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Exergy Analysis of an Industrial Sulphuric Acid Plant

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William Ruiz Civetta Ricardo Vasquez Padilla

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 International Journal of Emerging Technology and Advanced Engineering
Website: www.ijetae.com (ISSN 2250-2459, ISO 9001:2008 Certified Journal, Volume 4, Issue 3, March 2014)
Exergy Analysis of an Industrial Sulphuric Acid Plant
William Ruiz Civetta1, Ricardo Vasquez Padilla2, Antonio Bula Silvera3, Arturo Gonzalez Quiroga4
1,2,3,4
Department of Mechanical Engineering, Universidad del Norte, Km 5 Via Pto Colombia, Barranquilla, Colombia
Abstract— This paper presents an exergy analysis of an
industrial 45 Ton/day sulphuric acid plant. Magnitude and
location of irreversibilities for the main equipment of the
process have been quantified. Gross irreversibilities represent
78.4% and exergy gains represent 11.4%; i.e., net
irreversibilities of the plant are 67.1%. Irreversibilities due to
chemical reactions and heat transfer are 26.4% and 52.1%,
respectively. For chemical reactions the greatest
irreversibilities are located at the furnace, while for heat
transfer the greatest irreversibilities are located in the waste
heat boiler and the heat exchanging network of the catalytic
converter. The obtained exergy efficiencies are consistent with
those reported in the literature for sulphuric acid production
plants. Further improvements in exergy efficiencies could be
reached by resetting operating conditions and by
reconfiguring the heat exchanging network of the catalytic
converter.
Keywords—Chemical Reactions, Exergy Analysis, Exergy
Efficiency, Grassmann Diagram, Heat Transfer, Industrial
Plant, Irreversibilities, Sulphuric Acid
I. INTRODUCTION
Sulphuric acid (H2SO4) is considered the chemical with
the highest total annual production around the world.
Principal uses of H2SO4 include ore processing, fertilizer
manufacturing, oil refining, wastewater processing, and
chemical synthesis (Chemsystems, 2009). One approach
for increasing the efficiency of H2SO4 production plants is
related with decrease of energy expenses. This increase in
efficiency could be attained through more efficient
utilization of the thermal energy released during the
production process. Exergy, as a measure of the quality of
energy, can be considered to quantify and locate the
relative magnitudes and the nature of energy degradation,
and to expose the potential for improvements in the
efficiency of the plant.
Some previous studies have been focused on exergy
analysis of the H2SO4 manufacturing processes. Kotas
(1985) carried out an exergy analysis on a conceptual
H2SO4 production plant where thermal energy is used in the
process itself for sulphur melting, and steam production. In
that study, exergy flows and irreversibilities were
represented by means of the Grassmann Diagram.
730
The exergy efficiency of a H2SO4 production plant from
liquid sulphur was evaluated by Rasheva & Atanasova
(2002) with temperature and pressure data taken from the
literature. The plant analysed by Rasheva & Atanasova
(2002) presented two stages of conversion with
intermediate adsorption; H2SO4 throughput is not reported
in this study. Magaeva et al., (2000) carried out and exergy
analysis of a H2SO4 production plant with SO2 rich gases
from metallurgical processes as raw material. So far,
however, research has tended to focus either on literature
data or real plant data without reporting pressure,
temperature and exergy of each stream.
This study presents an exergy analysis of an industrial
45 Ton/day H2SO4 production plant. Real pressure and
temperature for each stream are reported along with the
calculated exergy. The magnitude and location of
irreversibilities for the main equipment of the process are
quantified. Results are depicted in a Grassmann diagram
which allows identifying exergy flows along with exergy
efficiencies. Results are compared with previous studies
and the main differences that were found are explained.
Finally, technical recommendations to reduce exergy losses
are given.
II. METHODOLOGY
Process description
The chemical reactions of the process consist of burning
sulphur (S) in air to form sulphur dioxide (SO2), converting
SO2 to sulphur trioxide (SO3) using molecular oxygen (O2)
from air, and absorbing SO3 in a diluted solution of
sulphuric acid (H2SO4) to form a concentrated solution of
sulphuric acid (around 97.8%). Equations 1 to 3 represent
the above mentioned chemical reactions (Kiss et al., 2010;
IDAE 1982).
( ) ( ) ⇔ ( )
( ) ( ) ⇔ ( )
 International Journal of Emerging Technology and Advanced Engineering
Website: www.ijetae.com (ISSN 2250-2459, ISO 9001:2008 Certified Journal, Volume 4, Issue 3, March 2014)

Figure I Process flow diagram (PFD) of the H2SO4 production plant

( ) () ⇔ () Solid sulphur is supplied to SMT and put into indirect

thermal contact with steam from WHB. Steam returns to
COT and then it is sent back to WHB to complete the
circuit. Filtered ambient air is drawn by the main fan
through ADT tower to remove moisture. After passing
A simplified process flow diagram (PFD) of the 45
through HE4, hot and dry air enters FU where molten
Ton/day H2SO4 production plant is depicted in Figure 1.
sulphur is burned to produce SO2. Hot SO2 combustion
The main equipment of the plant are: sulphur-melting tank
gases are then cooled in WHB and filtered in HGF.
(SMT), furnace (FU), waste-heat boiler (WHB), condensate
A multi-pass catalytic converter (MCC) is used as the
tank (COT), attemperator (A), hot gases filter (HGF),
multi-pass catalytic converter (MCC), heat exchangers SO2 oxidation reaction is limited by the chemical
equilibrium. O2 does oxidize SO2 to SO3 faster with a
(HE1, HE2, HE3, HE4), intermediate absorption tower
catalyst, so a vanadium oxide (V2O5) catalyst is used. The
(IAT), final absorption tower (FAT), air drying tower
overall process has been designed to give a conversion of
(ADT), chimney (CH), recirculation tanks (RT1, RT2),
SO2 to H2SO4 of over 99%.
cooling tower (CT), cooling coil (CC) and storage tank
(ST).
731
 International Journal of Emerging Technology and Advanced Engineering
Website: www.ijetae.com (ISSN 2250-2459, ISO 9001:2008 Certified Journal, Volume 4, Issue 3, March 2014)
Four conversions steps in MCC of 60%, 87%, 95% and Table I.
99%, with inter-stage cooling and conversions, are Temperature and pressure data taken directly at the sulphuric acid
plant. Streams are represented along with main equipment in
necessary. When SO2 reaches a conversion of 95% gases Figure 1.
are driven to IAT where direct contact with H2SO4, which
comes from CC, occurs. The outlet gas with SO2 is sent Stream Temperature (K) Pressure (kPa)
back to the fourth conversion step where a conversion of 1 298 101
99% is achieved. SO3 is driven to FAT where complete
transformation to H2SO4 takes place, followed by a cooling 2 418 119
stage carried out at CC. H2SO4 is finally sent to ST. 3 435 552
Residual gases (O2, N2, NOX and SOX) are released to the
atmosphere at CH. 22 323 552
Data acquisition 5 473 119
Data collected in this study comes from a 45 Ton/day 24 513 119
H2SO4 production plant. Local pressure and temperature 6 1291 119
where the plant is located are 101 KPa and 298 K,
7 471 119
respectively. Table 1 shows temperature and pressure of the
process streams detailed in the PFD of Figure 1. 8 773 119
Exergy balance 9 688 118
The exergy balance for any equipment is given by 10 723 118
(Bejan 1966, Campos et al., 1998; Tsatsaronis 1993): 11 873 118
12 773 117
∑ ∑
13 823 116
Where I denotes Irreversibility. 14 733 115
For any equipment exergy balances have been developed
using the method described by Campos et al., (1998), as 15 773 114
indicated by Equations 5 to 7: 16 533 113
17 343 111
[̃ ( )∑ ̃ ]
18 583 109
19 673 109
̃ ̅∑ ̃ 20 713 109
21 533 104
̃ ∑ ̃ ̃ ∑ 23 333 119
27 343 104
Where symbols denote:
E:exergy; nk:moles of substance of component k; ̃ : III. RESULTS AND DISCUSSION
standard chemical exergy of stream N; ̃ :standard The boundaries of the system of study are represented by
chemical exergy of component k; :Temperature of the dotted line in Figure 1. Temperature and pressure data
streams, : environment temperature; : molar fraction collected at the production plant are shown in Table 1.
of component k; ̃ :mean isobaric exergy capacity of Mean isobaric exergy capacities and standard chemical
component k. exergy were taken from Kotas (1985). Throughout this
The plant is thermally isolated so the process is assumed paper, the term ―Plant Exergy Efficiency‖ (η) is used to
to be adiabatic. Irreversibilities are assumed to be caused refer to the ratio between the exergy of the H2SO4 outlet
by exergy destruction and/or exergy discharge to the stream and the exergy of the S inlet stream; likewise the
atmosphere. Changes in macroscopic kinetic and potential term ―Plant Rational Efficiency‖ (ψ) is used to refer to the
energies are neglected. ratio between all exergy outputs and all exergy inlets.
732
 International Journal of Emerging Technology and Advanced Engineering
Website: www.ijetae.com (ISSN 2250-2459, ISO 9001:2008 Certified Journal, Volume 4, Issue 3, March 2014)

Figure II Grassmann diagram for the sulphuric acid plant.

733
 International Journal of Emerging Technology and Advanced Engineering
Website: www.ijetae.com (ISSN 2250-2459, ISO 9001:2008 Certified Journal, Volume 4, Issue 3, March 2014)
Irreversibilities for the entire plant are represented by
means of the Grassmann Diagram (Figure 2). Exergy,
irreversibilities and exergy gains values are in percentages
with respect to plant exergy input (E1) and are denoted by
letters E, i, and EG, respectively. Exergy flows take the
same direction of the production process as indicated in the
PFD of Figure 1. Irreversibilities and exergy are shown for
each equipment in the Grassmann diagram at the bottom
and above of the dotted line, respectively.
Figure 3 shows the contributions of each stage of the
process to the gross irreversibilities. Irreversibilities due to
chemical reactions and heat transfer are 26.4% and 52.1%
respectively. For chemical reactions the greatest
irreversibility are located at FU (15.5%), while for heat
transfer the greatest irreversibilities are located at WHB
(12.7%) and HE3 (10.6%). There were exergy gains due to
condensate return, tempering at A, and reactions taking
place in the MCC. Total exergy gains were of 11.4%, i.e.
the net irreversibility is 67.1%.
Figure III Irreversibilities by chemical reactions and heat transfer.
SMT, FU, WHB, HGB, HE1, HE2, HE3, HE4 and FAT correspond to
the equipment of Figure 1. (Dtt: due to transport).
―Plant exergy efficiency‖ η, and ―Plant rational
efficiency‖ ψ, were 33.3% and 53.5%, respectively. Some
authors have calculated the above mentioned efficiencies
for H2SO4 production processes (Kotas 1985; Rasheva &
Atanasova, 2002; Magaeva et al., 2000) however it should
be noted that differences in sulphur source or the number of
catalytic conversion stages does not allow a direct
comparison with the current results.
734
Rasheva & Atanasova (2002) conducted a comparative
exergy analysis between the process for obtaining H2SO4
by one and two catalytic conversion stages vs. the process
of obtaining H2SO4 from SO2 containing gases of
pyrometallurgical process. The resultants ―exergy
efficiencies‖ were of η=36.5%, η=36.3% and η=27.1%,
respectively. Meanwhile, Kotas, (1985) performed an
exergy analysis for a H2SO4 production plant using two
converters, an absorber, and implementing steam
generation. The calculated ―plant rational efficiency‖ was
ψ=47.2%. Magaeva et al., (2000) also conducted an exergy
analysis for a production plant of H2SO4 from liquid
sulphur using double contacting with intermediate
absorption, whose plant rational efficiency was ψ=55.1%.
Previous studies (Kotas 1985; Rasheva & Atanasova,
2002) reported irreversibilities due to chemical reaction in
the furnace (FU in the PFD of Figure 1) of 24.8% and
23.0%, respectively. To reduce irreversibilities in the
furnace, these studies proposed to increase the temperature
of the air stream entering the furnace. In the present study,
irreversibilities due to chemical reactions in FU represent
15.5%. This finding is consistent with the above mentioned
suggestion because for the current plant the air stream
entering FU (Stream 5) has been preheated from 333 K to
473 K in HE4.
Irreversibilities due to heat transfer have its greater
values in WHB and HE3 and can be explained by the gap
between temperature profiles of the fluids. For WHB, it is
suggested to reduce the irreversibility by decreasing water
inlet temperature (stream 22, Fig. 1) and thus recovering a
greater amount of exergy from hot gases leaving FU. This
temperature decrease could be achieved by redirecting the
output stream of SMT to any process requiring low quality
hot water. Also, these irreversibilities could be reduced by
causing an increase on pressure drop in the gases side from
FU to increase its residence time and consequently the
thermal energy transfer.
A large gap between temperature profiles is also
presented at HE3 where pressure drop on tubes and shell
sides are similar. Irreversibilities at HE3 could be reduced
by increasing residence times and modifying the internal
configuration of the heat exchanger. Also to decrease these
irreversibilities, it is suggested to smooth the temperature
profiles. Since the objective of HE3 is to increase the
temperature of stream 17 from 343 K to 583 K in stream
18, it could be possible to improve energy integration by
putting into thermal contact stream 4 and stream 17. In this
way, the temperature of stream 17 could be higher and it
could be possible to reduce the temperature of stream 22 at
the inlet of WHB.
 International Journal of Emerging Technology and Advanced Engineering
Website: www.ijetae.com (ISSN 2250-2459, ISO 9001:2008 Certified Journal, Volume 4, Issue 3, March 2014)
The four heat exchangers are used to regulate the inlet
temperature to the stages of MCC were the oxidation of
SO2 to SO3 takes place. Even though the thermal network
has been designed to take advantage of the energy of the
streams, it account for 32.4% of the irreversibilities. A
further study with more focus on Pinch Analysis is
therefore suggested to re-evaluate the heat exchanging
network.
IV. CONCLUSIONS
An exergy analysis of a 45 Ton/day H2SO4 production
plant was developed. The results were represented in a
Grassmann diagram, and magnitude, location and causes of
irreversibilities were discussed. The following conclusions
can be drawn from the present study:
Gross irreversibilities of the plant are 78.5%. There are
exergy gains of 11.4% due to condensate return (COT),
tempering at A, and reactions taking place in MCC; as a
consequence the net irreversibilities of the plant are 67.1%.
 Irreversibilities due to heat transfer (52.1%) are
significantly higher than those due to chemical
reactions (26.4%). For heat transfer the greatest
irreversibilities are located at WHB and HE3, while
for chemical reactions the greatest irreversibilities are
located at FU. Efforts to reduce irreversibilities
should be focused on improving the heat exchanging
network. On the other hand, irreversibilities due to
chemical reaction are not feasible to be reduced
because of the nature of the process.
 For the current plant, irreversibilities at FU are 15.5%,
a value significantly lower than the value reported for
furnaces in the literature (23%-25%) (Campos et al.,
1998; Chemsystems 2009). These results provide
further support for the suggestion of the literature
about preheating air entering FU to reduce
irreversibilities because this improvement has been
implemented in the present plant.
735
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 Despite the difference either in process configuration
or raw material of the H2SO4 production plants cited
in the literature when compared with the current
production plant, plant exergy efficiency (η) and plant
rational efficiency (ψ) are consistent with those
obtained in the present analysis. η and ψ for the
current plant are 33.3% and 53.1%, respectively.
REFERENCES
[1] Bejan A, Tsatsaronis G, Moran MJ. Thermal design and
optimization. 1996 John Wiley & Sons.
[2] Campos JC, Santos L, Cruz E. Calidad De La Energía. 1998.
Universidad De Cienfuegos. Cuba.
[3] Chemsystems. (2009). Retrieved from:
http://www.chemsystems.com/about/cs/news/items/PERP%200708S
8_Sulfuric%20Acid.cfm
[4] IDAE, Ministerio De Industria Y Energía.Técnicas De Conservación
Energética En La Industria. Volumen II, Ahorro en procesos. Centro
de Estudios de la Energía 1982.
[5] Kiss AA, Bildea CS, Grievink J. Dynamic modeling and process
optimization of an industrial sulfuric acid plant. Chemical
Engineering Journal 2010; 158(2): 241-249.
[6] Magaeva S, Patronov G, Lenchev A, Grancharov, I. Exergy analysis
of processing SO2 containing gases in metallurgy into sulphuric acid
and sulphur. Jorunal of Mining and Metallurgy 2000; 36(1-2): 77-92.
[7] Kotas, TJ. The Exergy Method Of Thermal Plant Analysis. 1985.
Krieger Publishing Company, UK.
[8] Rasheva DA, Atanasova LG. Exergy efficiency evaluation of the
production of sulfuric acid from liquid sulfur. Exergy, an
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[9] Tsatsaronis G. Thermoeconomic analysis and optimization of energy
systems. Prog. Energy Combustion Sci 1993 (19): 227 – 257.