Energy 29 (2004) 23732384

www.elsevier.com/locate/energy

Exergy analysis of industrial ammonia synthesis

Zornitza Kirova-Yordanova

Department of Inorganic Technology, University Prof. Assen Zlatarov, 1, Prof. Yakimov Str.,
8010 Bourgas, Bulgaria

Abstract
Exergy consumption of ammonia production plants depends strongly on the ammonia synthesis loop
design. Due to the thermodynamically limited low degree of conversion of hydrogennitrogen mixture to
ammonia, industrial ammonia synthesis is implemented as recycle process (so-called ammonia synthesis
loop). Signicant quantities of reactants are recycled back to reactor, after the removal of ammonia at
low temperatures. Modern ammonia synthesis plants use well-developed heat- and cold recovery to
improve the reaction heat utilisation and to reduce the refrigeration costs. In this work, the exergy
method is applied to estimate the eect of the most important process parameters on the exergy eciency
of industrial ammonia synthesis. A specic approach, including suitable denitions of the system boundaries and process parameters, is proposed. Exergy eciency indexes are discussed in order to make the
results applicable to ammonia synthesis loops of various designs. The dependence of the exergy losses on
properly selected independent process parameters is studied. Some results from detailed exergy analysis of
the most commonly used ammonia synthesis loop design congurations at a wide range of selected
parameters values are shown.
# 2004 Elsevier Ltd. All rights reserved.

1. Introduction
In modern ammonia plants, it takes 2830 GJ/te [1] to produce ammonia from natural gas
by the overall reaction
natural gas water air ) 3H2 N2 CO2 ) ammonia CO2

(1)

The exergy consumption for ammonia production depends strongly on the ammonia synthesis
loop design.
Therefore, industrial ammonia synthesis presents one of the most attractive opportunities of
application of second law-based methods in process engineering. Since the initial works

Tel.: +359-56-858274; fax: +359-56-880249.

E-mail address: zkirova@btu.bg (Z. Kirova-Yordanova).

0360-5442/$ - see front matter # 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.energy.2004.03.036

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Z. Kirova-Yordanova / Energy 29 (2004) 23732384

of Mobus [2] and Fratzscher [3], a number of papers were published on exergy analysis of
ammonia synthesis section as a part of large integrated single-train ammonia plants: Riekert [4],
Mundo [5], Cremer [6], Kirova-Yordanova [7], Fratzscher et al. [8], Trotter and Pinto [9],
Szargut et al. [10], Leites et al. [11], Kirova-Yordanova et al. [12], Brodjanskij et al. [13], Ali
et al. [14], Radgen [15], etc. In these papers, particular ammonia synthesis loop designs with corresponding sets of parameters are studied.
2. Problem statement, goals and approaches
Ammonia synthesis from hydrogen and nitrogen, described by the reaction
3H2 N2 2NH3

(2)

is restricted by the unfavourable position of the chemical equilibrium and by the relatively low
activity of the promoted iron catalysts. In general, even at high pressures up to 30 MPa, not
more than 2025% of the synthesis gas is converted to ammonia per pass. After the removal of
ammonia by its condensation at low temperatures, the unreacted hydrogennitrogen mixture is
returned to the reactor. Therefore, since its development in 1913 by Haber and Bosch, industrial
ammonia synthesis always has been implemented as a recycle process. Thus, to produce 1 kg
ammonia, 46 kg synthesis gas must be recycled through the reactor.
In this work, we consider a typical ammonia synthesis section (Fig. 1) of modern large
energy-integrated single-train ammonia plants. The basic components of an ammonia synthesis
loop are a catalytic reactor; a reaction heat utilisation subsystem and an ammonia condensation
subsystem.

Fig. 1. Flowsheet of typical ammonia synthesis loop.

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2375

Table 1
Basic process parameters of studied ammonia synthesis loops at 30 MPa
Ammonia Ammonia
synthesis concentration,
loop no. molar %

Degree of
conversion
y, mol/mol

Inlet
Outlet
reactor reactor

1A, 1B
2A, 2B
3A, 3B
4A, 4B
5A, 5B

0.0
2.0
2.0
4.0
8.0

20.0
20.0
14.0
16.0
20.0

0.1667
0.1500
0.1053
0.1034
0.1000

Circulation ratio n,
kg gas inlet
reactor/kg NH3

Approach to the equilibrium b

v
(at 30 MPa, 500 C), inlet/outlet reactor

Loops A,
no inerts

Loops A, no inerts

Loops B, inerts inlet

reactor: CH4 7.0%,
Ar 3.0%

Inlet

Outlet

Inlet

Outlet

0.0000
0.0018
0.0018
0.0084
0.0396

0.4332
0.4332
0.1589
0.2281
0.4332

0.0000
0.0038
0.0038
0.0166
0.0789

0.8625
0.8625
0.3164
0.4541
0.8625

3.000
3.400
4.845
5.027
5.400

Loops B,
inerts inlet
reactor:
CH4 7.0%,
Ar 3.0%
3.517
3.975
5.664
5.860
6.262

The energy eciency of an industrial ammonia synthesis process depends on two kinds of
parameters:
. Parameters dened by external systems: pressure and inerts (CH4 Ar) content of the makeup gas, eciencies of Rankine cycle, refrigeration plant and purge recovery.
. Internal parameters dened by the loop design: degree of conversion (or recycle ratio), reaction approach to equilibrium, inerts (CH4 Ar) content in the circulating gas and reaction
heat- and cold recovery system parameters.
The aim of this work is to study the eect of the internal loop parameters on the exergy
eciency of industrial ammonia synthesis in order to evaluate the potential for improvement of
the ammonia synthesis loop design.
We have selected 10 ammonia synthesis loops at 30 MPa in order to cover a wide range of
values for the degree of conversion, the approach to the equilibrium and the inerts content, used
contemporarily (Table 1).
The material ows going into and out of the analyzed system have to be independent from
the internal loop parameters, when mass balance is tted, in order to estimate the eect of the
loop parameters on the exergy losses and exergy degree of perfection. To meet this requirement,
the purge and ash gas recovery cryogenic unit, as well as the re-compression of the recovered
hydrogennitrogen mixture have to be included in the analyzed system (Fig. 1).
3. Ammonia synthesis loop: features, constraints and main parameters
The exergy eciency of an ammonia synthesis loop depends strongly on the degree of conversion, respectively, on the recycle ratio. The higher the conversion (respectively the lower the
recycled/fresh gas ratio), the better the heat utilisation and the less the exergy consumption for
gas recycling and for ammonia condensation. However, exergy eciency increases when the
reaction approaches equilibrium, because exergy consumption for ammonia condensation
decreases.

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Z. Kirova-Yordanova / Energy 29 (2004) 23732384

3.1. Recycle ratio, degree of conversion and approach to the equilibrium

The ratio of the recycled synthesis gas to the produced ammonia, respectively, of the recycled
to the fresh (make-up) synthesis gases
n

1 Mgas
y MNH3

(3)

is reciprocal to the degree of conversion of hydrogennitrogen mixture into ammonia

y

xNH3 ;out  xNH3 ;in

1 xNH3 ;out

(4)

The approach to equilibrium of the reaction can be dened as

b

x2NH3 x3eqH2 xeqN2

x3H2 xN2

x2eqNH3

(5)

In the above equations n is the ratio of recycled synthesis gas to produced ammonia, kg gas/kg
NH3; y is the degree of conversion of hydrogennitrogen mixture into ammonia; xNH3,in,
x
NH3,out are ammonia concentrations in recycled synthesis gas at the reactor input and output,
molar parts; Mgas, MNH3 are molar masses of synthesis gas entering the reactor and of
ammonia, respectively. xeqNH3 , xeqH2 and xeqN2 are the equilibrium molar concentrations, and
xNH3 , xH2 and xN2 are the actual molar concentrations.
The equilibrium concentrations of components in the ammonia synthesis reaction depend on
the pressure and the temperature, and, to a lesser extent, on the concentration of inerts. As catv
alysts are active over the narrow temperature range of 380500 C and unable to approach
more than 80% of the equilibrium, the maximum ammonia concentration in the recycling gas at
the reactor outlet depends in fact only on the pressure.
Actually, outlet ammonia concentration is being chosen somewhat lower in order to reduce
the catalyst volume, and the reactor costs. In most cases, the inlet and outlet ammonia concentrations are connected depending on the reactor design. The oldest quench and cooling
tube reactors aord a degree of conversion of no more than 1011%. As seen in Table 1, loops
no. 35, dierent approaches to the equilibrium of ammonia synthesis may be reached (respectively dierent outlet ammonia concentrations), depending on the inlet ammonia concentration.
Modern reactor designs with intercoolers between catalyst beds provide a degree of conversion as high as 15% (Table 1, loops no. 2). With maximum outlet ammonia concentration of
20%, a degree of conversion of more than 16% may be reached only in the case of full removal
of ammonia from recycling gas mixture, e.g. by water absorption (Table 1, loops no. 1). However, water absorption is not used in industrial ammonia plants and ammonia condensation is
still the only way to separate ammonia from the unreacted gas mixture.
3.2. Ammonia condensation
The inlet ammonia concentration depends on the vapourliquid equilibrium (VLE) in the system NH3N2H2CH4Ar. Ammonia is the only component of this system, which might be
condensed at non-cryogenic temperatures. However, the VLE position of ammonia in the pres-

Z. Kirova-Yordanova / Energy 29 (2004) 23732384

2377

ence of non-condensable gases at high pressures (830 MPa) is very unfavourable. The real
vapour pressure of ammonia in this system is up to twice as high as the equilibrium pressure of
pure ammonia at the same temperature. Thus the partial condensation of ammonia from the
outlet gas mixture, containing 20% ammonia at 30 MPa, begins at relatively low temperature
v
(6570 C). To obtain an ammonia content as low as 2%, the gas mixture must be cooled down
v
to temperatures such as 20 C (253 K). Therefore, the rst stage of condensation is carried out
v
in water-cooled or air-cooled condensers. But the ammonia content at temperatures 2530 C is
still high (78%) and in most modern ammonia plants an ammonia refrigeration unit is used to
cool the recycling gas down to 253283 K in order to decrease the converter inlet ammonia concentration down to 25%.
In the rst stage, the ammonia condensation heat is released to the environment and some
power is consumed in the air coolers or in the cooling water system. In the second stage, cold
recovery could not be complete because the heat capacity ow rate of the warm gas, in which
the ammonia condensation occurs, is much greater than the heat capacity ow rate of the cold
gas exiting the ammonia separator (Fig. 2). In most ammonia plants, a simple vapour-compression refrigeration cycle is used to reject the condensation heat at low temperatures. In this
case, all this heat is rejected from the recycle gas at the lowest temperature in the synthesis loop
and the irreversible losses are too large. If the ammonia content at the reactor inlet is given
(Table 1), the minimum temperature approaches in the cold exchanger and in the chiller are the
only independent parameters of the second-stage ammonia condensation subsystem (Fig. 2).
3.3. Heat recovery and utilisation in ammonia synthesis loop
The exergy eciency of modern ammonia synthesis plants is improved by the use of welldeveloped heat- and cold recovery. In most ammonia plants (Fig. 1), the reaction heat is utilised
at a relatively low temperature, e.g. for boiler feed water (BFW) preheating (Fig. 2). The temperature approach in high temperature (HT) heat exchanger depends only on the degree of conv
v
v
version increasing from 160 to 180 in loops nos. 35 to 260290 in loops nos. 2 and 1,

Fig. 2. TH diagrams of heat and cold recovery in studied ammonia synthesis loops Left: Icold unreacted gas; II
hot converted gas; Vboiler feed water; Pammonia dew point; PLrst stage partial ammonia condensation.

2378

Z. Kirova-Yordanova / Energy 29 (2004) 23732384

v

respectively. A small temperature approach (about 1020 C) along the low temperature (LT)
heat exchanger is possible and then a substantial (9095 %) part of the reaction heat could be
utilised. But the temperature level of heat utilisation is low and the exergy eciency of the
entire heat utilisation system is small. If the degree of conversion is given (Table 1), the minimum temperature approach in the low temperature heat exchanger and the hot gas BFW preheater
input temperature are the only independent parameters of heat recovery and utilisation subsystem (Fig. 2).
4. Exergy analysis
Exergy analysis is performed of a commonly used design conguration of ammonia synthesis
loop (Fig. 1) at a wide range of selected process parameters. An example of exergy balances of
studied ammonia synthesis loops is shown in Table 2.
4.1. Calculation procedure
The exergies of the material ows are calculated as a sum of the chemical and physical exergies [10]. Gaseous mixtures at high pressure are treated as real mixtures of real gases, specied
by the RedlichKwong equation [16,17]. The environment parameters are assumed as follows:
P0 101; 325 Pa, T 0 298:15 K and relative humidity 0.301.
4.2. System boundaries specication, exergy losses and degree of perfection
The results obtained from the exergy analysis of an ammonia synthesis loop depend strongly
on the specication of system boundaries. To obtain better results and to estimate the only
eect of internal loop parameters on the loop eciency, the purge and ash gas recovery cryogenic unit is included in the analyzed system, as well as the recompression of recovered hydrogennitrogen mixture from cryogenic unit pressure to loop pressure (Fig. 1).
If we assume that in the cryogenic unit:
. the hydrogennitrogen mixture is completely recovered and fed back to the ammonia synthesis process and
. both methane and argon are completely separated and obtained as pure substances, then liquid ammonia, methane and argon would be the only material ows exiting the analyzed system (Fig. 3).
Then both quantity and composition of make-up synthesis gas, entering the syngas compressor from the natural gas reforming section would be independent from the loop parameters.
The make-up gas consumption for production of 1 kg ammonia would be equal to theoretical
(stoichiometric) quantity of hydrogen and nitrogen mixture and would depend only on the inert
content in the make-up gas (Fig. 3). Quantity and composition of material ows going into and
out of the analyzed loop are the same for all analyzed loops, named loops A (and in much
the same way for loops B). Thus the total exergy losses D in each analyzed loop would
depend only on the loop parameters and could be expressed only by the exergy of energy ows,

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2379

Table 2
Exergy balances of studied ammonia synthesis loops at 30 MPa

Exergy ows, MJ/t NH3

Ammonia synthesis loop no.

Make-up synthesis gas

(30 MPa)
Refrigeration compressor
Circulation compressor
NH3 absorption and
desorption from purge
andash gas
Cryogenic purge
separation
Recovered H2/N2
mixture compression
to 30 MPa
Total input exergy ows
Liquid ammonia
Useful
Liquid argon
output
Gas methane
exergy
Shaft work obtained in
ows
steam cycle by reaction
heat recovery
Total useful output
exergy ows
Exergy losses total
Inclusive internal exergy losses
Exergy degree of perfection (Eq. (9))
Exergy degree of perfection (Eq. (10))
Exergy degree of perfection (Eq. (11))
Input
exergy
ows

2A

3A

4A

5A

2B

3B

4B

5B

22 535

22 535

22 535

22 535

23 486

23 486

23 486

23 486

198
48
23.5

330.5
59
15.5

100.5
71.5
45

80
86

245
40
43

411
46
34

133
58.5
62.5

67
121

189

236

212

212

21.5

19

23

25

148

184

165

165

22 826
20 340

821

22 959
20 340

781

22 775
20 340

797

22 726
20 340

825

24 151
20 340
13
946
822

24 397
20 340
13
946
784

24 117
20 340
13
946
798

24 051
20 340
13
946
826

21 161

21 121

21 137

21 165

22 121

22 083

22 097

22 125

1665
1612
0.927
0.927
0.330

1838
1804
0.920
0.920
0.298

1638
1589
0.928
0.928
0.327

1561
1476
0.931
0.931
0.346

2030
1980
0.916
0.912
0.288

2314
2283
0.905
0.901
0.253

2020
1975
0.916
0.913
0.283

1926
1845
0.920
0.917
0.300

Constant parameters
: make-up (fresh) synthesis gas composition: H2/N2 (molar ratio) 3:1. Inerts in make-up gas
v
(loops B) CH4 0.95%, Ar 0.35%. Minimum temperature approach in water cooler (ammonia condenser) 5 C. BFW
v
v
v
temperature: input 105 , output 290 C. BFW pressure 10 MPa. Cooling water temperature 25 C. Ammonia synthesis loop pressure drop 1.5 MPa. Mass velocity in tubes 300 kg/s m2; in catalyst bed 15 kg/s m2. Adiabatic
eciency: make-up syngas compressor stages: I, 0.68; II, 0.65; III, 0.63; IV, 0.60; circulation gas compressor 0.65.
Exergy eciency: steam Rankine cycle 0.80; ammonia refrigeration unit 0.300.37; power for cryogenic purge gas
separation (incl. Ar, CH4 and H2 N2 recovery), 24 600 J/mol recovered H2 N2 ; exergy of heat for ammonia recovv
ery from purge and ash gases 3357 kJ/kg NH3. Variable parameters: minimum temperature approach, DTmin C :
v
v
v
LT heat exchanger 10 C; cold exchanger and chiller 5 C. Temperature of hot gas inlet BFW preheater 400 C.

entering and leaving the loop:

D

pq
p
q
mn
m
n
X
X
X
X
X
X
Ei;in 
Ej;useful;out
Ei;in;mat
Ei;in;en 
Ej;out;mat 
Ej;useful;out;en
i1

j1

i1

i1

j1

p
M
X
X
Ei;in;mat 
Ej;out;mat Emake-up  Eliq:NH3  EAr  ECH4 const
i1

j1

(6)

j1

(7)

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Z. Kirova-Yordanova / Energy 29 (2004) 23732384

Fig. 3. Mass balance diagram of ammonia synthesis loops B with inerts in the make-up and circulating gas.

D const

q
n
X
X
Ei;in;en 
Ej;useful;out;en
i1

(8)

j1

where: Emake-up is the exergy of the make-up (fresh) synthesis gas from the reforming section,
compressed to the loop pressure, Eliq:NH3 is the exergy of the produced liquid ammonia, EAr and
ECH4 are the exergies of liquid Ar and gaseous CH4, recovered from purge and ash gas in the
cryogenic unit.
Table 2 claries the usefulness of this approach. The exergy of the incoming and outgoing
material ows is the same for all A and Btype loops, respectively. This allows us to estimate the only eect of the basic loop parameters, as circulation ratio, approach to equilibrium
and heat and cold recovery subsystem parameters. The detailed analysis of these eects is made
below.
This approach also provides a more realistic estimation of the exergy degree of perfection of
ammonia synthesis loops. As it is clear from Table 2, the exergies of incoming and outgoing
material ows are much larger than the exergies of the energy ows. This is the reason for the
abnormally high and very similar values of exergy degree of perfection ge of all the loops,
dened as
Ppq
j1 Ej;useful;out
ge Pmn
(9)
i1 Ei;in
The exergy of the material ows outgoing from all the A-loops is equal (it is the exergy of 1
v
metric ton liquid ammonia at 30 MPa and 30 C). This is also the case for the exergy of all the
material ows outgoing from loops B (the exergy of liquid ammonia, methane and liquid
argon).
A familiar approach in such cases is to subtract the transit exergy from both the numerator
and the denominator of the exergy degree of perfection expression. Following exactly the denition proposed from Brodjanskij [8,13], the only chemical exergy of inerts (CH4 and Ar) could

Z. Kirova-Yordanova / Energy 29 (2004) 23732384

be considered as transit exergy in ammonia synthesis loops

Ppq
j1 Ej;useful;out  Etransit
tr
ge Pmn
i1 Ei;in  Etransit

2381

(10)

However, this approach is not applicable if inerts are not present in the make-up gas, what is
the case for the A-loops. Even if inerts are present, it is not useful enough due to their low
content in the make-up gas (Table 2).
A very useful, but unfortunately not quite correct approach, could be applied if we consider
the exergy of the outgoing material ows as transit exergy and exclude it from the numerator
and the denominator of (9). Thus, the following expression could be stated:
Pq
0
J1 Ej;useful;out;en
 P
(11)
ge P
Pp
m
n

E

E
E
j;out;mat
i;in;mat
i;in;en
i1
i1
j1
It is clear from Eq. (7) that the dierence of the exergies of the incoming and the outgoing
material ows is constant for all A- and B-loops. Thus the values of g0e for the A-loops
depend only on the loops parameters and so is the case for the B-loops. The values of g0e are
much lower than those of ge and their dependence on the loops parameters is stronger (Table 2),
but they could only be used for comparison of the eciency of studied loops.
A conclusion was drawn from the above discussion that the distribution of exergy losses and
their dependence on the loop parameters are much more informative than the exergy degree of
perfection.
4.3. Exergy losses in ammonia synthesis loops
An example of exergy losses distribution in the studied loops is shown in Fig. 4. It is clear
that the irreversibilities of the ammonia synthesis reaction as well as of the heat exchange and
recovery are the major sources of exergy losses. They account for 10001150 MJ/t NH3 or
around 65% of total losses in loops no. 2A4A and around 52% in loops 2B4B, respectively.
The exergy losses in external subsystems are as follows:
. ammonia plant steam Rankine cycle about 200 MJ/t (1012%),
. refrigeration unit from 0 in loops no. 5A and 5B to 250 MJ/t in loops no. 2A and 2B (0
12%),
. cryogenic purge and ash gas recovery (only in B-loops) around 200250 MJ/t (10%),
. recovered H2N2 recompression (in B loops) around 100 MJ/t (5%).
It is interesting to note that the loops no. 5A and 5B have the least losses due to the absence
of second-stage ammonia condensation. However, this design is possible only at process pressure of minimum 30 MPa. In modern large-capacity single-train ammonia plants, lower process
pressures are preferable and the reactor size and weight have some limitations.
The comparison of two most representative loops: no. 2A and B with no. 4A and B (having
high and low degree of conversion, respectively) gives a rather unexpected result: the total
exergy losses in both kinds of these widely used designs are quite equal despite their rather dif-

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Z. Kirova-Yordanova / Energy 29 (2004) 23732384

Fig. 4. Exergy loss distribution in studied ammonia synthesis loops. Constant parameters as in Tables 1 and 2. Variv
v
able parameters: DTmin in LT heat exchanger 10 ; cold exchanger and chiller 5 .

ferent concepts. The smaller losses in the heat exchanger and utilization subsystem in loops no.
2 are balanced by greater irreversible losses in the reactor and in the second-stage ammonia
condensation and refrigeration.
Exergy losses in the reactor are due mainly to the irreversibilities of the ammonia synthesis
reaction as well as of the heat exchange in the reactor itself (Fig. 5). The former depends only
on approach to equilibrium and the latter on the degree of conversion. The pressure drop losses
are around 5% of total reactor losses.
The total exergy losses in reaction heat exchange and utilization subsystem depend only on the
degree of conversion and the minimum temperature approach in the LT heat exchanger. The tem-

Fig. 5. Exergy loss distribution in ammonia synthesis reactor subsystem. Space velocities, h1, in loops no. No.: 1A
25 000; 1B, 2A, 4A22 500; 2B, 4B, 5A20 000; 3A30 000; 3B27 500; 5B17 500.

Z. Kirova-Yordanova / Energy 29 (2004) 23732384

2383

Fig. 6. Exergy loss distribution in heat recovery and utilization subsystem. Ammonia synthesis loop no. 4A minimum
v
v
temperature approach in the LT heat exchanger: left 10 , right 60 C.

perature of the gas at BFW preheater inlet aects only the exergy losses distribution between the
HT and LT heat exchangers and the BFW preheater (Fig. 6).
5. Conclusions
A specic approach including suitable denitions of system boundaries and selection of process parameters is proposed. It is used to study the dependence of exergy losses in the commonly used ammonia synthesis loop design at 30 MPa on the selected process parameters:
degree of conversion, approach to the equilibrium, inert contents and minimum temperature
approaches in LT heat exchanger, cold exchanger and chiller.
The ammonia synthesis reaction and the heat exchange and recovery subsystem are the major
sources of exergy losses (5265% of the total losses). The only way to decrease the latter substantially and thus to improve the overall exergy eciency of ammonia plants is the utilization
of the reaction heat at a higher temperature level for HP steam generation and superheating.
The exergy losses in the second stage of the ammonia condensation and refrigeration subsystems aect substantially the exergy eciency of the ammonia synthesis loops. They determine
the selection of ammonia content in the reactor input and the corresponding degree of perfection. A possible way to decrease these losses is to use a multistage ammonia condensation and
refrigeration.
In a subsequent work, the proposed approach will be applied to study the eect of process
pressure as well as to analyze more ecient heat recovery and condensation subsystem designs.
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