From Sulfur to Sulfuric Acid

www.mecsglobal.com/.../difficultapplications.asp

The Contact Process

 History
universe-review.ca/F13-
atom.htm

Process of burning sulfur with

saltpeter was first described in the 15th
century

1746 – lead chamber process www.georgiaencyclopedia.org/ng

e/Multimedia.js...

1831 – contact process

- use of catalyst
- absorption of SO3 into 98.5 % to 99 %
H2SO4
 Process
S (l) O2 (g) SO2 (g) Η = − 298.3 kJ, 25 0C

SO2 (g) 1/2O2 (g) SO3 (g) Η = − 98.3 kJ, 25 0C

SO3 (g) H2SO4 (l) H2S2O7 (l) H = - 130.4 kJ, 25 0C

“Because sulphur is exothermic and burns in air, heat is

generated and most sulphuric acid plants generate
steam as a by-product.”
www.engineeringnews.co.za/article/new-sulphur...

• large plants can produce 1.3 tons in excess per metric ton of
acid
• in some countries, energy from sulfuric acid plants is used in
homes and offices saving ~ 35 700 tons of fuel oil per day!
 S (l) O2 (g) SO2 (g) Η = − 298.3 kJ, 25 0C

SO2 (g) 1/2O2 (g) SO3 (g) Η = − 98.3 kJ, 25 0C

SO3 (g) H2SO4 (l) H2S2O7 (l) H = - 130.4 kJ, 25 0C

How can more SO3 (g) be produced?

PSO3
Kp = 1
2
PSO2 x PO2
 Temp, 0C Kp
400 397
500 48.1
600 9.53
700 2.63
800 0.915
900 0.384
1000 0.1845
But, rate of reaction increases with 1100 0.0980
increase in temperature → balance
between rate of reaction and optimum
conversion

earlier catalysts included
Use of a catalyst: iron oxide and platinum

replaced with V2O5
(vanadium pentoxide) – can
last up to 20 years

is used in the shape of
hollow cylinders →
increased surface area
together with good flow of
gas through the catalyst

How else can we

optimize the
conversion to SO3?

Four-pass Converter SO2 (g) 1/2O2 (g) SO3 (g)

www.britannica.com/EBchecked/topic-art/572815...
 S (l) O2 (g) SO2 (g) Η = − 298.3 kJ, 25 0C

SO2 (g) 1/2O2 (g) SO3 (g) Η = − 98.3 kJ, 25 0C

SO3 (g) H2O (l) H2SO4 (l) H = - 130.4 kJ, 25 0C

SO3 (g) H2O (l) H2SO4 (aq) X

highly corrosive mist

of sulfuric acid fumes
 SO3 (g) H2SO4 (l) H2S2O7 (l)

98.5 – 99 % sulfuric acid is a good
Steel absorber of SO3 (g)

lined with acid proof bricks with
ceramic packing with conc acid flowing
over it allows for SO3 (g) to
have close contact with the conc acid
H2S2O7 (l) H2O (l) 2 H2SO4 (l)
H2O
H2 SO4 (l) H2SO4 (aq)

concentrated acid is withdrawn and

portion going back into tower is diluted
Absorbing tower with dilute H2SO4 or water
Typical flow chart for a sulfur-burning single-absorption contact sulfuric acid
plant. Monsanto Enviro-Chem from Shreve’s Chemical Process Industries
 “Heart” of the contact process. Discuss in terms
Remove CO2, of the equilibrium reaction, rate of reaction, rate
N2, moisture of conversion and increased SO3 formation?
& other
impurities

Furnace similar
to that used for
burning fuel oils

Removes heat from

sulfur burner gas →
steam
Cooling gases
 Absorption of
between passing
SO3 into H2SO4
through catalyst –
why?  Recirculated
H2SO4 is cooled
 What is a furnace?

www.oup.co.uk/.../pictures/industry/furnace/

www.petrocoke.com/pics1.html
 Schematic diagram of an
industrial process furnace

air blower directs air
towards burner that is
powered by fuel

heat transferred to
tubes in radiant section
→ flow of liquid through
the tubes is heated to
desired temperature

combustion gases
vented via the stack but
their heat is recovered in
the convection section
first
http://en.wikipedia.org/wiki/File:Furnace2-en.svg
 Secondary
combustion chamber
where vaporized
sulfur is burned –
650 – 900 oC O2 gas introduced
to molten sulfur

Combustion
chamber where the
molten sulfur is
partially burned
Steam heating and vaporized
coil
http://www.freepatentsonl
ine.com/2622007.pdf
Melt vessel
where the sulfur
is melted
 What is a heat exchanger?

A device that allows

for the exchange of
heat from a fluid on
one side of a barrier
to fluid on the other
side of the barrier
without the two
liquids coming into
contact with each
other.

Give examples of
heat exchangers. http://www.thefreedictionary.com/_/vie
wer.aspx?path=hm&name=A4heatex

Rate of heat transfer is dependent on:
- temperature difference between hot and
cold fluids/surfaces
- surface area available for heat transfer

the geometry and physical properties of

a system will also influence the heat
transfer system, for eg., if fluids are
involved then the flowrate is important

heat exchange or transfer is used in
industry to
- heat or cool reactions
- keep raw materials at an optimal
temperature (eg., keep solid fats in a
liquid state)
- conserve energy (eg., re-use of steam
condensate)

most commonly used between liquids but

may get transfer between gas and liquid
or between 2 gases.
Types of Heat Transfer Equipment

Jacketed vessel External coil

lower surface area → smaller contact area

not generally used for temperature control in reactors

used in low duty heating requirements, for eg.,
maintaining the temperature in raw material tanks or
heating pipe lines
 Internal helical coil Internal baffle type coil

Used in reactors even if contains viscous material.

High surface area for heat transfer

Problem? Makes cleaning of reactor difficult and
interferes with mixers in reactors
 External Heat Exchangers

external heat
exchanger

solution is pumped to
outside the vessel where
heat transfer occurs
 Double pipe heat exchanger
Hot and cold liquids move in a
counter current direction

outer annulus

inner tube
Most efficient operation is
achieved when inlet and
outlet temperatures are as
close together as possible
Single pass tubular heat exchanger
directs the
flow of liquid
counter
current

divides the header from

the rest of the
apparatus & prevents
the fluid from entering
the shell

larger surface area → many tubes inside a shell or cavity

Provide labels for this diagram

www.absoluteastronomy.com/topics/Shell_and_tu...
 Plate heat exchanger

is a series of metal plates

2 fluids pass through the
metal plates and are in
contact with each other
through the plates but do not
mix

plates are sealed with high
temperature rubber gaskets
for easy cleaning or repair

usually used where there
is a lot of fouling and the
system needs a lot of
cleaning
 “Heart” of the contact process. Discuss in terms
Remove CO2, of the equilibrium reaction, rate of reaction, rate
N2, moisture of conversion and increased SO3 formation?
& other
impurities

Furnace similar
to that used for
burning fuel oils

Removes heat from

sulfur burner gas →
steam
Cooling gases
 Absorption of
between passing
SO3 into H2SO4
through catalyst –
why?  Recirculated
H2SO4 is cooled
Is Continuous or Batch Processing
Better?

the aim is to produce the maximum amount of

product

the types of solutions dealt with on the plant

determine which process is better

costs of labour, amount of product, research

and instrumentation also play a role in
determining which process is used.

Continuous process:

- runs continuously

- fairly automated → minimize labour

- have much less material in process

therefore lower chance of ruining large
quantities of feedstock

- more uniform operating conditions→

requires good quality instrumentation for
concise control
- suitable for processes that are liquids
or gases. Why?

- entire plant cannot be shut down for

maintenance → shut down small sections
of the plant at a time to carry out
repairs and maintenance

- Disadvantage – very expensive to build


Batch process:

- Relatively smaller quantities of feedstock are

processed in individual reactors→ produce
smaller quantities of product
- Precise quantities for each batch can be
weighed out accurately but temperature
control can be a problem
- Easier to control the reaction in a small
reactor
- Maintenance is easier
- Disadvantage – very labour intensive
What type of process does the
Contact Process use?

Contact process:

- Gaseous feedstock → produce liquid

product

- Large demand for end product

 Environmental Awareness
 What are the main pollutants in a sulfuric
acid process?

 Identify, on the process chart, where these

pollutants would be present.

 Why are these regarded as pollutants?

 Describe in detail the methods that can be used

to reduce these pollutants
Why are these regarded as pollutants?

- SO2 is a throat and nose irritant and

causes breathing problems if high
concentrations are inhaled.
- Damage to vegetation and animals
- SO3 combines with water vapour
in the atmosphere to form sulfuric acid
mist.

Use of higher stacks:

- Tall stacks help

to disperse the
SO2 gas higher
into the
atmosphere
away from
ground life http://sine.ni.com/cms/images/casestudies/stacks_01.jpg

- Climate conditions and topography of the

surrounding must be considered during
emission of gases and building of stacks

Use of scrubbers:
- Scrub with
 water (very effective in
reducing 50 – 75 % of
SO2)
 soda ash (produce
sodium bisulfite as by-
product)
 lime slurries
 salt solutions (slightly
alkaline, heated conc salt
soln) http://www.thermalenergy.com.au/images/Gas
Cleaning/LandfillGas.jpg

Removal of acid mist
- The smaller the mist particles the greater
the visibility which results in plumes from
stacks
- Removal of acid mist is carried out by:
 Packed bed separators
containing sand, coke or
fibers of glass or metal
which cause the particles
to coalesce
 Wire mesh mist eliminators
cause particles to coalesce when
high velocity gas pass through
http://upload.wikimedia.org/wikipedia/commons/thum
them b/3/31/Packedtowerex.gif/250px-Packedtowerex.gif
 Porous ceramic filter tubes made up of
aluminium are effective in collecting
acid mist that passes through it from
the top downwards

 Electrostatic precipitators

 Sonic agglomerators use sound waves to

cause small particles to stick together
to form a large particle which is then
removed by cyclones
What is Sulfuric Acid Used for?
 ~ 70 % used to make superphosphate
fertilizers
 Processing of metal ores
 Manufacture of detergents
 Manufacture of paper
 Manufacture of rayon and other
polymers
 Manufacture of paints and
pigments
 Electrolyte in heavy duty batteries
 Laboratory reagent
Economic Role of Sulfuric Acid

sulfuric plays an important role in a
countries industrial economy

Post war (1940-

1965) – greatest
economic growth

WW2
WW1 (1938)
(1917-1919)

Stock market
crash (1929)
http://www.pafko.com/history/h_s_acid.html
• Most produced chemical in the US
• About 40 million tons produced per year
(US - 1990)
• Cost of sulfuric acid
is affected by supply &
demand which is
affected by the
demand for the chemicals
it is used to make

http://www.purchasing.com/article/talkback/227813-
Sulfuric_acid_prices_continue_to_decline_as_demand_dries_up.php#52758
“We may judge with great accuracy the
commercial prosperity of a country
from the amount of sulfuric acid it
consumes”

1840 Liebig