved.

1. Introduction conditioners. Other applications for urea are melamine production,

Urea is one of the important and widely produced chemicals in
the world. Based on growing world population, demand for crops
and fertilizers has been increased. Therefore, at the global level,
the fertilizer industries became a highly concentrated market with
increasing level of trade (Hernandez and Torero, 2011). Among all
common solid nitrogenous fertilizers, urea has the highest nitrogen
content. Therefore, more than 90% of world industrial production of
urea is used as fertilizer. It is also a raw material for many important
chemical compounds like various plastics. Recently, urea is used as
a source of hydrogen, nitrogen and clean water in which provides
safe, sustainable and long-term energy within valuable products
(Rollinson et al., 2011). Production of hydrogen by electrolysis of
urea solution occurs at a lower voltage than water, and urea can
be directly used as a source of hydrogen in fuel cells (Cowin et al.,
2011; Lan et al., 2010). Urea is non-toxic, stable, and therefore easy
to transport and store. It is also used as an expansion-reduction
agent to produce graphene from graphite (Wakeland et al., 2010).
It has also medical applications (Wang et al., 2013) and is used as
an ingredient in hair removers, skin creams, moisturizers and hair
Corresponding author. Tel.: +98 2164542611.
E-mail addresses: a.edrisi@aut.ac.ir (A. Edrisi), z.mansoori@aut.ac.ir
(Z. Mansoori), drbdabir@aut.ac.ir (B. Dabir).
feed supplement and manufacturing of adhesives and moulding
powders (Ma et al., 2013).
The main industrial route for urea production is initially produc-
ing ammonia and carbon dioxide from natural gas. Then, synthetic
ammonia and carbon dioxide are used in one of the urea synthesis
processes (Kaasenbrood, 1972). Nearly all commercial production
of ammonia is based on the Haber-Bosch synthesis process.
In the previous studies, optimum operating conditions of
chemical looping process were determined to achieve maximum
hydrogen production, complete oxygen consumption of air stream
and complete combustion of methane, which contributes to have
three pure and distinct streams of H2 , N2 and CO2 . Based on pure
N2 and H2 produced by chemical looping process, a novel ammo-
nia production plant was also proposed (Edrisi, 2013; Edrisi et al.,
2014a, 2014b). This plant can be used as a new route to simul-
taneously provide both the needed CO2 and ammonia for urea
production.
In this paper, based on the results and innovations achieved in
the previous papers, for the rst time a novel plant conguration
is proposed for urea production in which chemical looping process
is used as an intermediate stage to provide needed feed streams of
urea production unit. Unlike the previous studies, technical evalua-
tion of the novel plant is followed by economic assessment. Further-
more, all output streams of chemical looping process are used and
a novel route is introduced to produce the urea. For this purpose,

http://dx.doi.org/10.1016/j.ijggc.2015.10.020
1750-5836/ 2015 Elsevier Ltd. All rights reserved.
 A. Edrisi et al. / International Journal of Greenhouse Gas Control 44 (2016) 4251 43

carbon dioxide. Three typical industrial procedures (plants A, B and

Nomenclature C) for urea production are shown in Fig. 2.
Plant A consists of reforming, CO2 separation, CO removal,
IRR internal rate of return ammonia and urea synthesis units. In the rst step of reforming
PO payout period unit (steam primary reformer), CH4 reacts with steam (reaction 1)
E heat exchanger (under 3 to 25 bar pressure in the presence of nickel catalyst) to
J turbine produce H2 , CO and relatively small amount of CO2 . This reaction
R reactor is endothermic and external heat must be supplied for the reaction
T tower to proceed. It should be noted that in this step, steam ow rate is
C compressor not enough for the complete conversion of CH4 content of the feed
P pump stream. In the second reforming step (air secondary reformer), spe-
AC air cooler cial amount of ambient air is used to supply the required oxygen
FR fuel reactor for partial oxidation of remaining natural gas which introduces a
SR steam reactor considerable amount of nitrogen into the main stream. According
AR air reactor to the feed stock composition (natural gas), the air and steam ow
EPC engineering procurement construction rates should be justied to achieve complete conversion of fuel and
TSA temperature swing absorption provide needed nitrogen (H2 :N2 molar ratio of 3:1) for the ammo-
PSA pressure swing absorption nia synthesis unit. The nal step in the reforming unit is the shift
ASU air separation unit reaction where CO in the presence of iron catalyst (Fe2 O3 ) reacts
NPV net present value with steam (reaction 2) and is converted to CO2 and H2 . Then, pro-
R&D Research and Development cess gas is followed by CO2 separation unit. Absorption processes
using amine solvents are common industrial procedure to remove
CO2 and CO contents of a gas mixture. Although in the CO2 sep-
three types of conventional urea plant are briey introduced. Then aration unit most of CO2 is separated, but a little amount of CO2
the novel plant conguration is described in detail. Furthermore, always remains in the main stream and CO2 separation unit does
the main technical and environmental differences of the novel not work with 100% efciency. Since small quantities of CO and
and the conventional plants are discussed. The proposed plant is CO2 are poisons for ammonia synthesis catalyst, they should be
intended by reduction in the number of operating units, which completely removed from the gas mixture. Therefore, the gas mix-
provides signicant potential for investment cost reduction. In the ture is followed by a CO removal unit. Different procedures such as
proposed plant, four operating units of conventional processes are cryogenic distillation, temperature swing adsorption (TSA) process
replaced only by three reactors of chemical looping. Moreover, each with COSORB solution, membrane technology and pressure swing
unit of the proposed plant has pure output streams which can be adsorption (PSA) are used to remove CO from a gas mixture. Then,
considered as a nal product. Fig. 1 shows the major differences the gas stream is compressed and passed over a catalyst where
and novelties of the proposed plant schematically. the nitrogen and hydrogen react to form ammonia. Finally, sepa-
rated CO2 and synthetic ammonia are converted to urea as the nal
2. Conventional urea production process from natural gas product.

As it is mentioned before, the main industrial route for urea Ni,650 C&12 atm
production is initially converting the natural gas to ammonia and Q + RH + H2 O CO2 + CO + H2 (1)

Fig. 1. Scheme of the proposed plant and conventional process for urea production from natural gas.
44 A. Edrisi et al. / International Journal of Greenhouse Gas Control 44 (2016) 4251

Fig. 2. Typical conventional urea plant.

Fe2 O3 ,400 C that plant C has not the problem of air and steam ow rate
CO + H2 O CO2 + H2 + Q (2)
adjustment and is easy to control the streams composition.
In the plant B, CO separation unit is replaced with methanation 5- In the all conventional plants, produced ammonia is more than
and cryogenic distillation units in which remaining CO2 and CO are needed amount of urea synthesis unit. One option is to gener-
converted back to CH4 and then separated from the gas stream. ate excess CO2 in a supplementary power plant and using it to
Separated CH4 is recycled and mixed with feed stock. convert remaining ammonia into urea.
In the plant C, air separation unit is utilized to produce O2 and
N2 needed for secondary reformer and ammonia synthesis loop,
3. Plant conguration
respectively.
Key consideration of conventional plants:
The proposed urea production plant is schematically shown in
Fig. 3. As it is shown in this gure, the proposed plant consists of
1- The steam ow rate is affecting H2 production ow rate and the
four units: chemical looping reactors, compression and water sepa-
air ow rate is affecting both H2 and N2 ow rates. In plants A and
ration unit, ammonia and urea synthesis units. In the rst unit, input
B, it is difcult to adjust the steam and air ow rate considering
fuel is converted to the combustion products and three streams of
natural gas composition to achieve H2 :N2 molar ratio of 3 in the
CO2 , H2 and N2 are produced. Since H2 and CO2 streams contain
main gas stream.
signicant amounts of water vapor, the second unit objective is to
2- Although the presence of air in secondary reformer provides
purify and prepare the required streams. Three discrete and highly
needed N2 for ammonia synthesis reaction, it considerably
pure streams of N2 , H2 and CO2 are the output streams of this unit.
enhances the main stream ow rate. Therefore, in the plants
The pure nitrogen and hydrogen are used in the ammonia synthesis
A and B, the load (feedstock ow rate) of the following units
unit. Then synthetic ammonia and CO2 streams are used to produce
and consequently their capital and operating costs are increased.
urea. The details of the primary units of the proposed urea pro-
(Note that CO2 separation, methanation and cryogenic distilla-
duction plant has been presented in literature (Edrisi, 2013; Edrisi
tion units are working on the stream containing a considerable
et al., 2014a, 2014b). This work aims to assess the performance of a
amount of N2 .)
novel urea production plant using chemical looping process as the
3- In the plant B, one unit is superimposed to the CO removal unit
primary unit to simply provide the required feedstock.
where remained CO and CO2 are converted to CH4 . In the plant
A, CO is removed (wasting material) while in the plant B, CO is
converted back to CH4 and then recycled (saving material). 3.1. Chemical looping process
4- Although Plant C seems to be more compact than plants A and B
(N2 does not exist in the main gas stream), it has an air separa- In the chemical looping process, oxygen carrier particles are
tion unit with a high power requirement. It should be noted circulated among Air, Fuel and Steam reactors to prevent direct
 A. Edrisi et al. / International Journal of Greenhouse Gas Control 44 (2016) 4251 45

Fig. 3. Proposed plant for urea production using chemical looping process (before heat and power integration).

contact between air and fuel (Chiesa et al., 2008; Fan et al., 2012). et al., 2005; Rydn and Lyngfelt, 2006; Steinberg and Cheng, 1989).
Among the well-known oxygen carriers, iron (and its oxides) is In this paper, steam conversion is assumed to be 40% and steam-
favourable choice considering toxicity, thermodynamic, economic to-carbon ratio of 6.55 is used to achieve maximum H2 production
and abundance options. It can also react with steam and produce (Edrisi et al., 2014a, 2014b).
hydrogen (Fossdal et al., 2011; Jerndal et al., 2006; Kang et al., 2009; Due to insufcient kinetic data and excessive industrial appli-
Mattisson and Lyngfelt, 2001; Mattisson et al., 2001; Murugan et al., cation of adiabatic reactors, the fuel and air reactors of chemical
2011; Svoboda et al., 2007). There are three main reactions take looping are simulated by adiabatic Gibbs reactor of Aspen Plus sim-
place in the chemical loop (Isla et al., 1993; Zhang et al., 2005). The ulation software (Plus, 2011). The background of using this type of
rst reaction (reaction 3) is endothermic in which CH4 is converted reactor is based on minimization of Gibbs free energy instead of
to the combustion products. The second reaction (reaction 4) is giving full kinetic data of reactions. Furthermore, solid particles are
exothermic in which steam in the reaction with reduced oxygen considered as solid solution phase and the temperature approach
carrier particles (FeO) is converted to hydrogen. The third reaction of 5 C is assumed for each reactor.
(reaction 4) is highly exothermic in which oxygen carrier particles Although higher operating pressure has a negative effect on
are converted back to Fe2 O3 . The reaction 3, 4 and 5 are respectively the reaction rate of oxygen carrier (Garcia-Labiano et al., 2006),
performed in Fuel, Steam and Air reactors. the recent experimental studies show that increasing overall sys-
H25C =356.5 kJ/kgmole tem pressure has a positive effect on chemical looping efciency
4Fe2 O3 + CH4 8FeO + 2H2 O + CO2 (3)
and also carbon conversion (Bhavsar et al., 2014; Xiao et al., 2012;
8 H =199.3 kJ/kgmole 8 8 Zhang et al., 2011). In this paper, the operating pressure of chem-
8FeO + H2 O 25C Fe3 O4 + H2 (4)
3 3 3 ical looping process is assumed to be 20 bar comprising different
8 2 H =314.6 kJ/kgmole requirements such as reactor size reduction, higher gas density,
Fe3 O4 + O2 25C 4Fe2 O3 (5)
3 3
Chemical looping process is efciently used as a green process
to convert CH4 into H2 in which CO2 is inherently captured in a
discrete stream (Antzara et al., 2015; Azimi et al., 2012; Chiesa
et al., 2008; Edrisi, 2013; Edrisi et al., 2014a, 2014b; Fernndez et al.,
2012; Svoboda et al., 2007).
Since the presence of N2 is essential for ammonia production,
two oxidation steps in the air reactor are proposed. As it is shown in
Fig. 4, nitrogen as the third pure stream is producible and using two
oxidation steps grantees its pure production. Air enters the second
oxidation step and the exhaust gas is divided into two streams. The
reduced oxygen carriers exiting steam reactor enter the rst re-
oxidation step and consume all oxygen content of gaseous stream.
Therefore, the output gaseous stream of the rst oxidation step is
pure N2 .
In the previous studies, at temperature between 700 and 900 C,
conversion of 30% to 50% are reported for steam reaction (Chiesa
et al., 2008; Fraser et al., 2006; Hacker et al., 1998; Kindermann Fig. 4. Scheme of binary oxidation steps for chemical looping.
46 A. Edrisi et al. / International Journal of Greenhouse Gas Control 44 (2016) 4251
moderate pressure for reactions and mechanical stress limitation
of equipments (Chiesa et al., 2008).
3.2. Compression and water separation unit
In the compression and water separation unit, the output
streams of chemical looping reactors are initially expanded in the
turbines (J-101, J-201 and J-301) and cooled in the heat exchangers
(E-101, E-102, E-201, E-202, E-301 and E-302) to produce power
and separate signicant portion of water content of the H2 and CO2
streams. The remaining water content of H2 and CO2 streams are
separated through three inter-cooled compression steps. In these
compression steps, N2 and H2 streams are compressed to the same
pressure (100 bar) of ammonia synthesis unit, and the CO2 stream
is compressed to the pressure (138.27 bar) of urea synthesis unit.
Since the produced CO2 and N2 are respectively more than
needed stoichiometric ratio of urea and ammonia synthesis reac-
tions, the excess amount of each stream is sent to the reservoir.
Excess amount of N2 can be used as utility inert gas or purged to
the atmosphere. The stoichiometric ow rates of H2 and N2 are
mixed and sent to ammonia unit. Then the produced ammonia and
compressed CO2 are used in the urea synthesis unit.
It is more appropriate to initially use the high temperature
and pressure streams in turbo expanders which simultaneously
produce power and reduce the temperature of water containing
streams. It should be noted that produced power of turbines comes
from the main streams containing water vapour and this power is
used to compress the water separated streams with less ow rates.
Therefore, using turbo expanders not only provide the signicant
part of needed power for electrical equipments but also help to
purify CO2 and H2 streams. The whole N2 stream is also used in a
turbo expander and then its needed amount (for ammonia unit) is
pressurized.
3.3. Ammonia synthesis unit
Among the different chemical processes like Haber-Bosch pro-
cess, indirect electrochemical synthesis methods and membrane
reactors which are used to produce ammonia (Amar et al., 2011a,
2011b; Jacob et al., 2005; Wang et al., 2010), the Haber-Bosch pro-
cess is the main industrial route for ammonia production (Appl,
2006; Klinkenberg and Hartwig, 2011). In the proposed plant
conguration, Haber-Bosh process is considered as the ammo-
nia synthesis unit. The position of the equilibrium and the rate
of reaction are two opposite considerations of ammonia synthe-
sis reaction. Since the ammonia synthesis reaction is intrinsically
limited by thermodynamic equilibrium, the extent of conversion is
limited and considerable recycle of unreacted gas is required. Due
to the variety of catalysts and improving kinetics of catalytic reac-
tion, the ammonia synthesis reactor is simulated with an adiabatic
Gibbs reactor. The adiabatic reactors are more common in industry
and it does not require temperature regulation. The input temper-
ature of 275 C and the pressure of 100 bar is used to simulate the
ammonia synthesis reactor, which are in improved range of current
ammonia production processes (Appl, 2006; Gosnell et al., 2011;
Tanabe and Nishibayashi, 2013). All equipments of this unit are
adjusted to achieve mentioned operating condition. The ammonia
synthesis unit is modelled using the Amine thermodynamic uid
package of Aspen plus simulation software (Plus, 2011).
The main advantages of chemical looping based ammonia plant
are listed below (Edrisi et al., 2014a):
1- Reduction in the number of operating units and capital cost of
the process
2- Reduction in operating cost of plant by decreasing the heat loads
and the elimination of solvent and its recovery process
3- Produced feedstocks by chemical looping have no contaminant
poisoning the catalyst of ammonia reaction
4- Water is the only contaminant of the produced ammonia which
has no effect on urea synthesis reaction (the reaction between
CO2 and ammonia is accomplished in an aqueous phase)
3.4. Urea synthesis unit
There are several technologies like KM-CDR, Snamprogetti and
Stamicarbon processes which are used for urea production (Dente
et al., 1988; Kamijo, 2011). In this work, Stamicarbon CO2 stripping
process is selected as the popular and fast growing process to con-
vert CO2 and synthetic ammonia into the urea. As it is shown in
Fig. 5, the urea synthesis reactor (R-501), the CO2 stripper (T-501),
the high pressure condenser (E-501) and the scrubber (T-502) are
the main equipments of Stamicarbon process. In the urea synthesis
reactor, ammonium carbamate is converted to urea. The efuent of
this reactor enters the CO2 stripper where the unreacted carbamate
is decomposed during the external heating. In the high pressure
condenser, gaseous CO2 and NH3 are condensed and reacted to
form ammonium carbamate. The recycled carbamate solution from
downstream low pressure section is used in the high pressure
scrubber to absorb unreacted components of the gas stream. In this
work, the urea granulation or other nal preparation steps are not
simulated and 76 wt% urea solution is the nal product of the plant.
There are two main equilibrium reactions take place in the urea
synthesis loop (Isla et al., 1993; Zhang et al., 2005). The rst reaction
(reaction 6) is highly exothermic and fast in which ammonia and
carbon dioxide are converted to ammonium carbamate. The second
reaction (reaction 7) is endothermic and slow, so the equilibrium
is usually not reached in the reactor. Both reactions take place in
the liquid phase.
2NH3 + CO2  NH2 COONH4 (6)
NH2 COONH4  NH2 CONH2 + H2 O (7)
The urea reactor is modelled with adiabatic plug ow reac-
tor. The thermodynamic properties of the urea synthesis unit are
calculated based on the SR-POLAR model within the Aspen plus
simulation software (AspenTech, 2009). According to Fig. 3, the
main assumptions for equipments of each unit are given in Table 1.
According to this table, Air, Fuel and ammonia reactors are simu-
lated by adiabatic Gibbs reactor of Aspen plus simulation software,
while conversion type of reactors is used to simulate the Steam
reactor. The isentropic efciency of 90% is considered for all tur-
bines and compressors. The results of simulation such as operating
condition of equipments and net produced power of turbines are
also given in Table 1. For example, output stream of fuel reactor (is
shown in Fig. 3) enters the turbine J-101 at 563 C and 20 bar. Then
the gas stream exits this turbine at 285 C and 2 bar. In this tur-
bine, the power of 34.627 MW is produced. The operating pressure
of chemical looping process is 20 bar, while the operating pres-
sure of ammonia and urea reactors (R-401 and R-501) are 100 and
138.27 bar, respectively.
As it is mentioned before, optimum operating conditions of
chemical looping process were determined to achieve maximum
hydrogen production, complete oxygen consumption of air stream
and complete combustion of methane. In order to reach the opti-
mum condition, each mole methane requires 3.206 mol air (at
470 C and 20 bar) and 6.55 mol superheated steam (at 400 C and
22 bar). At the optimum operating condition, each mole methane
in chemical looping unit needs 4 mol circulating Fe2 O3 to produce
2.53, 2.65 and 0.99 mol of N2 , H2 and CO2 , respectively (Edrisi, 2013;
Edrisi et al., 2014a, 2014b). According to the proposed conguration
 A. Edrisi et al. / International Journal of Greenhouse Gas Control 44 (2016) 4251 47

Fig. 5. Scheme of Urea synthesis unit.

which is shown in Fig. 3, hydrogen and a portion of nitrogen are
used in ammonia unit to produce 1.765 mol of NH3 . Then produced
ammonia is combined with a portion of separated CO2 to produce
0.882 mol urea. The simulation result for output streams of each
unit is given in Table 2. Generally, for each mole of input methane
in the proposed novel plant; beside the urea, respectively 0.1164
and 1.645 mole of CO2 and N2 are produced as side products.
According to the simulation results which are given in Table 2,
the water separation unit is properly designed and the mole fraction
of H2 and CO2 in the puried streams are 0.997 and 0.989, respec-
tively. Furthermore, beside the unreacted N2 and H2 , water is the
only impurity of the produced ammonia. Since the urea production
reaction is performed in aqueous phase, impurities of produced
ammonia by this plant does not have adverse effect on the reac-
tion of urea production. As it is mentioned before, the granulation
or other nal preparation steps for the urea are not simulated and
76 wt% (48.7 mol%) urea solution is considered as the nal product
of the plant.
3.5. Steam recovery, heat integration and power generation unit
As it is shown in Fig. 6, due to the different heating and cooling
loads of plant, the heat exchangers and heat streams are arranged.
In this arrangement, the heat of low temperature streams is used
to preheat the water and the heat of high temperature streams is
used to raise the required steam (at 400 C and 22 bar with steam-
fuel molar ow ratio of 6.55) of chemical looping process. In order
to have a self-sufcient process and improve the thermal balance,
low temperature heat of streams is re-evaluated for higher temper-
ature levels, sufcient to raise the required steam and even more
to produce power.
According to Fig. 6, heat exchangers E-103, E-105 and E-303 are
pre-heaters which are using the heat of low temperature streams.
The heat of some high temperature streams is used in heat exchang-
ers E-102, E-106, E-201, E-202, E-204, E-205, E-302, E304, E-402
and E-505 to rise 15 bar saturated steam. Saturated high pres-
sure steams are collected and superheated in E-101 and E-301,

Table 1
Main unit equipments and their operating condition.

Unit Equipment Temperature [ C] Pressure [bar] Type Net work [MW]

Chemical looping Air reactor 880 20 Adiabatic- Gibbs

Steam reactor 727 20 Adiabatic- Conversion
Fuel reactor 723 20 Adiabatic- Gibbs
In Out In Out
Compression and water separation J-101 563 285 20 2 Isentropic 34.627
J-201 712 338 20 2 Isentropic 85.867
J-301 664 275 20 12 Isentropic 30.691
Ammonia R-401 420 100 Adiabatic- Gibbs
Min Max
Urea R-501 167 183 138.27 Adiabatic- Plug
Top Bottom
T-501 184 164 138.27 10 equilibrium stage with side heating jacket
T-502 81 118 138.27 5 equilibrium stage with cooling in bottom
In Out
E-501 140 167 138.27 Shell & tube
In Out
Steam recovery and power generation J-001 193 101 4 1 Isentropic 30.318
48 A. Edrisi et al. / International Journal of Greenhouse Gas Control 44 (2016) 4251

Table 2
Condition and composition of unit output streams of proposed plant for urea production from CH4 .

Unit Chemical looping Compression and Ammonia Urea

water separation

Stream AR-out SR-out FR-out H2 CO2 NH3 Urea

Pressure [bar] 20 20 20 95 141 160 1.4

Temperature [ C] 880 727 723 65 70 16.2 118
Flow rate [k mol/s] 2.54 6.55 3.00 2.67 1.01 1.79 1.79
Composition [mole fraction] CH4 0.0002 0.0007 Trace
CO2 0.3333 0.9888 Trace
H2 O 0.594 0.6665 0.0030 0.0105 0.0065 0.4988
N2 0.9981 0.0028
O2 0.0019
H2 0.406 0.9970 0.0051
NH3 0.9856 0.0140
Urea 0.4871

This table is respectively based on 1 and 6.55 k mol/s of CH4 and steam ow rate.

Fig. 6. The arrangement of heat exchangers and energy streams.

then pressurized to 22 bar which is the input pressure of steam
reactor.
In order to improve the water separation efciency, two low
pressure steams are generated from low temperature streams (E-
104, E-203, E-206 and E-506). The low pressure (4 bar) steams are
also expanded in the steam turbine J-001. The power balance of the
whole plant is given in Table 3. According to this table, the proposed
urea production plant has fully thermal integrated design and is
Table 3
The produced and consumed power of electrical equipments.
Produced power of all turbines [MW]
Consumed power of all compressors [MW]
Consumed power of all pumps [MW]
Net power of the whole plant [MW]
Based on designed conguration which is shown in Fig. 6.
self-sufcient in terms of its required power and steam. Moreover,
there is 11.048 MW excess produced power.
Due to considerable water content of H2 and CO2 streams,
achieving highly pure and pressurized streams is very complicated
task. Since enthalpy and mass ow rate of these streams after each
water separation step are extremely changed, determination of
operating conditions of inter-cooled compression and water sepa-
ration steps are very difcult. Although the proposed arrangement
of heat exchangers and compressors presents a self-sufcient plant
as its needed electrical and heat points of view, it may not be the
best arrangement and there could be a better design of these equip-
ments that provides more nancial interest.
181.483 Generally, there is no best arrangement. The base of presented
169.535 design is to keep MER (minimum energy requirement or Maximum
0.9 Energy recovery) at the lowest possible level equal to zero. The best
11.048 economic arrangement of the exchangers, hot and cold streams rely
on the energy availability in the area and the arrangement could be
 A. Edrisi et al. / International Journal of Greenhouse Gas Control 44 (2016) 4251 49

Table 4
Main economic parameters and project result summary.

Main economic assumptions

Facility type Petrochemical processing facility
Operating mode Continuous processing 24 h/day
Process uids Liquids, gasses, solids
Pressure vessel design code ASME
Price of fuel [USD/MMBTU] 3.36
Price of electricity [USD/kWh] 0.0775
1
Price of material [USD/kg] CH4 Urea CO2 N2
0.1594 0.3219 0.0509 0.2910
Project result summary
Total project capital cost [USD] 347,614,832
Total raw material cost [USD/year] 98,355,488
*
Total product sales [USD/year] 479,496,355
Operating labour cost [USD/year] 2,019,600
Maintenance cost [USD/year] 5,316,300
General and administrative cost [USD/year] 19,604,667
Total utility cost [USD/year] 135,194,106
Total Operating cost [USD/year] 264,663,011
Length of start-up period [weeks] 22
Duration of construction phase [weeks] 41

Project result summary is presented for 1.5 Mton/year urea production rate.
*
In this table, urea is considered as the only salable product.

changed based on the price of equipment and energy in different Table 5

Result of economic evaluation of proposed urea production plant.
countries.
Production capacity 1st scenario 2nd scenario EPC
4. Process economic evaluation [Mton/year] [week]
IRR [%] PO [year] IRR [%] PO [year]

According to the simulation results, rigorous size and cost esti- 1.5 36.92 6.91 60.17 4.47 91
1.0 32.89 7.9 55.98 4.59 85
mation for processing equipments are generated and preliminary
0.5 28.91 9.42 49.43 4.95 77
mechanical design is performed. Then purchase and installation
Methane is the only feed stream and plant is self sufcient in terms of steam, heat
costs, indirect costs, the total capital investment, the Engineer-
and power.
ing, Procurement and Construction (EPC) planning schedule, and
protability analyses are estimated using aspen process economic
analyzer software. This software enables rapid and condent eval- Table 6
Economic comparison of proposed and conventional plants.
uation of capital investment of the projects early in the design
process, understand the economical implications of engineering Plant type Conventional Proposed
decisions, and effectively manage the project. It contains built-in (Rahimi et al., 2013)
engineering and cost content to produce comprehensive and accu- NPV at start up [million USD] 53.24 34.95
rate conceptual estimates. IRR [%] 15 28.91
All simulation results of proposed plant are mapped and then Total project cost[million USD/year] 180.46 138.56
sized with appropriate real equipment. The project lifetime is Result is presented for 0.5 Mton/year urea production rate.
assumed to be 25 years with 24 working hours per day and 330
working days per year. 15 percent of initial capital cost is consid-
ered as the salvage value of plant (expected value of plant at the 5. Result and discussion
end of its usable life). The price of raw material and products are
accounted based on world market.1 Since the urea granulation and For each mole of input methane in the proposed novel plant;
periling parts are not simulated, the cost of this unit is individually beside 0.882 mol urea, respectively 0.1164 and 1.645 mole of CO2
accounted (Meessen et al., 2014; Roos and Buitink, 2010). The main and N2 are produced as side products. Although more than 60%
economic assumptions and the results for 1.5 Mton per year urea of the global ammonia production is used to produce fertilizers,
production rate are given in Table 4. Summary of economic eval- it is not only an intermediate product but also an important end-
uation results of the plant in three different production capacities product. It has industrial, utility and refrigeration applications (Choi
is given in Table 5. In this table, two different economic scenarios et al., 2009; Kortsen and Kristensen, 1998; Lee et al., 2008). The
are considered to evaluate the proposed plant. In the rst scenario, proposed plant for urea production is very exible in terms of
urea is the only marketable product while in the second scenario, ability to adjust the desired products. When the urea demand is
pure CO2 and N2 are also assumed to be salable side products. Both reduced and its production is not protable, proposed plant can
scenarios show that the proposed plant has considerable internal produce ammonia or even three pure streams of Hydrogen, Nitro-
rate of return (IRR between 28 and 60%) and acceptable payout gen and CO2 as interim main products by shutting down the other
period2 (PO between 4 and 8 years). However, the IRR of conven- units. Moreover, unlike the conventional technologies, the pro-
tional urea plants at the different production rate is almost about posed plant does not have steam and air ow rate adjustment
20% (Rahimi et al., 2013). The economic comparison of proposed problems and contains less number of equipments which is pre-
and conventional plants is given in Table 6. senting a simpler process. In the conventional plant, since the
needed N2 for ammonia production is provided by input air stream
early at the reforming steps, H2 to N2 ratio of the feed stream of
1
http://www.cmegroup.com (Henry Hub Natural Gas Future) & (Futures and
ammonia unit extremely depends on the air ow rate. Hence, input
Options Trading for Risk Management) date: Friday, August 16, 2013. air ow rate should be adjusted carefully. In the proposed plant,
2
Engineering Procurement Construction (EPC) is considered in payout period. since chemical looping process produces pure and discrete streams
50 A. Edrisi et al. / International Journal of Greenhouse Gas Control 44 (2016) 4251
Fig. 7. The proposed combined process for urea production.
of N2 , H2 and CO2 , a feed stream with a favourable ratio of H2 to
N2 can be provided for ammonia unit. Therefore, the novel plant
has more technical exibility in providing required feed streams of
ammonia and urea units. The proposed plant is also self sufcient in
terms of its required power and steam, even has a net power pro-
duction. At 1.5 Mton/year urea production rate, excess power of
11.048 MW is produced. According to the results of economic eval-
uation which are given in Tables 4 and 5, different production rate of
proposed urea plant has considerable rate of return and acceptable
payout period.
Generally, different urea technologies use somewhat different
process steps to maximize product yield and energy efciency.
Combined capital and operating cost are the principal determi-
nant to select the production procedure. While the proposed plant
produces excess CO2 , the conventional plant using natural gas does
not produce CO2 as much as it is needed to convert its entire
synthetic ammonia. According to the demands for agricultural
products (including urea), production of each by-product is unde-
sirable. Hence, as it is shown in Fig. 7, simultaneous application of
certain capacities of these two processes can be more efcient in
the production of urea, where the by-products of each process can
be used to produce more urea. Thus, there could be an integrated
plant which has no by-product and the only product is urea.
The supply and demand of urea play a critical role in determining
urea prices. New ammonia and urea projects tend to be cyclical,
driven by product demand and positioned where the feed stock
prices are low. Production of several pure streams (H2 , N2 , CO2 , NH3
and Urea) makes the proposed plant as a good alternative process
with periodic main products. The production of urea in conjunction
with other material production options, offers synergies that could
result in reducing the cost, as well as the risk of the total project in
terms of product market.
6. Conclusions
Production of three pure streams of H2 , N2 and CO2 makes the
chemical looping process as an attractive intermediate technol-
ogy to provide the feedstock of urea synthesis loop. As a goal of
paper, for the rst time, a novel plant conguration is presented
for urea production in which needed H2 and N2 for ammonia
production and CO2 for urea synthesis are provided by chemical
looping process. The proposed plant conguration is very interest-
ing as its environmental and economical points of view, since CO2
is produced as a pure and separated stream, and four operating
units of conventional plant are replaced only with three reactors
of chemical looping. The conventional urea production processes
can produce urea or ammonia as their products, while the pro-
posed plant is very exible to adjust its products. While the urea
production is not protable or the demands for it are reduced,
the proposed plant can produce pure hydrogen, nitrogen, CO2 or
NH3 as intermediate main products. Since the product streams
of chemical looping process are three discrete and pure streams,
variation of composition of feedstock can be easily controlled
in the proposed plant. Unlike the conventional technologies, the
proposed plant has not steam and air ow rate problems and con-
tains less number of equipments which is presenting a simpler pro-
cess. Even in the proposed combined process, the produced pure N2
stream of chemical looping process in the novel plant can help the
conventional plant to solve the adjustment problem of air ow rate.
Simulation results show that each mole of input methane in the
proposed plant can produce 0.882 mole urea as the nal product
and respectively 0.1164 and 1.645 mole of CO2 and N2 as side prod-
ucts. The proposed plant conguration is self sufcient as its needed
steam and power, even 11.048 MW excess power is produced. All
heat loads are supplied by internal heat sources and there is only
one cooling load in the ammonia unit that should be provided exter-
nally. Since the ammonia is the side product of conventional plants,
a combination of proper production capacity of the proposed and
the conventional plant can present an integrated plant which has no
by product and only produces urea. The excess N2 as an inert utility
gas can reduce the operating and capital costs of the whole plant.
Economic evaluation shows that the proposed plant has consider-
able internal rate of return (IRR between 28 and 60%) and acceptable
payout period (PO between 4 and 8 years), so deserves substantial
R&D activities in the near future.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.ijggc.2015.10.020.
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