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A

PROJECT REPORT
ON
Production of Sulphuric Acid from DCDA Process
SUBMITTED BY:
AKSHAY AGARWAL (Roll No. 1104351003)
ANURAG VERMA

(Roll No. 1104341009)

ISHA SHUKLA

(Roll No. 1104351015)

Report Submission Date:

Submitted in
Partial fulfillment of the requirements for the awarding of degree of
BACHELOR OF TECHNOLOGY IN
CHEMICAL ENGINEERING
Submitted To
UTTAR PRADESH TECHNICAL UNIVERSITY, LUCKNOW
UNDER THE EXPERT GUIDANCE OF:
Er. PRADEEP YADAV
DEPARTMENT OF CHEMICAL ENGINEERING
BUNDELKHAND INSTITUTE OF ENGINEERING AND TECHNOLOGY
JHANSI-284128
SESSION 2014-15
1

CERTIFICATE
This is certified that Akshay Agarwal, Anurag Verma and Isha Shukla have carried out this
project entitled Production of Sulphuric Acid from DCDA Process for the award of
Bachelor of Technology from Uttar Pradesh Technical University, Lucknow under my
supervision. The project embodies result of original work and studies carried out by student
themselves and the contents of the project do not form the basis for the award of any other
degree to the candidates or to anybody else.

Er. A.D. Hiwarikar

Er. Pradeep Yadav

Head of the department

Assistant Professor

BIET, Jhansi

BIET, Jhansi

Date:

ACKNOWLEDGEMENT
For the successful accomplishment of our project, we would like to thank The Almighty for His
blessings. A special thanks to our project guide Er. Pradeep Yadav whose help, stimulating
suggestions and encouragement, helped us to coordinate our project especially in writing this
report. We rather find words short to express our gratitude to him. His involvement and personal
interest has enabled us to accomplish this project work successfully.
We are highly thankful to Er. A.D. Hiwarikar, Er. Sudeep Yadav, Er.Ravindra Kumar , Er.
S.K.Srivastava, Er. Ajitesh Mehra and Er. Neeraj Singh, Department of Chemical
Engineering, B.I.E.T. Jhansi for their full cooperation in providing necessary facilities,
environment needed for the work.
Finally we wish to express our modest and sincere regards to our parents and friends for their
intensive support and encouragement for this project work.

ABSTRACT
The project includes the detailed designing of a four stage adiabatic catalytic bed reactor for a
sulphuric acid plant of capacity 1000 TPD (tons per day). The feed is at 1 atm and 4100 C. There
are two main processes for manufacturing of sulphuric acid namely the chamber process and the
contact process. The pioneer sulphuric acid manufacturing plants, adopted the chamber process
but at the beginning of the twentieth century with technological advancements, the contact
process gained popularity as the conversion achieved was much higher than that achieved
through chamber process. Chamber process produced sulphuric acid of concentration less than
80 %.The major disadvantage includes the limitations in throughput, quality and concentration of
the acid produced. All known new plants uses the contact process although some older chamber
process plants may still be in use.
The contact process has been gradually modified to use double absorption (also called double
catalyst), which increases yield and reduces stack emission of unconverted SO2. Conversions
using single absorption contact process were typically about 97-98 percent. While in the current
double absorption flow process, achievable conversions are as high as 99.7 percent.
The project mainly comprise of the basic parts of the sulphuric acid manufacturing plant, the
equipments and the catalyst used, flow of materials in and out of the equipments, their material
and energy balances, heat duty of the heat exchangers, weight of the catalyst required and
pollution control.

TABLE OF CONTENTS
1. List of Tables6
2. List of Figures...7
3. Notations...8
4. Introduction.....10
5. Literature Review....11
6. Uses and Applications.12
7. Sulphuric Acid- World Market....13
8. Status of Existing Sulphuric Acid Plants In India...14
9. The Contact Process........16
10. Available Technologies for Pollution Control........20
11. Material Balance........23
12. Energy Balance.......30
13. Weight of Catalyst......42
14. Summary Sheet.......55
15. Conclusion..57
16. References.......58
17. Appendix.....59

1. LIST OF TABLES

Table 1: Capacity wise number of sulphuric acid plants in India.


Table 2: Combustion Chamber Material Balance.
Table 3: Material Balance on First Three Catalytic Beds.
Table 4: Material Balance on Fourth Catalytic Bed.
Table 5: Heat Capacity equation constants for incoming gas mixture.
Table 6: Heat Capacity equation constants for outgoing gas mixture.
Table 7: Heat Capacity equation constants for incoming gas mixture.
Table 8: Heat Capacity equation constants for outgoing gas mixture.
Table 9: Heat Capacity equation constants for incoming gas mixture.
Table 10: Heat Capacity equation constants for outgoing gas mixture.
Table 11: Heat Capacity equation constants for incoming gas mixture.
Table12: Heat Capacity equation constants for outgoing gas mixture.
Table 13: Calculations of First Catalytic Bed.
Table 14: Rate Calculations of First Catalytic Bed.
Table 15: Calculations of Second Catalytic Bed.
Table 16: Rate Calculations of Second Catalytic Bed.
Table 17: Calculations of Third Catalytic Bed.
Table 18: Rate Calculations of Third Catalytic Bed.
Table 19: Calculations of Fourth Catalytic Bed.
Table 20: Rate Calculations of Fourth Catalytic Bed.
Table 21: Table for mole fractions expressed in terms of conversion.
Table 22: Mole percent of gases entering the converter.

2. LIST OF FIGURES
Figure 1: Structure of H2SO4 molecule.
Figure 2: Pie Chart showing Global Consumption of Sulphuric Acid.
Figure 3: Sulfuric acid- structure of the world production capacity by region, 2012.
Figure 4: Double Absorption Contact Process.
Figure 5: Four Stage Catalytic Reactor for Contact Process.
Figure 6: Activity of cesium based catalyst in comparison with conventional catalyst.
Figure 7: Combustion Chamber Balance
Figure 8: Material balance over first three catalytic beds.
Figure 9: Primary absorption tower material balance.
Figure 10: Fourth catalytic bed material balance.
Figure 11: Final absorption tower material balance
Figure 12: Enthalpy balance over first catalytic bed.
Figure 14: Enthalpy balance over third catalytic bed.
Figure 15: Enthalpy balance over fourth catalytic bed
Figure 16: Plot of 1/-RA versus XA for first bed
Figure 17: Plot of 1/-RA versus XA for second bed
Figure 18: Plot of 1/-RA versus XA for third bed
Figure 19: Plot of 1/-RA versus XA for fourth bed

3. NOTATIONS
HR

Sum of enthalpies of all materials entering the reaction process


relative to the reference state for the standard heat of reaction at
298 K and 101.32 kPa.

H298

Standard heat of reaction at 298 K and 101.32 kPa.

Net energy or heat added to the system.

HP

Sum of enthalpies of all leaving materials referred to the standard


reference state at

298 K

HRT

Standard heat of reaction at temperature T (K)

[ (ni Hf) ]products

Standard heat of formation of products.

[ (ni Hf )]reactants

Standard heat of formation of reactants.

Temperature expressed in K

k1

Rate of forward reaction expressed in gmol/s-(gm cat)-atm3/2

k2

Rate of backward reaction expressed in gmol/s-(gm cat)-atm

NA

Number of moles at conversion XA.

NA0

Initial number of moles.

Superficial mass velocity.

Fluid density

Superficial velocity in axial direction.

Reaction rate expressed in pseudo homogeneous form (i.e. number


of moles transformed per unit time per unit of total reactor volume)

Enthalpy change for the reaction at the indicated conditions.

Bulk density of the catalyst (total mass of catalyst / total volume of


8

reactor)

Global reaction rate per unit mass of catalyst.

PA

Partial pressure of A

Po

Total pressure.

yA

Mole fraction of A

Stoichiometric coefficient for reactant A (negative for reactants)

4. INTRODUCTION
Sulfuric acid is a highly corrosive strong mineral acid with the molecular formula H2SO4 and
structure shown in the figure below:

Figure 1: Structure of H2SO4 molecule.

It is a pungent-ethereal, colorless to slightly yellow viscous liquid which is soluble


in water at concentrations. Sometimes, it is dyed dark brown during production to alert people to
its hazards. The historical name of this acid is oil of vitriol. Sulphuric acid is an important
chemical, which has large-scale industrial uses.

Its major user is the phosphate fertilizer

industry. Other important applications are in petroleum refining, steel pickling, rayon & staple
fiber, alum, explosives, detergents, plastics and fibers etc. Sulphuric acid industry is very old and
has been continuously adopting the technological developments. The progress made in sulphuric
acid manufacture during recent decades has led to changes in the method and technology of its
manufacture, resulting mainly in the reduction of emissions of sulphur compounds to air and
reduction of harmful waste. [3]
It started with Lead Chamber process followed by contact process with Single
Conversion Single Absorption (SCSA) and now Double Conversion Double Absorption Process
(DCDA). The Sulphuric Acid production through Contact Process is very mature. However,
improvement in conversion and absorption stages are being introduced from time to time to
increase conversion and absorption efficiencies, which also result in reduction in emissions.
Most of the plants use elemental sulphur as raw material and in few cases Copper/ Zinc Smelters
gases are being used to produce Sulphuric Acid. [3]

10

5. LITERATURE REVIEW
Although sulphuric acid is now one of the most widely used chemicals, it was probably little
known before the 16th century. It was prepared by Johann Van Helmont (c.1600) by destructive
distillation of green vitriol (ferrous sulfate) and by burning sulfur. [3]
In the seventeenth century, the German-Dutch chemist Johann Glauber prepared sulfuric acid
by burning sulfur together with saltpeter (potassium nitrate, KNO3), in the presence of steam. As
saltpeter decomposes, it oxidizes the sulfur to SO3, which combines with water to produce
sulfuric acid. In 1736, Joshua Ward, a London pharmacist, used this method to begin the first
large-scale production of sulfuric acid.[3]
In 1746 in Birmingham, John Roebuck adapted this method to produce sulfuric acid in leadlined chambers, which were stronger, less expensive, and could be made larger than the
previously used glass containers. Sulfuric acid created by John Roebuck's process approached a
65% concentration. [3]
After several refinements, this method, developed into the so-called the lead chamber
process or "chamber process. Later refinements to the lead chamber process by French
chemist Joseph Louis Gay-Lussac and British chemist John Glover improved concentration to
78%. However, the manufacture of some dyes and other chemical processes require a more
concentrated product. Throughout the 18th century, this could only be made by dry
distilling minerals in a technique similar to the original alchemical processes. Pyrite (iron
disulfide, FeS2) was heated in air to yield iron(II) sulfate, FeSO4, which was oxidized by further
heating in air to form iron(III) sulfate, Fe2(SO4)3, which, when heated to 480 C, decomposed
to iron(III) oxide and sulfur trioxide, which could be passed through water to yield sulfuric acid
in any concentration. However, the expense of this process prevented the large-scale use of
concentrated sulfuric acid.[3]
In 1831, British vinegar merchant Peregrine Phillips patented the contact process, which
was a far more economical process for producing sulfur trioxide and concentrated sulfuric acid.
It was little used until a need for concentrated acid arose, particularly for the manufacture of
synthetic organic dyes. Today, nearly all of the world's sulfuric acid is produced using this
method. In the current flow process, achievable conversions are as high as 99.7 percent.[3]

11

6. USES AND APPLICATIONS


Sulfuric acid is one of the most important compounds made by the chemical industry. It
is used to make, literally, hundreds of compounds needed by almost every industry.

By far the largest amount of sulfuric acid is used to make phosphoric acid, used, in turn,
to make the phosphate fertilizers. It is also used to make ammonium sulfate, which is a
particularly important fertilizer in sulfur-deficient.

It is widely used in the manufacture of chemicals, e.g., in making hydrochloric acid,


nitric acid, sulfate salts, synthetic detergents, dyes and pigments, explosives, and drugs.

It is used in petroleum refining to wash impurities out of gasoline and other refinery
products, and in waste water treatment.

Also widely used in metal processing for example in the manufacture of copper and
the manufacture of zinc and in cleaning the surface of steel sheet, known as pickling.

It is also used to make caprolactam, which is converted into polyamide 6 and in


the manufacture of titanium dioxide, used, for example, as a pigment.

It is used in the production of numerous goods including various cleaning agents,


domestic acidic drain cleaners and electrolytes in lead-acid batteries.[2]

Global Sulphuric Acid Consumption By End


Use Sector in 2013
Fertilizer Production 56%
Other Applications 23%
Manufacture of Chemicals 11%
Agriultural Chemistry 10%

Figure 2: Pie Chart showing Global Consumption of Sulphuric Acid

12

7. SULPHURIC ACID - WORLD MARKET


The worldwide market for sulphuric acid witnessed stable growth between 2009-2012,
supported by increasing demand from major end-use industries. In 2012, sulphuric acid
production grew by more than 7 million tonnes and exceeded 230.7 million tonnes. Asia
ranks as the leading sulfuric acid manufacturer, accounting for around 45% of the overall
production. China, the US, India, Russia and Morocco are the top five sulfuric acid
manufacturing countries.[6]

Figure 3: Sulfuric acid- structure of the world production capacity by region, 2012

APAC (Uganda) is the major sulphuric acid consumer. In 2012, its consumption volume
surpassed the 106 million mark. The fertilizer industry is the products major end-use sector,
consuming over55% of the overall sulfuric acid output. In 2011, the world foreign trade in
sulphuric acid was valued at more than USD (US dollar) 1.87 billion. Europe is the leading
sulphuric acid exporter, whilst Asia is a market leader in terms of imports. The worldwide
sulphuric acid production is poised to increase in the forthcoming years to go beyond 257.6
million by end-2015. [6]

13

8. STATUS OF EXISTING SULPHURIC ACID PLANTS IN INDIA


In India, there are about 140 Sulphuric Acid Plants (130 Sulphur based & 10 Smelter Gas
based) with Annual Installed Capacity of about 12 Million MT. [6]
Table 1: Capacity wise number of sulphuric acid plants in India

Installed Capacity (MT/Day)

Number of Plants

upto 50

18

12.9

51-100

45

32.1

101-200

40

28.6

201-300

17

12.1

301-500

3.6

501-1000

6.4

1001- 2000

2.9

above 2000

1.4

140

100.0

Total

The current annual production of Sulphuric Acid is about 5.5 Million MT, against the
installed capacity of 12 Million MT/Annum from Sulphur based as well as Smelter Gas based
plants. The demand of Sulphuric Acid is fully met by the current production, as the installed
capacity is more than double the demand.
The environmental problems arising due to Sulphuric Acid manufacture include:

Off gases from absorption tower containing oxides of Sulphur (SOx) and acid mist.

Liquid effluent generated through waste heat boiler blow-down, spillage & leakage from
equipment, washing of equipment, cooling tower bleeding etc.

Generation of Solid Waste viz. Sulphur muck & spent catalyst.

14

Presently, Gaseous emission limits prescribed by CPCB for Sulphuric Acid Plants are as under:
SO2

4.0 Kg/MT of Sulphuric Acid produced (Conc. 100%)

Acid Mist

50 mg/Nm3

However, due to advancement in process and pollution control technologies, it may be


possible to further reduce & control the emissions of SOx and acid mist. In view of this, CPCB
took up a project to revisit the emission standards. [6]

15

9. THE CONTACT PROCESS


Until 1990 there were no plants using the contact process, the more popular process being
used was the chamber process. But, up to mid 1920s there were considerable changes in the
contact process technology, equipments and the catalyst being used. [2]
The primary raw material for producing intermediate product of sulphur dioxide is
elemental sulphur. This can either be made by burning sulphur in an excess of air or by heating
sulphide ores like pyrite in an excess of air. In either case, an excess of air is used so that the
sulphur dioxide produced is already mixed with oxygen for the next stage. [2]
These traditional contact plants can be further subdivided into the double contact double
absorption process (DCDA), which is the type of process now most commonly used in new
plants with intermediate absorption and the older, without intermediate absorption also referred
to as the single contact single absorption process (SCSA). In DCDA Plant, SO3 is removed from
the gas stream after 3rd bed, which shifts the equilibrium and increases the rate of the forward
SO2 to SO3 reaction resulting in higher overall conversion and reduces stack emission of
unconverted SO2.Conversions using single absorption contact process were typically about 97-98
percent. While in the current double absorption flow process, achievable conversions are as high
as 99.7 percent. [2]
6.1 Double Conversion Double Absorption (DCDA) Process
The main steps involved in DCDA process are as below:

Melting solid Sulphur with steam coils, followed by filtration or settling of impurities to
obtain clean sulphur containing less than 10 mg/l of ash.

Burning the molten Sulphur with air to produce gas-containing SO2.

Cooling the hot gas in Waste Heat Boiler System to produce superheated or saturated steam
at conditions fixed, as per requirements.

Catalytic oxidation of SO2 to SO3 in three consecutive passes of converter containing V2O5
catalyst with intercooling of gas in between. The exothermic heat of reaction is utilized to
produce steam in Waste Heat Boiler system and to reheat the gases going to pass IV from the
intermediate absorber.[6]

16

The process flow sheet is shown below:

Figure 4: Double Absorption Contact Process

6.2 Chemical Reactions


In the manufacture of sulphuric acid from sulphur, the first step is the burning of sulphur in a
furnace to form sulfur dioxide: [1]
SO2 (g)

S (l) + O2 (g)

H= -298.3 kJ

Following this step, the sulphur dioxide is converted to sulphur trioxide, using a catalyst,
SO2 (g) + O2 (g)

V 2O 5

SO3 (g)

H= -98.3 kJ

The final step is reacting sulphur trioxide with water to form sulphuric acid.
SO3 (g) + H2O (l)

H2SO4 (l)

H= -130.4 kJ

6.3 Catalyst
A commercial sulphur dioxide- converting catalyst consists of 4-9 wt % vanadium pentaoxide,
V2O5, as the active component, together with alkali metal sulphate promoters. At operating
temperatures the active ingredient is a molten salt held in a porous silica pellet. Normally
17

potassium sulphate is used as a promoter but in recent years also caesium sulphate 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. The lower temperature limit is 410430 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. These catalysts are long lived up to twenty years and are not
subject to poisoning except fluorine. [2]
6.4 Contact Process Equipments
The main equipments being used in the process are
1) Combustion Chamber
2) Converters
3) Absorbers
4) Heat Exchangers
6.4.1 Converters - heart of the contact sulphuric acid plant
The reactor is often the central unit around which a chemical plant is designed. Good
reactor design is thus important for the performance of the plant. The chemical conversion of
sulphur dioxide to sulphur trioxide is designed to maximize the conversion by taking into
consideration that:
1) Equilibrium is an inverse function of temperature and a direct function of oxygen to sulphur
dioxide ratio.
2) Rate of reaction is a direct function of temperature.
3) Gas composition and amount of catalyst affect the rate of conversion and kinetics of the
reaction.
4) Removal of sulphur trioxide formed allows more sulphur dioxide to be converted.
The commercialization of these basic conditions makes possible high overall conversion
by using a multi pass converter wherein, at an entering temperature of 410C to 440C (the
ignition temperature), the major part of conversion takes place (60 to 75 %) in the first catalytic
bed with an exit temperature of 600C or more, depending largely on the concentration of

18

sulphur dioxide in the gas. The successive lowering of temperatures between stages ensures an
overall high conversion. [2]
The converter is usually provided with trays for supporting the catalyst and manholes for
access to it. Converters have usually been made of cast iron and aluminum-coated steel, but
stainless steel is now the preferred material of construction. Pressure drop through the converter
must be minimized to reduce power consumption. All these must be optimized to secure the
maximum yield and profit. [2]
6.5 Additional Data & Specification
Total Pressure = 1 atm
Feed composition (Mole Percent)
SO2

10

O2

11

N2

79

Overall Conversion = 99.8 %. [1]


The four stage catalytic reactor is shown below:

Figure 5: Four Stage Catalytic Reactor for Contact Process

19

10. AVAILABLE TECHNOLOGIES FOR POLLUTION CONTROL


In upcoming plants, following features are considered important:

Selection of 5-stage converter for maximum conversion efficiency.

Use of sulphur filter for minimizing ash content.

Use of Cesium based catalyst in last bed of Converter for maximum conversion efficiency.

Selection of high efficiency mist eliminators ensuring minimum acid mist exhaust.

Use of Waste heat recovery from acid system.

Use of suitable start-up scrubbing system.[6]

10.1Modified Converter
Existing plants are generally based on 4 stage Converter except for very few plants based on
5 stage Converter that has come up recently. 5-stage converter helps in increasing the conversion
efficiency. This minimizes the stack emissions level of SO2. With conventional catalyst the
conversion efficiency can be increased from 99.7% to 99.8%.
(1 kg SO2 instead of 2 Kg SO2 per MT of acid). [6]
10.2 Cesium Based Catalyst
The addition of Cesium Catalyst (CS) to the conventional Alkali-Vanadium Catalyst has
long been known to enhance the low temperature properties of the catalyst. Cesium based
Catalyst offers high activity at low operating temperature. Emissions from existing plants can
roughly be cut in half without increasing catalyst volume. The acid production capacity can be
increased by using higher strength sulphur dioxide gas without increasing SO2 emissions and
plant pressure drop. New acid plants may be designed with low SO2 emission by selecting
different type of Catalysts for different stages. [6]

20

Figure 6: Activity of cesium based catalyst in comparison with conventional catalyst.

10.3Mist Eliminators
Mist is inevitably formed at various points in Sulphuric Acid Plants. If mist is unchecked,
and carried through rest of the plant in the gas stream, it causes corrosion inside the plant and
environmental menace outside it. Mist is distinct from acid spray, which is formed in the towers
by purely physical process of aspiration into the gas stream of liquid droplets. Now a days, Mist
eliminators that are designed to remove virtually any type of mist from any gas stream are
available. Mist eliminators excel at collecting, the very difficult to remove sub micron size mist
particles from gas stream. [6]
10.4

Waste Heat and Heat Recovery System

The waste heat system is completely integrated in DCDA plants. In economizers that cool
the gases from third & fourth bed of converter, heat is utilized for preheating feed water for
WHB System. Heat generated in Sulphur furnace, heats up this feed water and steam is
generated at about 2500C temperatures. This steam is superheated to about 4000 C for cooling the
1st stage out converter gases. This superheated steam can be used for generating power and
saturated steam for process heating. The Heat Recovery System is basically an absorber that
operates at about 2000 C and uses a boiler to remove the absorption heat as low pressure steam
(at upto 10 bar), instead of acid coolers (where heat is wasted). [6]

21

10.5 Scrubbing System


In DCDA Sulphuric Acid plants, emission levels of SO2 are higher during start-up or shut down
when SO2 to SO3 conversion is not proper. Also in SCSA Plant, the emission levels of SO2 are
normally high. While in first case, the start-up scrubbers are required to take care of extra SO2
load during unstabilized conditions, start-up & shutdown, in second case, a continuous scrubbing
unit is required to take care of tail gases going out for the stack.[7]

22

11. MATERIAL BALANCE


11.1 Assumptions
1. Complete burning of S in the burner.
2. 99.8% conversion of SO2 toSO3 in the reactor.
3. Overall absorption of SO3 in the process is 100%
4. 40% excess oxygen is provided.
5. Humidity of entering air is 65% at 300C
11.2 Calculations
Capacity: 1000 TPD H2SO4 plant
Basis: 1 hr of operation
Purity: 98 % pure acid
Reactions:
S (l) + O2 (g)

SO2 (g)
V2O 5

SO2 (g) + O2 (g)

SO3 (g)

SO3 (g) + H2O (l)

H2SO4 (l)

1000 TPD H2SO4 = (1000 x 103)/ 24 = 41,666.67 kg/hr


98% pure acid produced = 41,666.67 x 0.98 = 40,833 kg/hr
No. of moles of acid produced = 40,833.33 / 98 = 416.67 kmol/hr
(Molecular weight of H2SO4=98)
Overall absorption of acid = 100 %
SO3 (g) + H2O (l)

H2SO4 (l)

Therefore, by stoichiometry,
SO3 required =416.67 kmol/hr
Overall conversion of SO2 to SO3 = 99.8 %

23

V2O 5

SO2 (g) + O2 (g)

SO3 (g)

Let SO2formed be X kmol/hr


0.998 X=416.67
SO2 required =X= 416.67/0.998 = 417.501 kmol/hr
O2 required = 417.501 x 0.5 =208.75 kmol/hr
11.1.1 Combustion Chamber Balance

Figure 7: Combustion Chamber Balance

S (l) + O2 (g)

SO2 (g) (Assuming 100 % combustion)

S required = 417.501 kmol/hr =13,360.053 kg/hr


O2 required = 417.501 x 1 = 417.501 kmol/hr
Total O2 required = 417.501 + 208.75 = 626.25 kmol/hr
O2 is taken in 40% excess
O2 in the combustion chamber = 626.25 x 1.4 = 876.75 kmol/hr
(Dry air contains 21% O2)
Dry air in = 876.765/0.21 = 4175.07 kmol/hr
(Molecular weight of air=29)
Dry air in = 4175.07 x 29 = 121076.381 kg/hr
24

Table 2: Combustion Chamber Material Balance

Component

Inlet (kmol)

Inlet ( kg)

Outlet (kmol)

Outlet (kg)

417.501

13,360.032

O2

876.75

28,056.00

459.249

14,695.968

N2

3298.306

92,352.568

3298.306

92,352.568

SO2

417.501

26,720.064

Total

4592.557

133,768.6

4175.056

133,768.6

11.2.2 Overall Balance over First Three Catalytic Beds

Figure 8: Material balance over first three catalytic beds

SO2 (g) + O2 (g)

SO3 (g) (Conversion =96.7 %)

SO2 in = 417.501 kmol


O2 in = 459.249 kmol
SO2 reacted = 417.501*0.967=403.723 kmol/hr
O2reacted = 0.5*403.723 = 201.86 kmol/hr
SO3formed = 403.723 kmol/hr
SO2out = SO2 in SO2reacted

25

=417.501 403.723 =13.778 kmol/hr


O2out = O2 in O2reacted
= 459.249 201.86

=257.389 kmol/hr
Table 3: Material Balance on First Three Catalytic Beds

Component

Inlet (kmol)

Mole %

Inlet (kg)

Outlet (kmol)

Outlet (kg)

SO2

417.501

10

26,720.064

13.778

881.792

O2

459.249

11

14,695.968

257.389

8236.448

N2

3298.306

79

92,352.568

3298.306

92,353.568

SO3

403.723

32297.84

Total

4,175.056

100

133,768.6

3973.196

133769.648

After the third stage, 40 % of product goes to economizer and then to the Interpass Absorber.
11.2.3 Primary Absorber

Figure 9: Primary absorption tower material balance

26

(Assuming 100 % absorption)


SO2 in = 0.4*13.778 = 5.5112 kmol/hr
SO3 in = 0.4*403.723 = 161.489 kmol/hr
O2 in = 0.4 * 257.389 = 102.955 kmol/hr
N2 in = 0.4 * 3298.306 = 1319.3224 kmol/hr
SO3 (g) + H2O (l)

H2SO4 (l)

H2SO4 formed = 161.489 kmol/hr


(Sulphur dioxide, Oxygen and Nitrogen are recycled from inter pass absorber to the 4th stage of
reactor).
11.2.4 Fourth Catalytic Bed

Figure 10: Fourth catalytic bed material balance

Conversion = 3.1 % (Overall = 99.8 %)


Gases in to the fourth stage of reactor constitute 60 % of product from third stage and gases
recycled from Interpass absorber.
SO2 in = Total SO2out from the 3rd bed = 13.778 kmol/hr
O2 in = Total O2out from the 3rd bed = 257.389 kmol/hr
N2 in = 3298.306 kmol/hr
27

SO3 in = 60% of SO3out from the 3rd bed


= 0.6 * 403.723 = 242.23 kmol/hr
SO2 (g) + O2 (g)

SO3 (g) (Overall Conversion =99.8 %)

SO2 reacted upto 4th bed = 99.8 % of SO2 entering the 1st bed
= 0.998 * 417.501 = 416.67 kmol/hr
SO2 out = Initial SO2 Total SO2 reacted
= 417.501 416.67 = 0.831 kmol/hr
Therefore SO2 reacted in the 4th bed
= SO2 in SO2 out =13.778 0.831 = 12.947 kmol/hr
O2 reacted = 12.947 * 0.5= 6.473 kmol/hr
SO3 formed = 12.947 kmol/hr
O2 out = O2 in O2 reacted
=257.389 6.473 = 250.916 kmol/hr
Total SO3 outlet = SO3 inlet from the 3rd bed+ SO3 formed in the 4th bed
= 242.23 + 12.947 = 255.177 kmol/hr
Table 4: Material Balance on Fourth Catalytic Bed

Component

Inlet (kmol)

Inlet (kg)

Outlet (kmol)

Outlet (kg)

SO2

13.778

881.792

0.831

53.184

O2

257.389

8,236.448

250.916

8,029.312

N2

3298.306

92,353.568

3298.306

92,353.568

SO3

242.23

19378.4

255.177

20,414.16

Total

3,809.703

120,850.208

3,805.23

120,850.224

28

11.2.5 Final Absorption Tower

Figure 11: Final absorption tower material balance

SO3 in = 255.173 kmol/hr


SO2 in = 0.831 kmol/hr
O2 in = 250.916 kmol/hr
N2 in = 3298.306 kmol/hr
H2SO4 formed = 255.173kmol/hr
Total H2SO4 formed = 255.173 + 161.489=416.662kmol/hr

29

12. ENERGY BALANCE


12.1Theory
12.1.1 Law of Conservation of Energy
Energy can neither be created nor be destroyed; it can only be changed from one form to
another. In simpler words, all energy entering a process is equal to that leaving plus that left in
the process. Energy can appear in many forms. Some of the forms are enthalpy, electrical energy,
chemical energy (in terms of H reaction), kinetic energy, potential energy, work, and heat
inflow.
In many cases in process engineering , which often takes place at constant pressure ,
electrical energy , kinetic energy, potential energy, and work either are not present or can be
neglected. Then only the enthalpy of the materials (at constant pressure), the standard chemical
reaction energy (H) at 25 C, and the heat added or removed must be taken into account in the
energy balance .This is called heat balance. [5]
12.1.2 Heat Balance
The energy or heat coming into a process in the inlet materials plus any net energy added to
the process is equal to the energy leaving in the materials.
Expressed mathematically,
HR + ( H298 ) + q = HP

(1)

where, HR is the sum of enthalpies of all materials entering the reaction process relative to the
reference state for the standard heat of reaction at 298 K and 101.32 kPa.
H298 = standard heat of reaction at 298 K and 101.32 kPa.
The reaction contributes heat to the process, so the negative of H298 is taken to be positive
input heat for an exothermic reaction. [5]
q = net energy or heat added to the system.
HP =sum of enthalpies of all leaving materials referred to the standard reference state at 298 K.

30

12.2 Equations for calculating net enthalpy change at catalyst bed[2]


The temperature dependency of the heat capacity is given by the equation
CP = a+bT+cT2 +
HRT = T 298 (ni Cpi) Reactants dT + H298 + 298 T (ni Cpi) Products dT

(2)
(3)

where, HRT is the standard heat of reaction at temperature T (K)


HRT = H298 + 298T ( (ni Cpi) Products (ni Cpi) Reactants)dT

(4)

Enthalpy change, with 298 K as the reference temperature, can be calculated from the formula,
H = HRT H298 = ( ai ni )(T298) + (( bi ni)/2)(T2 2982) +

(5)

Similarly, Enthalpy change between T1 K and T2 K, can be calculated from the formula
H = ( ai ni )(T1T2) + (( bi ni)/2)(T12 T22) +

(6)

Standard heat of reaction at 298 K (H298 ) from heat of formation is given by


H298 = [ (ni Hf) ]Products [ (ni Hf )]Reactants

(7)

where [ (ni Hf) ]products = standard heat of formation of products and


[ (ni Hf )]reactants = standard heat of formation of reactants
Net heat to be removed from the catalytic bed ,
q = HP HR + H298
12.3 Data given
12.3.1 Inlet and Effluent Temperatures
First stage: Inlet temperature = 410C
Effluent temperature = 602C
Second stage: Inlet temperature = 438C
Effluent temperature = 498C
Third stage: Inlet temperature = 432C
Effluent temperature = 444 C
31

(8)

Fourth stage: Inlet temperature = 427C


Effluent temperature = 435C

12.3.2 Heat Capacities[1]


N2= 29.5909 5.14 x 10-3T

(9)

O 2=26.0257 + 11.755 x 10-3T

(10)

SO 2 = 24.7706 + 62.9481 x 10-3 T

(11)

SO 3 = 22.0376 + 121.624 x 10-3 T

(12)

where , Heat capacity is expressed in kJ/kmol-K and T is temperature in K.


12.4 Calculations
a = 22.036 24.771 0.5(26.026) = 15.748
b*103 = 121.624 62.948 0.5(11.755) = 52.799
c*106 = 91.867 ( 44.258) 0.5(2.343) = 46.438
d*109 = 24.369 11.122 0.5( 0.562) = 13.258
From equation (7)
H298 = 395720 ( 296810) = 98910 kJ/kmol SO2
Substituting T=298 K in equation (6)
98910 = Ho + ( 15.748*298) + (((52.799 * 103 ) /2)*2982) + (((46.438 * 106 )/3)*2983)
+ (((13.258 * 109 )/4)*2984)
Ho = 96178kJ/kmol SO2 reacted
Substituting the value of Ho in equation (6), we get
HRT = 96178 15.748 T+ (26.4*10-3) T2 (15.48*10-6)T3+ (3.382*10-9)T4

32

(13)

12.4.1 Calculation of Heat Duty Required In Each Bed


First Catalytic Bed
Table 5: Heat Capacity equation constants for incoming gas mixture

Component

ni (kmol/hr.)

ai

aini

bi

bini*103

SO2

417.501

24.7706

10341.75

62.9481

26280.89

O2

459.249

26.0257

11952.2767

11.7551

5398.518

N2

3298.306

29.5909

97599.843

-5.141

-16956.59

SO3

22.0376

121.624

Total

4175.056

119893.8697

14722.818

Enthalpy of incoming gas mixture at 683K over 298K can be calculated by substituting T=683 in
equation (5),
HR = 119893.8697(683298) + ((14722.818*10-3)/2) (68322982) =48939432.44 kJ/hr
HR = (48939432.44 /3600) = 13594.286 kW
Table 6: Heat Capacity equation constants for outgoing gas mixture

Component

ni (kmol/hr.)

ai

aini

bi

bini*103

SO2

108.55

24.7706

2688.848

62.9481

6833.016

O2

304.77

26.0257

7931.852

11.7551

3582.6018

N2

3298.306

29.5909

97599.843

-5.141

-16956.59

SO3

308.95

22.0376

6808.516

121.624

37575.7348

Total

4020.576

115029.0566

31034.76286

Enthalpy of outgoing gas mixture at 875K over 298K can be calculated by substituting T=875 in
equation (5),
Hp = 115029.0566(875298) + ((31034.763*10-3)/2)(87522982) =76874549.2 kJ/hr
Hp = (76874549.2 /3600) = 21354.04144 kW
33

Total heat of reaction at 298 K,


H298 = 98910 kJ/kmol SO2 reacted = (417.501 108.55) (98910/3600) = 8488.428 kW
Net enthalpy change, q = HP HR + H298
q = 21354.04144 13594.286 8488.428 = 728.67 kW
Thus, during the reaction, enthalpy equivalent to -728.67 kW is to be removed from the first
catalytic bed in order to maintain the temperature of the outgoing gas mixture at 875K.

Figure 12: Enthalpy balance over first catalytic bed

Second Catalytic Bed


Table 7: Heat Capacity equation constants for incoming gas mixture

Component

ni (kmol/hr.)

ai

aini

bi

bini*103

SO2

108.55

24.7706

2688.848

62.9481

6833.016

O2

304.77

26.0257

7931.852

11.7551

3582.6018

N2

3298.306

29.5909

97599.843

-5.141

-16956.59

SO3

308.95

22.0376

6808.516

121.624

37575.7348

Total

4020.576

115029.0566

31034.76286

34

Enthalpy of incoming gas mixture at 711K over 298K can be calculated by substituting T=711 in
equation (5),
HR = 115029.056(711298) + ((31034.763*10-3)/2) (71122982) =53973356.79 kJ/hr
HR = (53973356.79 /3600) = 14992.599 kW
Table 8: Heat Capacity equation constants for outgoing gas mixture

Component

ni (kmol/hr.)

ai

aini

bini*103

bi

SO2

31.73

24.7706

785.97

62.9481

1997.343

O2

266.36

26.0257

6932.2054

11.7551

3131.088

N2

3298.306

29.5909

97599.843

-5.141

-16956.59

SO3

385.77

22.0376

8501.144

121.624

46918.89

Total

3982.166

113819.46

35090.7314

Enthalpy of outgoing gas mixture at 778K over 298K can be calculated by substituting T=778 in
equation (5),
Hp = 1153819.46(778298) + ((35090.7314*10-3)/2)(77822982) =60879790.44 kJ/hr
Hp = (60879790.44 /3600) = 16911.053 kW
Total heat of reaction at 298 K,
H298 = 98910 kJ/kmol SO2 reacted
= (108.5531.73) (98910/3600) = 2110.6295 kW
Net enthalpy change, q = HP HR + H298
q = 16911.053 14992.599 2110.6295 = 192.1755 kW
Thus, during the reaction, enthalpy equivalent to 192.1755 kW is to be removed from the
second catalytic bed in order to maintain the temperature of the outgoing gas mixture at 778 K.

35

Figure 13: Enthalpy balance over second catalytic bed

Third Catalytic Bed


Table 9: Heat Capacity equation constants for incoming gas mixture

Component

ni (kmol/hr.)

ai

aini

bi

bini*103

SO2

31.73

24.7706

785.97

62.9481

1997.343

O2

266.36

26.0257

6932.2054

11.7551

3131.088

N2

3298.306

29.5909

97599.843

-5.141

-16956.59

SO3

385.77

22.0376

8501.144

121.624

46918.89

Total

3982.166

113819.46

35090.7314

Enthalpy of incoming gas mixture at 705K over 298K can be calculated by substituting T=705 in
equation (5),
HR = 113819.46(705298) + ((35090.7314*10-3)/2) (70522982) =53486906.95 kJ/hr
HR = (53486906.95 /3600) = 14857.474 kW

36

Table 10: Heat Capacity equation constants for outgoing gas mixture

Component

ni (kmol/hr.)

ai

aini

bi

bini*103

SO2

13.77

24.7706

341.091

62.9481

866.79

O2

257.38

26.0257

6698.494

11.7551

3025.5276

N2

3298.306

29.5909

97599.843

-5.141

-16956.59

SO3

403.77

22.0376

8898.1217

121.624

49103.257

Total

39732.226

113536.669

36038.989

Enthalpy of outgoing gas mixture at 717K over 298K can be calculated by substituting T=717 in
equation (5),
Hp = 113536.669(717298) + ((36038.989*10-3)/2) (71722982) =55235285.03 kJ/hr
Hp = (55235285.03 /3600) = 15343.1347 kW
Total heat of reaction at 298 K,
H298 = 98910 kJ/kmol SO2 reacted
= (31.7313.77) (98910/3600) = 493.451 kW
Net enthalpy change, q = HP HR + H298
q = 15343.1347 14857.474 493.451= 7.7903 kW
Thus, during the reaction, enthalpy equivalent to 7.7903 kW is to be removed from the third
catalytic bed in order to maintain the temperature of the outgoing gas mixture at 717 K.

37

Figure 14: Enthalpy balance over third catalytic bed

Fourth Catalytic Bed


Table 11: Heat Capacity equation constants for incoming gas mixture

Component

ni (kmol/hr.)

ai

aini

bi

bini*103

SO2

13.77

24.7706

341.091

62.9481

866.79

O2

257.38

26.0257

6698.494

11.7551

3025.5276

N2

3298.306

29.5909

97599.843

-5.141

-16956.59

SO3

242.238

22.0376

5338.344

121.624

29461.9545

Total

39732.226

109977.772

16397.686

Enthalpy of incoming gas mixture at 700K over 298K can be calculated by substituting T=700 in
equation (5),
HR = 109977.772(700298) + ((16397.686*10-3)/2) (70022982) =47500407.36 kJ/hr
HR = (47500407.36 /3600) = 13194.5576 kW

38

Table12: Heat Capacity equation constants for outgoing gas mixture.

Component

ni (kmol/hr.)

ai

aini

bini*103

bi

SO2

0.835

24.7706

20.6834

62.9481

52.5616

O2

250.9125

26.0257

6530.1734

11.7551

2949.5015

N2

3298.306

29.5909

97599.843

-5.141

-16956.59

SO3

255.173

22.0376

5623.4

121.624

31035.1609

Total

3805.2265

109774.0998

17080.634

Enthalpy of outgoing gas mixture at 708K over 298K can be calculated by substituting T=708 in
equation (5),
Hp = 109775.0998(708298) + ((17080.634*10-3)/2)(70822982) =48773723 kJ/hr
Hp = (48773723/3600) = 13548.256 kW
Total heat of reaction at 298 K,
H298 = 98910 kJ/kmol SO2 reacted
= (13.770.835) (98910/3600) = 355.389 kW
Net enthalpy change, q = HP HR + H298
q = 13480.533 13194.5576 355.389= 1.69 kW
Thus, during the reaction, enthalpy equivalent to 1.69 kW is to be removed from the fourth
catalytic bed in order to maintain the temperature of the outgoing gas mixture at 708 K.

39

Figure 15: Enthalpy balance over fourth catalytic bed

12.4.2 Calculation of Heat Load for Heat Exchangers


Heat load required between first and second catalytic bed:
At the outlet of first catalytic bed:
aini = 115029.0566
bini = 31034.76286* 10-3
First stage outlet temperature = 602C = 875K
Second stage inlet temperature = 438C =711K
Temperature change = 875 K to 711 K
Heat load is calculated by substituting T1=875K and T2=711K in equation (6),
H1 = 115029.056(711875) + ((31034.763*10-3)/2) (71128752) = 22900898.26 kJ/hr
H1 = (22900898.26 /3600) = 6361.36 kW
Heat load required between second and third catalytic bed:
At the outlet of second catalytic bed:
aini = 113819.46
bini = 35090.7314* 10-3
40

Second stage outlet temperature = 498C = 771K


Third stage inlet temperature = 432C =705K
Temperature change = 771 K to 705 K
Heat load is calculated by substituting T1=711K and T2=705K in equation (6),
H2 = 113819.46(705711) + ((35090.7314*10-3)/2) (70527112) = 831982.187 kJ/hr
H2 = (831982.187/3600) = 231.106 kW
Heat load required between third and fourth catalytic bed:
At the outlet of third catalytic bed:
aini = 109977.772
bini = 16397.686* 10-3
Third stage outlet temperature = 444 C = 717 K
Fourth stage inlet temperature = 427C =700 K
Temperature change = 717 K to 700 K
Heat load is calculated by substituting T1=700K and T2=717K in equation (6),
H3 = 109977.772(700717) + ((16397.686*10-3)/2) (70027172) = 1996876.366 kJ/hr
H3 = (1996876.366 /3600) = 544.68 kW

41

13. WEIGHT OF CATALYST


13.1 Theory and Data[1]
The kinetic data are represented by a rate expression of the form
=

1 2 2 2 3 0.5
2
0.5

(14)

that may be regarded as a degenerate form of typical Hougen-Watson kinetics. The rate constants
are given by
ln 1 = 12.07 31000

(15)

ln 2 = 22.75 53600

(16)

where
T is temperature expressed in K
R is expressed in cal/gmolK
k1 is expressed in gmol/s-(gm cat)-atm3/2
k2 is expressed in gmol/s-(gm cat)-atm
Derived equation for relationship between temperature and conversion:
=

+ 307.158( )
1 + 0.0248( )

(17)

Where, T is reference temperature and XA is conversion at this temperature.


T0 is initial temperature and XA0 is conversion at initial conditions.
Relationship between number of moles and conversion:[4]
=

(1 )
(1 + )

where
NA is number of moles at conversion XA.
NA0 is initial number of moles.

42

(18)

T0/T is temperature correction factor.


Relationship between partial pressure and mole fraction:
PA = yA Po

(19)

PA is partial pressure of A and Po is total pressure.


yA is mole fraction of A.
The partial pressures of the various species are numerically equal to their mole fractions since
the total pressure is one atmosphere.
Equation of Plug flow reactor for calculating weight of catalyst:[4]

where,
W is weight of catalyst required.
FA0 is molar flow rate of Sulphur dioxide entering in feed.
13.2 Calculations
13.2.1 First Catalytic Bed
Sample Calculation:
For T = 773 K, T0 = 683 K, XSO2 = 0
773 =

683 + 307.158 2
1 + 0.0248 2

2 = 0.3125
2 = 417.501

(1 0.3125)
683
(1 0.05 0.3125) 773

2 = 257.633
2 = 417.501 257.633 = 159.868
3 = 159.868
43

(20)

2 = 459.249 (159.8682) = 379.315


= 257.633 + 159.868 + 379.315 + 3298.306 = 4095.122
2 = 2 =
2 = 2 =

159.868
= 0.062
4095.122

379.315
= 0.0926
4095.122

3 = 3 =

159.868
= 0.0390
4095.122

Table 13: Calculations of First Catalytic Bed

T(K)

XSO2

NSO2

NO2

683

417.501

459.249

688

0.0172

407.674

725

0.1452

748

NSO3

NN2

TOTAL

PSO2(atm)

PO2(atm)

PSO3(atm)

3298.306

4175.056

0.099

0.1099

454.335

9.826

3298.306

4170.143

0.097

0.108

0.0023

338.649

419.823

78.851

3298.306

4135.63

0.081

0.1015

0.0190

0.2252

298.726

399.861

118.77

3298.306

4115.669

0.072

0.0971

0.0288

773

0.3125

257.633

379.315

159.86

3298.306

4095.122

0.062

0.0926

0.0390

793

0.382

226.33

363.664

191.16

3298.306

4079.472

0.055

0.0891

0.0468

798

0.400

218.711

359.854

198.78

3298.306

4075.661

0.053

0.0882

0.0487

823

0.488

181.753

341.375

235.74

3298.306

4057.182

0.044

0.0841

0.0581

848

0.576

146.579

323.788

270.92

3298.306

4039.595

0.036

0.0801

0.0670

856.4

0.606

135.132

318.064

282.36

3298.306

4033.871

0.033

0.0788

0.07

873

0.665

113.026

307.011

304.47

3298.306

4022.819

0.028

0.0763

0.0756

875

0.6726

110.408

305.702

307.09

3298.306

4021.51

0.027

0.0760

0.0763

44

Sample Calculation:
1 = (12.07

31000
) = 3 104
(1.987 773)

2 = (22.75

536000
) = 5.3 106
(1.987 773)

((3 104 ) 0.062 0.0926) ((5.3 106 ) 0.0390 0.09260.5 )


=
0.0620.5
= 6.71 106
1 = 149047.3
Table 14: Rate Calculations of First Catalytic Bed

k1

k2

(-rA) (kmol/s-kg catalyst)

1/(-rA)

2.09E-05

5.34E-08

7.27E-07

1375530

2.47E-05

7.12E-08

8.41E-07

1188741

7.87E-05

5.26E-07

2.27E-06

439566

1.53E-04

1.65E-06

3.94E-06

253862.4

3.00E-04

5.30E-06

6.71E-06

149047.3

4.98E-04

1.28E-05

9.7E-06

103124.2

5.64E-04

1.58E-05

1.05E-05

94832.17

1.02E-03

4.42E-05

1.47E-05

68182

1.79E-03

1.16E-04

1.57E-05

63794.88

2.14E-03

1.59E-04

1.38E-05

72398.6

3.02E-03

2.88E-04

2.76E-05

362480.6

3.15E-03

3.10E-04

2.98E-05

378674.7

45

Figure 16: Plot of 1/-RA V/S XA for first bed

FA0 = 417.501 kmol/hr = 417.501/3600 kmol/s = 0.1159725kmol/s


W = FA0 * Area under the curve= 0.1159725*250920
Weight of catalyst in first catalyst bed =29103.3 kg
13.2.2 Second Catalytic Bed
Sample Calculation:
For T = 715 K, T0 = 711 K, 2 = 0.672
715 =

711 + 307.158 (2 0.672)


1 + 0.0248 (2 0.672)

2 = 0.686
2 = 417.501

(1 0.686)
683
(1 0.05 0.686) 715

2 = 129.523
2 = 417.501 129.523 = 287.978
3 = 287.978
2 = 459.249 (287.978 2) = 315.26
46

= 129.523 + 287.978 + 315.26 + 3298.306 = 4031.067


2 = 2 =
2 = 2 =

129.523
= 0.03213
4031.067

315.26
= 0.0782
4031.067

3 = 3 =

287.978
= 0.0714
4031.067
Table 15: Calculations of Second Catalytic Bed

T(K)

XSO2

NSO2

NO2

NSO3

NN2

TOTAL

PSO2(atm.)

PO2(atm)

PSO3(atm)

711

0.672

110.408

305.702

307.09

3298.306

4021.51

0.027454

0.076017

0.076363

715

0.686

129.523

315.260

287.97

3298.306 4031.067

0.032131

0.078208

0.07144

718

0.696

124.784

312.890

292.71

3298.306 4028.697

0.030974

0.077665

0.072658

723

0.714

116.957

308.977

300.54

3298.306 4024.784

0.029059

0.076769

0.074673

728

0.731

109.22

305.108

308.28

3298.306 4020.915

0.027163

0.07588

0.076669

733

0.748

101.57

301.283

315.93

3298.306

4017.09

0.025284

0.075

0.078647

738

0.766

94.005

297.501

323.49

3298.306 4013.308

0.023423

0.074129

0.080606

743

0.783

86.523

293.760

330.97

3298.306 4009.567

0.021579

0.073265

0.082547

748

0.800

79.124

290.060

338.37

3298.306 4005.868

0.019752

0.072409

0.08447

753

0.818

71.805

286.401

345.69

3298.306 4002.208

0.017941

0.071561

0.086376

758.3 0.836

64.132

282.564

353.36

3298.306 3998.372

0.01604

0.07067

0.088378

763

0.85

57.4009

279.19

360.10

3298.306 3995.006

0.014368

0.069887

0.090138

768

0.87

50.312

275.654

367.18

3298.306 3991.462

0.012605

0.069061

0.091994

771

0.88

46.094

273.545

371.40

3298.306 3989.353

0.011554

0.068569

0.093099

778

0.90

36.355

268.676

381.14

3298.306 3984.483

0.009124

0.067431

0.095658

47

Table 16: Rate Calculations of Second Catalytic Bed

k1

k2

(-rA) (kmol/s-kg catalyst)

1/(-rA)

5.16E-05

2.53E-07

6.11585E-07

1635095

5.83E-05

3.13E-07

7.8216E-07

1278512

6.38E-05

3.66E-07

8.36552E-07

1195383

7.42E-05

4.75E-07

9.34367E-07

1070243

8.61E-05

6.14E-07

1.0383E-06

963113

9.96E-05

7.89E-07

1.14852E-06

870687.1

1.15E-04

1.01E-06

1.26386E-06

791225.4

1.33E-04

1.30E-06

1.38501E-06

722018.9

1.53E-04

1.65E-06

1.28608E-06

777554.9

1.75E-04

2.10E-06

1.31821E-06

758606.4

2.03E-04

2.69E-06

1.3143E-06

760864

2.29E-04

3.36E-06

1.25102E-06

799348

2.63E-04

4.42E-06

1.08457E-06

922027.9

2.84E-04

4.85E-06

9.94423E-07

1005608

3.41E-04

6.94E-06

3.92238E-07

2549474

Sample Calculation:
1 = (12.07

31000
) = 5.828 105
(1.987 715)

2 = (22.75

536000
) = 3.1278 107
(1.987 715)

((5.828 105 ) 0.03213 0.0782) ((3.1278 107 ) 0.0714 0.07820.5 )


=
0.032130.5
= 7.8216 107
48

1 = 1278512

Figure 17: Plot of 1/-RA v/s XA for second bed

FA0 = 110.408kmol/hr = 110.408/3600 kmol/s= 0.036688 kmol/s


W = FA0 * Area under the curve = 0.036688*161430
Weight of catalyst in first catalyst bed = 4950.878 kg

49

13.2.3 Third Catalytic Bed


Table 17: Calculations of Third Catalytic Bed

T(K)

XSO2

NSO2

NO2

NSO3

NN2

TOTAL

PSO2(atm)

PO2(atm)

PSO3(atm)

705

0.905

36.355

268.67

381.14

3298.306

3984.483

0.00912

0.0674

0.09565

707

0.912

37.152

269.07

380.34

3298.306

3984.882

0.00932

0.0675

0.09544

708

0.915

35.648

268.32

381.85

3298.306

3984.13

0.00894

0.0673

0.09584

710

0.922

32.652

266.82

384.84

3298.306

3982.632

0.00819

0.0669

0.09663

712

0.929

29.669

265.33

387.83

3298.306

3981.14

0.00745

0.0666

0.09741

714

0.936

26.700

263.84

390.80

3298.306

3979.656

0.00670

0.0662

0.09819

715

0.939

25.221

263.10

392.27

3298.306

3978.916

0.00633

0.0661

0.09859

716

0.943

23.745

262.37

393.75

3298.306

3978.178

0.00596

0.0659

0.09897

717

0.946

22.272

261.63

395.22

3298.306

3977.442

0.0056

0.0657

0.09936

Sample Calculation:
For T = 708 K, T0 = 705 K, 2 = 0.905
708 =

705 + 307.158 (2 0.905)


1 + 0.0248 (2 0.905)

2 = 0.915
2 = 417.501

(1 0.915)
683
(1 0.05 0.915) 708

2 = 35.648
2 = 417.501 35.648 = 381.85
3 = 381.85
2 = 459.249 (381.85 2) = 268.32
= 35.648 + 268.32 + 381.85 + 3298.306 = 3984.13
50

2 = 2 =
2 = 2 =

35.648
= 0.00894
3984.13

268.32
= 0.0673
3984.13

3 = 3 =

381.85
= 0.09584
3984.13
Table 18: Rate Calculations of Third Catalytic Bed

k1

k2

(-rA) (kmol/s-kg catalyst)

1/(-rA)

4.27E-05 1.83E-07

2.27E-07

4396699

4.55E-05 2.04E-07

2.44E-07

4094072

4.69E-05 2.15E-07

2.42E-07

4129794

4.99E-05 2.39E-07

2.37E-07

4224889

5.32E-05 2.67E-07

2.28E-07

4383353

5.65E-05 2.96E-07

2.15E-07

4641287

5.83E-05 3.13E-07

2.07E-07

4825010

6.01E-05 3.29E-07

1.98E-07

5053386

6.19E-05 3.47E-07

1.87E-07

5361426

Sample Calculation:
1 = (12.07

31000
) = 4.69 105
(1.987 708)

2 = (22.75

536000
) = 2.15 107
(1.987 708)

((4.69 105 ) 0.00894 0.0673) ((2.15 107 ) 0.09584 0.06730.5 )


=
0.008940.5
= 2.42 107
1 = 4129794

51

Figure 18: Plot of 1/-RA v/s XA for third bed

FA0 = 36.355kmol/hr = 36.355/3600kmol/s = 0.0100986kmol/s


W = FA0 * Area under the curve= 0.0100986*181425
Weight of catalyst in first catalyst bed = 1832.14kg
13.2.4 Fourth Catalytic Bed
Table 19: Calculations of Fourth Catalytic Bed

T(K)

XSO2

NSO2

NO2

NSO3

NN2

Total

PSO2(atm)

PO2(atm)

PSO3(atm)

700

0.946

22.27

261.63

395.22

3298.306

3977.442

0.0056

0.06578

0.099367

701

0.950

21.350

261.17

396.15

3298.306

3976.981

0.005369

0.065671

0.099611

702

0.953

19.851

260.42

397.64

3298.306

3976.231

0.004993

0.065495

0.100007

704

0.960

16.864

258.93

400.63

3298.306

3974.738

0.004243

0.065144

0.100796

705

0.963

15.376

258.18

402.12

3298.306

3973.994

0.003869

0.064969

0.101189

707

0.970

12.409

256.70

405.1

3298.306

3972.51

0.003124

0.06462

0.101974

708

0.97

10.931

255.964

406.57

3298.306

3971.771

0.002752

0.064446

0.102365

52

Sample Calculation:
For T = 704 K, T0 = 700 K, 2 = 0.96
704 =

700 + 307.158 (2 0.96)


1 + 0.0248 (2 0.96)

2 = 0.96
2 = 417.501

(1 0.96)
683
(1 0.05 0.96) 704

2 = 16.864
2 = 417.501 16.864 = 400.63
3 = 400.63
2 = 459.249 (400.63 2) = 258.93
= 16.864 + 258.93 + 400.63 + 3298.306 = 3974.738
2 = 2 =
2 = 2 =

16.864
= 0.004243
3974.738

258.93
= 0.065144
3974.738

3 = 3 =

400.63
= 0.100796
3974.738
Table 20: Rate Calculations of Fourth Catalytic Bed

k1

k2

(-rA) (kmol/s-kg catalyst)

1/(-rA)

3.65E-05

1.39E-07

1.32E-07

7557000

3.76E-05

1.47E-07

1.3E-07

7713771

3.89E-05

1.55E-07

1.24E-07

8072529

4.14E-05

1.73E-07

1.07E-07

9315462

4.27E-05

1.83E-07

9.67E-08

10343043

4.55E-05

2.04E-07

6.97E-08

14342480

4.69E-05

2.15E-07

5.19E-08

19276120

53

Sample Calculation:
1 = (12.07

31000
) = 4.14 105
(1.987 704)

2 = (22.75

536000
) = 1.73 107
(1.987 704)

((4.14 105 )0.004243 0.065144) ((1.73 107 ) 0.100796 0.0651440.5 )


=
0.0042430.5
= 1.07 107
1 = 9315462

Figure 19: Plot of 1/-RA v/s XA for fourth bed

FA0 = 22.27kmol/hr = 22.27/3600 kmol/s = 6.18611*10-3kmol/s


W = FA0 * Area under the curve = 6.18611*10-3*2474750
Weight of catalyst in first catalyst bed = 15309.078 kg

54

14. SUMMARY SHEET


1. Diameter of converter = 6 m.
2. Heat load for heat exchanger after first bed = -6361.36 kW
3. Heat load for heat exchanger after second bed = -231.106 kW
4. Heat load for heat exchanger after third bed = -554.68 kW
5. Design Pressure for reactor = 0.1114 N/mm2
6. Design Temperature for reactor =610C =883 K
7. Material of Construction =SS 304
14.1 First Catalytic Bed

Inlet temperature = 410C

Effluent temperature = 602C

Conversion = 0.66

Weight of catalyst = 29103.3 kg.

Heat duty required= -728.67 kW

14.2 Second Catalytic Bed

Inlet temperature = 438C

Effluent temperature = 498C

Conversion = 0.85

Weight of catalyst = 4950.878

Heat duty required= -192.1755 kW

14.3 Third Catalytic Bed

Inlet temperature = 432C

Effluent temperature = 444 C

Conversion = 0.96

Weight of catalyst = 1832.14 kg

Heat duty required= -7.7903 kW

55

14.4 Fourth Catalytic Bed

Inlet temperature = 427C

Effluent temperature = 435C

Conversion = 0.985

Weight of catalyst = 15309.078 kg

Heat duty required = -1.69 kW

56

15. CONCLUSION
The next step to the Contact Process is DCDA or Double Contact Double Absorption. In this
process the product gases (SO2) and (SO3) are passed through absorption towers twice to achieve
further absorption and conversion of SO2 to SO3 and production of higher grade sulfuric acid.
SO2-rich gases enter the catalytic converter, usually a tower with multiple catalyst beds, and are
converted to SO3, achieving the first stage of conversion. The exit gases from this stage contain
both SO2 and SO3 which are passed through intermediate absorption towers where sulfuric acid
is trickled down packed columns and SO3 reacts with water increasing the sulfuric acid
concentration. Though SO2 too passes through the tower it is unreactive and comes out of the
absorption tower.
This stream of gas containing SO2, after necessary cooling is passed through the catalytic
converter bed column again achieving up to 99.8% conversion of SO2 to SO3 and the gases are
again passed through the final absorption column thus resulting not only achieving high
conversion efficiency for SO2 but also enabling production of higher concentration of sulfuric
acid.
The industrial production of sulfuric acid involves proper control of temperatures and flow rates
of the gases as both the conversion efficiency and absorption are dependent on these.

57

16. REFERENCES

[1] Hill, Charles G. (1977). An Introduction to Engineering Kinetics and Reactor Design, Third Edition,
506,507,509-513.
[2] Douglas K. Louie, (2005). Handbook of Sulphuric Acid Manufacturing , Second Edition, 3-3, 3-8, 310, 3-11, 3-14, 3-28, 3-78, 4-5 4-11, 4-58,6-16-3.
[3] Matt King, Michael Moats and William G.I. Davenport (2013). Sulfuric Acid Manufacture (Second
Edition) Analysis, Control and Optimization, 11-14, 19-21, 73-80, 91-99, 229-234, 262-271.
[4] Levenspiel, Octave, (1999). Chemical Reaction Engineering, Third Edition, 208, 209, 212, 394.
[5] Christie John Geankoplis, (2003). Transport Processes and Separation Process Principles (Includes
Unit Operations) Fourth Edition, 22.
[6] Central Pollution Control Board Ministry of Environment and Forests (May 2007). Comprehensive
Industry Document on Sulphuric Acid Plant, 3, 6-7, 10-14, 22, 25-28, 35-36, 38.
[7] Fogler, H.S., 1999. Elements of chemical reaction engineering, Third edition. Prentice Hall, New
York.
[8] Bhatt, B.I., Vora, S.M., 1996. Stoichiometry. Third edition. Mc-Graw Hill, New Delhi.
[9] Austin G.T., Shreve, 1984 Chemical process industries, Fourth edition.Mc-Graw Hill, Singapore.

58

17. APPENDIX (DERIVATIONS)

17.1 Derivation of relationship between equilibrium conversion and temperature.


Reaction taking place in the reactor:
SO2 (g) + O2 (g)

V2O 5

SO3 (g)

Rate Equation:
The kinetic data are represented by a rate expression of the form

1 2 2 2 3 0.5
2

(21)

0.5

that may be regarded as a degenerate form of typical Hougen-Watson kinetics.


At equilibrium, the rate of forward reaction becomes equal to the rate of backward reaction.

1 2 2 2 3 0.5
2
0.5

=0

(22)

Therefore at equilibrium,
1 2 2 = 2 3 0.5
2

(23)

The partial pressures of the various species are numerically equal to their mole fractions since
the total pressure is one atmosphere. These mole fractions can be expressed in terms of a single
reaction progress variable-the degree of conversion-as indicated in the following mole table.[8]

59

Table 21: Table for mole fractions expressed in terms of conversion

Initial moles
Component

(kmol/hr)

SO2

417.501

Mole fraction at fractional


Moles at conversion XA
conversion XA

417.501 (1 )

417.501 (1 )
4175.056 208.7505
459.249

(417.501 )

208.7505

O2

459.249

459.249

N2

3298.306

3298.306

3298.306
4175.056 208.7505

SO3

0.0

417.501

417.501
4175.056 208.7505

Total

4175.056

4175.056 208.7505

1.0

4175.056 208.7505

At equilibrium,
1 2 2 = 2 3 0.5
2

(24)

417.501 (1 )
459.249 208.7505
1 (
)(
)=
4175.056 208.7505 4175.056 208.7505
417.501
459.249 208.7505 0.5
2 (
)(
)
4175.056 208.7505 4175.056 208.7505

60

(25)

1
=
=
2

417.501

(4175.056208.7505
)

417.501 (1 )

459.249208.7505

0.5

(26)

(4175.056208.7505 ) (4175.056208.7505 )

20

=
2 (1 ) 2.2

(27)

17.2 Derivation of relationship between conversion and temperature.


The differential form of energy balance equation for one-dimensional, plug flow model, for
adiabatic operation is as follows, [9]

( )

= () = ()

(28)

where,
= = superficial mass velocity, which does not vary along the length of reactor.
= fluid density
= superficial velocity in axial direction.
= reaction rate expressed in pseudo homogeneous form (i.e. number of moles transformed per
unit time per unit of total reactor volume)
= enthalpy change for the reaction at the indicated conditions.
= bulk density of the catalyst (total mass of catalyst / total volume of reactor)

= = global reaction rate per unit mass of catalyst.

The equation for material balance is as follows:


( )
= =

where
= stoichiometric coefficient for reactant A (negative for reactants) = 1 in this case

61

(29)

= (1 + )

(30)

(1 )
(1 + )

(31)

( )

(32)

=
Therefore

(33)

( )

()
=

(34)

Table 22: Mole percent of gases entering the converter


Inlet Moles

Molecular

(Percent )

Weight

SO2

10

64

O2

11

32

N2

79

28

Component

Average molecular weight of the inlet gas:


Mavg = 0.10*64+ 0.11*32+0.79*28 = 32.04
For the temperature range of interest (875K to 683K), the heat capacity per unit mass is
substantially independent of the conversion level. Hence, we take the heat capacity as constant at
0.250 cal/gm-K.
( ) = ( )
Diameter of Converter is taken as 6m. [1]

62

(35)

() =

4175.056 32.04
(62 )

= 4731.1033

= 1.314
2
m
2

2 = =

417.501 103
3600

(6)2

= 4.101688

Heat of reaction at temperature T = (H) = 24.60 + 1.99 x 10-3T kcal/gmol


for T in degrees Kelvin.
1.314 0.250 ( ) = (24.60 1.99 x 103 T) 4.101688( )

+ 307.158( )
1 + 0.0248( )

63

(36)