Energy 35 (2010) 3221e3229

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Energy
journal homepage: www.elsevier.com/locate/energy

Application of the exergy method to environmental impact estimation: The

ammonium nitrate production as a case study
Zornitza Kirova-Yordanova*
University “Prof. Assen Zlatarov”, Department of Inorganic Technology, 8010 Bourgas, Bulgaria

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

Article history: The exergy method is used to compare different production processes and various methods for emission
Received 30 October 2008 abatement with respect to their overall environmental impact. Some ammonium nitrate production
Received in revised form processes are studied as examples, because the pollutants (ammonia and ammonium nitrate), emitted
28 March 2010
from these processes into the air and/or into the water, are really a feedstock and a product from the
Accepted 30 March 2010
production process. Therefore, the essential result of the waste flows treatment is the recycling of the
Available online 31 May 2010
pollutants (ammonia and ammonium nitrate) back into the production process, decreasing simulta-
neously the exergy input and cumulative exergy consumption
Keywords:
Exergy
Ó 2010 Elsevier Ltd. All rights reserved.
Cumulative exergy
Mineral fertilizers
Environment
Emissions
Pollutants
Ammonium nitrate
Ammonia
Nitric acid

1. Introduction remaining water from the AN solution can be performed at atmo-

Ammonium nitrate (AN) is the second (after urea) major
nitrogen fertilizer with respect to its high nutrient content
(33.5e34.5% N) as well as to its actual world production (about 16
million t/year).
The AN production process comprises three main unit opera-
tions: neutralization, evaporation and solidification (prilling or
granulation) [1e4].
The neutralization of diluted (55e65%) nitric acid with gaseous
ammonia by the reaction:
NH3 þ HNO3 ¼ NH4NO3 þ Q
is a highly exothermic process, which can be performed at
atmospheric or at elevated pressure (up to about 4.5 bar). The
neutralizers are designed to ensure that the most part of the
reaction heat is used to evaporate as much as possible water from
the obtained AN solution. The subsequent evaporation of the
* Tel.: þ359 56 858274, þ359 0899 195613 (mobile); fax: þ359 56 880249.
E-mail address: zkirova@btu.bg
spheric pressure or under vacuum.
The process steam, generated in the neutralizer and the evap-
orator, contains rather high concentrations of ammonia and AN.
Ammonium nitrate emissions from neutralizers are very difficult to
remove because the particles are very fine.
In most of the AN plants, the latent heat of the process steam is
used partially to preheat feed stocks (ammonia and nitric acid) and
thus some process condensate is formed.
Various techniques are used for treatment of the process steam
and condensate. The most widespread is the absorption of AN and
ammonia from the process steam with recycled solution of 15e25%
AN in water containing nitric acid. The recovered ammonia and AN
(1)
are recycled back into the process. Certain more efficient abatement
techniques are recommended to be used in new plants: like air or
steam stripping, evaporation systems, and membrane separation
processes [5,6].
As a consequence of the fact that the recovered pollutants
(ammonia and AN) are recycled back into the process, a deeper
pollutants removal from the process steam and condensate would
result in a lower feedstock consumption.
An additional effect would be a relevant reduction of the
emissions from the production of the precursors (ammonia and
nitric acid), namely CO2, NOx and N2O (Table 1). However, the

0360-5442/$ e see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.energy.2010.03.063
3222 Z. Kirova-Yordanova / Energy 35 (2010) 3221e3229

The application of exergy as a measure of the impact of the

Nomenclature emissions and wastes has been proposed first by G. Wall [9] and
then by R. Ayres [10], Rosen [11], etc. R Ayres [10] pointed out that
AN ammonium nitrate the exergy content of a waste stream could be a rough measure of
BAT best available techniques its potential to cause harm, despite of its incapability to measure
CEnC cumulative energy consumption human or eco-toxicity. Szargut [8] proposed to evaluate the impact
CExC cumulative exergy consumption of waste products by means of their monetary index of harmful-
D exergy losses ness. Another approach is developed by Valero and Botero [12].
E exergy They regard the exergy of the resources consumed by the processes
GHG greenhouse gases of the emissions abatement as a measure of environmental impact
HP high pressure of technical systems. Cornelissen [13], Gong and Wall [14], etc., use
LP low pressure the exergy method in the context of Life Cycle Analysis in order to
MP middle pressure specify a Second-Law based ecological indicator.
Q heat of reaction (DH) As the exergy by definition is connected with the environment,
it could be an appropriate measure of the environmental impact of
some human activities, especially process industry, energetics,
treatment processes need heat (steam) and power to be consumed, transport, etc., which use natural resources like fuels, ores,
hence additional fuel should be burnt and additional emissions minerals, water, air, etc., and release gaseous and liquid emissions
would arise from the steam and power production facility (Fig. 1). and solid wastes into the environment.
Thus, the overall net effect from a treatment process should include The total exergy of a material flow is the sum of chemical,
both the positive and the negative effects. physical (mechanical and thermal), potential and kinetic
In order to compare the various treatment processes and to components.
mark the most appropriate ones not only by economic but also by In two previous papers [15,16] some attempts were made to
environmental criteria, it is necessary to estimate all these multi- estimate the environmental impact of the mineral fertilizers
form effects on a common basis. production processes by the chemical exergy of the pollutants.
Various approaches have been proposed and developed in the The exergy of the waste flows released to the environment from
last years with the intention to obtain environmental impact chemical plants account for the main fraction of the external exergy
indicators based on both the First and Second Laws of Thermody- losses. In most cases the temperature and the pressure of the dis-
namics. The exergy method appears to be the most suitable to charged fluids or solids are close to the environmental parameters,
achieve this purpose, as the exergy of a system is by definition the therefore, their physical exergy is rather small. Besides that, the
potential of this system related to the environment. The relation- potential of the emissions to damage the environment depends
ships between the exergy and the environment concern both the mainly on their chemical composition and especially, on the
consumption of natural resources and the impact of the discharges concentration and chemical properties of the pollutants. Therefore,
on the environment. the chemical exergy of pollutants as well as of the material flows,
The exergy method and the Cumulative Exergy concept (Szargut released to the environment, appears to be a more representative
et al. [7]) have been used successfully for many years for evaluation index, than their total exergy.
of the overall consumption of all kinds of natural resources at every However, no direct correlation was found between the chemical
step of a production process. Szargut proposed also the term exergy of the pollutants and their impact on various components of
ecological costs as a measure of their depletion [7,8]. the environment, despite that some dependence was shown to
However, the numerous attempts to obtain a direct correlation exist between the oxidation potential of some nitrogen compounds
between exergy and the indicators used for estimation of the and their chemical exergy.
impact on the environment are still not quite satisfying. Therefore, another approach appears to be more fruitful, namely
the application of the exergy method and cumulative exergy
Table 1
Emissions and liquid effluents from the production of ammonium nitrate and its concept to estimate and compare various designs of a production
intermediates: ammonia and nitric acid. process as well as various processes for waste water and/or gases
Emissions and liquid effluents from AN plant
treatment and pollutants removal.
Basic reaction NH3 þ HNO3 (45e62%) 0 NH4NO3 The aim of this work is to use the exergy method and the
Emissions into Process steam: NH3, AN dust and droplets cumulative exergy concept in order to compare different processes
atmosphere Air from prilling towers: NH3, AN dust for emission abatement with respect to their overall environmental
Liquid effluents Process condensate (water from nitric acid solution):
impact. The ammonium nitrate production process is studied as an
NH3, NH4NO3
interesting example in view of its features, considered above. To
Emissions and liquid effluents from NH3 plant achieve this goal, various exergy-based indices are defined and
Basic reaction Natural gas þ Water (Steam) þ Air 0 3
used.
H2 þ N2 þ CO2 0 Ammonia þ CO2
Emissions into Vent gas from CO2 removal unit: 98.5e99% CO2
atmosphere Flue gas from reforming furnace: 8e12% CO2; <300
ppm NOx 2. Data sources and calculation procedures
Liquid effluents Process condensate (from surplus steam): 0.1% NH3,
0.1% CH3OH
2.1. Data sources
Emissions from nitric acid plant
Basic reactions 4NH3 þ 5O2 (Air) 0 4NO þ 6H2O
The basic process data, used in this work, are extracted from a work
2NO þ O2 0 2NO2
3NO2 þ H2O 0 2HNO3 þ NO of Bouilloud and Boujnah [17], comparing various waste steam and/
Undesirable parallel 4NH3 þ 4O2 (Air) 0 2N2O þ 6H2O or condensate treatment techniques, combined with 4 various
reactions 4NH3 þ 3O2 (Air) 0 2 N2 þ 6H2O processes of the AN synthesis (at atmospheric and at elevated
Emissions into Tail (waste) gas: NOx, N2O pressure, with and without a tube reactor). The following emissions
atmosphere
abatement techniques are compared in [17]:
 Z. Kirova-Yordanova / Energy 35 (2010) 3221e3229 3223

Fig. 1. Block flow diagram of an ammonium nitrate production site.

- Absorption column with acidified ammonium nitrate solution;
- Two- and three-stage vacuum evaporation system;
- Vacuum evaporation system with mechanical compressor
(heat pump).
All these techniques ensure full recycling of the pollutants (AN
and ammonia) back into the AN synthesis process.
Some emission treatment techniques basic data, extracted from
[17], are shown in Table 2.
The basic parameters of the analyzed AN production plant are:
AN synthesis at atmospheric pressure; concentration of nitric acid
62% HNO3, concentration of the produced AN solution 96% NH4NO3.
All data for the feedstock and energy consumption in ammonia,
nitric acid and ammonium nitrate production, as well as all data for
the emissions from these processes, are extracted from EFMA and
European Commission publications on Best Available Techniques
(BAT) [5,6].
2.2. Calculation procedures
The mass balances of three different waste flows treatment
processes are calculated on the basis of the process data from [17].
The exergy of material flows is calculated by a method, proposed
by Szargut as a sum from chemical and physical (thermal and
mechanical) exergy [7].
Gaseous emissions are released at pressures close to atmo-
spheric pressure and are treated as ideal mixtures. Liquid effluents
are extremely diluted and are treated as ideal mixtures, despite off
some lack of precision. The environment parameters are assumed
as follows: P0 ¼ 101,325 Pa, To ¼ 298.15 K and relative humidity
0.301. The cumulative exergy consumption (CExC) of natural
resources is also calculated by the method proposed by Szargut [7].
Some data obtained in previous work of the author [18,19] on the
exergy analysis and CExC in mineral fertilizers production
processes are also used.
3. Results and discussion
3.1. Exergy losses and degree of perfection of waste steam and/or
condensate treatment processes
Mass flow rates, concentrations of pollutants and exergy of
input and output flows of 3 different waste steam and/or conden-
sate treatment processes, combined with AN synthesis at atmo-
spheric pressure, are shown in Table 3. The exergy flows of these
processes are shown in Table 4.
The exergy losses are defined as:
X X
D ¼ Ei;in  Ei;out;useful (4)

and the degree of perfection is calculated as:

Table 2
Emissions to the atmosphere and liquid effluents from ammonium nitrate produc- X X
tion, according to Bouilloud and Boujnah [17]. he ¼ Ei;out;useful = Ei;in (5)
P
Gaseous emissions and Pollutant Absorption column Vacuum where: Ei,out,useful is the sum of the exergies of the outlet flows,
liquid effluents ppm w/w with AN solution evaporation P
which are useful products. Ei, in, is the sum of the exergies of all
systems
inlet streams.
Process steam before NH3 3000e5000
The absorption of ammonia and AN droplets and dust by an
treatment NH4NO3
Process condensate before NH3 1000e1200 acidified solution of ammonium nitrate is the process with the best
treatment NH4NO3 degree of perfection and minimum exergy losses, because no heat
Process steam and/or NH3 <100 0 and only little power are consumed in this case. Unfortunately, this
condensate after NH4NO3 <100 <10 process can’t remove AN and ammonia from the waste steam (and/
treatment
or condensate) below 100 ppmw.
3224 Z. Kirova-Yordanova / Energy 35 (2010) 3221e3229

Table 3 200
Mass flow rate, concentration and exergy of input and output flows in different
waste steam and/or condensate treatment subsystems. AN synthesis at atmospheric
pressure. Concentration of nitric acid 62% HNO3. Concentration of the obtained AN 160
solution 96% NH4NO3.

Flows Mass flow Concentration, Exergy kJ/kg

rate kg/t AN mass % 120

MJ / t AN
NH4NO3 NH3
Absorption column with AN solution 80
Process steam (1.2 bar, 170  C) 441.0 0.3 0.3 769.76
HNO3 (62%) 7.7 e e 459.66
Input flows total 448.7 e e e
40
Purified steam 404.4 0.01 0.01 675.68
Recycled solution (17% AN) 44.3 16.5 e 729.85
Output flows total 448.7 e e e
0
Two stage vacuum evaporation system Absorption column Evaporation system Evaporation system
Process steam (1.2 bar, 170  C) 242.55 0.3 0.3 769.76 with compressor
Process condensate (1.2 bar) 198.45 0.3 0.3 266.33
HNO3 (62%) 7.9 e e 459.66 Exergy losses in waste flows treatment subsystem
Input flows total 448.9 e e
Purified condensate 418.7 0.001 0.000 199.80 Exergy losses in waste flows treatment and power
Recycled solution (25% AN) 30.2 25.0 e 1025.5 generation subsystems
Output flows total 448.9 e e e

Vacuum evaporation system with mechanical compressor Fig. 2. Exergy losses in different waste steam and/or condensate treatment subsys-
Process condensate (1.2 bar) 441.0 0.3 0.3 266.33 tems. AN synthesis at atmospheric pressure.
HNO3 (62%) 7.9 e e 459.66
Input flows total 448.9 e e e
Purified condensate 418.7 0.001 0.000 199.80 However, in modern AN plants a part of the condensation heat
Recycled solution (25% AN) 30.2 25.0 e 1025.5
of the process steam is used for preheating of nitric acid and/or
Output flows total 448.9 e e e
ammonia before the neutralization reactor. Both first and third
treatment processes ensure the possibility for the condensation
A comparison of the two evaporation processes (Table 4) shows heat to be used for preheating, after or before purification,
that the evaporation system with mechanical compressor (heat respectively. The second process limits this possibility only for
pump) appears to be more efficient: it consumes only power and no a part of the condensation heat.
heat. However, if the analyzed system also includes the power Thus, in order to compare more correctly the efficiency of the
plant, where the consumed power is generated from natural gas, treatment processes, it would be necessary to analyze not the
the effect is reversed: the exergy indices of this process are the treatment unit only, but the whole AN production plant. However,
worst (Fig. 2). various neutralization and AN solution evaporation processes are
Another feature of the analyzed treatment processes should be used in modern plants, combined with various waste flows treat-
also considered: the different state of input and output waste flows ment techniques and it is rather difficult to estimate the efficiency
(Table 3). of the treatment process itself.
The first process is designed to purify the process steam, and no For this reason in the next sections attempts are made to use some
change in the flow state occurs. The third process treats the other exergy-based indices in order to compare the overall effects
condensate only. In the second process a part of the input waste from the waste steam and/or condensate treatment processes.
flow is in gaseous state but the remaining part is liquid, while the
output flow is the purified condensate. Thus in the second process
a part of the condensation heat of the process steam is used as the 3.2. Reduction of the emissions and additional emissions as a result
only energy source. As the exergy of this low pressure steam is low, from the waste steam and/or condensate treatment processes
this process appears to be the most effective.
As the result of the waste flows treatment is also the recycling of
the pollutants (ammonia and ammonium nitrate) back into the
Table 4 production process, the overall effect includes also some reduction
Exergy flows, exergy losses and degree of perfection in different waste steam and/or of feedstock and energy consumption. As a result of this, some
condensate treatment subsystems. AN synthesis at atmospheric pressure.
reduction of the emissions from ammonia and nitric acid production
Exergy flows Absorption Two stage Vacuum processes is obtained. However, all treatment processes need some
MJ/t AN column with vacuum evaporation additional power and/or steam consumption and as a result some
AN solution evaporation system with
additional emissions from power and/or steam generation arise.
system mechanical
compressor The problem is what effect is more significant, i.e., is the net
Process steam 339.5 186.7 e
overall effect positive or negative.
Process condensate e 52.8 117.5 In order to estimate the overall effects from treatment processes
HNO3 (62%) 3.5 3.6 3.6 a building block model and a top-down approach are used.
Power 1.4 1.0 60.3 The structure of the building block model of a whole ammonium
Exergy input total 344.4 244.1 181.4
nitrate production site includes ammonia and nitric acid units as
Purified steam 273.2 e e
Purified condensate e 83.7 83.7 intermediates, ammonium nitrate as final product and a steam and
Recycled AN solution 32.3 30.9 30.9 power plant (Fig. 1.).
Useful exergy 305.5 114.6 114.6 The feedstock and intermediates consumption and emissions
Exergy losses total 38.9 129.5 66.8 data used in the building block model, are extracted from EFMA and
Degree of Perfection, % 88.71 46.94 63.17
EC publications for BAT plants [5,6] and are shown in Table 5.
 Z. Kirova-Yordanova / Energy 35 (2010) 3221e3229 3225

Table 5 Table 7
Feedstock consumption and emissions data for BAT plants [5,6], used in the building Mass and exergy of the additional emissions from production of power and steam in
block model. the power plant.

Feedstock consumption and emissions for BAT plants [5,6] Mass and exergy of the Absorption Two- and Vacuum
Ammonium Nitrate Production Plant additional emissions from column with three- stage evaporation
Feedstock consumption, kg/t AN, incl.: production of power and steam AN solution vacuum system with
- NH3 214 in power plant evaporation mechanical
- HNO3 790 system compressor

kg/t MJ/t kg/t MJ/t kg/t AN MJ/t

Ammonia Production Plant
AN AN AN AN AN
Natural gas (CH4) consumption, Nm3/t NH3, incl.: 900
- as feedstock 635 Additional emissions from power production
- as fuel 265 Power production total, incl.: 0.2462 0.1128 0.1641 0.0752 10.3962 4.7633
Emissions into atmosphere, kg/t NH3, incl.: - CO2 in flue gas 0.2460 0.1126 0.1640 0.0751 10.3883 4.7536
- 99% CO2 from CO2 removal unit 1200 - NOx (as NO2) in flue gas 0.0002 0.0002 0.0001 0.0001 0.0079 0.0097
- CO2 in flue gas from reforming furnace 500
Additional emissions from steam production
- NOx in flue gas from reforming furnace 1.0
Steam for evaporation of 7.2954 3.3426 4.4650 2.0456 4.4650 2.0456
Liquid effluents (process condensate) kg/t NH3, incl.:
circulated solution, incl.:
- NH3 0.001
- CO2 in flue gas 7.2899 3.3358 4.4619 2.0418 4.4619 2.0418
Nitric Acid Production Plant - NOx (as NO2) in flue gas 0.0055 0.0068 0.0031 0.0038 0.0031 0.0038
Feedstock consumption, kg/t HNO3, incl.: Steam produced to compensate 0.0909 0.0416 0.0935 0.0428 0.0935 0.0428
- NH3 286 the lost steam production in
Steam export, kg/t HNO3 500 HNO3 plant, incl.:
Emissions into atmosphere (waste gas), kg/t 100% HNO3, incl.:  CO2 in flue gas 0.0908 0.0415 0.0934 0.0427 0.0934 0.0427
- NOx 1.6  NOx (as NO2) in flue gas 0.0901 0.0001 0.0001 0.0001 0.0001 0.0001
- N2O 8.0 Total additional emissions 7.6326 3.4971 4.7226 2.1636 14.9547 6.8517

Steam Power Plant (Natural Gas based) in a Fertilizer Production Site

Energy efficiency (First Law) h ¼ W/Q
Thermal efficiency of utility boilers
Emissions into atmosphere (flue gas), kg/MWh, incl.:
- CO2
- NOx
The accumulated reduction of the emissions is calculated by
tracing out from the AN unit back down to the nitric acid and
ammonia units and also to the steam and power plant. The calcu-
lated values of the reduction of quantities and exergy of the
emissions are shown in Table 6.
The additional emissions arise from steam and power plant only
and thus include CO2 and NOx (Table 7).
The net reduction of the mass and exergy of the emissions from
production of AN, NH3, and nitric acid as a result of the waste flows
treatment are shown in Table 8.
Table 6
Reduction of the mass and exergy of the emissions from production of AN, NH3, and
nitric acid as a result of the waste flows treatment.
0.32
0.90
620
Table 7 shows that in two of the three treatment methods, the
0.47 mass of the additional emissions generated from steam and power
production is larger than the reduction of the total mass of the
emissions from the overall AN production route (including
ammonia, nitric acid and AN production).
However, the total reduction of the emission’s exergy is much
larger than the exergy of the additional emissions. As a result of
each of the three methods, the total net reduction of the emissions
is positive and all three values are very similar (Table 8).
3.3. Reduction of the energy and exergy consumption. Cumulative
Energy Consumption (CEnC) and Cumulative Exergy Consumption
(CExC)
The building block model and the top-down approach are used
also to calculate the reduction of energy and exergy consumption as
a result from the recycling of the pollutants back into the process.

Reduction of the mass and exergy of the Absorption Vacuum Table 8

emissions from production of ammonium column with AN evaporation Net reduction of the mass and exergy of the emissions from production of AN, NH3,
nitrate, ammonia and nitric acid solution systems and nitric acid as a result of the waste flows treatment.
kg/t MJ/t AN kg/t MJ/t AN Reduction of the Absorption Two- and three Vacuum evaporation
AN AN mass and exergy column with stage vacuum system with
NH4NO3 in waste steam and condensate 1.2789 4.7703 1.3185 4.9183 of the emissions AN solution evaporation mechanical
system compressor
NH3 total, incl.: 1.2791 25.6124 1.3232 26.4956
- Waste flows from AN plant 1.2789 25.6087 1.3230 26.4918 Reduction of the mass of the emissions (kg/t AN)
- Waste condensate from NH3 plant 0.0002 0.0037 0.0002 0.0038 Total emissions 5.8144 5.8889 5.8889
reduction
CO2 total, incl.: 3.2448 1.4848 3.2353 1.5344 Additional 7.6326 4.7226 14.9547
 Vent gas 99% CO2 2.2098 1.0112 2.2837 1.0450 emissions
 Flue gas from reforming furnace 0.9208 0.4213 0.9516 0.4354 Net emissions L1.8182 1.1663 L9.0658
 Flue gas from power plant 0.1142 0.0523 0.1180 0.0540 reduction
NOx (as NO2) total, incl.: 0.0035 0.0043 0.0036 0.0045 Reduction of the exergy of the emissions (MJ/t AN)
 Flue gas from reforming furnace 0.0019 0.0022 0.0019 0.0023 Total emissions 31.8913 32.9729 32.9729
 Tail gas from HNO3 plant 0.0016 0.0020 0.0017 0.0020 reduction
 Flue gas from power plant 0.0080 0.00001 0.0083 0.00001 Additional 3.4971 2.1636 6.8517
emissions
N2O in tail gas from HNO3 plant 0.0081 0.0195 0.0083 0.0201
Net emissions 28.3942 30.8093 26.1212
Total emissions reduction 5.8144 31.8913 5.8889 32.9729 reduction
3226 Z. Kirova-Yordanova / Energy 35 (2010) 3221e3229

Table 9
Reduction and additional consumption of feedstock and power in the production of ammonium nitrate, ammonia and nitric acid as a result of the waste flows treatment and
recycling of ammonia and NH4NO3.

Reduction and additional consumption of Absorption column with AN solution Two- and three- stage vacuum Vacuum evaporation system with
feedstock and evaporation system mechanical compressor
power in the production of ammonium nitrate
Reduction of feedstock and power consumption
Natural gas for ammonia production Nm3/t AN 1.657 1.713 1.713
Power for ammonia production kWh/t AN 0.184 0.190 0.190

Additional steam and power consumption

LP (0.12 MPa) steam for evaporation of the 36.990 22.650 22.650
circulated solution, kg/t AN
MP (4 MPa) steam to compensate the lost steam 0.507 0.521 0.521
production in HNO3 plant, kg/t AN
Power for waste flows treatment, kWh/tAN 0.397 0.265 16.758

The feedstock and intermediates consumption data from Table 6
are used by tracing out from the AN unit back down to the nitric
acid and ammonia units in order to calculate the reduction of
overall natural gas and power consumption in the technological
chain of the AN production (Table 9). The natural gas is assumed to
be pure methane and the values of the energy consumption
reduction in Table 10 are calculated on the basis of lower heating
value of CH4.
The additional steam and power consumption in the treat-
ment processes are shown also in Table 9. The additional steam is
used mostly to evaporate the recycled AN solution from 17% or
25% AN, respectively to 96% AN product solution. As the addi-
tional steam is only a heating agent, the energy values shown in
Table 10 represent the enthalpy changes and the exergy values
shown in Table 11 represent the thermal exergy changes of the
steam used.
The comparison of Tables 10 and 11 shows that the additional
energy and exergy consumption values are very different.
As the energy values shown in Table 10 are based on the
First Law only, the enthalpy of LP steam and power are included
as equivalent in the total additional energy consumption. Thus
Table 10 represents an erroneous picture about the additional
energy consumption and thence about the net reduction of the
energy consumption, with enormous values of the energy of
steam.
The exergy values shown in Table 11 are based on combined
First and Second Laws and thus the results for the additional exergy
and net exergy consumption are much more reasonable, because
the exergy of the low pressure steam, used for AN solution evap-
oration is much lower than its enthalpy.
However, the consumed additional power is generated in
a power plant, included in the same production site (Fig. 1). As in
the case of AN production, it would be more correct to apply top-
down approach and include the additional exergy of the natural
gas, burned in the power generation unit, instead of the consumed
power.
The same approach should be applied for the exergy of the
additional steam, but the problem exists whether the LP steam,
used for evaporation of the recycled solution, is produced in
a separate boiler or is extracted from the turbine in the power plant.

Table 11
Table 10 Reduction of the exergy consumption in the production of ammonium nitrate,
Reduction of the energy consumption in the production of ammonium nitrate, ammonia and nitric acid as a result of the waste flows treatment and recycling of
ammonia and nitric acid as a result of the waste flows treatment and recycling of ammonia and NH4NO3.
ammonia and NH4NO3.
Reduction of the exergy Absorption Two- and three Vacuum evaporation
Reduction of the Energy Absorption Two- and three Vacuum consumption MJ/t AN column with stage vacuum system with
Consumption MJ/t AN column with stage vacuum evaporation system AN solution evaporation mechanical
AN solution evaporation with mechanical system compressor
system compressor
Reduction of the exergy consumption
Reduction of the Energy Consumption Natural gas for ammonia 62.477 64.566 64.566
Natural gas for ammonia 59.350 61.356 61.356 production
production Power for ammonia 0.664 0.685 0.685
Power for ammonia 0.664 0.685 0.685 production
production
Total reduction of exergy 63.141 65.251 65.251
Total reduction of the 60.014 62.041 62.041 consumption
energy consumption
Additional exergy consumption
Additional Energy Consumption LP (0.12 MPa) steam for 18.622 11.403 11.403
LP (0.12 MPa) steam for 87.890 53.803 53.803 evaporation of the
evaporation of the circulated solution
circulated solution MP (4 MPa) steam to 0.586 0.604 0.604
MP (4 MPa) steam to 1.484 1.527 1.527 compensate the lost
compensate the lost steam steam production in
production in HNO3 plant HNO3 plant
Power for waste flows 1.429 0.953 60.329 Power for waste flows 1.429 0.953 60.329
treatment treatment
Total additional exergy 20.637 12.960 72.336
Total additional energy 90.803 56.283 115.659
consumption
consumption
Net reduction of the energy L30.789 5.758 L53.618 Net reduction of the exergy 42.504 52.291 L7.085
consumption consumption
 Z. Kirova-Yordanova / Energy 35 (2010) 3221e3229 3227

Table 12 methane and the values are identical with these in Table 10. All
Reduction of the Cumulative Energy Consumption (CEnC) in the production of AN, values of CEnC for power consumption are calculated on the basis of
NH3, and nitric acid as a result of the waste flows treatment.
the 32%. energy efficiency (First Law-based) of power generation.
Reduction of the Absorption Two- and three Vacuum evaporation The values of the CEnC for additional steam consumption are
Cumulative Energy column with stage vacuum system with calculated on the basis of the 90% thermal efficiency of steam
Consumption (CEnC) AN solution evaporation mechanical
MJ/t AN system compressor
generation in a separate boiler (Table 6). As was shown above, the
additional CEnC consumption appears to be strongly over-
Reduction of the Cumulative Energy Consumption (CEnC)
Natural gas for ammonia 59.35 61.36 61.36 estimated, due to the assumption for the steam generation in
production a separate boiler.
Power for ammonia 2.07 2.14 2.14 The calculation of the Cumulative Exergy Consumption (CExC) is
production based on the method, proposed by Szargut [7]. The values of exergy
Total reduction of the CEnC 61.42 63.50 63.50 consumption from Table 10 are divided by the values of the
Cumulative Degree of Perfection (CDP), extracted from [7] for
Additional Cumulative Energy Consumption (CEnC) natural gas production (0.875), power generation (0.24) and steam
LP (0.12 MPa) steam for 97.65 59.78 59.78
generation (0.35), respectively.
evaporation of the
circulated solution The CExC results for natural gas and power, shown in Table 13,
MP (4 MPa) steam to 1.65 1.70 1.70 are rather similar to the values of CEnC in Table 12. The CExC
compensate the lost values for LP steam are lower than the CEnC and thus represent
steam production in
a better estimation of the additional consumption of natural
HNO3 plant
Power for waste flows 4.47 2.98 188.53
resources (fuel) for the treatment processes. However, these
treatment values (as those in Tables 10e12) are based on the assumption
that steam is generated in a separate boiler by natural gas
Total additional CEnC 103.77 64.46 250.01
Net reduction of the CEnC L42.35 L0.96 L186.51 burning. In reality the LP steam is usually extracted from the
turbine (or generated in an utility boiler from low temperature
waste heat), so the CExC values should be lower than those in
Table 13.
The former case is rather unrealistic and would give an abnormally
high value of the natural gas consumption, but the latter is difficult
to be estimated correctly. 3.4. Comparison of three waste steam and/or condensate treatment
The top-down approach in analysis of complex production processes by overall sets of energy- and exergy-based indices
systems naturally lead to the Cumulative Energy Consumption
(CEnC) and Cumulative Exergy Consumption (CExC) concepts [7]. The overall sets of the energy- and exergy-based indices of the
The calculation of the Cumulative Energy Consumption (CEnC) treatment processes are shown in Figs. 3e5.
in this work is based on the conversion of all consumed energy to All the indices based on the reduction of the emissions and
the natural gas (methane). related reduction of energy, exergy, CEnC and CExC consumption
The reduction of CEnC as a result from the waste flows treat-
ment is shown in Table 12. The reduction of the natural gas
consumption is calculated on the basis of the lower heating value of

Table 13
Reduction of the Cumulative Exergy Consumption (CExC) in the production of AN,
NH3, and nitric acid as a result of the waste flows treatment (CDP [7]: natural gas
production 0.875, power generation 0.24, steam generation 0.35).

Reduction of the Absorption Two- and three Vacuum

Cumulative Exergy column with stage vacuum evaporation system
Consumption (CExC) AN solution evaporation with mechanical
MJ/t AN system compressor
Reduction of the Cumulative Exergy Consumption (CExC)
Natural gas for ammonia 71.40 73.79 73.79
production
Power for ammonia 2.77 2.85 2.85
production

Total reduction of the 74.17 76.64 76.64

CExC

Additional Cumulative Exergy Consumption (CExC)

LP (0.12 MPa) steam for 53.21 32.58 32.58
evaporation of the
circulated solution
MP (4 MPa) steam to 1.67 1.73 1.73
compensate the lost
steam production in
HNO3 plant
Power for waste flows 5.95 3.97 251.37
treatment Fig. 3. Some positive effects of process steam and condensate treatment with recycling
of pollutants back into the process: reduction of quantity and exergy of the emissions;
Total additional CExC 60.83 38.28 285.68
reduction of exergy consumption, CEnC and CExC for production of AN and interme-
Net reduction of the CExC 13.34 38.36 L209.04
diates (NH3 and nitric acid).
3228 Z. Kirova-Yordanova / Energy 35 (2010) 3221e3229

300 All indices have highest values for the evaporation system with
compressor, lowest e for 2-stage evaporation system.
As a consequence from the large margin between the values
250 of additional emissions and consumption related indices of the
analyzed processes, the total net reduction indices of the three
treatment processes differ substantially from one another
200
(Fig. 5).
All net indices have positive (or near zero) values only for the 2-
150 stage evaporation system suggesting that this treatment process
could be estimated as environmental friendly, regarding emissions
and natural resources (fuels) consumption.
100 The values of the net reduction of energy and exergy
consumption for the absorption column process are negative, while
the remaining net reduction indices are positive. This result is
50
rather indefinite and therefore this process could be considered as
environmentally neutral.
0 All but one net reduction values for the evaporation system with
Absorption column Evaporation system Evaporation system compressor are negative, only the net reduction of the emission’s
with compressor exergy has a positive value. Furthermore, the cumulative energy
and the cumulative exergy net reduction values are strongly
Additional emissions, kg/t AN
Additional emissions exergy, MJ/t AN
negative. Thus this process appears to be the worst, especially
Additional energy consumption, MJ/t AN regarding the consumption of natural resources (fuels).
Additional exergy consumption, MJ/t AN
Additional CEnC, MJ/t AN
Additional CExC, MJ/t AN 4. Conclusions

Fig. 4. Some negative effects of process steam and condensate treatment with recy-
cling of pollutants back into the process: additional quantity and exergy of the emis-
sions; additional exergy consumption, CEnC and CExC for production of AN and
intermediates (NH3 and nitric acid).
are identical for the evaporation systems and slightly lower for the
absorption column process (Fig. 3)
However, the values for the additional emissions and related
additional energy, exergy, CEnC and CExC consumption, are very
specific for each process, irrespective of the identical nature of the
additional emissions (CO2 and NOx) and the additional energy
sources consumed (steam and power) in all three processes (Fig. 4).
80
40
0 processes a building block model and a top-down approach are
-40
-80
The exergy method is used to obtain a thermodynamically based
estimation and comparison of the environmental impact of some
waste flows treatment processes. The purification of the waste
steam and/or condensate from an ammonium nitrate (AN)
production plant is selected as an example due to its specific
feature: the recycling of the pollutants back into the production
process and in consequence of this, some reduction of the feedstock
and intermediates consumption.
Three waste steam and/or condensate treatment methods are
analyzed: absorption column with circulated acidified AN solution,
2-stage vacuum evaporation system and vacuum evaporation
system with mechanical compressor (heat pump).
The calculation of the exergy losses and degree of perfection of
the analyzed systems shows that in order to obtain more reason-
able results, the whole AN production site should be included in the
analyzed system.
In order to estimate the overall effects from the treatment
used. Some other exergy-based indices are defined and calculated
for three analyzed treatment processes:

-120 - Reduction of exergy of the emissions, reduction of energy and

exergy consumption, reduction of CEnC and CExC.
-160 - Additional exergy of the emissions, additional energy and
-200 exergy consumption, additional CEnC and CExC.
- Net reduction of exergy of the emissions, reduction of energy
-240
and exergy consumption, reduction of CEnC and CExC.
Absorption column Evaporation system Evaporation system
with compressor
The results show that overall sets of energy- and exergy-based
Net reduction of emissions, kg/t AN indices should be used in order to obtain a reasonable estimation
Net reduction of emissions exergy, MJ/t AN and comparison of the analyzed treatment processes, regarding
Net reduction of energy consumption, MJ/t AN their environmental impact.
Net reduction of exergy consumption, MJ/t AN The 2-stage evaporation system process appears to be more
Net reduction of CEnC, MJ/t AN environmental friendly, regarding both emissions and natural
Net reduction of CExC, MJ/t AN
resources (fuels) consumption. The absorption column process
could be considered as environmentally neutral, while the evapo-
Fig. 5. Overall effects of process steam and condensate treatment with recycling of
pollutants back into the process: net reduction of quantity and exergy of the emissions;
ration system with compressor process appears to have worst
net reduction of exergy consumption, CEnC and CExC for production of AN and environmental impact, especially regarding the consumption of
intermediates (NH3 and nitric acid). natural resources (fuels).
 Z. Kirova-Yordanova / Energy 35 (2010) 3221e3229 3229

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