Sulfur and Sulfuric Acid

Sulfur
Atomic Weight: 32.07
Allotropes
Rhombic: Melting Pt: 112.8 ⁰C
Sp. Gravity: 2.07 (at 18 ⁰C) Crystals of Crystals of
Monoclinic: Melting Pt: 119 ⁰C rhombic sulfur monoclinic sulfur
Boiling Pt: 444.6 ⁰C
Sp. Gravity: 1.803 (at 18 ⁰C)
Solubility: Insoluble in water but soluble
in organic solvent and liq. NH3

• Raw Materials:
1. FRASCH Process: Natural sulfur
2. Oxidation and Reduction of H2S
3. Iron pyrites (FeS2)
4. Recovery of elemental sulfur from
petroleum refineries
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 FRASCH Process
 In the Frasch process, three
concentric tubes are introduced into
the sulfur deposit. Superheated
water (165 °C, 2.5-3 MPa) is
injected into the deposit via the
outermost tube. Sulfur (m.p. 115 °C)
melts and flows into the middle tube.
Water pressure alone is unable to
force the sulfur into the surface due
to the molten sulfur's greater density,
so hot air is introduced via the
innermost tube to froth the sulfur,
making it less dense, and pushing it
to the surface.

The sulfur obtained can be very pure (99.7 - 99.8%). In this form, it is light
yellow in color. If contaminated by organic compounds, it can be dark-
colored; further purification is not economic, and usually unnecessary.
Using this method, the United States produced 3.89 million tons of sulfur in
1989, and Mexico produced 1.02 million tons of sulfur in 1991.
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FRASCH Process

Major Engineering Issues

Heat transfer in melting operation
Finding suitable sources of treated water
Corrosion
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Oxidation and Reduction of H2S

• Chemical Reaction
2H 2 S  3O 2  2SO 2  2H 2 O, ΔH o  247.89 Kcal
4H 2 S  2SO 2  S 6 (g)  4H 2 O, ΔH o  42.24 Kcal

Raw Material
H2S from natural gas and petroleum refinery streams
(Recovered by scrubbing with ethanolamines and high-
temperature stripping).
1 metric ton of Sulfur: 1.2 tons H2S and 1700 m3 air
required.

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Oxidation and Reduction of H2S

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Sulfur from Pyrites (FeS2): Finnish Process
• Raw Material
• Iron Pyrites (FeS2)
• For 1 ton of elemental sulfur (99+% purity)
• Iron Pyrites: 4.4 tons
• Fuel Oil: 0.76 ton
• Water: 25 tons
• Electricity: 1800 KWh
• Co-products
• SO2 from FeS roasting: 1.2 tons
• Fe2O3 from FeS roasting: 2.8 tons
• Electricity: 3200 KWh

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Sulfur from Pyrites (FeS2): Finnish Process
Chemical Reaction
Thermal Dissociation
1
FeS2     S 2 ( g )  FeS (l ), H  15.98Kcal
1atm,1300o C

2
General Combustion Reaction
C  H  S  O2  SO2 , H 2 S , CO2 , CO, H 2O
Sulfur recovery from gases-Hot stage
2COS  CS 2  2SO 2    S 6  3CO 2
Catalyst , 600o C

Sulfur recovery from gases-Cold stage

Al 2 O 3 , 280o C
4H 2 S  2SO 2   
 4H 2 O  S 6
Roasting of FeS (Pyrrohotite) for SO2 recovery
1
2 FeS  3 O2     Fe2O3  2 SO2 , H  295.02Kcal
1atm,1000o C

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Flow sheet for Sulfur synthesis from Iron Pyrites (FeS2)

Major Engineering Issues

 Pyrites ore beneficiation (SiO2 5-7%) [Froth Flotation Unit]
 Grinding
 Substitution of coal for fuel oil
 Gaseous reaction in the smelting furnace
 Heat recovery and generation of electrical energy
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 Sulfuric Acid (H2SO4) Industry
Sulfuric acid is produced in greater quantities than any other chemical in both Australia
and the world.
Annual worldwide production is estimated at about 170 million tonnes and Australian
production at 4 million tonnes.
In future years it is anticipated that Australia will become a major exporter of the
chemical
Transport and storage of sulfuric acid are hazardous.
Most sulfuric acid plants are located near smelting and refining industries that produce
waste sulfur dioxide, a raw material for the production of sulfuric acid.
Properties and Application of H2SO4
Properties
 Mol Wt: 98.08
 Melting Point: 10.5 °C and Boiling pt: 340 °C
 Solubility: Completely miscible with water with large heat of
solution
 Sp. Gravity: depends on grade
E.g., 95% H2SO4 : 1.840 (at 18 °C)
98% H2SO4 : 1.843 (at 18 °C)
Applications
It is also used in the manufacturing of paper, household
detergents, pigments, dyes and drugs.
It is the electrolyte in car batteries.
Two methods are used for H2SO4 production
Chamber Process
Contact Process
Contact Process
 Sulfuric acid is made in several stages from SO2, obtained from the
oxidation of sulfur or collection of SO2 from the smelting of sulfide ores
such as copper, zinc or lead. This second collection of SO2 is very
attractive as it is utilising the by-products of other processes and reduces
emissions and waste.
SO2(g)  SO3(g)  H2SO4(aq)

S (S )  O2 ( g )  SO2 (g) ΔH  70Kcal

1
SO2 ( g )  O2 ( g )    SO3 (g)
V2 O 5 catalyst
ΔH  23Kcal/mole
2

SO3(g)  H 2 SO4(l)  H 2 S 2O7(l)

H 2 S 2O7(l)  H 2O(l )  2 H 2 SO4 (l )

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Raw Material
S
Iron Pyrites
CuS, ZnS, PbS, MoS2
H2S
Quantitative Requirement
To produce 1 ton 100% H2SO4
SO2 : 0.67 ton
Air: 1,450-2,200 m3

Conversion of SO2 to SO3

1. Oxidation of SO2 into SO3 by V5+:
2SO2 + 4V5+ + 2O2− → 2SO3 + 4V4+
2. Oxidation of V4+ back into V5+ by dioxygen (catalyst
regeneration):
4V4+ + O2 → 4V5+ + 2O2−
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Flow sheet of Sulfuric acid production by
Contact Process

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SO2(g)  SO3(g) Conversion

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DCDA Process

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Chamber Process
 In 1746 in Birmingham, England, John Roebuck began producing sulfuric
acid in lead-lined chambers, which were stronger, less expensive, and
could be made much larger than the glass containers which had been
used previously.
 The process is highly exothermic, and a major consideration of the design
of the chambers was to provide a way to dissipate the heat formed in the
reactions.
 Sulfur dioxide is generated by burning elemental sulfur or by
roasting pyritic ore in a current of air:
S8 + 8 O2 → 8 SO2
3 FeS2 + 8 O2 → Fe3O4 + 6 SO2
 Nitrogen oxides are produced by decomposition of niter in the presence
of sulfuric acid or hydrolysis of nitrosylsulfuric acid:
2 NaNO3 + H2SO4 → Na2SO4 + H2O + NO + NO2 + O2
2 NOHSO4 + H2O → 2 H2SO4 + NO + NO2

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Camber Process
 In the reaction chambers, sulfur dioxide and nitrogen dioxide dissolve in
the reaction liquor. Nitrogen dioxide is hydrated to produce nitrous
acid which then oxidizes the sulfur dioxide to sulfuric acid and nitric oxide.
The reactions are not well characterized but it is known that
nitrosylsulfuric acid is an intermediate in at least one pathway. The major
overall reactions are:
2 NO2 + H2O → HNO2 + HNO3
SO2 (aq) + HNO3 → NOHSO4
NOHSO4 + HNO2 → H2SO4 + NO2 + NO
SO2 (aq) + 2 HNO2 → H2SO4 + 2 NO
 Nitric oxide escapes from the reaction liquor and is subsequently re-
oxidized by molecular oxygen to nitrogen dioxide. This is the overall rate
determining step in the process.
2 NO + O2 → 2 NO2
 Nitrogen oxides are absorbed and regenerated in the process, and thus
serve as a catalyst for the overall reaction:
2 SO2 + 2 H2O + O2 → 2 H2SO4
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