Beruflich Dokumente
Kultur Dokumente
a r t i c l e
i n f o
Article history:
Received 24 February 2015
Received in revised form 20 October 2015
Accepted 27 October 2015
Keywords:
Urea
Chemical looping
Green plant
Economic evaluation
CO2 utilization
a b s t r a c t
Chemical looping is an attractive technology which can produce three pure streams of N2 , H2 and CO2 .
In this paper, for the rst time, a novel and green plant conguration is proposed for urea production
in which chemical looping process is used as primary stage to prepare feedstock of urea synthesis unit.
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
the number of plant units and also production of economically valuable intermediate streams of N2 ,
H2 , CO2 and NH3 , the proposed plant provides more technical exibility compared to the conventional
technologies. Economic evaluation of the proposed plant shows a considerable rate of return and nancial
interest. In the different production rate, the proposed plant has a rate of return (IRR) above 28%, while the
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
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
43
Q + RH + H2 O
Nomenclature
IRR
PO
E
J
R
T
C
P
AC
FR
SR
AR
EPC
TSA
PSA
ASU
NPV
R&D
CO2 + CO + H2
Fig. 1. Scheme of the proposed plant and conventional process for urea production from natural gas.
(1)
44
CO + H2 O
Fe2 O3 ,400 C
CO2 + H2 + Q
(2)
that plant C has not the problem of air and steam ow rate
adjustment and is easy to control the streams composition.
5- In the all conventional plants, produced ammonia is more than
needed amount of urea synthesis unit. One option is to generate excess CO2 in a supplementary power plant and using it to
convert remaining ammonia into urea.
3. Plant conguration
The proposed urea production plant is schematically shown in
Fig. 3. As it is shown in this gure, the proposed plant consists of
four units: chemical looping reactors, compression and water separation unit, ammonia and urea synthesis units. In the rst unit, input
fuel is converted to the combustion products and three streams of
CO2 , H2 and N2 are produced. Since H2 and CO2 streams contain
signicant amounts of water vapor, the second unit objective is to
purify and prepare the required streams. Three discrete and highly
pure streams of N2 , H2 and CO2 are the output streams of this unit.
The pure nitrogen and hydrogen are used in the ammonia synthesis
unit. Then synthetic ammonia and CO2 streams are used to produce
urea. The details of the primary units of the proposed urea production plant has been presented in literature (Edrisi, 2013; Edrisi
et al., 2014a, 2014b). This work aims to assess the performance of a
novel urea production plant using chemical looping process as the
primary unit to simply provide the required feedstock.
3.1. Chemical looping process
In the chemical looping process, oxygen carrier particles are
circulated among Air, Fuel and Steam reactors to prevent direct
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).
Among the well-known oxygen carriers, iron (and its oxides) is
favourable choice considering toxicity, thermodynamic, economic
and abundance options. It can also react with steam and produce
hydrogen (Fossdal et al., 2011; Jerndal et al., 2006; Kang et al., 2009;
Mattisson and Lyngfelt, 2001; Mattisson et al., 2001; Murugan et al.,
2011; Svoboda et al., 2007). There are three main reactions take
place in the chemical loop (Isla et al., 1993; Zhang et al., 2005). The
rst reaction (reaction 3) is endothermic in which CH4 is converted
to the combustion products. The second reaction (reaction 4) is
exothermic in which steam in the reaction with reduced oxygen
carrier particles (FeO) is converted to hydrogen. The third reaction
(reaction 4) is highly exothermic in which oxygen carrier particles
are converted back to Fe2 O3 . The reaction 3, 4 and 5 are respectively
performed in Fuel, Steam and Air reactors.
4Fe2 O3 + CH4
(3)
8
8
H
=199.3 kJ/kgmole 8
8FeO + H2 O 25C
Fe3 O4 + H2
3
3
3
(4)
8
2 H =314.6 kJ/kgmole
Fe3 O4 + O2 25C
4Fe2 O3
3
3
(5)
et al., 2005; Rydn and Lyngfelt, 2006; Steinberg and Cheng, 1989).
In this paper, steam conversion is assumed to be 40% and steamto-carbon ratio of 6.55 is used to achieve maximum H2 production
(Edrisi et al., 2014a, 2014b).
Due to insufcient kinetic data and excessive industrial application of adiabatic reactors, the fuel and air reactors of chemical
looping are simulated by adiabatic Gibbs reactor of Aspen Plus simulation software (Plus, 2011). The background of using this type of
reactor is based on minimization of Gibbs free energy instead of
giving full kinetic data of reactions. Furthermore, solid particles are
considered as solid solution phase and the temperature approach
of 5 C is assumed for each reactor.
Although higher operating pressure has a negative effect on
the reaction rate of oxygen carrier (Garcia-Labiano et al., 2006),
the recent experimental studies show that increasing overall system pressure has a positive effect on chemical looping efciency
and also carbon conversion (Bhavsar et al., 2014; Xiao et al., 2012;
Zhang et al., 2011). In this paper, the operating pressure of chemical looping process is assumed to be 20 bar comprising different
requirements such as reactor size reduction, higher gas density,
46
(6)
(7)
The urea reactor is modelled with adiabatic plug ow reactor. 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 simulated 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 turbines 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 turbine, the power of 34.627 MW is produced. The operating pressure
of chemical looping process is 20 bar, while the operating pressure 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 optimum 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
47
Table 1
Main unit equipments and their operating condition.
Unit
Equipment
Chemical looping
Air reactor
Steam reactor
Fuel reactor
J-101
J-201
J-301
R-401
Ammonia
Urea
R-501
T-501
T-502
E-501
J-001
Temperature [ C]
Pressure [bar]
880
727
723
20
20
20
Out
285
338
275
In
563
712
664
In
20
20
20
420
Min
167
Top
184
81
In
140
193
Out
2
2
12
101
Isentropic
Isentropic
Isentropic
Adiabatic- Gibbs
34.627
85.867
30.691
138.27
Adiabatic- Plug
138.27
138.27
138.27
In
4
Adiabatic- Gibbs
Adiabatic- Conversion
Adiabatic- Gibbs
100
Max
183
Bottom
164
118
Out
167
Type
Isentropic
30.318
48
Table 2
Condition and composition of unit output streams of proposed plant for urea production from CH4 .
Unit
Chemical looping
Stream
AR-out
SR-out
Pressure [bar]
Temperature [ C]
Flow rate [k mol/s]
Composition [mole fraction]
20
880
2.54
20
727
6.55
CH4
CO2
H2 O
N2
O2
H2
NH3
Urea
0.594
Compression and
water separation
Ammonia
Urea
FR-out
H2
CO2
NH3
Urea
20
723
3.00
0.0002
0.3333
0.6665
95
65
2.67
141
70
1.01
0.0007
0.9888
0.0105
160
16.2
1.79
1.4
118
1.79
Trace
Trace
0.4988
0.0030
0.9981
0.0019
0.406
0.9970
0.0065
0.0028
0.0051
0.9856
0.0140
0.4871
This table is respectively based on 1 and 6.55 k mol/s of CH4 and steam ow rate.
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.
181.483
169.535
0.9
11.048
49
Table 4
Main economic parameters and project result summary.
Main economic assumptions
Facility type
Operating mode
Process uids
Pressure vessel design code
Price of fuel [USD/MMBTU]
Price of electricity [USD/kWh]
1
Price of material [USD/kg]
CH4
0.1594
N2
0.2910
347,614,832
98,355,488
479,496,355
2,019,600
5,316,300
19,604,667
135,194,106
264,663,011
22
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.
1
http://www.cmegroup.com (Henry Hub Natural Gas Future) & (Futures and
Options Trading for Risk Management) date: Friday, August 16, 2013.
2
Engineering Procurement Construction (EPC) is considered in payout period.
Table 5
Result of economic evaluation of proposed urea production plant.
Production capacity
[Mton/year]
1.5
1.0
0.5
1st scenario
2nd scenario
IRR [%]
PO [year]
IRR [%]
PO [year]
36.92
32.89
28.91
6.91
7.9
9.42
60.17
55.98
49.43
4.47
4.59
4.95
EPC
[week]
91
85
77
Methane is the only feed stream and plant is self sufcient in terms of steam, heat
and power.
Table 6
Economic comparison of proposed and conventional plants.
Plant type
Conventional
(Rahimi et al., 2013)
Proposed
53.24
15
180.46
34.95
28.91
138.56
50
proposed plant has not steam and air ow rate problems and contains less number of equipments which is presenting a simpler process. 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 products. 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 externally. 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 considerable 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.
References
Amar, I.A., Lan, R., Petit, C.T.G., Arrighi, V., Tao, S., 2011a. Electrochemical synthesis
of ammonia based on a carbonate-oxide composite electrolyte. Solid State
Ionics 182, 133138.
Amar, I.A., Petit, C.T.G., Zhang, L., Lan, R., Skabara, P.J., Tao, S., 2011b.
Electrochemical synthesis of ammonia based on doped-ceria-carbonate
composite electrolyte and perovskite cathode. Solid State Ionics 201, 94100.
Antzara, A., Heracleous, E., Bukur, D.B., Lemonidou, A.A., 2015. Thermodynamic
analysis of hydrogen production via chemical looping steam methane
reforming coupled with in situ CO2 capture. Int. J. Greenh. Gas Control 32,
115128.
Appl, M., 2006. Ammonia. Wiley Online Library.
AspenTech, 2009. Aspen Technology: tutorial and application-Version Number 7.1.
Inc. Cambridge., pp. 0214102201.
Azimi, G., Keller, M., Mehdipoor, A., Leion, H., 2012. Experimental evaluation and
modeling of steam gasication and hydrogen inhibition in Chemical-Looping
Combustion with solid fuel. Int. J. Greenh. Gas Control 11, 110.
Bhavsar, S., Najera, M., More, A., Veser, G., 2014. Chapter 7 - Chemical-looping
processes for fuel-exible combustion and fuel production. In: Shi, F. (Ed.),
Reactor and Process Design in Sustainable Energy Technology. Elsevier,
Amsterdam, pp. 233280.
Chiesa, P., Lozza, G., Malandrino, A., Romano, M., Piccolo, V., 2008. Three-reactors
chemical looping process for hydrogen production. Int. J. Hydrogen Energy 33,
22332245.
Choi, W.-J., Min, B.-M., Shon, B.-H., Seo, J.-B., Oh, K.-J., 2009. Characteristics of
absorption/regeneration of CO2- SO2 binary systems into aqueous AMP;
ammonia solutions. J. Ind. Eng. Chem. 15, 635640.
Cowin, P.I., Petit, C.T., Lan, R., Irvine, J.T., Tao, S., 2011. Recent progress in the
development of anode materials for solid oxide fuel cells. Adv. Energy Mater. 1,
314332.
Dente, M., Pierucci, S., Sogaro, A., Carloni, G., Rigolli, E., 1988. Simulation program
for urea plants. Comput. Chem. Eng. 12, 389400.
Edrisi, A., 2013. Investigation of the chemical-looping systems for hydrogen
production with inherent CO2 separation and feasibility study of using this
51
Lan, R., Tao, S., Irvine, J.T., 2010. A direct urea fuel cellpower from fertiliser and
waste. Energy Environ. Sci. 3, 438441.
Lee, G.-W., Shon, B.-H., Yoo, J.-G., Jung, J.-H., Oh, K.-J., 2008. The inuence of mixing
between NH3 and NO for a De-NOx reaction in the SNCR process. J. Ind. Eng.
Chem. 14, 457467.
Ma, Y., Zhang, W., Wang, C., Xu, Y., Li, S., Chu, F., 2013. Preparation and
characterization of melamine modied urea-formaldehyde foam. Int. Polym.
Process. 28, 188198.
Mattisson, T., Lyngfelt, A., 2001. Capture of CO2 using chemical-looping
combustion. Scandinavian-Nordic Section of Combustion Institute, pp.
163168.
Mattisson, T., Lyngfelt, A., Cho, P., 2001. The use of iron oxide as an oxygen carrier
in chemical-looping combustion of methane with inherent separation of CO2 .
Fuel 80, 19531962.
Meessen, J.H., Roos, W.F., Kursten, J.L., 2014. Process for producing granules.
Google Patents.
Murugan, A., Thurseld, A., Metcalfe, I., 2011. A chemical looping process for
hydrogen production using iron-containing perovskites. Energy Environ. Sci. 4,
46394649.
Plus, A., 2011. 11.1 User Guide. Aspen Technology, September-2011.
Rahimi, A., Bonabi, M.F., Mohaghegh, N., 2013. Energy Subsidies Removal Act; an
economic modeling for urea & ammonia industries (Case Study: Iran). Life Sci.
J., 10.
Rollinson, A.N., Jones, J., Dupont, V., Twigg, M.V., 2011. Urea as a hydrogen carrier:
a perspective on its potential for safe, sustainable and long-term energy
supply. Energy Environ. Sci. 4, 12161224.
Roos, W.F., Buitink, F.H.M., 2010. Process for producing granules. Google Patents.
Rydn, M., Lyngfelt, A., 2006. Using steam reforming to produce hydrogen with
carbon dioxide capture by chemical-looping combustion. Int. J. Hydrogen
Energy 31, 12711283.
Steinberg, M., Cheng, H.C., 1989. Modern and prospective technologies for
hydrogen production from fossil fuels. Int. J. Hydrogen Energy 14, 797820.
Svoboda, K., Slowinski, G., Rogut, J., Baxter, D., 2007. Thermodynamic possibilities
and constraints for pure hydrogen production by iron based chemical looping
process at lower temperatures. Energy Convers. Manage. 48, 30633073.
Tanabe, Y., Nishibayashi, Y., 2013. Developing more sustainable processes for
ammonia synthesis. Coordination Chem. Rev.
Wakeland, S., Martinez, R., Grey, J.K., Luhrs, C.C., 2010. Production of graphene
from graphite oxide using urea as expansionreduction agent. Carbon 48,
34633470.
Wang, W.B., Cao, X.B., Gao, W.J., Zhang, F., Wang, H.T., Ma, G.L., 2010. Ammonia
synthesis at atmospheric pressure using a reactor with thin solid electrolyte
BaCe0.85Y0.15O3 membrane. J. Membr. Sci. 360, 397403.
Wang, Z., Hou, Z., Wang, Y., 2013. Fluorinated waterborne shape memory
polyurethane urea for potential medical implant application. J. Appl. Polym.
Sci. 127, 710716.
Xiao, R., Chen, L., Saha, C., Zhang, S., Bhattacharya, S., 2012. Pressurized
chemical-looping combustion of coal using an iron ore as oxygen carrier in a
pilot-scale unit. Int. J. Greenh. Gas Control 10, 363373.
Zhang, S., Saha, C., Yang, Y., Bhattacharya, S., Xiao, R., 2011. Use of
Fe2 O3 -containing industrial wastes as the oxygen carrier for chemical-looping
combustion of coal: effects of pressure and cycles. Energy Fuels 25, 43574366.
Zhang, X., Zhang, S., Yao, P., Yuan, Y., 2005. Modeling and simulation of
high-pressure urea synthesis loop. Comput. Chem. Eng. 29, 983992.