NKB 30703

PLANT DESIGN AND MANAGEMENT SYSTEM

Progress Report

Nur ‘Aina Amira binti Rashidi 55220116010

Muhammad Sufi Sariyan 55220116165
Ameerul Afiq bin Abd Halim 55220218047
Arina Hazirah binti Zulkifli 55220116087
Mohamad Ariful Islam 55220116233
 Executive Summary

Production of sulfuric acid is one of the oldest factory process exist. The demand
kept increasing over the years from 150 thousand ton per year in 1985 up to 200 thousand ton
per year in year 2000. Asia has the biggest share in production of sulfuric acid compared to
other region in the world. Sulfuric acid has many important function in the industry world
including as electrolyte in the lead-acid batteries and remove oxide from surface of metal in the
iron and steel making industry. This report is for plant design project for manufacture of sulfuric
acid using the most effective and efficient way.

There are several processes can be used in manufacturing sulfuric acid such as
Contact Process,Sulfacid process, Peroxide Scrubbing and Petersen-Fattinger (Lead Chamber
Process). Sulfacid process need relatively low capital, operating and production cost but this
process is used to produce low percentage of sulphuric acid. Peroxide Scrubbing process is
simple, need low capital cost and has high SO2 removal efficiency. This process produce low
acid strength approximately 50% of 𝐻2 𝑆𝑂4 . As for lead chamber process, it can produce high
strength of acid but in low operating cost. However, disadvantage of this process are presence
of nitrosyl compounds in its product acid, material of construction sensitivity, presence of NO x in
tail gas and provide large-scale commercial installation. Meanwhile in Contact Process,
preparation of sulfuric acid by contact process is based upon the catalytic oxidation of SO2 to
sulfur trioxide (SO3).

For our project, we choose Double Contact Process, which is much more effective
in getting 99% concentration of product compared to Single Contact Process. Equipment used in
this process is compressor, air filter, air dryer, sulfur storage, furnace, waste heat boiler,
intermediate and final absorber, contact tower, and heat exchanger. Compressor are used in this
process in order to compress in the air into the air dryer. Sulfur from sulfur storage then being
burnt in the furnace that commonly used to burn fuel oils. Then, sulfur dioxide is produced. After
that, the sulfur dioxide will get into waste heat boiler and proceed to the heart of the process,
contact tower. Vanadium pentaoxide is used as catalyst in the reaction to produce sulfur trioxide.
The last operation will be carried out in absorber. Sulfur trioxide gas will be absorbed into sulfuric
acid and will produced oleum. Then, the oleum formed will react will water and form sulfuric acid.
The reaction product is absorbed in a final absorber resulting in sulfuric acid with a concentration
up to 98 percent.

The double contact process can be improved by energy recovery,utilizing a waste

heat boiler, as well as introducing feed effluent heat exchangers. In the design that was proposed,
the primary energy recovery unit implemented was the waste heat boiler to recover the heat
carried out by the hot gas stream at temperatures in excess of 1000OC to 350OC. The waste heat
boiler was used to recover the high quality heat in the Sulfur furnace as steam. The feed effluent
heat exchanger is used for making the reactor cooled down because the reactor used high
temperature approximately 450-550OC.
 Table of Content

No. Page Content

1.0 Executive Summary 1

2.0 Table of Content 2

3.0 Introduction 3

4.0 Process Selection 4 – 10

5.0 Pipe Flow Diagram 11

6.0 Plant Layout 12

7.0 Process Equipment & Design requirement 13

8.0 Process & Design Requirement 14

9.0 Reference 15
 Introduction

Asia is the world largest sulfuric acid manufacturer in the world with almost 30
percent share, followed by U.S, Africa, Europe and others. The demand for sulfuric acid kept
increasing over the years from 150 thousand metric tons per year in 1985 to almost 200 thousand
metric ton per year in 2000. This means increasing amount of world supply.

Manufacture of sulfuric acid was discovered by a Persian alchemist in ninth century

and it is one of the oldest industrially applied processes. Sulfur was mixed with salt peter in a gas
chamber and burnt in moist atmosphere. The product collected was acid. Then, in eighteenth
century, lead chamber reactor was invented in England, thus increase production rates of acid by
78 percent. In 1831, the oxidation of sulfur dioxide using platinum as catalyst, Contact Process,
was filed, and increasing the yield up to 95 percent. In 90s, the use of vanadium pentaoxide was
introduced and used widely as catalyst in Contact Process because it is not sensitive to poisons
and low in cost. In 1960, the double-catalyst process (double absorption) was introduced.

Sulfuric acid, H2SO4 is a very corrosive mineral acid and it is colorless to slightly
yellow and water-soluble. It is also a strong oxidizing and dehydrating agent with high boiling point
and density of 1.84 gram per centimeter cube. There are several importance of sulfuric acid. The
uses of sulfuric acid ranging from becoming lead-acid batteries, in ore processing, fertilizer
production, oil refining process, and wastewater processing. Sulfuric acid can be manufactured
by either of two processes, Lead Chamber Process or Contact Process. Sulfuric acid produced
in lead chamber process is limited to 35 percent and produced precipitates on lead walls and
totally replaced by contact process.

Raw material needed for sulfuric acid production is sulfur, air, and water. Sulfur of
greater than 99 percent purity is used. Sulfur usually take place in flakes or granules form. In
optimum condition, one ton of sulfur can produce three ton of sulfuric acid. Water function is to
ease the process equipment. Raw water is used in heat exchanger area and one mole of sulfuric
acid require one mole of water normally. Product produced, sulfuric acid, is reactive violently with
some bases, but non-flammable. It is a clear, colorless liquid and odorless. Plant location and
environmental condition are also important. The sulfuric acid plant should be built near the
residential area as it is easier to produce paints and pigments, soaps and detergent and other
chemicals. It will also generate more income for the state or area. The plant also will be built near
residence because this will lower the product distribution cost. It is important to consider the
proximity to major markets. With nowadays technology and Industrial Revolution 4.0, the plant
can operate longer and efficiently by using artificial intelligence.
 Process Selection

Sulphuric acid be the most important electrolyte in the lead-acid batteries and used in
large quantities by the iron and steel making industry to remove oxide from the surface of metal.
In order to produce sulphuric acid, there are several different methods with using many type of
raw materials like by burning molten waste elemental sulphur that has percentage of 70% of world
production, from high sulphur dioxide (SO2) strength metallurgical off-gases with amount of 20%
and by decomposing spent of sulphuric acid catalyst of 10%. Product of sulphuric acid
manufacture is liquid acid (93-98%) H2SO4 and water with the range of 2 until 7%.

Type of processing method to produce sulphuric acid are Sulfacid process, Peroxide
Scrubbing, Petersen-Fattinger process and Contact process. Sulfacid process need relatively low
capital, operating and production cost but this process can be used to produce low percentage of
sulphuric acid. This process is using SO2, H2O and O2 react with activated carbon catalyst.
Normally used in this process is multiple activated carbon beds that arrange in parallel. This
process can treat feed gases with maximum amount of dust minimizing activated carbon fouling
of 30mg/Nm3, minimum volume of 7 % of O2 and less than 1% of SO2.

Figure 1: Sulfacid process for removing SO2

Based on figure 1, feed gases are mixed with steam in the mixing chamber before entering
the reactor that filled with activated carbon as catalyst. Sulphuric acid is formed when the oxidation
take place of SO2 in the presence of H2O and activated carbon. Holding tank is used after the
acid has been washed on the activated carbon then pumped to the acid plant’s circulation system
to sell to the customer or make dilution.

Peroxide scrubbing or mainly known as Peracidox process is developed by Sud-Chemie

and Lurgi Metallurgie is used to remove residual of SO2 from tail gases from double absorption
sulphuric acid plants. Main chemical used in the process is hydrogen peroxide (H2O2) to oxidise
SO2 to sulphuric acid:

𝑆𝑂2 (𝑔) + 𝐻2 𝑂2 (𝑎𝑞) → 𝐻2 𝑆𝑂4 (𝑎𝑞)

Scrubbing is achieved by direct contact in a counter –current spray tower. Hydrogen

peroxide reacts with SO2 in the first chamber and overflows to the second chamber. This process
is simple, need low capital cost and has high SO2 removal efficiency. This process produce
relatively low acid strength product approximately 50% of 𝐻2 𝑆𝑂4 . Peracidox process is suitable
for acid plant tail-gas treatment as the SO2 concentrations are low or temporarily high during start
up.

Figure 2: Peracidox process flow schematic.

Figure 2 shows 50% of H2O2 is react with SO2 to form 50% of 𝐻2 𝑆𝑂4 solution. 20ppm of
SO2 at tail gases meanwhile of 𝐻2 𝑆𝑂4 vapour and SO3 are removed from the feed gas stream.

Petersen-Fattinger or known as lead chamber process can produce high strength of acid
but in low operating cost. 65% of H2SO4 containing nitrosyl sulphuric acid (NOHSO4) is contacted
with a series of packed tower is used with feed gases of H2O and SO2 . This reaction can promote
formation of H2SO4 from SO2, O2 and H2O7. To form more acid catalyst, reaction to generate NO
(g) and NO2 need to reabsorb into higher strength of acid. Nitric acid must be added to ensure
correct level of NOHSO4 are present for catalysis. End product will produce range of 70-76%
H2SO4 with some nitrosyl present. Disadvantage of this process are presence of nitrosyl
compounds in its product acid, material of construction sensitivity, presence of NOx in tail gas and
provide large-scale commercial installation.
 Figure 3: Block Flow Diagram of Lead Chamber Process

Last method to produce sulphuric acid is by using Contact Process. Preparation of

sulphuric acid by contact process is based upon the catalytic oxidation of SO2 to sulfur trioxide
(SO3) then convert to oleum and form concentrated sulphuric acid. To make SO2 can be obtained
by burning sulphur in an excess air. Chemical reaction shows below:

𝑆 (𝑠) + 𝑂2 (𝑔) → 𝑆𝑂2 (𝑔)

An excess air is used to convert sulphur trioxide. Chemical reaction to convert into sulphur
trioxide shows below. This is a reversible reaction, and the formation of the sulfur trioxide is
exothermic. This stage can promote rapid SO2 oxidation at cool temperature by using catalyst. As
increase in tempearture will increase rate of reaction but decrease in maximum attainable
(equilibrium) SO3 production in the absence of catalyst. The catalyst is molten Na, V, O, S, Cs
solution on porous silica substrate. Figure 4 below shows the reaction goes almost to completion
at 600K but not at 1000K.

Figure 4: Maximum percentage of sulphur dioxide that can be oxidize when equilibrium is
attained.
 2𝑆𝑂2 (𝑔) + 𝑂2 (𝑔) → 2𝑆𝑂3 (𝑔)

To form sulphuric acid cannot be done by adding water only. It must be dissolved in
concentrated sulphuric acid to prevent uncontrollable fog of sulphuric acid that can cause hazard.
The product is known as oleum (H2S2O7) or fuming sulphuric acid. Dilution of oleum with water
can form sulphuric acid of required concentration .

𝐻2 𝑆𝑂4 (𝑙) + 𝑆𝑂3 (𝑔) → 𝐻2 𝑆2 𝑂7

𝐻2 𝑆2 𝑂7 (𝑙) + 𝐻2 𝑂 → 𝐻2 𝑆𝑂4

Nowadays, sulphuric acid is prepared by contact process all over the world. Contact
Process be the best process compared to Lead Chamber Process and other process as it is much
more economical. Lead Chamber Process can produce more dilute acid that Contact Process
which yields concentrated sulphuric acid. 99.5% conversion of sulphur dioxide into sulphur
trioxide present even at low pressure. Thus, these small improvement can achieve by increasing
the pressure is not worth the expense of producing those high pressures. Oleum that produce
during Contact Process can be used in oil refining process to make crude oil distillates.

Chemical Properties of Sulphur

Property Value
Toxicity >5.43mg/L (Inhalation)
Reactivity Not reactive
Acidity or basicity Acidic
Specific gravity 2.07 at 21.1oC
Flammable Limits LEL: 3.3 UEL: 46.0

Physical Properties of Sulphur

Property Value

Color Pale yellow

Solubility Insoluble in water

Conductivity A poor conductor of heat and electricity

Odour Skunk scent

 Phase Solid

Density 2.07 g.cm-3 at 20oC

Boiling point The boiling point of sulphur is 444.6oC

Melting point The melting point of sulphur is 113oC

Flash point The flash point of sulphur is 207.2oC

Chemical Properties of Sulphur Dioxide

Property Value
Toxicity Classification criteria are not met.
No reactivity hazard other than the effects
Reactivity
described in sub-sections below
Acidity or basicity Acidic
Specific gravity 2.285
Flammable Limits Non flammable

Physical Properties of Sulphur Dioxide

Property Value

Color Colourless

Solubility Completely soluble

Odour Pungent

Phase Gas

Density 1.5 g/cm3

Boiling point -10 °C

Melting point -75.5 °C

Flash point Not applicable for gases and gas mixtures

Chemical properties of Sulphur Trioxide

Property Value
Toxicity 30 mg/m3 (inhalation)
The product does not present hazards by their
Reactivity
reactivity
Acidity or basicity Acidic
Specific gravity 1.85
Flammable Limits Not applicable

Physical Properties of Sulphur Trioxide

Property Value

Color Colourless

Solubility No data available

Odour Not applicable

Phase Solid

Density 1.92 g/cm3

Boiling point 235oC

Melting point

Flash point
Chemical properties of Sulphuric Acid

Property Value
Toxicity 2140 mg/kg (oral)
Reactivity Reacts violently with some bases
Acidity or basicity Acid
Specific gravity 1.85
Flammable Limits Non flammable

Physical Properties of Sulphuric Acid

Property Value

Color Clear, colourless liquid

Solubility Miscible

Odour Odourless

Phase Liquid

Density 1.8302g/cm3

Boiling point 335oC

Melting point 10oC

Flash point Not applicable

Pipe Flow Diagram
Plant Layout
 Process Equipment and Design Requirement

Based on discussion among group members, the decision had be finalize, that is
production of sulfuric acid by using contact process. In contact process, sulfur trioxide is
absorbed into 98.5% to 99% sulfuric acid in the presence of catalyst. In contact process,
it has three step to accomplish, first step is the oxidation of sulfur (S) that will form sulfur
dioxide (SO2). Then the SO2 will undergoes the second step, converting into sulfur trioxide
(SO3) in the presence of excess oxygen. This reaction is a reversible reaction which is the
main key of the process. Step three is involving absorption of SO3. SO3 in gases form will
be absorbed into liquid sulfuric acid and forming disulfuric acid (H2S2O7) in the presence
of vanadium pentaoxide (V2O5) as catalyst.

For our project, we choose Double Contact Process, which is much more effective
in getting 99% concentration of product compared to Single Contact Process. Equipment
used in this process is:-

 Compressor
 Air filter
 Air dryer

 Sulphur storage

 Furnace
 Waste heat boiler
 Intermediate absorber
 Contact tower
 Final absorber
 Heat exchanger

Compressor are used in this process in order to compress in the air into the air
dryer because oxygen in the air composition is needed in the reaction. The compressed raw air
will pass through air filter to remove out any kind of dust particle in the air because the catalyst
can become poisoned and rendered ineffective by dust. Next, the filtered wet air will get into air
dryer to remove out the moisture content in the air because moisture in the air will be poisonous
toward catalyst and it will disturb the process. To remove the water content in the moist air, sulfuric
acid with concentration of 98-99% will be sprayed over the moist air inside the air dryer. Sulfuric
acid that leaving air dryer will have the concentration of 93-97%. The dry air obtained will later
being used in furnace, contact tower and heat exchanger.

Sulfur from sulfur storage then being burnt in the furnace that commonly used to
burn fuel oils. Molten sulfur and dry air are being introduced to oxidation process taking over when
the sulfur being burnt with the presence of oxygen in the dry air. The oxidation of sulfur will form
sulfur dioxide. This reaction is an exothermic reaction which meant the temperature of the reaction
will increase.

After that, the sulfur dioxide will get into waste heat boiler. In waste heat boiler, the heat from
the sulfur dioxide is used to make steam and in the same time it will cool down the sulfur dioxide
gas. It will take the water from the boiler feed and converting it to the steam. This process will
increasing the energy efficiency of the whole process. The gas leaving the waste heat boiler at
the temperature of 425-440oC.

Next, sulfur dioxide will enter the contact tower, the heart of the process. Contact
tower contains four stages and each stage has V2O5 catalyst packed tray. In this process, sulfur
dioxide reacts in the contact tower with excess oxygen to sulfur trioxide and this reaction is a
reversible reaction. This reaction will be much favorable if the temperature is lower according to
Le Chatelier’s Principle. The lower temperature between each stage in contact tower will ensure
the conversion of sulfur dioxide to sulfur trioxide will be almost 99.7%. The lower temperature
became viable by the help of catalyst.

The final operation will be carried out in absorber, both intermediate absorber and
final absorber. Sulfur trioxide gas will be absorbed into sulfuric acid and will produced disulfuric
acid, which we called as oleum. Then, the oleum formed will react will water and form sulfuric
acid. The reaction product is absorbed in a final absorber resulting in sulfuric acid with a
concentration of 96 – 98%.
 Process and design improvement

The energy economy of double contact process can be improved by energy

recovery by utilizing a waste heat boiler as well as introducing feed effluent heat exchangers. In
the design that was proposed, the primary energy recovery unit implemented was the waste heat
boiler located downstream of the Sulfur burning furnace to recover the heat carried out by the hot
gas stream at temperatures in excess of 1000OC to 350OC. About 10% of this heat is utilized for
the Sulfur melting process heating. Thus the excess steam available were utilized for in house
power generation. The waste heat boiler was used to recover the high quality heat in the Sulfur
furnace as steam. The feed effluent heat exchanger is used for making the reactor become cooled
down. Because in the reactor used high temperature and that was approximate 450-550OC. The
outlet gas streams from the converter to the absorption columns could also be considered as a
point of heat recovery since they too carry gas at temperatures approximate 450-550OC, which
can also be utilized to produce steam.

Since the high heating temperatures prevents usage of saturate steam, thermic
liquid of heat is dispensed in the structure for procedure heating of the converter and its bordering
lines. In spite of the fact that thermic liquid is surely the preferred option to the extent high
temperature heating is concerned high weight superheated steam may be an alternative however
superheated steam is preferred for power generation. The converter energy recoverable sections
can be generally considered as high evaluation energy that could be utilized for procedure heating
and power generator while the rest of for the mostly low grade that could be utilized for minor
heating applications, for example, as water heating, inline heating of process lines such as molten
Sulfur transfer lines etc.

If the heat in the converter outlet gas streams is recovered in full up to the
temperatures recommended as gas inlet temperatures of absorption columns this target could be.
A proper analysis would reveal exactly how much is possible to be recovered along by a suitable
cold stream also in the process, which is still likely to indicate an on par recovery of energy in
comparison.
 Reference

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Inc

King, M., Moats, M., & Davenport, W. G. (2013). Sulfuric acid manufacture, analysis, control and
optimization. Newness.

Carlson, R. W., Anderson, M. S., Johnson, R. E., Schulman, M. B., Yavrouian, A. H. (2002).
Sulfuric acid production on Europa: the radiolysis of sulfur in water ice. Icarus, 157(2), 456-463.

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https://www.citycollegiate.com/sulphuric_acid1.htm

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https://www.academia.edu/19401832/Sulfuric_Acid_Production

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Teck. (2015, 25 March). Sulphur Safety Data Sheet. Retrieve from

https://www.teck.com/media/Sulfur.pdf

Northeastern. (2009, 1 August). Sulphuric Acid. Retrieve from

http://www.northeastern.edu/wanunu/WebsiteMSDSandSOPs/MSDS/Msds_Sulfuric_Acid.pdf

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http://docs.airliquide.com.au/msdsau/AL013.pdf

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https://www.fishersci.com/store/msds