A Thesis

Submitted by

Sujala Tajneen Sultana

Student No. 0411022003

In partial fulfillment of the requirement for the degree of

Masters of Science in Chemical Engineering

Department of Chemical Engineering

Bangladesh University of Engineering and Technology

Dhaka-1000, Bangladesh

July, 2012
The current legislation imposes tighter restrictions in order to reduce the impact of chemical process
industry on the environment. In this context, this study presents the steady state model, simulation and
optimization results for an industrial sulfuric acid plant. The model, implemented in Aspen-Hysys
includes a catalytic reactor (four pass converter), heat exchangers, mixers, splitters and reactive
absorption columns. The kinetic parameters were estimated for the degenerated form of Hougan-
Watson kinetics considering a catalyst consisting of V2O5, while the remaining model parameters were
estimated using classical correlations. Catalyst specification, bed height and diameter were conducted to
avoid excessive pressure drop in each converter bed. The optimum heatup path with maximum %SO 2
oxidized was determined for each bed using the Microsoft Excel Goal seek operation. Aspen-Hysys V7.1
has been successfully used to design every sub-process of the sulfuric acid plant in one integrated
environment. The simulation of sulfuric acid process included automatic chemistry generation and the
capacity of handling electrolyte reactions for all unit models. Aspen-HYSYS provides specialized
thermodynamics models and built-in data to represent the non-ideal behavior of liquid phase
components in order to get accurate results. The simulation results agree very well with the real plant
data and theoretical data for maximum %SO2 oxidized in each bed. The SOx emission was reduced nearly
80% from the existing plant with this simulation model and 650 psi steam was generated in waste heat
boiler using the heat of the exothermic reactions. Material and energy flows, sized unit operations
blocks can be used to conduct economic assessment of each process. The simulation model developed
can also be used as a guide for understanding the process and the economics, and also a starting point
for more sophisticated models for plant designing and process equipment specifying.
The author is heartily thankful to Dr. Rafiqul Gani who financially supported the work from Shedu Bhai
Kallyan Trust. The technical and administrative backup given by Bangladesh Chemical Engineering Forum
(BCEF) and Department of Chemical Engineering, BUET is highly valuable and appreciated.

The author would like to recognize the invaluable support of Dr. Ruhul Amin, Assistant Professor,
Department of Chemical Engineering under whose supervision the research has been accomplished.

Author is also indebted to the faculty members of Department of Chemical Engineering for their
technical advice and support. Author is grateful to lecturer Shah Md. Toufiqur Rahman for his cordial
support in installation and learning of the Aspen-Hysys software.

Finally author would like to acknowledge the contribution of Wata Chemicals Limited, Murapara,
Narayangonj, for providing the required data. Without this generous provision it would be difficult to
conduct the research.
Abstract ii
Acknowledgement iii
Content iv
List of figures vi
List of tables vii

Chapter 1 Introduction 1

1.1 Background 1
1.2 Objective 2
1.3 Scope of study 2
Chapter 2 Literature Review 4

2.1 Overview of Sulfuric Acid Plant 4

2.2 AspenONE Engineering for Sulfuric acid Plant 7
2.3 Previous works on Sulfuric acid Plant 8
2.4 Limitation of Aspen-Hysys in Sulfuric acid plant 9
Chapter 3 Optimization Parameters 10

3.1 Material processing 10

3.1.1 Conversion of SO2 into SO3 10
3.1.2 Absorption of SO3 11
3.2 Product finishing 11
3.2.1 Dilution of absorber acids 11
3.2.2 SO3- Stripping 11
3.2.3 Purification 11
3.3 Use of auxiliary chemicals /materials 12
3.4 Intermediate and final product storage 12
3.5 Energy generation / consumption 13
3.6 Handling of waste gas / stack height 14
3.7 Single contact Acid making 15
 3.8 Double contact Acid Making 15

Chapter 4 Steady-State Sulfuric Acid Model 18

Chapter 5 Unit Operation Models 22

5.1 Sulfur Burner 22

5.2 Catalytic bed reactor 22
5.2.1 Maximum %SO2 Oxidation 23
5.2.2 Aspen-Hysys Model for 4 Catalyst bed Converter 25
5.3 Absorption Tower 28
5.4 Waste Heat Boiler 28

Chapter 6 Result and Discussion 29

Chapter 7 Conclusion 36

References 37

Appendices 39

Appendix A Calculations for Converter 39

Appendix B Optimum Heatup path calculation 41

Appendix C Aspen-Hysys Simulated data 49

Figure 1 Sulfuric acid production (left) and consumption (right) in the world 1
Figure 2 Maximum percentage of SO2 -in-feed-gas 6
Figure 3 Engineering Workflow 8
Figure 4 Schematic of single contact, 3 catalyst bed sulfuric acid plant 15
Figure 5 Schematic of 3-1 double contact acid plant 16
Figure 6 Fluid Package selection in Aspen Hysys 19
Figure 7 Sulfuric Acid Plant Simulation Model 21
Figure 8 Sulfur Burning and Dehydration unit 22
Figure 9 Equilibrium- Heatup path intercept Temperature for Bed 1 24
Figure 10 Equilibrium- Heatup path intercept Temperature for Bed 2 24
Figure 11 Reaction specifications in Aspen Hysys 25
Figure 12 Temperature-Conversion Diagram 29
Figure 13 Temperature Profile 30
Figure 14 Component Profile 30
Figure 15 Mass fraction of 4th bed outlet gas 31
Figure 16 Reaction rate 31
Figure 17 Pressure profile in bed1 32
Figure 18 Stack gas composition from Absorption tower 32
Figure 19 High pressure steam generation 33

Figure B.1 Solving matrix in Excel 42

Figure B.1 Using Excel Goal seek operation to determine optimum heatup path for bed1 42
Figure B.2 Equilibrium Curve Generation Spreadsheet for bed1 43
Table 1. % SO2 oxidized-temperature points near heatup path-equilibrium curve intercept 23

Table 2 Conversion in each bed from Hysys model 27

Table 3 Key simulation results with 100% excess air 33

Table 4 Process simulation results with 100% excess air 34

Table 5 Key simulation results with 20% excess air 34

Table 6 Process simulation results with 20% excess air 34

Table 7 Data of Existing plant in Bangladesh (WATA Chemicals Ltd.) 35

Table B.1. Optimum heatup path calculation in excel for 4 beds 44

 Certification of Thesis Work
The thesis titled “Simulation and Optimization of Sulfuric Acid Plant” submitted by Sujala Tajneen
Sultana Roll No: 0411022003 has been accepted as satisfactory in partial fulfillment for the degree of
Master of Science in Engineering (Chemical) on July 19, 2012.

1. _______________________
Dr. Muhammad Ruhul Amin Chairman
Assistant Professor
Department of Chemical Engineering
BUET, Dhaka.

2. _______________________
Dr. Dil Afroza Begum Member
Professor and Head
Department of Chemical Engineering
BUET, Dhaka.

3. _______________________
Dr. Ijaz Hossain Member
Professor
Department of Chemical Engineering
BUET, Dhaka.

4. _______________________
Dr. Iqbal Hossain Member
Assistant Professor
Department of Chemical Engineering
BUET, Dhaka.

5. _______________________
Sk. Shafi Ahmed Member
Chief Operations Officer, KAFCO (External)
Rangadia, Anowara, Chittagong.
1. Introduction
1.1 Background

As the largest-volume industrial chemical produced in the world, consumption of sulfuric acid is often
used to monitor a country’s degree of industrialization. Sulfuric acid is produced every year in quantities
larger than any other chemical. Nowadays, the worldwide production exceeds 160 million of tones, with
US and Asia as the top consumers (Fig. 1).

Figure 1. Sulfuric acid production (left) and consumption (right) in the world in 2006 (Kiss et
al., 2010).

Remarkably, sulfuric acid is also a particularly corrosive and dangerous acid, with extreme
environmental and health hazards if not manufactured, used, and regulated properly. Sulfuric acid has a
wide range of uses including: phosphate fertilizer production, dyes, alcohols, plastics, rubber, ether,
glue, film, explosives, drugs, paints, food containers, wood preservatives, soaps and detergents,
pharmaceutical products, petroleum products, pulp and paper. The common lead-acid storage battery is
one of the few consumer products that actually contain H2SO4. Sulfuric acid is also used extensively as a
solvent for ores and as catalyst for petroleum refining and polymer manufacture. Note that agricultural
fertilizers represent the largest single application for sulfuric acid, accounting for up to 65% of its usage
(Davenport, 2005).

Most of the sulfuric acid plants are located near their product acid’s point of use—i.e. near
phosphate fertilizer plants, nickel ore leach plants and petroleum refineries. The reason for this is
because elemental sulfur is cheaper to transport than sulfuric acid. Note also that the volatility of the
sulfuric acid price is due to the small imbalances between acid demand and supply, as well as the
difficulty of storing large quantities of acid. The recent large increase in price is due to increasing
demand for fertilizer, hence sulfuric acid. There is a need in the market to produce high value products
at lower costs. Technology is fundamental to the profitable design and operation of environmentally
friendly sulfuric acid plants and processes.
Operation of a sulfuric acid facility can be challenging because of the high cost of maintenance of
sulfuric acid plants, stringent requirements on SO2 emissions, catalyst distribution, importance of energy
efficiency, and accurate equipment sizing and rating (Bhat, 2010). For acid plants, tail gas treatment is
very important considering the environmental impact. Tail gases can be as low as 20ppm SO2. H2SO4
vapor and SO3 are also removed from the feed gas stream for producing various by-products
(Davenport, 2005). Many simulation and optimization software has been successfully used by many
companies all over the world, to design every sub-process of the sulfuric acid plant. Davenport, Bhat,
Rase etc., have worked on optimum modeling of sulfuric acid plant.

In context of Bangladesh there are a few sulfuric acid plants and even those are rather old and are facing
now additional challenges that aim to maximize the amount of energy produced while reducing the
environmental impact. Moreover the existing plants in Bangladesh have very limited data and the
monitoring of plant is very poor. In such a case the idea of simulation and optimization of the Sulfuric
acid processing plant will surely pave a way to a sustainable solution. Thus the purpose of this research
is to develop and implement an effective knowledge on Simulation and Optimization of Sulphuric acid
processing plant in process simulator software.

1.2 Objective
The purpose of this study was to examine how modeling technology can help in debottlenecking existing
plants, achieving high product purity, increasing energy recovery, and automate process analysis to
optimize plant operations. A simulation model of the contact process Sulfuric acid plant along with
proper catalytic bed distribution in converter was proposed and developed in Aspen-Hysys. Different
parameters influencing converter performance was observed. Optimum heat-up path and equilibrium
curve was generated from the extracted feed data for the 1st catalytic bed. Intercept temperature for
maximum SO2 oxidation for each bed was determined and further used in the model. Sulfuric acid plants
are net producers of steam; so it was also determined how effective decisions on steam boilers can be
made using sulfuric acid plant models. Moreover current legislation imposes tighter restrictions in order
to reduce the impact of chemical process industry on the environment. The proposed model
implemented in Aspen-Hysys is useful for evaluating the static behavior of the plant and for
minimization of the total amount of SOx emissions. The simulation model was also compared with
existing plant with same operating condition to verify the acceptability of the model.

1.3 Scope of Study

Previously researches have been conducted on either on designing sulfur-di-oxide converter or Sulfur-
tri-oxide absorption. In this study a steady state simulation model was build up in Aspen-Hysys V7.1
using aspen properties in one integrated environment. The extracted result data was compared with the
existing design data of a real plant (Wata Chemicals Ltd.). Aspen Properties is part of aspenONE
Engineering and provides up to date physical property methods, models, algorithms, and data that
enables chemists and engineers to easily perform engineering calculations based on rigorous and proven
thermophysical property models and data. It enables users to capture and organize consistent physical
property data and knowledge across the project. Aspen Properties contains the world’s largest database
of pure components and binary parameter databanks. For simulation aqueous acids such as sulfuric acid
processes it is recommended to turn the electrolytes feature on in Aspen-Hysys. An electrolyte system is
defined as one in which some of the molecular species dissociates partially or completely into ions in a
liquid solvent, and/or some of the molecular species precipitate as salts. These dissociation and
precipitation reactions occur fast enough that the reactions can be considered to be at chemical
equilibrium. The liquid phase equilibrium reactions that describe this behavior are referred to as the
solution chemistry. In Aspen, solution chemistry is often referred to simply as Chemistry. Solution
chemistry has a major impact on the simulation of electrolyte systems. For non-electrolyte systems,
chemical reactions generally occur only in reactors. In Aspen, all unit operation models can handle
electrolyte reactions. Moreover using Aspen Properties provides specialized thermodynamic models and
built-in data to represent the non-ideal behavior of liquid phase components in order to get accurate
results. The steady state model included typical process areas including: sulfur burning, sulfur dioxide
conversion, absorption of sulfur trioxide and the main streams connecting these units. Thus the
performance model developed for this process can be re-used for operational monitoring and
improvement of the plant using Aspen Simulation Workbook. The performance model can also be
deployed to non-expert users who may not have background in simulation to perform “what if analysis”
studies over the web using Aspen Online Deployment (Bhat, 2010).
2. Literature Review
2.1 Overview of Sulfuric Acid Plant
Sulfuric acid is a dense clear liquid. It is used for making fertilizers, leaching metallic ores, refining
petroleum and for manufacturing a myriad of chemicals and materials. Worldwide, about 160 million
tones of sulfuric acid are consumed per year (Davenport, 2005).

The raw material for sulfuric acid is SO2 gas. It is obtained by:

(a) Burning elemental sulfur with air

(b) Smelting and roasting metal sulfide minerals
(c) Decomposing contaminated (spent) sulfuric acid catalyst.
Elemental sulfur is far and away the largest source.

Sulfuric acid is made from SO2, O2, and N2 gases produced from burning of elemental Sulfur by:

(a) Catalytically reacting their SO2 and O2 to form SO3 (g)

(b) reacting (a)'s product SO3(g) with the H20(g) in 98.5 mass% H2SO4, 1.5 mass% H2O sulfuric acid.

From literature it is observed that industrially, both processes are carried out rapidly and continuously.
Explanation of the reasons for these process steps, control and optimization of acid making has been
studied in literature. Special emphasis is placed on SO2 (g) oxidation efficiency and how it is
influenced by feed gas composition, feed gas temperature, catalyst composition, catalyst bed
pressure, number of catalyst beds, and double versus single contact acid making. In addition, a review of
various other treatment methods for SO2 -bearing gases is provided. A brief description of each process
is included along with commentary on their technical and economic applicability for use at metallurgical
facilities (Davenport, 2005).

Study shows the product of sulfuric acid manufacture is liquid acid, 93 to 98% H2SO4, 2 to 7% H2O.

Manufacturing Process

Sulfuric acid manufacturing consists of:

(a) Gas cleaning and removal of H2O (g) by condensation

(b) Gas dehydration with sulfuric acid desiccant, i.e.:

˷390 K
H2O (g) + H2SO4 (l) → H2SO4 (l) + H2O (l) ……. *1] ΔH = -80 MJ per kg-mole H2O (g)
In strong acid slightly weakened acid
(c) Oxidation of SO2 to SO3 in contact with supported liquid phase catalyst, i.e.:

700-900 K
SO2 (g) + ½ O2 (g) → SO3 (g)……….. *2+ ΔH = -100 MJ per kg-mole SO2 (g)
in SO2 , O2 , in feed gas or catalyst in SO3 , SO2 ,
N2 feed gas added to it O2 , N2 , gas
in air

(d) Reaction of (c)'s SO3 product with strong sulfuric acid to make strengthened sulfuric acid, i.e.:

350-380 K
SO3 (g) + H2O (l) → H2SO4 (l)………… *3+ ΔH = -130 MJ per kg-mole H2SO4 (l)
in SO3 , SO2 in 1.5% H2O, in strengthened
O2, N2 , gas 98.5% H2SO4 sulfuric acid
Sulfuric acid

(e) Mixing of (b)'s and (d)'s liquid products (+ water) to make the acid plant's range of products.

Gas Cleaning

The gas entering dehydration must be dust free (0.001 to 0.01 g/Nm3 of gas) to avoid plugging
downstream SO2-oxidation catalyst. Dust is removed from the gas by a series of electrostatic
precipitation and scrubbing steps. Metallurgical off-gas requires the most attention. Sulfur burning
requires the least. Sulfuric acid catalyst decomposition gas is intermediate.

Condensation and Dehydration

Acid plants must be built and operated so that liquid sulfuric acid is not produced in unexpected
locations in equipment and flues. The easiest way to ensure this is to remove all H2O (g) from catalytic
SO2 oxidation input gas. It is removed by water-cooling condensation then dehydration with sulfuric
acid desiccant. Typical H2O (g)-in-gas levels entering catalytic SO2 oxidation are ~50 mg H2O (g) per Nm3
of input gas. In sulfur burning acid plants, it is the sulfur combustion air that is dehydrated (with
no prior condensation).

Catalytic SO2 + ½ O2 → SO3 Oxidation

SO2 is oxidized to SO3 in preparation for H2SO4 making. The oxidation is done by blowing clean dry SO2
gas down through horizontal beds of catalyst. Industrially, the beds are typically 0.8 m thick and 10 m
diameter.

Figure 2 is a stoichiometry-equilibrium curve for SO2 oxidation. It shows that the reaction goes almost
to completion at 600 K but not at 1000 K. This indicates that raising reaction temperature to increase
reaction rate is counteracted by a large decrease in maximum attainable (equilibrium) SO3 production.
This problem is overcome by using catalyst, which promotes rapid SO 2 oxidation at cool
temperatures (~700 K) where equilibrium SO3 production is efficient. The catalyst is molten V, K,
Na, Cs, S, O solution on porous silica substrate. A simplified reaction scheme with this catalyst is:

SO2 + 2V5+ + O2- → 2V4+ + SO3………… *4+

½ O2 + 2V4+ → 2V5+ + O2-……………….. *5+

which combine to give:

SO2 + ½ O2 → SO3……………………. *2+

Reactions [4] and [5] have lower activation energies than Reaction [5], giving rapid reaction at
700-900 K.

Figure 2: Maximum percentage of SO2 -in-feed-gas that can be oxidized when equilibrium is
attained in a bed of catalyst. It decreases markedly with increasing temperature. The curve applies
only to the specified conditions (Davenport, 2005).

Catalyst Temperature Limitations

The V, K, Na, Cs, S, O catalyst must be molten for Reactions [4] and [5] to occur. It typically melts
around 680 K, slightly cooler when it contains cesium ions. Unfortunately, it begins to lose its
catalytic power above about 900 K due to the formation of unreactive vanadate ions and by non-
reversible reaction with the silica substrate. Thus, SO2 oxidation must be done between ~700 and 900 K.
H2 SO4 Making
In principle, H2SO4 (l) can be made by reacting the SO3 (g) from catalytic oxidation with water.
However, Reaction [3] is so exothermic that the product of reacting strong SO3 with water would be hot
H2SO4 vapor. Condensation of H2SO4 (l) from this vapor is slow and expensive, so the SO2 -water process
is not used for strong gas. Instead, the SO3 (g) is reacted with the H2O (l) in strong sulfuric acid.

The small amount of H2O and the massive amount of H2SO4 in Reaction [3]'s input acid avoids this
problem. The small amount of H2O limits the extent of the reaction. The large amount of H2SO4
warms only 25 K while it absorbs Equation [3]'s heat of reaction.

Limits to other Industries

Many processes of sulfuric acid production have been developed according to the large number of
sources of raw materials (SO2), and their specific characteristics.

It is possible to draw a general diagram of sulfuric acid production distinguishing the two fundamental
steps of the process:
(a) Conversion of SO2 into SO3
(b) Absorption of SO3

2.2 AspenONE Engineering for Sulfuric acid Plant

AspenONE Engineering enables engineers to model the sulfuric acid processes in one integrated
environment. Process Engineering has been successfully utilized by plant owners/operators, engineering
and construction companies, and technology providers to improve yields, increase plant efficiency and
quality, and reduce capital and operating costs (Bhat, 2010).

Operation of a sulfuric acid facility can be challenging because of the high cost of maintenance of
sulfuric acid plants, stringent requirements on SO2 emissions, importance of energy efficiency, and
accurate equipment sizing and rating. aspenONE Engineering has been successfully used by many
companies over the world to design every sub-process of the sulfuric and phosphoric acid plant in one
integrated environment (Bhat, 2010).

Aspen Properties is an integral part of aspenONE Engineering and contains the world’s largest database
of pure components and phase equilibrium data for conventional chemicals, electrolytes, solids, and
polymers. The physical property database is regularly updated with data from the U. S. National Institute
of Standards and Technology (NIST). Having accurate physical properties data is critical to the precision
of the simulation results and directly affects the cost of process equipment. The electrolytes feature in
Aspen Properties improves the accuracy of the vapor-liquid equilibrium calculations in the adsorption
units of sulfuric and phosphoric acid processes.

Figure 3 illustrates the overall engineering workflow and life cycle process of designing a sulfuric acid
plant. Based on the process concept and business objective, one can establish the performance of the
concept and then improve the concept using conceptual design methodologies in Aspen Plus. The base
case and the improved case economic feasibility can be compared using standard cost analysis
environment such as Aspen Process Economics Analyzer. It is also important to establish a detailed
performance model for critical equipment. This helps identify a practical design option during the
conceptual phase.

Figure 3: Engineering Workflow

After developing an improved process concept, Aspen plus Dynamics can then test the process for
safety, operability, and controllability issues; this defines the key control loops and the instrumentation
for the process. Once the process control strategy and key instrumentation is defined, the definition of
the process intent for the design is complete.

Aspen Basic Engineering can then be used to develop the FEED package, incorporating the PFD or
process P&ID for the improved concept, equipment designs, data sheets, summary sheets and basic
control loops and instrumentation. The process design information can then be further transferred into
detailed P&ID and instrumentation environments.

The performance models developed for the process can be re-used for operational monitoring and
improvement of the plant using Aspen Simulation Workbook. The performance model can also be
deployed to non-expert users who may not have background in simulation to perform “what if analysis”
studies over the web using Aspen Online Deployment (Bhat, 2010).

2.3 Previous works on Sulfuric acid Plant

The literature study shows that during the last two decades the research in the area of sulfuric acid
production captures interesting topics requiring reliable modeling, as for example: numerical-simulation
of a periodic flow reversal reactor for SO2 oxidation (Snyder et al., 1993), modeling of hot and cold start-
ups (Gosiewski, 1993), study of unsteady-state catalytic oxidation of SO2 by periodic flow reversal (Wu
et al., 1996), modeling the oxidation of SO2 in a trickle-bed reactor (Ravindra et al., 1997), modeling of
SO2 oxidation in a fixed-bed reactor with periodic flow reversal (Hong et al., 1997), modeling of SO2
oxidation taking into account dynamic properties of the catalyst (Vernikovskaya et al.,1999), oxidation of
SO2 in a trickle-bed reactor packed with activated carbon at low liquid flow rates (Suyadal, 2000),
optimization studies in H2SO4 production (Kiss et al., 2006), optimization of an adiabatic multi-bed
catalytic reactor for the oxidation of SO2 (Nodehi, 2007), simultaneous determination of SO3 and SO2 in
flowing gases (Ibanez et al., 2008), model-based experimental analysis of fixed-bed reactors for SO2
oxidation (Schoneberger et al., 2009).

The previous studies focused either only on the SO2 oxidation reactor or solely on the SO3
absorption. In contrast, this study presents a complete model of an industrial sulfuric acid plant in one
integrated environment along with the results of the simulation and optimization of the plant.

2.4 Limitation of Aspen-Hysys in simulation of Sulfuric acid plant

There are some limitations of simulation of sulfuric acid in Aspen-Hysys. First of all the catalytic bed
converter used in industry is a single reactor with 4 beds of catalyst along with inter cooler for each bed
outlet, whereas there is no provision or built in model of such reactor in Aspen-Hysys. Each bed has to
be designed as a single plug flow reactor and outlet of each bed would pass through separate heat
exchanger as an alternate of inter cooler before entering the next bed. The choice of reaction kinetics is
also limited concerning the built-in rate expression and its required parameters in Aspen-Hysys reaction
models. Another limitation of aspen-hysys for sulfuric acid plant was simulation of reactive absorption
unit. It is difficult to converge and also time consuming to simulate the reactive absorption unit. That’s
why in this study the absorption unit was chosen as conversion reactor in Aspen-Hysys assuming 100%
conversion of SO3.
3. Optimization Parameters
Sulfuric acid manufacture is most efficient when the acid plant is run continuously with ultra clean
feed gas and ultra efficient dehydration. Cool catalyst bed input gas temperatures (with low melting
point Cs-enhanced catalyst) also help. They increase SO2 oxidation efficiency and avoid destructive
overheating of the catalyst (Davenport, 2006). Acid plants are now being designed to capture every last
MJ of energy.

For optimum operation of sulfuric acid plant there are some parameters to be considered. The
constraints arise in this plant are mainly in the SO2 Converter and SO3 absorption to minimize the SOx
emission. These parameters are discussed below.

3.1 Material processing

3.1.1 Conversion of SO2 into SO3
The design and operation of sulfuric acid plant are focused on the following gas phase chemical
equilibrium reaction with a catalyst:

SO2 + 1/2 O2 ⇔ SO 3 ΔH = –99 kJ/mole

This reaction is characterized by the conversion rate, which is defined as follows:

Conversion rate = (SO2 in - SO2 out)/ SO2 in x 100 (%)

Both thermodynamic and stoechiometric considerations are taken into account in maximizing the
formation of SO3. In deciding how to optimize the equilibrium, usually the Lechatelier-Braun Principle,
which states that when an equilibration system is subjected to stress, the system will tend to adjust
itself in such a way as to partly relieve the stress, is taken into account. The stresses are, for instance, a
variation of temperature, of pressure, or of concentration of a reactant (BAT, 1999).

For SO2/SO3 systems, the following methods are available to maximize the formation of SO3:

- Heat removal, a decrease in temperature will favor the formation of SO3 since this is an exothermic
process
- Increase oxygen concentration
- remove SO3 (as in the case of the double absorption process)
- raise system pressure
- Select a catalyst, in order to reduce the working temperature (equilibrium)
- Longer reaction time
Optimum overall system behavior requires a balance between reaction velocity and equilibrium.
However, this optimum depends also on the SO2 concentration in the raw gas and on its variability in
time. Consequently, each process is more or less specific for a particular SO2 source.

3.1.2 Absorption of SO3

Sulfuric acid is obtained from the absorption of SO3 and water into H2SO4 (with a concentration of at
least 98%).

The efficiency of the absorption step is related to:

- The H2SO4 concentration of the absorbing liquid (98.5 - 99.5%)

- The range of temperature of the liquid (normally 70 °C - 120 °C)
- The technique of the distribution of acid
- The raw gas humidity (mist passes the absorption equipment)
- The mist filter
- The temperature of incoming gas
- The co-current or counter-current character of the gas stream in the absorbing liquid

SO3 emissions depend on:

- The temperature of gas leaving absorption

- The construction and operation of the final absorber
- The device for separating H2SO4 aerosols
- The acid mist formed upstream of the absorber through the presence of water vapor

3.2 Product finishing

3.2.1 Dilution of absorber acids
The acid produced, normally 95.5% - 96.5% or 98.5% - 99.5%, is diluted with water or steam condense
down to the commercial concentrations : 25%, 37%, 48% ,78%, 96% and 98% H2SO4 .The dilution can be
made in batch process or continuously through inline-mixing.

3.2.2 SO2-Stripping
The warm acid produced is blown with little air in a column or in a tower to reduce the remaining SO 2 in
the acid to < 20 mg SO2 /kg. The SO2 containing air returns to the process.

3.2.3 Purification
Sulfuric acid can be soiled by start up of acid plants after long repair. Acid is then clouded by insoluble
iron sulfate or silicate of bricks or packages. Filtration of acid is possible with conventional methods.
Filter elements in the filling lines for car or railway loading is necessary for quality reasons.
3.3 Use of auxiliary chemicals /materials
Catalysts
When producing sulfuric acid by the contact process an important step is to produce sulfur trioxide by
passing a gas mixture of sulfur dioxide and oxygen over a catalyst (Eq. 2).

SO2 + ½ O2 = SO3 - Δ H

Without a catalyst this reaction needs a very high temperature to have a realistic rate. The equilibrium is
however in favor of SO2 -formation at higher temperatures which makes the conversion very poor.

Of all substances tested for catalytic activity toward sulfur dioxide oxidation only vanadium compounds,
platinum and iron oxide have proven to be technically satisfactory. Today vanadium pentoxide is used
almost exclusively. Commercial catalysts contain 4-9 wt % vanadium pentoxide, V2O5, as the active
component, together with alkali-metal sulfate promoters. Under operating conditions these form a
liquid melt in which the reaction is thought to take place. Normally potassium sulfate is used as a
promoter but in recent years also caesium sulfate has been used. Caesium sulphate lowers the melting
point, which means that the catalyst can be used at lower temperatures. The carrier material is silica in
different forms (BAT, 1999).

The catalyst components are mixed together to form a paste and then usually extruded into solid
cylindrical pellets, rings or star-rings which are then baked at elevated temperatures. Ring (or star-ring)
shaped catalysts, which are mostly used today, give a lower pressure drop and are less sensitive to dust
blockage. The lower temperature limit is 410-430 °C for conventional catalysts and 380-390 °C for
caesium doped catalysts. The upper temperature limit is 600-650 °C above which, catalytic activity can
be lost permanently due to reduction of the internal surface (BAT, 1999).

The average service life for the catalyst is about 10 years. Service life is generally determined by catalyst
losses during screening of the catalyst which must be done from time to time to remove dust (BAT,
1999).

3.4 Intermediate and final product storage

Due to very low vapor pressure of H2SO4 in normal temperature conditions, there is no air pollution
problem connected with the storage, handling and shipping of sulfuric acid. The handling of pure SO 3
and oleum requires safety procedures and management in order to avoid atmospheric pollution in the
case of accidental release.

With regard to the ancillary operations referred to above, important considerations are as follows:
• The receipt, handling and storage of powdered raw materials should be carried out so as to
minimize the emission of dust. Liquid and gaseous feeds should be carefully contained to prevent the
emission of odorous fumes or gases.

• Oleum and SO3 storage and handling operations, which are often linked with H2SO4 production,
should be installed with means of controlling fume emissions. Venting should be directed towards acid
tanks or scrubbing systems. Installations should be built by following the best engineering practice. The
emissions can condense and solidify in cool areas so this must be very carefully guarded against to
prevent over-pressurization of storage tanks.

• During storage and handling of sulfuric acid, leaks may have an impact on the soil or on waters.
Precautions have to be taken in order to reduce the possibility and the gravity of these leaks.

3.5 Energy generation / consumption

The process steps: sulfur - burning, SO2 - conversion and SO3 -absorption are exothermic processes, this
means that from technical point of view installations for removing energy are of great importance for
the production of sulfuric acid. This is coupled most effectively with energy winning in different levels
and forms. Energy winning is dependent on the process strategy for the target products, for the local
conditions, for a possible relationship to other productions.

The age of production units decides over energy generation / consumption because materials of
construction and specific buildings fix the technical possibilities for energy optimization. The most
energy efficiency shows the sulfur burning process in conjunction with double absorption.

The different energy-winning techniques are:

-all techniques of steam generation as known from electrical power generation with special apparatus
as super-heater, economizer, steam boiler for sulfur burning

-steam generation by the inter-pass absorption with temperatures from 110°C to 180°C and steam
pressures from 1.5 bar abs to 11 bar abs .

-steam turbines with power generation up to 15 MWh (1250 t H2SO4 100% Plant/ day)

-water preheating in the end absorption from 40°C to 80°C

For the optimization of the process (e.g. saving costs and winning energy) special programs are used.

An essential characteristic of a conventional cold-gas plant (metallurgical gases) is that almost all the
energy is discharged as waste heat at low temperature. Double absorption processes based on
metallurgical gases, differ from hot-gas plants based on sulfur combustion in that cold feed gases must
be heated to the converter-inlet temperature using the energy liberated in the oxidation of sulfur
dioxide.
At a feed-gas concentration 8.5 % SO2 and a dryer inlet temperature of 30-40°C about 2.7 GJ of thermal
energy is liberated per ton of sulfuric acid (5,4 GJ in the case of sulfuric acid produced from elemental
sulfur). This corresponds to a thermal output of 31 Mw for a 1000t/d plant. About 45 % of the total
energy is discharged through the intermediate absorber acid cooling system, 23% through the final
absorber acid cooling system and about 22% through the dryer-acid cooling system.

In terms of heat recovery, in a conventional cold-gas double-absorption plant for processing relatively
low-grade sulfur dioxide containing feed gases, there is no excess high - temperature heat that can be
used for generation high-pressure steam. However, where the sulfuric acid plant is linked to a modern
smelter, high SO2 is available and to increase the output of high pressure steam, low temperature heat
from the absorber acid circuits can be used for preheating the boiler feed water (BAT, 1999).

3.6 Handling of waste gas / stack height

The height of the exhaust stack conditions the maximum SO2 /SO3 concentration value in the ambient
air surrounding a sulfuric acid plant. It is also well known that this concentration is widely fluctuating in
space and in time due to the thermo-aerodynamic conditions of the low-level atmosphere (0 to 500m),
these conditions can vary due to the following factors:

- Vertical temperature and humidity structure

- Wind speed and direction
- Turbulence of the atmosphere
- Sunshine intensity etc.

3.6.1 SO2 emissions

Origins:

• Bad conversion efficiency

• Gas bypassing (acid cross bleed or convector)

Minimization techniques without additional process:

Gases:

• Composition (O2, SO2, inert, etc.)

• Velocities through catalyst and repartition
• cooling quality (heat exchangers or air cooling)
• operating pressure
• Acid cross-bleeds (SO2 stripping, SO2 gases drying processes).
• Temperature

Catalyst:

• Converter design
• Number of beds
• Catalyst quality and quantity
• Converter loading

3.7 Single contact Acid making

The contact process without intermediate absorption is usually used in existing plants In Bangladesh. It
process SO2 gases with low and widely varying SO2 contents.

The SO2 -containing gases, which have been carefully cleaned and dried, are oxidized to sulfur trioxide in
the presence of catalysts containing alkali and vanadium oxides. The sulfur trioxide is absorbed by
concentrated sulfuric acid in absorbers, where if necessary preceded by oleum absorbers. In the
absorbers, the sulfur trioxide is converted to sulfuric acid by the existing water in the absorber acid.

The absorber acid is kept at the desired concentration of approximately 99% by wt. by adding water or
dilute sulfuric acid as shown in Figure 4.

Figure 4. Schematic of single contact, 3 catalyst bed sulfuric acid plant (Davenport, 2006).

It is a single contact acid plant because it has only one H2SO4 making step. Note gas cooling between
catalyst beds. It is this that permits additional SO2 oxidation in the next catalyst bed.

The single contact process is generally used with SO2, content inlet gases of 3 to 10%; in new plants, the
conversion efficiency is about 98.5% as a daily average and can be upgraded till 99.1 % depending on
good design and use of specially adapted doped Cs-catalyst.

In existing plants, it is difficult to obtain better than 98.0% conversion, however, in some existing plants;
a conversion efficiency of 98.5% can be achieved (BAT, 1999).
3.8 Double contact Acid Making
In the double contact process, a primary conversion efficiency of 80% to 93%, depending on the
arrangement of the contact beds and of contact time, is obtained in the primary contact stage of a
converter preceding the intermediate absorber. After cooling the gases to approx. 190°C in a heat
exchanger, the sulfur trioxide already formed is absorbed in the intermediate absorber by means of
sulfuric acid with a concentration of 98.5 to 99.5% by weight. The intermediate absorber is preceded by
an oleum absorber if required. The absorption of the sulfur trioxide brings about a considerable shift in
the reaction equilibrium towards the formation of SO3, resulting in considerably higher overall
conversion efficiencies when the residual gas is passed through one or two secondary contact beds. The
sulfur trioxide formed in the secondary stage is absorbed in the final absorber (BAT, 1999).

The double contact processes including double absorption are seen in Figure 5.

Figure 5: Schematic of 3-1 double contact acid plant (Davenport, 2006).

The increase in total SO2 oxidation after each bed is notable. Note the intermediate H2SO4 making step,
bottom right.

In general, SO2 feed gases containing up to 12 Vol % SO2 are used for this process. The conversion
efficiency in new plants can achieve about 99.6 % as a daily average in the case of sulfur burning.
Sulfuric Acid Plant
Model in Aspen-Hysys
4. STEADY-STATE SULFURIC ACID
MODEL
This model simulates the production process of sulfuric acid from sulfur with contact process. The model
includes the following features:

 A set of electrolyte components for this process

 Typical process areas including: sulfur burning, sulfur dioxide conversion, absorption of sulfur
trioxide and the main streams connecting these units.
 Definition of methods for calculating and reporting electrolyte systems
 Supports precise design, rating, or simulation.

4.1 Components:
The table below lists the components modeled in the simulation.
Components Component name Formula
H2O Water H2O
H2SO4 Sulfuric Acid H2SO4
SO2 Sulfur di-oxide SO2
SO3 Sulfur tri-oxide SO3
S Sulfur S
N2 Nitrogen N2
O2 Oxygen O2
H3O+ Hydronium Ion H3O+
-
HSO4 Bi- Sulfate ion HSO4-
SO4-- Sulfate ion SO42-

SO2, O2, N2 and CO2 are selected Henry’s components. The Electrolytes Expert System can be used to
generate electrolyte species and reactions. In this model, acidic species are treated as hydronium ion
H3O+ and choose components H2O and H2SO4 for the electrolytes system.

4.2 Physical Properties:

IMPORTANCE OF PHYSICAL PROPERTIES

Sulfuric acid has consistently ranked #1 in world chemical production. Considerable work has been done
in the steady state simulation area of sulfuric acid processes. Sulfuric acid models have been used to
design, de-bottleneck, and troubleshoot plants, converter profile optimization (with the Equation
Oriented (EO) capability), evaluate catalyst purchases and rate present catalyst condition, energy
recovery analysis, and to emulate gas-to-gas hex leaks (Bhat, 2010). Some of the key variables in sulfuric
acid production are: gas strength, production rate, stack SO2, converter catalyst loading and
temperature profile, acid strength, steam production, gas pressure drop, and gas dew-point.

Physical properties are the most important part of any simulation, it is critical to have accurate and
updated physical properties to perform engineering calculations which eventually dictate the sizing and
rating of plant equipment which affects the capital costs, operating costs, and safety of the plant.

Aspen Properties is part of aspenONE Engineering and provides state-of-the-art physical property
methods, models, algorithms, and data that enables chemists and engineers to easily perform
engineering calculations based on rigorous and proven thermo-physical property models and data. It
enables users to capture and deploy consistent physical property data and knowledge across the
enterprise. Aspen Properties contains the world’s largest database of pure components and binary
parameter databanks.

For simulation aqueous acids such as sulfuric acid processes it is recommended to turn the electrolytes
feature on in Aspen-Hysys. In Aspen Hysys, an electrolyte system is defined as one in which some of the
molecular species dissociates partially or completely into ions in a liquid solvent, and/or some of the
molecular species precipitate as salts. These dissociation and precipitation reactions occur fast enough
that the reactions can be considered to be at chemical equilibrium. The liquid phase equilibrium
reactions that describe this behavior are referred to as the solution chemistry. In Aspen, solution
chemistry is often referred to simply as Chemistry. Solution chemistry has a major impact on the
simulation of electrolyte systems. For non-electrolyte systems, chemical reactions generally occur only
in reactors. In Aspen Plus, all unit operation models can handle electrolyte reactions (Bhat, 2010).

Solution chemistry also impacts physical property calculations and phase equilibrium calculations. The
presence of ions in the liquid phase causes highly non-ideal thermodynamic behavior. Aspen provides
specialized thermodynamic models and built-in data to represent the non-ideal behavior of liquid phase
components in order to get accurate results (Bhat, 2010).

Figure 6: Fluid Package selection in Aspen Hysys

The global property option used in this model is ELECNRTL. This option set is used for the simulations
with non-ideal electrolyte solutions. ELECNRTL calculates liquid phase properties from the Electrolyte-
NRTL activity coefficient model. Also, Henry’s Law is used to calculate gas (SO2, O2, N2 and CO2) solubility
in sulfuric acid. The Ideal property option is used for vapor phase at high temperature in the converter
and heater unit operation. The STEAMNBS property option is used for the steam system unit operations.

4.3 Reactions:
Sulfur Burner

Specification Type Stoichiometry

Conversion S + O2 → SO2

Converters

Specification Type Stoichiometry

Kinetic SO2 + 0.5O2 → SO3

Absorption Reaction

Specification Type Stoichiometry

Conversion H2O + SO3 → H2SO4

4.4 Process Summary

Sulfur is mixed with the dry air after the removal of water from the feed air in the drying column. An
oxidation reaction takes place in the sulfur burner. Then the sulfur dioxide gas and the un-reacted air
are cooled from 1310K to 690K prior to entering the first pass of the converter where sulfur dioxide is
converted to sulfur trioxide.

Sulfur dioxide and air undergo the catalytic oxidation reaction in the converter. Since the heat released
from the sulfur dioxide oxidation will increase the temperature of the catalysts, the equilibrium
conversion rate will decrease. So the sulfur dioxide conversion process is divided into 4 stages and the
temperature of the catalysts in each stage can be kept suitable by stepwise cooling among the stages.
Thus the reaction can get higher conversion and reaction rate. Because of the limitation of Aspen HYSYS
software four individual converters were used as converter bed.
 Figure 7: Sulfuric Acid Plant Simulation Model

The cooled outlet from Cooler1, containing Sulfur trioxide is passed to an absorption tower where it
reacts with 98% H2SO4 to form 98.5% H2SO4. The stack gas is vented from absorption tower which
consists predominantly of Nitrogen. Stack SO2 concentration is lowered below 500ppm so the exhaust
gas can be discharged to atmosphere. Since the absorbing acid is continuously becoming concentrated,
so it is necessary to provide some means of diluting the part of the acid which is discharged from
absorbers and is to be re-circulated. Consequently the 98.5% H2SO4 is fed to circulation tank along with
de-mineralized water and 97.5% H2SO4 that comes from the drying tower. The resulting concentration of
the H2SO4 exiting from the circulation tank is to be 98.1%, which is split into two parts. One portion is
cooled and recycled back to the absorption tower. The rest is also cooled and further split into another
two portions. One of these portions is the final product containing 98% H2SO4. The other portion is
recycled back to the drying tower.
5. Unit Operation Models
5.1 Sulfur Burner
In this study element sulfur burning was considered as the source of SO2 which is the key element for
Sulfuric acid Production. The elemental sulfur is received molten or melted with pressurized steam
(sulfur melting point--390 K) and burnt in the furnace with excess dry air to form hot SO2, O2, N2 gas.

Usually air for sulfur burning is filtered through fabric and dried. It is then blown into the sulfur burning
furnace. It is blown in behind the sulfur spray to maximize droplet-air contact. In this model the drying is
done by contacting the air with strong sulfuric acid as described in section 4.4.

Figure 8: Sulfur Burning and Dehydration unit

The Sulfur and air feed stream data were collected from Wata Chemicals Ltd., Murapara, Narayangonj
and further corrected from suggested values in literature. All the physical property data was used as per
suggested in literature for maximum SO2 conversion to be achieved (Davenport, 2006). These data are
given in Appendix B.

5.2 Catalytic Bed Converter

Industrial SO2 oxidation consists of blowing warm (--700 K), clean and dry gases. The inlet gas mainly
consists of SO2, O2 and inert. SO2 and O2 bearing gas from Sulfur burner is first cooled to required
temperature and these goes down through a 'bed' of warm V, K, Na, Cs, S, O, silica catalyst for
further oxidation. Industrial SO2 oxidation is done in a 'converter' of 3 to 5 such beds.

SO2 oxidation proceeds as the feed gas descends the bed. It:

(a) Produces SO3

(b) Consumes SO2 and O2
(c) Heats the descending gas.

5.2.1 Maximum %SO2 Oxidation

Oxidation of furnace gases goes through a 4 catalyst bed converter. As warm SO2, O2, N2 feed gas
descends a catalyst bed oxidation of SO2 changes in terms of:

(a) % SO2 oxidized-temperature equilibrium curves

(b) % SO2 oxidized-temperature heatup paths

Together, they indicate that maximum oxidation in a catalyst bed is obtained where a feed gas's
heatup path intercepts its equilibrium curve (Davenport, 2006). So for better performance of converter
it is very important to determine this parameter for each bed.

Firstly calculations for each of the bed was conducted separately in Microsoft excel to determine the
heatup equilibrium intercept temperature at which maximum % SO2 is oxidized. This was done both
graphically and with Goal seek function in Excel. The calculations are attached in Appendix B.

Table 1: % SO2 oxidized-temperature points near heatup path-equilibrium curve intercept. They have
been calculated as described in Appendix B. They are plotted in Figure 9.

Temperature Heatup % SO2 oxidized Equilibrium % SO2

oxidized
895 69.820 68.750
894 69.470 69.050
893 69.130 69.350
892 68.790 69.640
891 68.450 69.940
890 68.100 70.230
889 67.760 70.520
888 67.420 70.815
887 67.075 71.106
886 66.730 71.400
885 66.400 71.680

The table shows that at 893K and below heatup path % SO2 oxidized is less than equilibrium curve % SO2
oxidized. This indicates that at 893K and below, SO2 oxidation can proceed further up the heatup path
towards equilibrium (Figure.9). Though at 894K and above heatup path % SO2 oxidized is greater than
equilibrium % SO2 oxidized but this is impossible because equilibrium % SO2 oxidized cannot be
exceeded up a heatup path.
Maximum (equilibrium) % SO2 oxidized occurs, therefore, between 893K and 894K. Interpolation shows
that it occurs at: 893.3 K and 69.2 % SO2 oxidized. This is confirmed by the Excel Goal Seek calculation
(Figure B.2, Appendix B).

Pressure: 1.4 bars

Feed: 10% SO2, 11% O2

and 79% N2

Figure 9: Equilibrium- Heatup path intercept Temperature for Bed 1

Similar calculation procedure was followed for 2nd, 3rd and 4th catalyst bed.

Figure 10: Equilibrium- Heatup path intercept Temperature for Bed 2

5.2.2 Aspen-Hysys Model for 4 Catalyst bed Converter
Industrial scale production of sulfuric acid is dependent on the oxidation of sulfur dioxide to sulfur tri-
oxide in fixed bed catalytic reactors. Because of the limitation of Aspen Hysys each of the bed are
modeled as individual plug flow reactor. The conversion from these models was further used in the total
plant model where converter reactor was used as individual catalyst bed.

5.2.2.1 Reaction Specification

Through the years several catalyst formulations have been employed, but one of the traditional catalytic
agents has been vanadium pentoxide. Calderbank has indicated that for a catalyst consisting of V2O5
supported on silica gel, the kinetic data are represented by a rate expression of the form (Hill, 1977):

rm =

This is a degenerate form of typical Hougen-Watson kinetics. The rate constants are given by:

lnk1 = 12.07 - and lnk2 = 22.75 -

Where T is expressed in Kelvin

R is expressed in Calmol-1K-1
K1 is expressed in moles /sec-gm of catalyst-atm3/2
K2 is expressed in moles /sec-gm of catalyst-atm

This rate expression was set in Aspen-Hysys and with proper catalyst data the reactor model was solved.
 Figure 11: Reaction specification in Aspen Hysys

5.2.2.2 Reactor model Specifications

Plug flow reactor model was selected for each of the catalyst bed. Each reaction was specified in the
reactors with catalyst specifications and proper reactor sizing. These sizing of each bed represents each
of the bed size.

Catalyst data

The Catalyst particle size was chosen as per literature considering the pressure drop in the reactor.

For Catalyst particle size= 0.00635m, density = 1172.9 Kg/m3

Porosity (Void fraction) = 0.78 and Sphericity = 0.303 [Foust.,et. al., 2nd Ed., Figure B-12]

Reactor Sizing

Bed Diameter:

Industrial catalytic converter (hence catalyst bed) diameters are function of measured 1st catalyst bed
feed gas volumetric flowrates (Davenport, 2005):

Diameter = -7.45E-05*(gas rate)2 + 6.45E-02*(gas rate) + 3.25

From this co-relation the diameter of each bed was found to be 3.27m.
Bed Height:

The suggested co-relation for bed height was followed.

Average bed thickness, m = 0.11*bed number + 0.51

Thus the bed heights for each bed are:

Bed1 0.62 m
Bed2 0.72 m
Bed3 0.84 m
Bed4 0.95 m

From the reactor model the %SO2 conversion found is shown in Table 2:

Table 2: Conversion in each bed from Hysys model

Bed No. Conversion (%) [With 100% excess air] Conversion (%) [With 20% excess air]
1 68.49 63.36
2 25.68 27.14
 3 4.071 6.579
4 1.409 2.009
This conversion result was used for total simulation model.

From the reactor model changes in different important parameters like temperature, pressure drop,
component mass fraction etc. along the bed length was observed.

5.3 Absorption Tower

For design limitations the reactive absorption tower was replaced by converter in Hysys with 100%
conversion reaction of SO3 and water. The SOx emission from absorption tower stack gas is nearly
negligible.

The absorption reaction components were selected for electrolyte system in Aspen-Hysys. Electrolyte
system is defined as one in which some of the molecular species dissociates partially or completely into
ions in a liquid solvent, and/or some of the molecular species precipitate as salts. These dissociation and
precipitation reactions occur fast enough that the reactions can be considered to be at chemical
equilibrium. The liquid phase equilibrium reactions that describe this behavior are referred to as the
solution chemistry.

5.4 Waste heat Boiler

Sulfuric acid manufacturing process consists of mainly exothermic reaction like sulfur burning, oxidation
etc. Most of the hot product streams from furnace and converter bed undergoes cooling. This heat can
be utilized by producing high pressure steam in large quantity. For the purpose this model contains
several heat exchangers which use water as cooling medium and thus produce steam. Especially the 1 st
converter bed inlet (SO2-1) requires to be cooled before moving to Bed-1. Large amount of steam is
produced from that heat exchanger (HE-1) which can be used further in energy generation.
6. Result and Discussion
The heatup path of the reaction can be conveniently shown in the % SO2 oxidized vs T diagram, as
illustrated by Figure 12. The 1st catalyst bed inlet composition extracted from the Aspen hysys model
was used as basis of generation of the equilibrium curve and heatup path which is analyzed in Table B.1
(Appendix B). One equilibrium curve corresponds to each composition of the reaction mixture at reactor
inlet. The operating lines represent the simultaneous increase of conversion and rise of temperature
which take place along each catalytic bed. The slope of the operating lines is proportional to the
reciprocal value of the adiabatic temperature rise, 1/ΔTad. The horizontal lines represent cooling of the
reaction mixture which takes place in the external heat exchangers. The evolution of temperature and
conversion in the industrial reactor with 20% excess air is represented in Figure 12 by a point dotted
line. The dashed line (green and blue) represents the same variables as predicted by the simulation
model with 100% and 20% excess air respectively. The model practically coincides with the equilibrium
reactor with very small error. The heatup path for Hysys model with same operating conditions as the
existing industrial reactor (blue dashed line) almost coincides with the practical plant heat up path
(dotted line). For a given inlet composition, the operating lines can approach the equilibrium curve
(continuous line in Figure 12) but can never cross it.
 Figure 12: Temperature-Conversion Diagram

The 4th Catalyst bed SO2 oxidation shifts upwards the equilibrium curve and therefore allows higher
conversions. Figure 13 & 14 presents the steady-state temperature and composition profiles along the
SO2 oxidation reactor. From the simulation result in Table 4 it is observed that highest temperatures are
reached at the end of the first and second catalytic bed, the following steps having less impact on
conversion and temperature. Along with the increased conversion, the SO2 mass fraction is reduced
from about 13.2% at the reactor inlet down to less than 12.3% in the 1st bed outlet. This concentration
decreases to 0.04% at the final 4th bed outlet (Figure 15).

Figure 13: Temperature Profile

Figure 14: Component profile

 Figure 15: Mass fraction of 4th bed outlet gas

Equilibrium constant for SO2 oxidation is a function of temperature. It decreases nearly 80000 times
between 600 and1400 K. Stoichiometry-equilibrium curve for SO2 oxidation shows that the reaction
goes almost to completion at 600 K but not at 1000 K. This indicates that raising reaction temperature
to increase reaction rate is counter-acted by a large decrease in maximum attainable (equilibrium) SO3
production [4]. Figure 16 shows the same phenomena as reaction rate is highest at inlet temperature
690K and decreases along the reactor length as the temperature increases.
 Figure 16: Reaction rate

The pressure drop in plug flow reactor is normal phenomena and figure 17 shows decrease in pressure
with reactor length. Here figure 17 represents the pressure profile along the length of 1st catalyst bed
which is assumed as a single plug flow reactor in hysys. To avoid excessive pressure drop each converter
bed was previously designed with proper dimension in section 5.2.2.2. A slight decrease in converter
diameter may cause excessive pressure drop [Appendix A].

Figure 17: Pressure profile in bed1

For environmental consideration tail gases are recommended to be lowered to 20ppm SO2 (Bhat, 2010).
Again according to CAI-Asia Factsheet No.4 (2010) the 24-hr SO2 standard in Bangladesh is 366μg/m3.
From figure 18 it is observed that with 100% excess feed air the stack gas of this model contains ppm
level of SO2 and no SO3, whereas in the practical plant (Wata chemicals Ltd.) with only 20% excess feed
air 0.175% SO2 is exhausted. Even the simulated model result with 20% excess air shows 0.114% SO2 in
the stack gas which is nearly 317.86μg/m3. Thus this model minimizes the SOx emission, which is a
challenging parameter in sulfuric acid plant. The optimization results reveal that – for the nominal
operating point (i.e using optimal heatup path) – the flow rate of air fed to sulfur burner should be
increased by 80% from that of the conventional one to reduce SOx emission.
 Figure 18: Stack gas composition from Absorption tower

It should be remarked that the plant produces a significant amount of energy in the sulfur burner and
the heat exchangers HE1–HE5. Therefore, the model designed aiming at maximizing the amount of
energy produced. Increasing energy production is equivalent to maximizing the amount of SO2
converted into products. A flat optimum is expected because practically the entire amount of heat
generated in the reaction is recovered due to tight energy integration. This model gives production of
650 Psi steam with spec target of Steam temperature 400K in HE-1, whereas the practical plant
produces 10kg pressure only.

Figure 19: High pressure steam generation

Simulation Results:

The key simulation results and process simulation results are shown in the following table:

Table 3: Key simulation results with 100% excess air

Flowsheet Variable Value Unit

Feed Air 7348 kg/hr
Sulfur 803.3 kg/hr
Air/Sulfur Ratio 9.15
Water for Absorption 540.2 kg/hr
column
Water for steam 1942 kg/hr
generation
Product Sulfuric Acid 2482.5 kg/hr
Steam Production 1942 kg/hr
650 Psi
Exhaust gas 6200.6 kg/hr
Table 4: Process simulation results with 100% excess air

Process Variable Value Unit

Sulfur Burner Temperature 1963 K
Water content of feed air 0.026 Mole Fraction
Water content of dry air 0.0009 % Vol
Converter Temperature In Out ΔT K
Bed1 690 850 160 K
Bed2 700 719.4 19.4 K
Bed3 710 712.2 2.2 K
Bed4 690 696.5 6.5 K
SO2 in Stack gas 0.0002 Mole Fraction
Sulfuric acid concentration 98.5 % Wt
Sulfuric acid 65.7 t/day

Table 5: Key simulation results with 20% excess air

Flowsheet Variable Value Unit

Feed Air 4155 kg/hr
Sulfur 803.3 kg/hr
Air/Sulfur mass Ratio 5.17
Water for Absorption 170 kg/hr
column
Water for steam 1942 kg/hr
generation
Product Sulfuric Acid 2234 kg/hr
Steam Production 1942 kg/hr
650 Psi
Exhaust gas 4197 kg/hr

Table 6: Process simulation results with 20% excess air

Process Variable Value Unit

Sulfur Burner Temperature 1922 K
Water content of feed air 0.026 Mole Fraction
Water content of dry air 0.0009 % Vol
Converter Temperature In Out K
Bed1 803 900 K
Bed2 734 767.4 K
Bed3 702 716.3 K
Bed4 698 704.6 K
SO2 in Stack gas 0.00114 Mole Fraction
Sulfuric acid concentration 98.5 % Wt
Sulfuric acid 60 t/day

Table 7: Data of Existing plant in Bangladesh (Wata Chemicals Ltd.)

Flowsheet Variable Value Unit

Feed Air 4155 Kg/hr
Sulfur 803.3 kg/hr
Air/Sulfur mass Ratio 5.17
Water for Absorption 170 kg/hr
column
Water for steam 374.80 kg/hr
generation
Product Sulfuric Acid 5000 kg/hr
Steam Production 1191 kg/hr
160 Psi
Process Variable Value Unit
Sulfur Burner Temperature 1435 K
Water content of feed air 0.026 Mole Fraction
Water content of dry air 0.0009 % Vol
Converter Temperature In Out K
Bed1 803 866 K
Bed2 734 791 K
Bed3 702 709 K
Bed4 698 693 K
SO2 in Stack gas 0.00175 Mole Fraction
Sulfuric acid concentration 98.5 % Wt
Sulfuric acid 60 t/day

Table 3 and 4 show that, the simulated model gives better performance with minimum SOx emission and
better energy consumption. Both of these are two major concerns for Sulfuric acid plant. Again Table 5
and 6 show that with 20% excess air and same operating condition with that of the plant the simulation
result is almost similar to the plant. The slight differences arise because of the reaction kinetic model
chosen in the Aspen-Hysys model. As there were no document of data of the plant, so some data was
estimated from literature.
7. Conclusion
In this work a simulation model of Sulfuric acid process plant was developed. The simulation takes
advantage of Aspen Properties capabilities of modeling electrolyte components. This includes automatic
chemistry generation and the capacity of handling electrolyte reactions for all unit models. Aspen-Hysys
provides specialized thermodynamics models and built-in data to represent the non-ideal behavior of
liquid phase components in order to get accurate results. Further material and energy flows were used
to design each unit operations blocks especially converter to achieve maximum %SO2 oxidation and thus
minimum SOx emission. As no suitable kinetics model was available in Aspen-Hysys, the kinetic
parameters were estimated from a degenerated form of typical Hougan-Watson kinetics, while the
remaining parameters required for modeling were estimated using classical correlations.

In addition, a Microsoft Excel interface was developed to determine maximum %SO2 oxidized and
optimum heatup path for each converter bed. The model includes a catalytic reactor (four pass
converter), heat exchangers, mixers, splitters and reactive absorption columns. The proposed model
was also simulated with 100% excess air and recommended inlet conditions from literature. This shows
similarity with optimum result observed from Excel.

Along with minor benefits in energy production, the amount of SOx emissions could be significantly
reduced by around 80% from the existing plant just by optimizing operating parameters such as air feed
flow rates or split fractions. Again the result satisfies the 24-hr SOx standard in Bangladesh. Besides
controllability, operability and optimization studies the plant model is also useful for operator training
and scenario assessments.

The simulation model developed can also be used as a guide for understanding the process and the
economics, and also a starting point for more sophisticated models for plant designing and process
equipment specifying. Other optimization studies, such as tuning the amount of energy produced by the
plant or optimize the air feed policy accounting for day/night temperature variations can also be
conducted using this model.

Future Work:

In this model the reaction kinetics for converter was estimated. The four converter passes in this process
can be modeled in details in Aspen Plus using four RCSTR reactors with user reaction kinetics. FORTRAN
subroutine USRKIN represents the kinetics in all converter passes. USRKIN have to be included compiled
and linked in file (.dll form). In that case all three files (.bkp, .dll, and .opt) is to be placed in the same
directory. The Radfrac column can be selected as reactive absorption tower to get better performance in
solution chemistry. Sulfur Burn can also be modeled using the Gibbs free energy minimum method in
the RGibbs model. This determines the equilibrium composition of the products resulting from the many
reactions that can occur (Bhat, 2010).
References
[1] Aspen Technologies Inc. Getting Started Modeling Processes with Electrolytes. V7.1.

[2] BAT (1999)., “Best Available Techniques Reference Document on the Production of Sulphuric acid”.

[3+ Chen, C.C., Tremblay, D., Bhat, C., “A Rate-Based Process Modeling Study of CO2 Capture with
Aqueous Amine Solutions using aspenONE Process Engineering”.

[4] CAI-Asia (2010)., “Factsheet No.4 – Sulfur dioxide (SO2) Standards in Asia”, Clean Air Initiative for
Asian Cities Center, Pasig City, Philippines.

[5] Davenport, W.G., King, M.J. (2005)., “ Sulfuric Acid Manufacture, Analysis, Control and Optimization”,
Elsevier Science.

[6+ Davenport, W.G.,et.al., (2006)., “Sulphuric Acid Manufacture”, Southern African Pyrometallurgy,
South African Institute of Mining and Metallurgy, Johannesburg.

[7] Foust, A. S., et. al., (1980)., “Principles of Unit Operations”, 2nd Ed., John Wiley & Sons, Inc., New York,
USA, pp.711-713.

[8+ Gosiewski, K.,(1993)., “Dynamic modeling of industrial SO2 oxidation reactors. 1. Model of hot and
cold start-ups of the plant”, Chemical Engineering & Processing, Vol. 32, pp. 111–129.

[9+ Hill, C.G., (1977) “An Introduction to Chemical Engineering Kinetics & Reactor Design”, John Wiley &
Sons, Inc., New York, USA, pp.500-516.

[10+ Hong, R.Y., Li, X., Li, H.Z., Yuan, W.K., (1997)., “Modeling and simulation of SO2 oxidation in a fixed-
bed reactor with periodic flow reversal”, Catalysis Today, Vol. 38, pp. 47–58.

[11+ Ibanez, J.G., Batten, C.F., Wentworth, W.E., (2008)., “Simultaneous determination of SO3 and SO2 in
a flowing gas”, Industrial & Engineering Chemistry Research, Vol. 47, pp. 2449–2454.

[12+ Kiss, A.A., et.al., (2010)., “Dynamic modeling and process optimization of an industrial sulfuric acid
plant”, Chemical Engineering Journal, issue.158,pp. 241–249. Elsevier B.V.

[13] Kiss, A.A., Bildea, C.S., Verheijen, P.J.T., (2006)., “Optimization studies in sulphuric acid production”,
Computer Aided Chemical Engineering, Vol. 21A, pp. 736–742.

[14+ Nodehi, A., Mousavian, M.A., (2007)., “Simulation and optimization of an adiabatic multi-bed
catalytic reactor for the oxidation of SO2”, Chemical Engineering & Technology, Vol. 30, pp. 84–90.

[15+ Rase, H. F., “Chemical Reactor Design for Process Plant: Case Studies and Design Data”, Vol.2. Wiley-
Interscience publication, John Wiley and Sons, New York.
[16+ Ravindra, P.V., Rao, D.P., Rao, M.S., (1997)., “A model for the oxidation of sulfur dioxide in a trickle-
bed reactor”, Industrial & Engineering Chemistry Research, Vol. 36, pp. 5125–5132.

[17] Schoneberger, J.C., Arellano-Garcia, H., Wozny, G., Korkel, S., Thielert, H., (2009)., “Model-based
experimental analysis of a fixed-bed reactor for catalytic SO2 oxidation”, Industrial & Engineering
Chemistry Research, Vol. 48, pp. 5165–5176.

[18+ Snyder, J.D., Subramaniam, B.,(1993)., “ Numerical-simulation of a periodic-flow reversal reactor for
sulfur-dioxide oxidation”, Chemical Engineering Science, Vol. 48, pp. 4051–4064.

[19] Bhat, C., Pinjala, V., (2010)., “Sulphuric acid plant modelling”, Sulphur Magazine, Vol. 330

[20] Sultana, S.T. and Amin, M. R., (2011)., “Aspen-Hysys Simulation Of Sulfuric Acid Plant”, Journal of
Chemical Engineering, IEB, Vol. 26, pp. 47-49.
http://banglajol.info/index.php/JCE

[21] Suyadal, Y., Oguz, H., (2000)., “Oxidation of SO2 in a trickle bed reactor packed with activated
carbon at low liquid flow rates”, Chemical Engineering & Technology, Vol. 23, pp. 619–622.

[22] Vernikovskaya, N.V., Zagoruiko, A.N., Noskov, A.S., (1999)., “SO2 oxidation method. Mathematical
modeling taking into account dynamic properties of the catalyst”, Chemical Engineering Science, Vol. 54,
pp. 4475–4482.

[23+ Wu, H.X., Zhang, S.Z., Li, C.Y., (1996)., “Study of unsteady-state catalytic oxidation of sulfur dioxide
by periodic flow reversal”, Canadian Journal of Chemical Engineering, Vol. 74, pp. 766–771.
Appendix A
Catalyst Data [6, 12]:

Size: ¼ in spherical pellets

From Foust et.al., Figure B-12: Shape factor, Ψ = 0.303 and porosity, ε = 0.78

Where, Ψ =

Reaction Rate:

Various kinetics and mechanism has been proposed for SO2 oxidation the following is a typical one [12].

Various rate equations have been proposed using this mechanism. For fine catalyst with unit
effectiveness factor degenerated form of Hougan-Watson kinetics can be used.

rm =

lnk1 = 12.07 - and lnk2 = 22.75 -

Where T is expressed in Kelvin

R is expressed in Calmol-1K-1
K1 is expressed in moles /sec-gm of catalyst-atm3/2
K2 is expressed in moles /sec-gm of catalyst-atm

K1 = 1.746 x 105 e-31000/RT lb moles/ lb catalyst atm3/2sec

K2 = 7.589 x 109 e-53600/RT lb moles/ lb catalyst atm3/2sec

Equations for Calculation:

For 0.141 lbmols/s SO2 1st Catalyst bed inlet feed gas and average molecular weight, M = 31.4

Mass Velocity, G =

CAouo = = lbmols/ft2-s,

Assuming adiabatic plug flow reactor energy and material balance equation gives:
GCP(T-To) = (-ΔH)CAouo(f-fo)
Thus,

T=

Again, = rm

And

Combining these equations give:

Thus,

Here, D = Converter Diameter [depends on Volume flow rate of feed gas in each bed]
For 1st Catalyst Bed: D = 3.27 m, f=0 and Thus, β = 0.42
Similarly calculations were done for other beds.
Pressure Drop:

Where,
( ) = Pressure drop
Dp = Particle diameter
L = Bed height

APPENDIX-B
All the equations used in the calculations are taken from literature [4].

% SO2 Oxidized Calculation, Φ:

……… (10.1)

Equilibrium %SO2 oxidized, ΦE, is related to equilibrium temperature [4]:

Where,

TE = equilibrium temperature

A and B = empirical constants for calculating ΔGoT from T,

A= - 0.09357; B = -98.41,

R = gas constant, 0.008314 MJ kg-mole SO2-1 K-1

ΦE = equilibrium % SO2 oxidized,

e = volume % SO2 in feed gas

f = volume% O2 in feed gas

Pt = total equilibrium gas pressure, bar.

Matrix Solve in Microsoft Excel:

Co-efficient from all the material and energy balance equations for each component were written in
matrix form in excel spreadsheet and solved using excel matrix solve command as per figure B.1. Thus
similar calculations were made to determine each bed’s outlet composition.

Figure B.1: Solving matrix in Excel to calculate 1st bed outlet composition

Calculation Strategy for Intercept point:

The iterative intercept strategy is to find the temperature at which a feed gas's heatup path % SO2
oxidized, f, equals its equilibrium curve % SO2 oxidized, fE. This temperature and its equivalent %SO2
oxidized define the intercept point.
 Figure B.2: Using Excel Goal seek operation to determine optimum heatup path for bed1

Figure B.3: Equilibrium Curve Generation Spreadsheet for bed1

The table below shows the calculation spreadsheet for optimum heatup path determination for each
beds.

Table B.1: Optimum heatup path calculation in excel for 4 beds

Table 1.1, 1st catalyst bed All quantities are per kg-mole of 1st catalyst bed
feed gas

1st catalyst bed d, % vol 0 e, % vol 10 f, % vol 11 % vol 79

specification: SO3= SO2= O2= N2=

1st catalyst bed kg-mol SO2 = 0.1 fed gas temperature,K= 690
e/100 =G3/100
catalyst bed pressure, 1.2
bar =

SO3 = 0 SO2= 0.1 O2= 0.11 N2= 0.79

suggested equilibrium curve intercept % SO2 68.48485

oxidized, 671

Equilibrium curve temperature equivalent to % SO2 oxidized

(Eqn.10.13)
891.116003 891.116003

1st catalyst bed heatup

path matrix
Eqn description kg-mol kg-mol O2 kg-mol kg-mol kg-mol kg mol O2 kgmol
[Ref. 2] SO2 in in N2 in SO3 out SO2 out N2 out
out
11.1 input SO2 0. 1 0 0 0 0 0 0
kg-mol 1
 11.2 input O2 kg- 0. 0 1 0 0 0 0 0
mol 11
11.3 input N2 kg- 0. 0 0 1 0 0 0 0
mol 79
14.6 S balance 0 -1 0 0 1 1 0 0
17.6 O balance 0 -2 -2 0 3 2 2 0
11.6 N balance 0 0 0 -2 0 0 0 2
11.7 enthalpy 0 278.7 -12.21 -11.662 -356.9387 - 18.91090 17.91671
balance 268.30
95

feed gas 690 intercept temperature, 891.116003

temp, K= A14
Matrix result equivalent to intercept
temperature
kg-mol 0.1
SO2 in
kg-mol O2 0.11
in
kg-mol N2 0.79
in
kg-mol 0.06848543 Heatup path %SO2 oxidized equivalent 68.48543 Eqn (10.1)
SO3 out 1 to 143
kg-mol 0.03151456 intercept temperature incells J30 and SO2 %oxidized after 1st
SO2 out 9 A14 bed
kg-mol O2 0.07575728
out 4
kg-mol N2 0.79
out

goal seek calculation

Equilibrium curve % SO2 oxidized- heatup path %SO2 oxidized -0.000574718

Table 2.1, 2nd catalyst bed Optimum All quantities are per kg-mole of 1st catalyst
heatup bed feed gas

1st catalyst bed specification: d, % vol 0 e, % vol 10 f, % vol 11 % vol 79

SO3= SO2= O2= N2=

1st catalyst bed kg-mol SO2 = e/100 0.1 fed gas 700
=G3/100 temperature,K=
catalyst bed pressure, 1.2
bar =

SO3 = 0 SO2= 0.1 O2= 0.11 N2= 0.79

suggested equilibrium curve intercept % SO2 oxidized, 92.2999

5024

Equilibrium curve temperature equivalent to % SO2 oxidized (Eqn.17.1)

784.6997 784.6998
674
2nd catalyst bed heatup path
matrix
Eqn description kg-mol kg-mol SO2 kg-mol kg-mol kg-mol kg-mol kg mol kgmol
SO3 in in O2 in N2 in SO3 out SO2 out O2 out N2 out
14.2 input SO3 0.06 1 0 0 0 0 0 0 0
kg-mol 85
14.3 input SO2 0.03 0 1 0 0 0 0 0 0
kg-mol 15
14.4 input O2 0.07 0 0 1 0 0 0 0 0
kg-mol 58
14.5 input N2 0.79 0 0 0 1 0 0 0 0
kg-mol
14.6 S balance 0 -1 -1 0 0 1 1 0 0
14.7 O balance 0 -3 -2 -2 0 3 2 2 0
14.8 N balance 0 0 0 0 -2 0 0 0 2
14.9 enthalpy 0 370.802 278.173 -12.541 -11.973 - - 15.3640 14.6071
balance 364.5410 273.8016 4325 6277
486 45

feed gas 700 intercept temperature, 784.699

temp, K= A14 7674
Matrix result equivalent to intercept
temperature
kg-mol 0.0685
SO3 in
kg-mol 0.0315
SO2 in
kg-mol 0.0758
O2 in
kg-mol 0.79 Heatup path %SO2 oxidized 92.29981 Eqn-
N2 in equivalent to 897 10.1
kg-mol 0.097574 intercept temperature incells J30 SO2 %oxidized after
SO3 out and A14 1st bed
kg-mol 0.002426
SO2 out
kg-mol 0.061263
O2 out
kg-mol 0.79
N2 out

goal seek calculation

Equilibrium curve % SO2 oxidized- heatup path %SO2 0.000131
oxidized 264

Table 3.1, 3rd catalyst bed All quantities are per kg-mole of 1st catalyst bed feed
Optimum heatup gas

1st catalyst bed d, % vol 0 e, % vol 10 f, % vol 11 % vol 79

specification: SO3= SO2= O2= N2=

1st catalyst bed kg-mol SO2 = 0.1 fed gas 710

e/100 =G3/100 temperature,K=
catalyst bed pressure, 1.2
bar =
SO3 = 0 SO2= 0.1 O2= 0.11 N2= 0.79

suggested equilibrium curve intercept % SO2 98.0111

oxidized, 4518
Equilibrium curve temperature equivalent to % SO2
oxidized (Eqn.17.1)
716.3415 716.34152
269 69

3rd catalyst bed heatup path

matrix
Eqn descriptio kg-mol kg-mol kg-mol kg-mol kg-mol kg-mol kg mol kgmol N2 out
n SO3 in SO2 in O2 in N2 in SO3 out SO2 out O2 out
input SO3 0.097 1 0 0 0 0 0 0 0
kg-mol 574
input SO2 0.002 0 1 0 0 0 0 0 0
kg-mol 426
input O2 0.061 0 0 1 0 0 0 0 0
kg-mol 263
input N2 0.79 0 0 0 1 0 0 0 0
kg-mol
S balance 0 -1 -1 0 0 1 1 0 0
O balance 0 -3 -2 -2 0 3 2 2 0
N balance 0 0 0 0 -2 0 0 0 2
enthalpy 0 370.090 277.6569 - -12.284 - -277.33 13.0856 12.48
balance 6 12.8743 369.4245 6 122
6
feed gas 710 intercept 716.341
temp, K= temperature, A14 5
Matrix result equivalent to intercept
temperature
kg-mol 0.097574
SO3 in
kg-mol 0.002426
SO2 in
kg-mol 0.061263
O2 in
kg-mol 0.79 Heatup path %SO2 oxidized equivalent to 98.01104 Eqn-
N2 in 10.1
kg-mol 0.0999517 intercept temperature incells J30 and A14 SO2 %oxidized after 1st
SO3 out 48 bed
kg-mol 4.82522E-
SO2 out 05
kg-mol 0.0600741
O2 out 26
kg-mol 0.79
N2 out

goal seek calculation

Equilibrium curve % SO2 oxidized- heatup path %SO2 0.000105
oxidized 25

Table 4.1 4th catalyst bed All quantities are per kg-mole of 1st catalyst bed feed
gas

1st after H2SO4 making catalyst d', % vol 0.012 e', % vol 0.234 f', % vol 7.15
bed specification: SO3= SO2= O2=

1st catalyst bed kg-mol 0.002 fed gas temperature,K= 690

SO2
catalyst bed pressure, 1.2
bar =
SO3 = 0.0001 SO2= 0.002 O2= 0.061 N2= 0.79
suggested equilibrium curve intercept % 98.8276
SO2 oxidized, 822
Equilibrium curve temperature equivalent to % SO2 oxidized
(Eqn.10.13)
697.3022 697.30225
511 11

1st after acid making catalyst bed heatup

path matrix
Eqn description kg-mol kg-mol kg-mol kg-mol kg-mol kg-mol kg mol O2 kgmol N2
SO3 in SO2 in O2 in N2 in SO3 out SO2 out out out
input SO3 0.00 1 0 0 0 0 0 0 0
kg-mol 01
input SO2 0.00 0 1 0 0 0 0 0 0
kg-mol 2
input O2 0.06 0 0 1 0 0 0 0 0
kg-mol 1
input N2 0.79 0 0 0 1 0 0 0 0
kg-mol
14.6 S balance 0 -1 -1 0 0 1 1 0 0
17.6 O balance 0 -3 -2 -2 0 3 2 2 0
11.6 N balance 0 0 0 0 -2 0 0 0 2
enthalpy 0 371.513 278.6891 -12.207 -11.66 -370.785 -278.312 12.4511 11.
balance 4 89

feed gas 690 intercept 697.302251

temp, K= temperature, A14

Matrix result equivalent to intercept

temperature
kg-mol 0.0001
SO3 in
kg-mol 0.002
SO2 in
kg-mol 0.061
O2 in
kg-mol 0.79 Heatup path %SO2 oxidized equivalent to 98.82 Eqn-
N2 in 772 10.1
kg-mol 0.0020765 intercept temperature incells J30 and A14 SO2 %oxidized after acid making
SO3 out 54 1st catalyst bed
kg-mol 2.34456E-
SO2 out 05
kg-mol 0.0600117
O2 out 23
kg-mol 0.79
N2 out
goal seek calculation
Equilibrium curve % SO2 oxidized- heatup path %SO2 -3.5792E-05
oxidized
Appendix C