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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 The exergy efficiency of a H2SO4 production plant from
industrial 45 Ton/day sulphuric acid plant. Magnitude and liquid sulphur was evaluated by Rasheva & Atanasova
location of irreversibilities for the main equipment of the (2002) with temperature and pressure data taken from the
process have been quantified. Gross irreversibilities represent literature. The plant analysed by Rasheva & Atanasova
78.4% and exergy gains represent 11.4%; i.e., net
(2002) presented two stages of conversion with
irreversibilities of the plant are 67.1%. Irreversibilities due to
chemical reactions and heat transfer are 26.4% and 52.1%, intermediate adsorption; H2SO4 throughput is not reported
respectively. For chemical reactions the greatest in this study. Magaeva et al., (2000) carried out and exergy
irreversibilities are located at the furnace, while for heat analysis of a H2SO4 production plant with SO2 rich gases
transfer the greatest irreversibilities are located in the waste from metallurgical processes as raw material. So far,
heat boiler and the heat exchanging network of the catalytic however, research has tended to focus either on literature
converter. The obtained exergy efficiencies are consistent with data or real plant data without reporting pressure,
those reported in the literature for sulphuric acid production temperature and exergy of each stream.
plants. Further improvements in exergy efficiencies could be This study presents an exergy analysis of an industrial
reached by resetting operating conditions and by
45 Ton/day H2SO4 production plant. Real pressure and
reconfiguring the heat exchanging network of the catalytic
converter. temperature for each stream are reported along with the
calculated exergy. The magnitude and location of
Keywords—Chemical Reactions, Exergy Analysis, Exergy irreversibilities for the main equipment of the process are
Efficiency, Grassmann Diagram, Heat Transfer, Industrial quantified. Results are depicted in a Grassmann diagram
Plant, Irreversibilities, Sulphuric Acid which allows identifying exergy flows along with exergy
efficiencies. Results are compared with previous studies
I. INTRODUCTION and the main differences that were found are explained.
Sulphuric acid (H2SO4) is considered the chemical with Finally, technical recommendations to reduce exergy losses
the highest total annual production around the world. are given.
Principal uses of H2SO4 include ore processing, fertilizer
manufacturing, oil refining, wastewater processing, and II. METHODOLOGY
chemical synthesis (Chemsystems, 2009). One approach Process description
for increasing the efficiency of H2SO4 production plants is
The chemical reactions of the process consist of burning
related with decrease of energy expenses. This increase in
efficiency could be attained through more efficient sulphur (S) in air to form sulphur dioxide (SO2), converting
utilization of the thermal energy released during the SO2 to sulphur trioxide (SO3) using molecular oxygen (O2)
from air, and absorbing SO3 in a diluted solution of
production process. Exergy, as a measure of the quality of
sulphuric acid (H2SO4) to form a concentrated solution of
energy, can be considered to quantify and locate the
sulphuric acid (around 97.8%). Equations 1 to 3 represent
relative magnitudes and the nature of energy degradation,
the above mentioned chemical reactions (Kiss et al., 2010;
and to expose the potential for improvements in the
efficiency of the plant. IDAE 1982).
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
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 Rasheva & Atanasova (2002) conducted a comparative
means of the Grassmann Diagram (Figure 2). Exergy, exergy analysis between the process for obtaining H2SO4
irreversibilities and exergy gains values are in percentages by one and two catalytic conversion stages vs. the process
with respect to plant exergy input (E1) and are denoted by of obtaining H2SO4 from SO2 containing gases of
letters E, i, and EG, respectively. Exergy flows take the pyrometallurgical process. The resultants ―exergy
same direction of the production process as indicated in the efficiencies‖ were of η=36.5%, η=36.3% and η=27.1%,
PFD of Figure 1. Irreversibilities and exergy are shown for respectively. Meanwhile, Kotas, (1985) performed an
each equipment in the Grassmann diagram at the bottom exergy analysis for a H2SO4 production plant using two
and above of the dotted line, respectively. converters, an absorber, and implementing steam
Figure 3 shows the contributions of each stage of the generation. The calculated ―plant rational efficiency‖ was
process to the gross irreversibilities. Irreversibilities due to ψ=47.2%. Magaeva et al., (2000) also conducted an exergy
chemical reactions and heat transfer are 26.4% and 52.1% analysis for a production plant of H2SO4 from liquid
respectively. For chemical reactions the greatest sulphur using double contacting with intermediate
irreversibility are located at FU (15.5%), while for heat absorption, whose plant rational efficiency was ψ=55.1%.
transfer the greatest irreversibilities are located at WHB Previous studies (Kotas 1985; Rasheva & Atanasova,
(12.7%) and HE3 (10.6%). There were exergy gains due to 2002) reported irreversibilities due to chemical reaction in
condensate return, tempering at A, and reactions taking the furnace (FU in the PFD of Figure 1) of 24.8% and
place in the MCC. Total exergy gains were of 11.4%, i.e. 23.0%, respectively. To reduce irreversibilities in the
the net irreversibility is 67.1%. 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
Figure III Irreversibilities by chemical reactions and heat transfer. by increasing residence times and modifying the internal
SMT, FU, WHB, HGB, HE1, HE2, HE3, HE4 and FAT correspond to
the equipment of Figure 1. (Dtt: due to transport).
configuration of the heat exchanger. Also to decrease these
irreversibilities, it is suggested to smooth the temperature
―Plant exergy efficiency‖ η, and ―Plant rational profiles. Since the objective of HE3 is to increase the
efficiency‖ ψ, were 33.3% and 53.5%, respectively. Some temperature of stream 17 from 343 K to 583 K in stream
authors have calculated the above mentioned efficiencies 18, it could be possible to improve energy integration by
for H2SO4 production processes (Kotas 1985; Rasheva & putting into thermal contact stream 4 and stream 17. In this
Atanasova, 2002; Magaeva et al., 2000) however it should way, the temperature of stream 17 could be higher and it
be noted that differences in sulphur source or the number of could be possible to reduce the temperature of stream 22 at
catalytic conversion stages does not allow a direct the inlet of WHB.
comparison with the current results.
734
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  Despite the difference either in process configuration
temperature to the stages of MCC were the oxidation of or raw material of the H2SO4 production plants cited
SO2 to SO3 takes place. Even though the thermal network in the literature when compared with the current
has been designed to take advantage of the energy of the production plant, plant exergy efficiency (η) and plant
streams, it account for 32.4% of the irreversibilities. A rational efficiency (ψ) are consistent with those
further study with more focus on Pinch Analysis is obtained in the present analysis. η and ψ for the
therefore suggested to re-evaluate the heat exchanging current plant are 33.3% and 53.1%, respectively.
network.
REFERENCES
IV. CONCLUSIONS [1] Bejan A, Tsatsaronis G, Moran MJ. Thermal design and
optimization. 1996 John Wiley & Sons.
An exergy analysis of a 45 Ton/day H2SO4 production [2] Campos JC, Santos L, Cruz E. Calidad De La Energía. 1998.
plant was developed. The results were represented in a Universidad De Cienfuegos. Cuba.
Grassmann diagram, and magnitude, location and causes of [3] Chemsystems. (2009). Retrieved from:
irreversibilities were discussed. The following conclusions http://www.chemsystems.com/about/cs/news/items/PERP%200708S
can be drawn from the present study: 8_Sulfuric%20Acid.cfm
Gross irreversibilities of the plant are 78.5%. There are [4] IDAE, Ministerio De Industria Y Energía.Técnicas De Conservación
exergy gains of 11.4% due to condensate return (COT), Energética En La Industria. Volumen II, Ahorro en procesos. Centro
de Estudios de la Energía 1982.
tempering at A, and reactions taking place in MCC; as a
consequence the net irreversibilities of the plant are 67.1%. [5] Kiss AA, Bildea CS, Grievink J. Dynamic modeling and process
optimization of an industrial sulfuric acid plant. Chemical
 Irreversibilities due to heat transfer (52.1%) are Engineering Journal 2010; 158(2): 241-249.
significantly higher than those due to chemical [6] Magaeva S, Patronov G, Lenchev A, Grancharov, I. Exergy analysis
reactions (26.4%). For heat transfer the greatest of processing SO2 containing gases in metallurgy into sulphuric acid
irreversibilities are located at WHB and HE3, while and sulphur. Jorunal of Mining and Metallurgy 2000; 36(1-2): 77-92.
for chemical reactions the greatest irreversibilities are [7] Kotas, TJ. The Exergy Method Of Thermal Plant Analysis. 1985.
Krieger Publishing Company, UK.
located at FU. Efforts to reduce irreversibilities
should be focused on improving the heat exchanging [8] Rasheva DA, Atanasova LG. Exergy efficiency evaluation of the
production of sulfuric acid from liquid sulfur. Exergy, an
network. On the other hand, irreversibilities due to International Journal 2002 (2): 51-54.
chemical reaction are not feasible to be reduced [9] Tsatsaronis G. Thermoeconomic analysis and optimization of energy
because of the nature of the process. systems. Prog. Energy Combustion Sci 1993 (19): 227 – 257.
 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.

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