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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND

SULPHURIC ACID PLANT


DESIGN OF INTEGRATED LIQUID SULPHUR
DIOXIDE AND SULPHURIC ACID PLANT

MANGOSUTHU UNIVERSITY OF TECHNOLOGY


P. O BOX 12363
JACOBS
4026
Submitted to
EXMINER: Dr. KANIKI TUMBA (MUT)
MODERATOR: Mrs. ANUSHA SINGH (UKZN)

DEPARTMENT OF CHMICAL ENGINEERING


MANGOSUTHU UNIVERSITY OF TECHNOLOGY
CONDENSER DESIGN

Partial fulfillment of
Bachelor of Technology in Chemical Engineering

Submitted by
MAKHATHINI S. F
STUDENT NO. 21102054
DATE: 26 SEPTEMBER 2016

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LETTER OF DECLARATION
D 326 Masakhane Street

UmlazI, Durban

4031

30 September 2016

Dr. K. Tumba

Mangosuthu University of Technology

P. O Box 12363

Jacobs

4026

From: Mr. Makhathini S. F (engineer in training)

Preliminary Design of Liquid Sulphur Dioxide production

It is of great importance to be part of the initiative of being assigned with a task of


designing a condenser as part of theoretical training. I also acknowledge the opportunity to use
the engineering expertise to precisely present the proper results of designing partial parts of this
plant. Thorough research was performed, which was integrated with material and energy
balances to help size the unit assigned as my task to complete in this plant.

I hereby declare that the entire content of this report is purely my work. Information that I
have used in compiling this report has been sourced to avoid plagiarism. The calculations that
have done are mainly taken from Coulson and Richardson volume 6 by Sinnot.

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ACKNOWLEDGEMENTS

I would like to extend my heartfelt gratitude to MR. S. Gcaba for his invaluable input in
compiling this report. I would also like to thank Miss N Mkhize, since we teamed up in order to
breakdown the given task.

The above mentioned individuals have played a vital role in the completion of this report
without their support this report might have not been successfully completed in time.

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Contents
LETTER OF DECLARATION ................................................................................................................... ii
ACKNOWLEDGEMENTS ........................................................................................................................ iii
List of Figures ............................................................................................................................................. v
List of Tables .............................................................................................................................................. vi
NOMENCLATURE ................................................................................................................................... vii
SUMMARY ................................................................................................................................................. ix
1.0 INTRODUCTION ................................................................................................................................. 1
1.1 Aim ..................................................................................................................................................... 1
1.2 Background....................................................................................................................................... 1
1.3 Production Methods ........................................................................................................................ 2
1.3.1 Compression and Condensing ................................................................................................... 2
1.3.2 Partial Condensing ....................................................................................................................... 3
1.3.3 Absorption and Acidification ....................................................................................................... 3
1.3.4 Sulphur Trioxide and Sulphur ..................................................................................................... 5
2.0 BACKGROUND THEORY ................................................................................................................. 7
2.1 Types of Condensers ...................................................................................................................... 8
2.2 Condenser Design ......................................................................................................................... 10
3.0 MATERIAL AND ENERGY BALANCES ........................................................................................ 11
4.0 DESIGN CALCULATIONS ............................................................................................................... 12
5.0 HAZOP STUDY ................................................................................................................................. 14
6.0 PROCESS FLOW DIAGRAM .......................................................................................................... 15
6.1 PROCESS FLOW DIAGRAM ...................................................................................................... 16
9.0 COST ESTIMATION ......................................................................................................................... 17
7.0 ENVIRONMENTAL IMPACT ASSESSMENT (EIA) ..................................................................... 18
7.1 Safety Consideration ..................................................................................................................... 18
8.0 DISCUSSION ..................................................................................................................................... 19
10.0 CONCLUSIONS AND RECOMMENDATIONS .......................................................................... 21
11.0 REFERENCES ................................................................................................................................ 22
12.0 APPENDICES .................................................................................................................................. 23
12.1 Sample of Calculations ............................................................................................................... 23

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12.1.1 Material and Energy Balances ............................................................................................... 23
12.1.2 Condenser Design Sample of Calculation ........................................................................... 25
12.2 Correlation Charts ....................................................................................................................... 32
12.3 Material Safety Data Sheet ........................................................................................................ 53

List of Figures
Figure 1: Condensation Temperature for Various Gas Concentrations of Sulphur Dioxide
(Trickett, A.A., Horsley, D. and Talbot, M et al., 1986) ......................................................................... 4
Figure 2: Condensation Skid of Liquid Sulphur Dioxide Plant (Cameron, G.M. and Trickett,
A.A.,) ............................................................................................................................................................ 4
Figure 3: Production of Sulphur Dioxide from Sulphur an Sulphur Trioxide .................................... 5
Figure 4: Flow Diagram for Sulphur Burning Liquid Sulphur Dioxide Plant ..................................... 6
Figure 5: Physical Properties of Sulphur Dioxide (Ashar N. G, Advances in Sulphonation
Techniques, Springer Briefs in Applied Sciences and Technology, 2016) ....................................... 7
Figure 6: Down-flow vertical condenser with condensation inside tube ........................................... 9
Figure 7: Horizontal condenser with condensation outside horizontal tubes................................. 10
Figure 8: Physical properties data bank .............................................................................................. 32
Figure 9: Overall coefficients (join process side duty to service side and read U from centre
scale) .......................................................................................................................................................... 33
Figure 10: Convective boiling factor ..................................................................................................... 34
Figure 11: Tube-side friction factor....................................................................................................... 35
Figure 12: Convective boiling enhancement ....................................................................................... 36
Figure 13: Fouling coefficients .............................................................................................................. 37
Figure 14: Moody chart, friction factor ................................................................................................. 38
Figure 15: Nucleate boiling suppression factor .................................................................................. 39
Figure 16: Temperature correlation chart (1-2 shell and tube heat exchanger) ............................ 40
Figure 17: Temperature correlation chart (2-4 shell and tube heat exchanger) ............................ 40
Figure 18: Physical properties equation correlations ......................................................................... 41
Figure 19: Physical properties data bank (Coulson and Richardson vol.6) .................................. 42
Figure 20: Discharge coefficient Figure 21: Shell and tube clearance .................................. 43
Figure 22: Shell-side friction factor, segmental baffles ..................................................................... 44
Figure 23: Tube-side transfer factor ................................................................................................. 45
Figure 24: Heat-transfer factor for cross-flow tube banks................................................................. 46
Figure 25: Shell-side heat-transfer factors, segmental baffles ......................................................... 47
Figure 26: Typical overall coefficient .................................................................................................... 48
Figure 27: Toxicology details, Integrated Liquid Sulphur Dioxide and Sulphuric Acid ................. 49
Figure 28: Transportation table of the integrated Sulphur Dioxide and Sulphuric Acid plant
(http://www.sulphuric-acid.com/techmanual/Plant_Safety/safety_sulphur.htm)............................. 50
Figure 29: Tanker specification for transporting liquid Sulphur dioxide and Sulphuric Acid
(http://www.sulphuric-acid.com/techmanual/Plant_Safety/safety_sulphur.htm .............................. 51

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Figure 30: Shell and tube heat exchangers. Time base mid 2004 .................................................. 52

List of Tables

Table 1: Molar flow condenser and condenser separator calculations ........................................... 11


Table 2: Mass flow condenser and condenser separator calculations ........................................... 11
Table 3: Energy Balances ...................................................................................................................... 11
Table 4: Condenser Specification Sheet, E-104 ................................................................................. 12
Table 5: Hazop Study, Condenser ........................................................................................................ 14

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NOMENCLATURE

A Heat transfer area 𝒎𝟐


A Surface area 𝑚2
C Clearance m
𝑪𝒑 Heat capacity at constant pressure J/kg.K
𝑪𝒗 Heat capacity at constant pressure J/kg.K
𝝆𝒇 Fluid density Kg/𝑚3
𝑫𝒃 Bundle diameter m
𝑫𝒊 Inside tube diameter m
𝑫𝒔 Shell diameter m
𝑫𝒐 Outside tube diameter m
𝑷𝑫 Discharge pressure kPa
𝑻𝑫 Discharge temperature ℃
𝑸 Duty 𝑘𝑊
𝒇𝒔 nucleate boiling suppression factor -
𝒅𝒆 Equivalent diameter m
𝒅𝒐𝒑𝒕 Optimum diameter m
𝝆𝒍 Liquid density Kg/𝑚3
𝝆𝒗 Vapor density Kg/𝑚3
𝑭𝒕 Temperature correction factor -
∆𝑯𝒗𝒂𝒑 Heat of vaporization 𝐽/𝑚𝑜𝑙
F Friction factor -
G Mass flow rate per unit area Kg/s
̅𝒊
𝒉 Mean coefficient 𝑊/𝑚2 . ℃
G Gravitational acceleration m/s 2
∆𝑷𝒔 Pressure drop in the shell side 𝑘𝑃𝑎
∆𝑷𝒕 Pressure drop in the tube side 𝑘𝑃𝑎
𝒉𝒊𝒅 Inside dirt factor 𝑊/𝑚2 . ℃

𝒉𝒐𝒅 Outside dirt factor 𝑊/𝑚2 . ℃

𝒉𝒐 Heat transfer coefficient outside a tube W/𝑚2 ℃

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𝒉𝒊 Film heat transfer coefficient inside a tube W/𝑚2 ℃
𝒉𝒏𝒃 Nucleate boiling heat transfer coefficient W/𝑚2 ℃
K Specific heat ratio of a compressor -
𝑲𝒇 Thermal conductivity of fluid W/m.K
𝑲𝒘 Thermal conductivity of tube wall material W/m.K
L Pipe length m
L Liquid depth m
𝑻𝒎𝒄 Mean temperature condensate ℃
MM Molecular weight of fluid g/mole
NPSH Net positive suction head rpm
𝑵𝒕 Number of tubes in a tube bundle -
𝑵𝒕 Total molar flow rate kmol
N Number of moles 𝑚𝑜𝑙/𝐾𝑚𝑜𝑙
𝑵𝒓 Number of tubes in a row -

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SUMMARY

The entire content of this report provides a thorough design and economic analysis for
the manufacture of liquid Sulphur dioxide as part of a stand-alone package of Sulphuric acid
plant in the Democratic Republic of Congo. Process flow sheet of the Sulphur dioxide cryogenic
section is attached and a detailed process description of all utility requirements and equipment
are provided and analyzed. With design commencing in 2017, the proposed plant will utilize
liquid Sulphur dioxide from a Sulphuric acid internal upstream plant and will produce 90 tons of
liquid Sulphur dioxide per day. Recalling the objective set forth, maximize the plant capacity by
a factor of 1.35 which therefore ends up increasing the production of liquid Sulphur dioxide to
79.10 kmol/hr which corresponds to 121.5 tons per day. An environmental impact assessment
report has been complied to raise awareness of the dangers of liquid Sulphur dioxide with
inhabitants and other living organisms. Also Material Safety Data Sheet of liquid Sulphur dioxide
is attached on the appendices to ensure that dangers and any possible fatalities are mitigated. It
can be witnessed from the Material Safety Data Sheet that liquid Sulphur dioxide production
plant can cause harm or even fatalities to inhabitants. But when handled with cautiousness,
extra care human beings and other living organisms are not at any danger. Methods of dealing
with any possible threats posed by liquid Sulphur dioxide have been enclosed to ensure a safe
and conducive environment for all as it is one of the key priority of this project.

Condenser design, while heat transfer area calculations are conducted, overall heat
transfer coefficients are determined with respect to nature of process. From the law of
conservation energy, it is said that heat cannot be created nor destroyed but can be
transformed from one form to another. Given that the calculated heat lost by the processing
stream is gained by the refrigerant stream (ammonia), the mass flow rate of ammonia is
calculated to be 0.508 kg/s. The preliminary cost of purchase is found to be R1224 using the
correlation chart on the appendices figure 30 when compared to the current market in 2016.

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1.0 INTRODUCTION
1.1 Aim

The main objective of this report, is to do a feasibility study on the integrated liquid Sulphur
dioxide and sulphuric acid plant. The feasibility study includes design of condenser (equipment
sizing), cost estimation of the condenser, environmental impact assessment of liquid Sulphur
dioxide and material and energy balances as well as Hazop study. It is also required to
maximize the plant capacity by scaling up the mass and energy balance calculations by a factor
of 1.35.

1.2 Background

Verri and Baldelli discovered that the production of liquid Sulphur dioxide from elemental
Sulphur, by cryogenic condensation from a gaseous stream, can be easily integrated or
combined with a sulphuric acid production plant. A portion of the SO2-bearing gas that is fed to
the first stage of the SO2-SO3 catalytic converter can be diverted to a unit dedicated to the
condensation of SO2 at low temperature. The off-gas leaving this unit after condensation still
holds a residual amount of SO2, which needs to be removed before release to the atmosphere.
SO2 removal is conveniently effected by returning the off-gas to the first stage of the catalytic
converter, and thereby producing sulphuric acid. When a new plant is designed, once the
required liquid SO2 production capacity has been fixed, the amount of sulphuric acid that can be
coproduced varies from a minimum inevitable production that is necessary to allow the
operation of an acid plant, up to a large capacity modern plant. The liquid SO2 unit is a stand-
alone package, which can also be integrated into an existing sulphuric acid production plant with
minor modifications subject to a revamping study.

They further said that, “This section focuses on the identification of the most effective
design parameters for the SO2 cryogenic condensation unit, which can be integrated with a
Sulphur-burning acid plant having the typical capacity requirements for a copper/cobalt mining
operation. The cryogenic process is based on the condensation of SO2 vapors, and is thus
related to the vapor/liquid equilibrium behavior of SO2. The SO2 condenser operating
temperature and pressure can have a strong impact on both capital and operating costs of the

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unit, and therefore need to be selected through an optimization exercise following the
conceptual design phase”.

Since the production of liquid Sulphur dioxide is a stand-alone package as regarded by


Verri and Baldelli, the cryogenic unit will be fed with a portion of the gaseous stream from the
Sulphur-burning section of an acid plant. In conducting their study certain considerations were
to be taken into account, namely considering a standard Sulphur furnace capable of operating
within an SO2 concentration range of 10–13% by volume. The higher the SO2 concentration in
the feed gas to the SO2 unit, the lower the energy consumption and the better the efficiency of
the unit. However, in practice, integration with a sulphuric acid plant limits the SO 2 concentration
to 14% by volume with standard Sulphur furnace designs. Concentrations up to 18% are
possible with major upgrades in the furnace design, although with such a high SO 2
concentration, NOx production could be high and post-dilution with dry air could be necessary to
achieve the optimal oxygen level at the converter inlet.

1.3 Production Methods

There are several different processes for the production of liquid SO2:

 Compression and Condensing


 Partial Condensation
 Absorption and Acidification
 Sulphur Trioxide and Sulphur

1.3.1 Compression and Condensing

Ashar, N.G, found that at atmospheric pressure, pure SO2 will begin to condensate at -
10.1 C (13.9 oF). If the gas is compressed to 388 kPa (g) (56.3 psig), SO 2 will begin to
o

condensate at 32.2 oC (90 oF). This temperature is high enough that normal cooling water can
be used to condense SO2.

When the concentration of SO2 is less than 100%, the gas must be compressed to
higher pressures to obtain a high enough condensing temperature to use cooling water as the
condensing medium. The tail gas leaving the system may be further cooled in a refrigeration
unit to achieve nearly 100% or full condensation of the SO2 (Trickett, A.A., Horsley, D. and
Talbot, M).

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1.3.2 Partial Condensing

Recent work from “Sulphur Dioxide – Technical Bulletin, CIL Chemicals” show that when
the concentration of SO2 in the gas is low (typically 7-14%), it becomes impractical to attempt to
fully condense all the SO2 contained in the gas. Extremely high pressures re required in order to
use cooling water to condense SO2 from the gas. The alternative to full condensation is partial
condensation of the SO2 using refrigeration only. Refrigeration systems can achieve
temperatures as low s -55oC (-67oF). Typically, only 50% of the SO2 can be condensed from the
gas. The tail gas from the refrigeration process is used to pre-cool the incoming gas prior to
being directed to some other process, such as a sulphuric acid plant, for further treatment.

1.3.3 Absorption and Acidification

Gas containing low concentration of SO2 (typically 1-2% vol) is scrubbed using an ammonia
solution to form ammonium bisulphite according to the following reaction:

𝑆𝑂2(𝑔) + 𝑁𝐻4 𝑂𝐻 ↔ 𝑁𝐻4 𝑆𝑂3

The ammonium bisulphite solution is reacted with sulphuric acid to form ammonium sulphate,
water and SO2.

2𝑁𝐻4 𝐻𝑆𝑂3 + 𝐻2 𝑆𝑂4 → (𝑁𝐻4 )2 𝑆𝑂4 + 2𝐻2 𝑂 + 2𝑆𝑂2(𝑔)

The production of liquid SO2 is unfortunately tied stoichiometrically to the production of


ammonium sulphate. If there is no requirement for ammonium sulphate, liquid SO 2 cannot be
produced using this process (“Sulphur Dioxide – Technical Bulletin, CIL Chemicals”).

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Figure 1: Condensation Temperature for Various Gas Concentrations of Sulphur Dioxide


(Trickett, A.A., Horsley, D. and Talbot, M et al., 1986)

Figure 2: Condensation Skid of Liquid Sulphur Dioxide Plant (Cameron, G.M. and Trickett,
A.A.,)

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1.3.4 Sulphur Trioxide and Sulphur

Pure Sulphur trioxide (SO3) will react with Sulphur to produce SO2.

𝑆 + 2𝑆𝑂3 → 3𝑆𝑂2

The process was first developed in Germany. Molten Sulphur is mixed with oleum in a
reactor operating at a temperature of 110oC (230oF). The gas produced from the reactor passes
through a column containing solid Sulphur where any remaining SO3 is converted to SO2. The
pure SO2 gas is then condensed to liquid in a condenser circulating cooling water. Further
development of this process involves feeding both oleum and liquid SO3 to the reactor at the
same time.

Figure 3: Production of Sulphur Dioxide from Sulphur an Sulphur Trioxide

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Figure 4: Flow Diagram for Sulphur Burning Liquid Sulphur Dioxide Plant

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2.0 BACKGROUND THEORY

Cameron, G.M. and Trickett, A. A, highlights that liquid Sulphur dioxide (SO2) is a
versatile chemical with many uses, both in liquid form or as a source of gaseous SO2. Liquid
SO2 is used in the pulp and paper industry, mining industry, and in the food industry as a
preservative. It can function as a reducing agent, an oxidizing agent, a pH controller, purifying
agent, preservative, germicide and bleaching agent. SO2 can also be used as a refrigerant, heat
transfer fluid and selective solvent. Liquid SO2 can be produced from gas containing SO2
concentration in the range of 1% to 100% using different processes. The figure below which
consists of physical properties of Sulphur dioxide witness the core functions of Sulphur dioxide
as highlighted by Cameron, G.M. and Trickett, A. A.

Figure 5: Physical Properties of Sulphur Dioxide (Ashar N. G, Advances in Sulphonation


Techniques, Springer Briefs in Applied Sciences and Technology, 2016)

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According to (James R. Couper; W. Roy Penney, James R. Fair, Stanley M. Walas,


Chemical Process Equipment: selection and design, Elsevier Inc., 2nd ed. 2005) the change
from liquid phase to vapor phase is called vaporization and the reverse phase transfer is
condensation. The change from liquid to vapor or vapor to liquid occurs at one temperature
(called saturation or equilibrium temperature) for a pure fluid compound at a given pressure.
The industrial practice of vaporization and condensation occurs at almost constant pressure;
therefore the phase change occurs isothermally. Condensation occurs by two different physical
mechanisms for example drop-wise condensation and film condensation.

The nature of the condensation depends upon whether the condensate (liquid formed
from vapor) wets or does not wet the solid surface. If the condensate wets the surface and flows
on the surface in the form of a film, it is called film condensation. When the condensate does not
wet the solid surface and the condensate is accumulated in the form of droplets, is drop-wise
condensation. Heat transfer coefficient is about 4 to 8 times higher for drop wise condensation.
The condensate forms a liquid film on the bare-surface in case of film condensation. The heat
transfer coefficient is lower for film condensation due to the resistance of this liquid film.

Drop-wise condensation occurs usually on new, clean and polished surfaces. The heat
exchanger used for condensation is called condenser. In industrial condensers, film
condensation normally occurs.

2.1 Types of Condensers


There are two general types of condensers:

 Vertical condenser: Down-flow vertical condenser: The vapor enters at the top of
condenser and flows down inside tubes. The condensate drains from the tubes by
gravity and vapor induced shear (Figure 1.7). Up-flow vertical condenser: In case of up-
flow condenser, the vapor enters at the bottom and flows upwards inside the tubes. The
condensate drains down the tubes by gravity only.

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 Horizontal condenser: The condensation may occur inside or outside the horizontal
tubes (Figure 1.8). Condensation in the tube-side is common in air-cooled condensers.
The main disadvantage of this type of condenser is that the liquid tends to build up in the
tubes. Therefore the effective heat transfer co-efficient is reduced significantly.

Figure 6: Down-flow vertical condenser with condensation inside tube

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Figure 7: Horizontal condenser with condensation outside horizontal tubes

2.2 Condenser Design

James R. Couper; W. Roy Penney, James R. Fair, Stanley M. Walas, Chemical Process
Equipment: selection and design, Elsevier Inc., 2nd ed. 2005. Further said that the design of
condenser is similar to a typical shell and tube exchangers. A condenser must have a vent for
removal of non-condensable gas. The non-condensable gas decreases the heat transfer rate.
Condenser usually use a wider baffle spacing of𝐵 = 𝐷𝑠 (ID of shell) as the allowable pressure
drop in shell side vapor is usually less. Vertical cut-segmental baffles are generally used in
condensers for side-to-side vapor flow and not for top to bottom. An opening at the bottom of
the baffles is provided to allow draining of condensates.

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3.0 MATERIAL AND ENERGY BALANCES


Table 1: Molar flow condenser and condenser separator calculations

Species Molecular weight Condenser inlet Condenser output/ off-gas (separator) Bottoms (separator)
(kg/kmol) separator input
SO2 (liquid) 64.06 - 58.53886981 - 58.53886981

SO2 (vapor) 64.06 61.01989866 2.481028846 2.481028846 -

O2 32 6.034935032 6.034935032 6.034935032 -

Total - 67.05483369 67.05483369 8.515963878 58.53886981


(kmol/hr)

Table 2: Mass flow condenser and condenser separator calculations

Species Molecular weight Condenser inlet Condenser off-gas (separator) bottoms (separator)
(kg/kmol) output/ input
SO2 (liquid) 64.06 - 1.041666667 - 1.041666667
SO2 (vapor) 64.06 1.085815197 0.04414853 0.04414853 -
O2 32 0.053643867 0.053643867 0.053643867 -
Total (kg/s) - 1.139459064 1.139459064 0.097792397 1.041666667

Table 3: Energy Balances

Latent Heat of Vaporization (process fluid), J/mol 27697.45

Latent Heat of Vaporization (refrigerant), J/mol 23940.99

Duty (kW) 715.32

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4.0 DESIGN CALCULATIONS

Table 4: Condenser Specification Sheet, E-104

Heat Exchanger Specifications

ID Number: 531E2 Date: 30 September 2016


Description: Column T-103 Condenser
Number Required: 1 Prepared by: Makhathini S. F
Checked by: Mkhize N
Unit Performance and Fluid Properties

Tube Side Shell Side

Inlet Outlet Inlet Outlet

Fluid Cooling Water Process Fluid

Flow Rate - Vapor (kg/s) 1.578 0.131 0.508 0.508

Flow Rate - Liquid (kg/s) - 1.448 0.508 0.508

Temperature (℃ ) -54 -54 -70 -70

Pressure (kPa) 293 293 10.9 10.9

Density (kg/m3) - (liquid) 630.39 630.39 - 674.72

Density (kg/m3) – Vapor 11.67 11.67 0.109 none

Viscosity - Vapor (Pa.s) 9.19 × 10−6 9.19 × 10−6 6.65 × 10−5 6.65 × 10−5

Viscosity - Liquid (Pa.s) 8.7 × 10−4 8.7 × 10−4 2.26 × 10−5 2.26 × 10−5

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Specific Heat capacity vapor (J/kg.K) 572 572 1023.79 1023.79

Specific Heat capacity liquid(J/kg.K) 1358.97 1358.97 4551.67 4551.67

Latent Heat (J/mol.K) 30199.95 30199.95 23940.99 23940.99

Thermal Conductivity – Vapor (W/m.K) 0.0182 0.0189 None None

Thermal Conductivity – Liquid (W/m.K) 0.598 0.615 0.24 0.24

Pressure Drop calculated (kPa) 58.77 0.0825

Fouling Factor 6500 6000

Heat transfer

Duty (kW) Total Heat Transfer Area (m2) Heat Flux (J/m2.s)

715.32 71.25 10039.58

Unit Construction

Tube Side Shell Side

Number of Passes 4 1

Number of tubes 124 1

Material of Construction Stainless steel Stainless steel

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5.0 HAZOP STUDY

Table 5: Hazop Study, Condenser

HAZARD AND OPERABILITY STUDY REORT


Project Title: Production of Sulphur Dioxide

Report Number: 1 Date: 26 SEPTEMBER 2016

Drawing Number: 531E6 Cryogenic SO2Condenser Chairman: MR S. F Makhathini

Line Number:

Intention: To convert processing stream from vapour/gaseous to liquid Parameter: Flow

More More cooling Very low output temperature Inlet cooling refrigerant (ammonia) valve None  Install temperature indicators before and after the process line.
refrigerant (ammonia) of process fluid failed open
flow

None No refrigerant Temperature is not lowered Inlet cooling refrigerant (ammonia) valve None  Regular inspection and maintenance on equipment. Install high
(ammonia) flow accordingly failed closed temperature alarm

Less Less refrigerant High output temperature of  Pipe leakage None  Install low flow alarm. Regular inspection and maintenance on
(ammonia) flow process fluid  Valve partially closed equipment inspect / repair / change valve.

Reverse Reverse process fluid Disturbed product quality Process fluid inlet valve failed closed None  Inspect / repair / change valve.
output
Temperature More temperature Temperature is not lowered  Decrease in cooling water flow None  Periodically checking of the temperature
accordingly.  Increase in cooling refrigerant  Increase cooling refrigerant (ammonia) flow rate.
(ammonia) temperature.
Less Less temperature Temperature not decreased Too much cooling refrigerant (ammonia) None  Temperature and flow controls to be periodically inspected.
accordingly  Equipment to be tested periodically
 Decrease cooling refrigerant (ammonia) flow rate.

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND SULPHURIC ACID PLANT

6.0 PROCESS FLOW DIAGRAM


SECTION 100: SULPHUR DIOXIDE CRYOGENIC PLANT

SULPHURIC ACID TO
DRYING TOWER 528C1
531E1
HOT REHEAT 531E3
EXCHANGER ACID COOLER
PROCESS GAS FROM
514H1

531E2
TO CONVERTER BED COLD REHEAT
514R1*1BED EXCHANGER
531C1 P-17

SO2
WASHING
TOWER
DILUTION WATER

531K1
GAS
BOOSTER

531V1 531P1
ACID TANK ACID PUMP

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND SULPHURIC ACID PLANT

6.1 PROCESS FLOW DIAGRAM

SECTION 200: CONDENSATION OF SULPHUR DIOXIDE

531E6
CRYOGENIC SO2
CONDENSER
CONDENSER
SEPARATOR

CRYOGENIC
PACKAGE

531R31 TO LIQUID SO2


STORAGE TANKS
531E7
531P2 LIQUID
LIQUID SO2 PREHEAT
PUMP

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND
SULPHURIC ACID PLANT

9.0 COST ESTIMATION

Cost estimation is a specialized subject and a profession in its own right. The design
engineer, however, needs to be able to make quick, rough, cost estimates to decide between
alternative designs and for project evaluation. Chemical plants are built to make a profit, and an
estimate of the investment required and the cost of production are needed before the
profitability of a project can be assessed.
Happle and Jordan (1975) and Guthrie (1974), recommended the use of this method of
cost projection using various components that make up the capital cost of a plant and the
components of the operating costs are discussed, and the techniques used for estimating
reviewed briefly. Simple costing methods and some cost data are given, which can be used to
make preliminary estimates of capital and operating costs at the flow-sheet stage.
Garrett (1989), further mentioned that for a more detailed treatment of the subject the reader
should refer to the numerous specialized texts that have been published on cost estimation
which is an alternative processing schemes and equipment.

Condenser Cost estimation


Type: horizontal, floating head
Stainless steel
From figure 30 on the appendices, the cost projected in 71.25 m2

𝐶 = 85$
Type factor: 1
Pressure factor: 1.0
𝑃𝑢𝑟𝑐ℎ𝑎𝑠𝑒 𝑐𝑜𝑠𝑡 = 𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑓𝑎𝑐𝑡𝑜𝑟 × 𝑇𝑦𝑝𝑒 𝑓𝑎𝑐𝑡𝑜𝑟 × 𝑏𝑎𝑟𝑒 𝑐𝑜𝑠𝑡 𝑓𝑟𝑜𝑚 𝑓𝑖𝑔𝑢𝑟𝑒 30
𝑃𝑢𝑟𝑐ℎ𝑎𝑠𝑒 𝑐𝑜𝑠𝑡 = 85$
Therefore the cost of the condenser in (ZAR) is 𝐶𝑒 = 𝑅1224

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND
SULPHURIC ACID PLANT

7.0 ENVIRONMENTAL IMPACT ASSESSMENT (EIA)


7.1 Safety Consideration

The liquid SO2 cryogenic section is considered as a stand-alone package according to


Verri and Baldelli, therefore the plant design of Sulfuric acid production has an environmental
impact in the form of pollution problems in the area where the plant is located. According to
central environmental authority (CEA), it is the responsibility of the management to consider
possible techniques to minimize the emission of gaseous compounds such as oxides of Sulfur
or Sulfuric acid mist and other solid and liquid waste by complying with the emission standards
and discharge limits which are provided by the. Waste generated mostly on the cryogenic
section can be treated in house prior to discharging them into the environment. Possible
pollutants in the liquid sulfur dioxide production using contact process include dust particles of
raw sulfur, oxygen, oxides of sulfur, acid mist and liquid sulfuric acid apart from that spent
catalyst and other waste from blow down. One of the main reason for the oxides and acid mist
to release to the environment is poor conversion in the sulfur burning section and absorption in
the cryogenic section process. Efficient processing methods will reduce the emission of these
gaseous elements.
Liquid Sulphur dioxide production contributes to various environmental impacts such
deforestation when spilled to the ground. Also can contribute to global warming as well as acid
rain. Environmental Impact Assessment (EIA) and Environmental Protection License (EPL) are
regarded as one of the main instruments measuring sustainability development. An EIA can be
used to find adverse impacts on the environment at early stages so precaution can be taken.
The identification of impacts should be followed during selection of the plant location. The EIA is
obtained through the CEA and is essentially a way of identifying the extent of compliance that
will be needed with CEA regulations.
Exposure to human beings can either by inhalation or contact which liquid Sulfur dioxide.
Side effects in human health, are noticeably when it is breathed in. The exposure tends to
irritate the nose, throat, and airways to cause coughing, wheezing, shortness of breath, or a
tight feeling around the chest. The effects of sulfur dioxide are felt very quickly and most people
would feel the worst symptoms in 10 or 15 minutes after breathing it in. Material Safety Data
Sheet has been attached on the appendices to safety precautions if ever should be exposed to
liquid Sulphur dioxide.

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND
SULPHURIC ACID PLANT

8.0 DISCUSSION

The objective of this study is to make preliminary design of a stand-alone package


(Sulphur dioxide cryogenic section) for a sulphuric acid production plant. The integrated liquid
Sulphur dioxide and sulphuric acid plant produces 362 tons/day as 100% H2SO4 and 90
tons/day of sulphuric acid and liquid Sulphur dioxide simultaneously respectively. In order to
achieve this aim, the production process of integrated liquid Sulphur dioxide and Sulphuric acid
plant includes the use of vanadium oxide as a catalyst, double-contact absorption (3+1
configuration), 99.7% conversion of Sulphur to Sulphur dioxide, condensation temperature of (-
54oC) t atmospheric pressure also using a ratio of 1.2 (by volume) of Sulphur dioxide to oxygen.
This is considered as an initial design since the new design includes scale up values from the
initial plant. The increment factor to be used to scale up the plant capacity is 35%.

While heat transfer area calculations are conducted, overall heat transfer coefficients are
determined with respect to nature of process. The material of construction chosen for the
condenser is stainless nickel steel. Having noted that refrigerant on the shell side is ammonia
which evaporates at a constant temperature of (-70 oC). In order to account for the heat transfer
area, 25 mm and 20 mm outer and inner diameter chosen respectively. Applying the (TEMA L
standards), the number of tubes inside the shell is found to be 124, the shell diameter is
determined to be 438 mm. Also a maximum length tubes of 7.32 m long is chosen for the
condenser design. Having assumed the overall heat transfer (U) to be 700 (W/m2.oC), the heat
transfer coefficients of both the tube and shell-side is determined to be 526.82 (W/m2.oC) and
590.45 (W/m2.oC) respectively. The pressure drops for both the tube and shell-side also
calculated to be 58.77 kPa and 0.0824 kPa respectively.

Liquid Sulphur dioxide possess features that prove to be dangerous to living organisms
when handled inappropriately. Therefore, an environmental impact assessment report has been
compiled and also Material Safety Data Sheet has been attached on the appendices to ensure
that dangers and any possible fatalities are mitigated. It can be witnessed from the Material
Safety Data Sheet that liquid Sulphur dioxide production plant can cause harm or even fatalities
to inhabitants. When handled with cautiousness, extra care human beings and other living
organisms are not at any danger. Methods of dealing with any possible threats posed by liquid

19
EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND
SULPHURIC ACID PLANT

Sulphur dioxide have been enclosed to ensure a safe and conducive environment for all as it is
one of the key priority of this project.

Economic analysis is crucial since it is the main factor to determine the success of a
project. Economic analysis reveals the amount of profit under operating condition of a plant. In
order to examine if the integrated liquid Sulphur dioxide and sulphuric acid plant is conducive or
not, both capital investment cost and production cost must be examined for a successful
economic analysis. For this project the study is based on the condenser only, therefore the
preliminary cost of purchase of the condenser is estimated to be 𝑅1224.

20
EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND
SULPHURIC ACID PLANT

10.0 CONCLUSIONS AND RECOMMENDATIONS

In conclusion the, the main aim of this report was to design a grass root facility that will
safely and efficiently produce 90 tons per day of liquid Sulphur dioxide as a stand-alone
package from 360 tons per day of integrated Sulphuric acid plant. In achieving the goals set
forth, sizing of equipment’s and a cost projection on each functional unit as well as an
Environmental Impact Assessment report was also required to ensure that the production of
liquid Sulphur dioxide would not harm the environment and human beings as well as any other
living organisms. After gathering data from various sources as referenced, the environmental
report displays that the production of liquid Sulphur dioxide may be harmful if handled
inappropriately and can cause injuries and fatalities as well. Therefore adequate care must be
taken to ensure safety. Cost of the equipment’s are satisfactory based on the current exchange
rate. Also the design of integrated liquid Sulphur dioxide and Sulphuric acid plant includes a
compilation of hazard and operability study around the condenser which is constructed
according to heuristics and main results are summarized in specification sheets. Either material
or energy balance is performed for each equipment participating in the production of liquid
Sulphur dioxide. Because of the specified variables, material balances and energy balance is
performed in the condenser separator to be able to determine the condenser specification
variable such as the duty.

21
EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND
SULPHURIC ACID PLANT

11.0 REFERENCES

1. Verri, M. and Baldelli, A., 2013. Integrated production of liquid Sulphur dioxide and
sulphuric acid via a low-temperature cryogenic process. Journal of the Southern African
Institute of Mining and Metallurgy, 113(8), pp.602-609.
2. Lindquit, B., “Recent Developments within the process Gas System at the Boliden
Ronnskar Smelter Process Gas Handling
3. Cameron, G.M. and Trickett, A.A., “Liquid Sulphur Dioxide and Elemental Sulphur plants
– Design an Operation”. Presented to A Professional Enhancement Seminar –
Reduction of Sulphur Dioxide Emissions from Non-Ferrous Smelters, Toronto, Canada.
August 16 1986.
4. Ashar, N.G., “Liquid Sulphur Dioxide without Compression or refrigeration – A New
Technology Already in Operation”, Sulphur 99, Calgary, Alberta, Canada, October 17-
20, 1999, pp. 173-181.
5. Trickett, A.A., Horsley, D. and Talbot, M., “Product Quality Aspects of liquid SO 2
Production from Metallurgical Off-Gases”
6. “Recommendation for the Safe Handling of liquid Sulphur Dioxide”, CESAS, Belgium.
7. “Sulphur Dioxide – Technical Bulletin”, CIL Chemicals.
8. “Material Safety Data Sheet – Sulfur Dioxide”, Marsulex, August 2002.
9. Sinnott, R. K. (1999). Coulson & Richardson's Chemical Engineering Volume 6
(Chemical Engineering Design) (3 ed., Vol. 6). Butterworth-Heinemann.
10. Riegel, E., & Kent, J. (2003). Riegel's Handbook of Industrial Chemistry. Springer
11. Perry, R. H. (1999). Perry's Chemical Engineering Handbook (7 ed.). (D. W. Green, & J.
O. Maloney, Eds.) McGraw Hill Companies Inc.
12. Moeller, W., & Winkler, K. (1968). The Double Contact Process for Sulfuric Acid. Air and
waste Management, 18(5), 324 -325.
13. Louie, D. K. (2005). Handbook of Sulphuric Acid Manufacturing. DKL Engineering, Inc.
Chemical Engineering Plant Cost Index (averaged over year). (n.d.). Retrieved June 18.

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND
SULPHURIC ACID PLANT

12.0 APPENDICES
12.1 Sample of Calculations

12.1.1 Material and Energy Balances

Balance around the condenser separator

V (Kmol/hr)
n4=SO2(g)
n5=O2(g)

F (Kmol/hr)
n1=SO2(l)
n2=SO2(g)
n3=O2(g)

B (kmol/hr)

N6=SO2(g)

Given:
𝑛6 = 90 𝑡𝑜𝑛𝑠/𝑑𝑎𝑦
𝑛3 = 9%
𝑛2 = 3.4%
𝑛1 = 87.6

Therefore,
90 𝑡𝑜𝑛𝑠 1000 𝑘𝑔 1 𝑘𝑚𝑜𝑙 1 𝑑𝑎𝑦
𝑛6 = × × × = 58.59 𝑘𝑚𝑜𝑙𝑆𝑂2 /ℎ𝑟
𝑑𝑎𝑦 1 𝑡𝑜𝑛 64 𝑘𝑔 𝑆𝑂2 24 ℎ𝑟𝑠

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND
SULPHURIC ACID PLANT
𝑛6 = 𝑛1 = 𝐵 = 58.59 𝑘𝑚𝑜𝑙𝑆𝑂2(𝑙) /ℎ𝑟

58.59 𝑘𝑚𝑜𝑙 𝑆𝑂2 /ℎ𝑟


𝐹= = 66.88 𝑘𝑚𝑜𝑙/ℎ𝑟
0.876
𝑛2 = 𝑛4 = 0.034 × 66.88 = 2.27 𝑘𝑚𝑜𝑙𝑆𝑂2(𝑔) /ℎ𝑟

𝑛3 = 𝑛5 = 0.09 × 66.88 = 6.02 𝑘𝑚𝑜𝑙𝑂2(𝑔) /ℎ𝑟

Balance around the condenser


Assumption is that in the condenser there is only a phase change, therefore the input to the
condenser separator stream is the same as the condenser input stream.

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND
SULPHURIC ACID PLANT
12.1.2 Condenser Design Sample of Calculation

Heat transferred from vapor

𝑄 = 𝑛̇ 𝑃𝐹 × ∆𝐻𝑣𝑎𝑝
92.974
𝑄= × 27697.449
3600
𝑄 = 715318.197 𝐽/𝑠 (715.32 × 103 𝑘𝑊)

Cooling (refrigerant) medium flow


From literature, it is said that the refrigerant is evaporating at a constant temperature. Therefore
they is only a phase change no temperature change.

𝑄𝑙𝑜𝑠𝑡 = 𝑄𝑔𝑎𝑖𝑛𝑒𝑑

𝑄𝑔𝑎𝑖𝑛𝑒𝑑 = 𝑚̇𝑤 × ∆𝐻𝑣𝑎𝑝

715318.197 = 𝑛̇ 𝑁𝐻3 × 23940.99


𝑚̇𝑁𝐻3 = 0.508 𝑘𝑔/𝑠

Assuming the overall coefficient to be 700 𝑤. 𝑚−2 ℃ (table 12.1) Coulson and Richardson
volume 6

Mean temperature difference: the condensation range is small and the change in saturation
temperature will be linear, so the corrected logarithmic mean temperature difference can be
used.

A horizontal exchanger will be designed, condensation in the tube-side, four tube passes. For
one shell, four passes, from figure below𝐹𝑡 = 1

Trial Area
𝑄
𝐴=
𝑈𝑎𝑠𝑠 × ∆𝑇𝑀
𝐴 = 63.87 𝑚2

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND
SULPHURIC ACID PLANT

Surface area of one tube (ignoring the tube sheet thickness)


𝐴𝑡 = 𝜋 × 𝑂𝐷 × 𝐿

𝐴𝑡 = 25 × 10−3 × 𝜋 × 7.32

𝐴𝑡 = 0.575 𝑚2
Number of tubes
𝐴
𝑁𝑡 =
𝐴𝑡
63.87
𝑁𝑡 =
0.575
𝑁𝑡 = 111.14 ≈ 111
Based on the standards of baffles and tubes, in accordance with the TEMA L (1 in OD on 1.1/4
in triangular pitch the number of tubes is 124 and shell diameter is 438 mm for a 1-4 shell and
tube.

Selection of square pitch arrangement as the tube layout, 𝑃𝑡 = 1.25 × 𝑂𝐷

𝑃𝑡 = 31.25 𝑚𝑚 (0.03125 𝑚)

Shell-Side Coefficient

Firstly determine the wall temperature 𝑇𝑤 , assuming condensing coefficient of 6500 𝑊/𝑚2 ℃
Mean temperature

Shell-side
−70 + (−62)
∆𝑇𝑎𝑣𝑒 =
2
∆𝑇𝑎𝑣𝑒1 = −66 ℃

Tube-side
−54 + (−62)
∆𝑇𝑎𝑣𝑒2 =
2
∆𝑇𝑎𝑣𝑒2 = −58℃

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND
SULPHURIC ACID PLANT

(∆𝑇𝑎𝑣𝑒1 − 𝑇𝑤 )𝐻𝑜 = (∆𝑇𝑎𝑣𝑒1 − ∆𝑇𝑎𝑣𝑒2 )𝑈

𝑇𝑤 = −62 ℃

Mean temperature condensate


−70 + (−70)
𝑇𝑚𝑐 =
2
𝑇𝑚𝑐 = −70 ℃
Physical properties at −𝟕𝟎. 𝟎℃

Mean coefficient for a tube bundle


1⁄
𝜌𝐿 (𝜌𝐿 − 𝜌𝑣 )𝑔 3
ℎ𝑐 = 0.95𝐾𝐿 [ ]
𝜇𝐿 𝛤ℎ
1/3
630.38(630.38 − 11.67)9.81
ℎ𝑐 = 0.95 × 0.248 [ ]
8.72 × 10−4 × 0.203

ℎ𝑐 = 590.46 𝑊/𝑚2 ℃

After iteration several times, the value close enough to the assumed value of 700 𝑊/𝑚2 ℃ was
found to be 590.46 𝑊/𝑚2 ℃, so no correction to 𝑇𝑤 needed.

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND
SULPHURIC ACID PLANT
Tube–side coefficient
Tube cross-sectional area
𝜋 2 𝑁𝑡
𝐴𝑡 = 𝑖𝑑 ×
4 4
𝜋 124
𝐴𝑡 = (20 × 10−3 )2 ×
4 4
𝐴𝑡 = 0.00974 𝑚2

Tube velocity

𝐺̇𝑃𝐹
𝑢𝑡 =
𝜌𝑣 × 𝐴𝑡
1.57
𝑢𝑡 =
11.67 × 0.00974
𝑢𝑡 = 13.89 𝑚/𝑠
Inside coefficient, for water

4200(1.35 + 0.02 × ∆𝑇𝑎𝑣𝑒2 )𝑢0.8


ℎ𝑖 =
𝑖𝑑0.2
4200(1.35 + 0.02 × 25)1.310.8
ℎ𝑖 =
210.2
ℎ𝑖 = 590.4 𝑊/𝑚2 ℃

Fouling factors: as neither fluid is heavily fouling, use (light hydrocarbons) 5000 𝑊/𝑚2 ℃ for
each side, from table Coulson and Richardson volume 6.

𝐾𝑤 = 100 𝑊/𝑚2 ℃

Overall coefficient
𝑑𝑜
1 1 1 𝑑𝑜 × ln ( 𝑑 ) 𝑑 1 𝑑𝑜 1
𝑖 𝑜
= + + + × + ×
𝑈 ℎ𝑐 ℎ𝑜𝑑 2×𝑘 𝑑𝑖 ℎ𝑖𝑑 𝑑𝑖 ℎ𝑖

25
1 1 1 25 × 10−3 ln (20) 25 1 25 1
= + + + × + ×
𝑈 590.4 6000 2 × 100 20 6500 21 4430.27

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND
SULPHURIC ACID PLANT

𝑈 = 526.81 𝑊/𝑚2 ℃

The value of overall coefficient obtained is close enough to the assumed (𝑈𝑎𝑠𝑠 =
𝑤
700 ℃ 𝑎𝑛𝑑 𝑈𝑐𝑎𝑙 = 526.81 𝑊/𝑚2 ℃).This value was obtained through various iterations.
𝑚2

Shell-side pressure drop


The use of a pull-through floating head was chosen, therefore no need for close clearance.
Baffle spacing = Shell diameter (45 per cent cut)

Using the TEMA L standards of baffles and tubes the estimated shell diameter that corresponds
to the number of tubes was found to be 438 mm.

Using Ken’s method to make an appropriate estimate.

Cross-flow area
Assumption made: Baffle spacing is equal to the shell inner diameter (𝐷𝑠 = 𝑙𝐵 )
(𝑃𝑡 −𝑑𝑜 )𝐷𝑠 𝑙𝐵
𝐴𝑠 =
𝑃𝑡
𝐴𝑠 = 0.00767 𝑚2
Mass flow-rate, based on inlet conditions
𝑚̇𝑁𝐻3
𝐺𝑠 =
𝐴𝑠
𝐺𝑠 = 66.23 𝑘𝑔/𝑚2 𝑠

Equivalent diameter
1.27
𝑑𝑒 = × (𝑃𝑡 2 − 0.785𝑑𝑜 2 )
𝑑𝑜
1.27
𝑑𝑒 = × ((31.25)2 − 0.785(25)2 )
25

𝑑𝑒 = 17.75 𝑚𝑚 (0.0178 𝑚)

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND
SULPHURIC ACID PLANT
Vapor viscosity
Using the physical data bank in Coulson and Richardson volume 6, the vapor viscosity of the
mixture was determined as follows:

log 𝑣𝑖𝑠𝑐𝑜𝑠𝑖𝑡𝑦 = [𝑉𝐼𝑆𝐴] × [(1/𝑇) − (1/𝑉𝐼𝑆𝐵)]

𝜇𝑀𝐼𝑋 = 2.258 × 10−5 𝑃𝑎. 𝑠

𝜌𝑃𝐹 × 𝑑𝑒
𝑅𝑒 =
𝜇𝑃𝐹
674.72 × 0.0178 × 0.098
𝑅𝑒 =
2.258 × 10−5
𝑅𝑒 = 52019.44
From Figure 11
𝐽𝑓 = 3.8 × 10−2
𝑚̇𝑁𝐻3
𝑢𝑠 =
𝐴𝑠 × 𝜌𝑣
0.508
𝑢𝑠 =
674.72 × 0.00767
𝑢𝑠 = 0.098 𝑚/𝑠

Taking the pressure drop as 50 per cent of that calculated using the inlet flow, neglecting
viscosity correction (The viscosity correction factor will normally only be significant for viscous
liquids, to apply the correction an estimate of the wall temperature is needed).
.

1 𝐷𝑠 𝐿 𝜌𝑢𝑠 2 𝜇 −0.14
∆𝑃𝑠 = [8𝐽𝑓 ( ) ( ) ( ) ]
2 𝑑𝑒 𝑙𝐵 2 𝜇𝑤

1 −2
787 7.32 674.72(0.098)2
∆𝑃𝑠 = [8 × 3.8 × 10 ( )( ) ]
2 24.69 787 × 10−3 2

∆𝑃𝑠 = 82.75 𝑁/𝑚2


∆𝑃𝑠 = 0.0827 𝑘𝑃𝑎

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND
SULPHURIC ACID PLANT

Tube-side pressure drop

Viscosity of process fluid


𝜇𝑃𝐹 = 9.19 × 10−6 𝑁𝑠/𝑚2
𝜌𝑢𝑡 𝑑𝑖
𝑅𝑒 =
𝜇𝑃𝐹
13.89 × 11.67 × 20 × 10−3
𝑅𝑒 =
9.19 × 10−6
𝑅𝑒 = 352899.99 (3.53 × 105 )
From Figure 11
𝐽𝑓 = 3.6 × 10−3

Neglecting the viscosity correction (The viscosity correction factor will normally only be
significant for viscous liquids, to apply the correction an estimate of the wall temperature is
needed).
𝐿 𝜇 −𝑚 𝜌𝑢𝑡 2
∆𝑃𝑡 = 𝑁𝑃 [8𝐽𝑓 ( ) ( ) + 2.5]
𝑑𝑖 𝜇𝑤 2
3.7 11.67 × 13.892
∆𝑃𝑡 = 4 [8 × 3.7 × 10−3 ( ) + 2.5]
20 × 10−3 2
∆𝑃𝑡 = 58771.44 𝑁/𝑚2
∆𝑃𝑡 = 58.77 𝑘𝑃𝑎

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND SULPHURIC ACID PLANT

12.2 Correlation Charts

Figure 8: Physical properties data bank

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND SULPHURIC ACID PLANT

Figure 9: Overall coefficients (join process side duty to service side and read U from centre scale)

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND SULPHURIC ACID PLANT

Figure 10: Convective boiling factor

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND SULPHURIC ACID PLANT

Figure 11: Tube-side friction factor

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND
SULPHURIC ACID PLANT

Figure 12: Convective boiling enhancement

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND
SULPHURIC ACID PLANT

Figure 13: Fouling coefficients

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND SULPHURIC ACID PLANT

Figure 14: Moody chart, friction factor

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND SULPHURIC ACID PLANT

Figure 15: Nucleate boiling suppression factor

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND SULPHURIC ACID PLANT

Figure 16: Temperature correlation chart (1-2 shell and tube heat exchanger)

Figure 17: Temperature correlation chart (2-4 shell and tube heat exchanger)

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND SULPHURIC ACID PLANT

Figure 18: Physical properties equation correlations

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND SULPHURIC ACID PLANT

Figure 19: Physical properties data bank (Coulson and Richardson vol.6)

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND SULPHURIC ACID PLANT

Figure 20: Discharge coefficient Figure 21: Shell and tube clearance

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND SULPHURIC ACID PLANT

Figure 22: Shell-side friction factor, segmental baffles

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND SULPHURIC ACID PLANT

Figure 23: Tube-side transfer factor

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND SULPHURIC ACID PLANT

Figure 24: Heat-transfer factor for cross-flow tube banks

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND SULPHURIC ACID PLANT

Figure 25: Shell-side heat-transfer factors, segmental baffles

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND SULPHURIC ACID PLANT

Figure 26: Typical overall coefficient

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND SULPHURIC ACID PLANT

Figure 27: Toxicology details, Integrated Liquid Sulphur Dioxide and Sulphuric Acid

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND SULPHURIC ACID PLANT

Figure 28: Transportation table of the integrated Sulphur Dioxide and Sulphuric Acid plant (http://www.sulphuric-
acid.com/techmanual/Plant_Safety/safety_sulphur.htm)

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND SULPHURIC ACID PLANT

Figure 29: Tanker specification for transporting liquid Sulphur dioxide and Sulphuric Acid (http://www.sulphuric-
acid.com/techmanual/Plant_Safety/safety_sulphur.htm

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND SULPHURIC ACID PLANT

Figure 30: Shell and tube heat exchangers. Time base mid 2004

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND SULPHURIC ACID PLANT

12.3 Material Safety Data Sheet


SULFUR DIOXIDE MATERIAL SAFETY DATA SHEET

SECTION 1. PRODUCT AND COMPANY IDENTIFICATION

Product Identity: Sulfur Dioxide

Manufacturer: Supplier:

Teck Cominco Metals Ltd. Teck Cominco American Incorporated Industrial Chemicals

Trail Operations Trail, British Columbia 501 North Riverpoint Blvd., Suite 300,

V1R 4L8 Spokane, WA. 99202

Emergency Telephone: 250-364-4214

MSDS Preparer:

Teck Cominco Metals Ltd.

600 - 200 Burrard Street Vancouver, British Columbia

V6C 3L9

Date of Last Revision/Update: December 15, 2006.

Product Use: Used in the manufacture of chlorine dioxide (a pulp and paper bleaching chemical), as a dechlorination agent
in the pulp and paper industry and waste water treatment plants, in the food processing industries as a preservative, as a chemical
additive in the gold industry cyanide destruction process, in the manufacture of sodium bisulfite solution and in the manufacturing of
sodium hydrosulfite.

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND SULPHURIC ACID PLANT
SECTION 2. COMPOSITION/INFORMATION ON INGREDIENTS

Hazardous Approximate CAS Occupational Exposure Limits LD50/ LC50


Ingredient Percent by Number (OELs) Species and Route
Weight
Sulfur Dioxide 99.9% 7446-09-5 OSHA PEL 5 ppm (13 mg/m3) LD50 No Data
ACGIH TLV 2 ppm (5 mg/m3) LD50 ihl-rat 2520 ppm/1Hr
NIOSH REL 2 ppm (5 mg/m3) LD50 ihl-mouse 3000 ppm/30min
LD50 rat (calculated) 1260 ppm/4Hr

NOTE: OELs for individual jurisdictions may differ from OSHA PELs. Check with local authorities for the applicable OELs in
your jurisdiction. OSHA - Occupational Safety and Health Administration; ACGIH - American Conference of Governmental Industrial
Hygienists; NIOSH - National Institute for Occupational Safety and Health. OEL – Occupational Exposure Limit, PEL – Permissible
Exposure Limit, TLV – Threshold Limit Value, REL – Recommended Exposure Limit

Trade Names and Synonyms: Sulfurous acid anhydride, sulfurous oxide, Sulphur dioxide, SO2

SECTION 3. HAZARDS IDENTIFICATION

Emergency Overview: A colorless gas or liquefied compressed gas with a pungent, irritating odor and taste. Sulfur dioxide
does not burn but cylinders or tanks may rupture and explode if heated, releasing clouds of irritating and toxic SO2 gas. Contact with
liquid SO2 can cause freezing of tissue and frostbite. Wear full protective clothing and a positive pressure full face-piece SCBA in
emergency situations involving SO2.

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND SULPHURIC ACID PLANT
Potential Health Effects: Irritating to the eyes and upper respiratory tract, becoming a severe irritant at high concentrations.
Most inhaled SO2 only penetrates as far as the nose and throat because it dissolves so rapidly in the moist tissues of the upper
airways. In severe cases at very high concentrations serious respiratory effects have been reported. Direct skin or eye contact with
liquid SO2 may cause frostbite. Sulfur dioxide is not listed as a carcinogen by OSHA, NTP, IARC, ACGIH or the EU. (See
Toxicological Information, Section 11)

Potential Environmental Effects: Sulfur dioxide is a common air contaminant in most industrialized areas. Green plants are
extremely sensitive to atmospheric sulfur dioxide. It is also the precursor of acid rain. Release to the environment should be avoided
if possible or minimized when necessary. (See Ecological Information, Section 12)

SECTION 4. FIRST AID MEASURES

Eye Contact: Avoid direct contact. Wear chemical protective gloves if necessary. Remove source of contamination or move
victim to fresh air. Immediately flush the contaminated eye(s) with lukewarm, gently flowing water for at least 5 minutes for the gas
(20 minutes for the liquid) or until the chemical is removed, while holding the eyelid(s) open. Take care not to rinse contaminated
water into the unaffected eye or onto the face. Quickly transport victim to an emergency care facility.

Skin Contact: (Gas) If irritation occurs, flush contaminated area with lukewarm, gently flowing water for at least 5 minutes. If
irritation persists, obtain medical attention immediately. (Liquid SO2) Avoid direct contact. Wear chemical protective clothing, if
necessary. Quickly remove victim from source of contamination and briefly flush with lukewarm, gently flowing water until the
chemical is removed. DO NOT attempt to re-warm the affected area on site. DO NOT rub area or apply dry heat. Gently remove
clothing or jewelry that may restrict circulation. Carefully cut around clothing that sticks to the skin and remove the rest of the
garment. Loosely cover the affected area with a sterile dressing. DO NOT allow victim to drink alcohol or smoke. Quickly transport
victim to an emergency care facility.

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND SULPHURIC ACID PLANT
Inhalation: Take proper precautions to ensure your own safety before attempting rescue (e.g. wear appropriate protective
equipment, use the buddy system). Remove source of contamination or move victim from exposure area to fresh air immediately. If
breathing is difficult, trained personnel should administer medical oxygen. DO NOT allow victim to move around unnecessarily.
Symptoms of pulmonary edema can be delayed up to 48 hours after exposure. Quickly transport victim to an emergency care facility.

Ingestion: Ingestion is not an applicable route of exposure for gases.

SECTION 5. FIRE FIGHTING MEASURES

Fire and Explosion Hazards: Sulfur dioxide is not flammable. However, heat from a surrounding fire can rupture vessels
causing a dangerous explosion and release of toxic sulfur dioxide gas. Cool any containers of sulfur dioxide that are exposed to heat
or flames by the application of water streams until well after the fire has been extinguished since pressure will increase rapidly with
temperature increase. For large fires that threaten tanks or cylinders of SO2 consider evacuating downwind areas. Use caution in
applying water to an SO2 leak, as the run-off will be acidic and corrosive to other materials as well as harmful to the environment.
Run-off may require collection and neutralization.

Extinguishing Media: Use any fire- fighting agent appropriate for surrounding fire conditions such as water spray, carbon
dioxide, dry chemical, or foam.

Fire Fighting: Toxic fumes of sulfur dioxide may be released during a fire. Fire fighters must be fully trained and wear full
protective clothing including an approved, self-contained breathing apparatus which supplies a positive air pressure within a full face-
piece mask. Flashpoint and Method: Not Applicable.

Upper and Lower Flammable Limit: Not Applicable.

Auto-ignition Temperature: Not Applicable

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND SULPHURIC ACID PLANT
SECTION 6. ACCIDENTAL RELEASE MEASURES

Procedures for Cleanup: Isolate hazard area and deny entry to unprotected personnel. Properly trained personnel equipped
with protective clothing and respiratory protection should locate and stop release. Can be neutralized with aqueous alkaline solutions
of lime, caustic or soda ash. Dispose of waste material from neutralization process in accordance with applicable regulations.
Thoroughly ventilate area before permitting re-entry.

Personal Precautions: Protective clothing, gloves, and respirator equipment are recommended for persons responding to an
accidental release (see also Section 8). Close-fitting safety goggles and face shield may be necessary to prevent contact with liquid
SO2. A positive pressure full-face self-contained breathing apparatus (SCBA) is required for emergency or planned entry into
unknown high concentrations of SO2 that may exceed the IDLH level (100 ppm).

Environmental Precautions: This product can pose a threat to the environment. Contamination of water should be
prevented. Liquid spills will produce high concentrations of SO2 gas. Such gas clouds would be heavier than air and may flow
downhill or collect in low spots and not be easily dispersed.

SECTION 7. HANDLING AND STORGE

Store in a registered steel pressure vessel, constructed to comply with ASME Section 8 Code, at appropriate temperatures.
Keep containers tightly closed and store outdoors or indoors in a dry, cool, well-ventilated fireproof area. Protect against physical
damage. SO2 gas is heavier than air and leaked gas can accumulate in low areas. Do not store below ground. Flooring and sumps
should be acid-proof and drain to a collection system. Avoid exposure to moisture, high temperatures and incompatible materials
(see Section 10 - Stability and Reactivity).

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND SULPHURIC ACID PLANT

SECTION 8. EXPOSURE CONTROLS/PERSONAL PROTECTION

Protective Clothing: When handling liquid SO2, gloves and coveralls or other protective clothing are recommended to
prevent the skin from becoming frozen by contact with the liquid or from contact with very cold vessels and equipment handling the
liquid (especially loading and off-loading of trucks and railcars). Face shield and close-fitting safety goggles must be worn when
handling this material in liquid form. An eyewash and quick drench should be provided within the immediate work area for emergency
use where there is any possibility of exposure to liquids that are extremely cold or rapidly evaporating.

Ventilation: Use adequate local or general ventilation to maintain the concentration of sulfur dioxide gas in the working environment
well below recommended occupational exposure limits.

Respiratory Protection: Where sulfur dioxide gas is generated and cannot be controlled to within acceptable levels by
engineering means, use appropriate NIOSH-approved respiratory protection equipment (a chemical cartridge respirator with
cartridge(s) to protect against sulfur dioxide up to 20 ppm, a full face-piece chemical cartridge respirator or half mask PAPR or SAR
up to 100 ppm).

For emergency or planned entry into an unknown concentration or IDLH condition, workers must be fully trained and wear full
protective clothing including a NIOSH-approved, self-contained breathing apparatus which supplies a positive air pressure within a
full face-piece mask.

NOTE: - IDLH = Immediately Dangerous to Life or Health, PAPR = Powered Air Purifying Respirator, SAR = Supplied Air Respirator

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND SULPHURIC ACID PLANT

SECTION 9. PHYSICAL AND CHEMICAL PROPERTIES

Appearance Odor Physical State pH


Colorless Gas or Liquid Pungent and irritating Liquid (liquefied compressed Not Applicable
gas)

Vapor Pressure Vapor Density Boiling Point/Range Freezing/Melting


Point/Range
47.8 PSIG at 68°F, 20°C 2.26 @ 0°C -10 °C, (14°F) -76°C, (-104°F)

Specific Gravity Evaporation Rate Coefficient of Water/Oil Odor Threshold


Distribution
1.44 at 32°F, 0°C 40.18 g/m2 /s at 70°F, 21°C Unknown 1-3 ppm

Solubility in Water
11.9 % by weight at 60°F,
16°C

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND SULPHURIC ACID PLANT
SECTION 10. STABILITY AND REACTIVITY

Stability & Reactivity: Stable under conditions of normal use. SO2 is extremely stable to heat even up to 2000°C. Forms a
moderately acidic solution (pH<3) on contact with moisture in the atmosphere or on the skin. Moist SO2 gas is corrosive to most
common metals.

Incompatibilities: Strong alkalis, ammonia, oxidizing agents, chlorates, powdered chromium, manganese or aluminum,
halogens (fluorine, chlorine) and interhalogens (chlorine trifluoride, etc.), metal oxides, hydrides, azides and acetylides, sodium
carbide and acrolein.

Hazardous Decomposition Products: None.

SECTION 11. TOXICOLOGICAL INFORMATION

General: Sulfur dioxide is a moderate to strong irritant gas and the major effects are on the upper respiratory tract.
Asthmatics may be particularly sensitive to the bronchospastic properties of sulfur dioxide. The major route of exposure to the gas is
by inhalation. Skin and eye contact with liquid SO2 are also serious risks. Since sulfur dioxide is a gas at temperatures greater than -
10 degrees Celsius, ingestion is unlikely to occur.

Acute:

Skin/Eye: Contact with liquid sulfur dioxide can cause frostbite and severe burns. Eye contact may result in severe burns and
corneal damage that can result in blindness. High concentrations of SO2 gas (>10 ppm) are very irritating to the eyes as well,
causing smarting, stinging and tearing. The gas will react with moisture on the skin and cause irritation.

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EQUIPMENT DESIGN FOR INTEGRATED LIQUID SULPHUR DIOXIDE AND SULPHURIC ACID PLANT
Inhalation: Inhalation of sulfur dioxide gas may cause wheezing, tightness of the chest, cough, difficult breathing, nasal
irritation and discharge and alteration in the sense of taste and smell. Pulmonary edema and permanent lung injury have been
reported as a result of exposure to very high levels of SO2 gas in accident situations.

Ingestion: Though unlikely to occur, ingestion of liquid sulfur dioxide would cause severe burning of the mouth, throat and stomach.

Chronic: A number of studies of occupationally exposed workers have been done, with some studies showing a decrease in
lung function of workers and other studies showing no measurable effect. Sulfur dioxide is not listed as a human carcinogen by the
Occupational Safety and Health Administration (OSHA), the National Toxicology Program (NTP), the International Agency for
Research on Cancer (IARC), or the American Conference of Governmental Industrial Hygienists (ACGIH).

SECTION 12. ECOLOGICAL INFORMATION

Sulfur dioxide in water forms sulfurous acid that is harmful to aquatic life. Releases as a gas may damage green vegetation
and be hazardous to birds and mammals.

SECTION 13. DISPOSAL CONSIDERATIONS

Do not wash down drain or allow to reach natural watercourses. Dispose of neutralized waste consistent with regulatory
requirements. Good ventilation is required during neutralization because of the presence of sulfur dioxide gas.

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