ChE 423:

Sulfur and Sulfuric Acid

Dr. Cristina E. Tiangco
Dr. Beatriz A. Belmonte
Engr. Jhulimar M. Celedonio
UST, ChE Department

2nd Term, A.Y. 2018-2019

Review: Sulfur Cycle

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Sulfur: Uses and Economics
Ø Sulfuric Acid
Ø Paper Manufacture
Ø Wood Pulping
Ø Medicinals
Ø Rubber
Ø Sulfur Dyes
Ø Insecticides
Ø Fungicides

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Sulfur: Sources
Ø Elemental
Ø Pyrites
Ø Hydrogen Sulfide à natural and refinery gases
Ø Smelter Gases
Ø Calcium Sulfate
Ø Coal
Ø Low-grade Sufur Deposits

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Synthetic Ammonia

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Sulfur: Mining and Manufacture
q Frasch Process
Ø Sulfur bearing limestones à 90% of elemental sulphur
Ø Herman Frasch , 1890’s : melting sulphur underground
Ø 500 – 2,500 ft underground
à three concentric pipes (1in – 6in)

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Sulfur: Mining and Manufacture
q Sulfur from Smelter Gases
Ø Sulfur recovery from SO2 and H2S à air pollution regulations
Ø Sources:
§ Roasting of sulphide ores
§ Coal combustion
§ Burning of acid sludge from petroleum refining
Ø Products:
§ Elemental sulfur
§ Sulfuric acid
§ Liquid sulfur dioxide

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Sulfur: Mining and Manufacture
q Sulfur from Industrial Gases
Ø Removal of H2S
à purification of natural and manufactured gas and in petroleum refining

q Sulfur from Pyrites

Ø Flash roasting of sulphide ores

q Sulfur Dioxide from By-products

Ø Liquid waste from steel industry (pickling of metals)
à 2-15% sulfuric acid and 10 -15% ferrous sulphate
Ø Sludge and alkylation acids
à recovered by decomposing to sulphur dioxide à remade to sulphuric acid

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Sulfuric Acid: History
Ø Valentinus, 15th Century: burning saltpetre with sulphur
Ø Dr. Joe Roebuck of Birmingham, 1746: Lead-Chamber Process
§ Chambers: Birmstone + Saltpeter (Steam)
§ Glover tower: denitrating the nitrous acid without too much
dilution
§ Gay-Lussac tower: recovery of nitrogen oxides
Ø Peregrine Phillips, 1831: Contact Process
§ Decomposition of chamber acid à passing a mixture of sulphur dioxide
over a catalyst à absorption of sulphur trioxide in water

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Sulfuric Acid: Properties
Ø Former known as oil of vitriol
Ø A chemical formula of H2SO4
Ø Colorless to yellowish in color
Ø Highly corrosive
Ø Highly oxidizing
Ø Miscible in water
Ø Dehydrating agent à important in nitration, esterification and
sufonation

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Sulfuric Acid: Properties
Ø Sulfuric Acid: H2SO4 in water
Ø Oleum: SO3 in H2SO4
Ø Common Sulfuric Acid Concentrations:

1.5M CORROSIVE
Hydrolysis
Dehydration

0.5M IRRITANT

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Sulfuric Acid: Uses
Ø Fertilizer
Ø Superphosphate manufacture
Ø Sulfates of ammonia, copper (bluestone), alumina (alum), magnesium (Epsom
salts) and other metals
Ø Manufacture of chemicals, drugs
Ø Paints and dyes
Ø Car batteries
Ø Pickling of iron and and steel
Ø Refining of heavy metals (pickling of iron and steel before plating them with Sn or
Zn)
Ø Electroplating
Ø Purification of petroleum products

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Sulfuric Acid: Manufacture
Ø Lead Chamber Process
à Weak acid: 62-70% H2SO4
Ø Contact Process
à Strong acid: 98-100% H2SO4
§ Based on sulphur dioxide
§ Catalytic
§ Uses air as source of oxygen
for making SO3
§ Operated on a large scale
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Manufacture: Lead Chamber Process

Oxidation of Sulfur
dioxide to sulfur Hydration of sulphur Absorption of
Burning of
trioxide (with trioxide to sulphuric nitrogen dioxide from
Sulfur or Pyrite
nitrogen oxides acid residual gas
catalyst)

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Manufacture: Lead Chamber Process
q Reactions

Gas Phase

Liquid Phase

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Manufacture: Lead Chamber Process
q Manufacturing Procedure

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Manufacture: Lead Chamber Process
q Manufacturing Procedure
Ø Melting and burning of sulphur or sulphides
Ø Recovery of heat from hot sulphur dioxide gas
Ø Purification of sulphur dioxide gas
Ø Mixing of sulfur dioxide gas with nitrogen oxides catalyst
Ø Glover Tower: Oxidation of sulphur dioxide to sulphur trioxide
Ø Glover Tower and Chambers: Hydration of sulphur trioxide to sulphuric acid
Ø Settling of sulphuric acid mist and dissipation of heat of reactions
Ø Gay-Lussac Tower: Absorption of nitrogen oxides from residual gas à Gay Lussac Acid

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Manufacture: Lead Chamber Process
q Manufacturing Procedure

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Manufacture: Lead Chamber Process
q Manufacturing Procedure

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Manufacture: Lead Chamber Process
q Manufacturing Procedure

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Manufacture: Lead Chamber Process
q Manufacturing Procedure

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Manufacture: Contact Process

Oxidation of
Sulfur dioxide to Absorption of Concentration
Burning of
sulfur trioxide SO3 in strong to 98.5-99%
Sulfur or Pyrite
(over vanadium acid H2SO4
catalyst)

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Manufacture: Contact Process
q Reactions

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Manufacture: Contact Process
q Catalysts
Ø Platinum Catalysts
§ Carriers: silica gel, calcined magnesium sulphate, and asbestos
§ Advantages:
ü 90% recovery of metal
ü Lower operating cost
ü Lower initial capital cost à higher proportions of SO2 may be used
§ Disadvantages:
o Suffers a decline of activity with use
o Shorter life à subject to poisoning under some conditions
o Difficulty to to handle à fragile

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Manufacture: Contact Process
q Catalysts
Ø Vanadium Catalysts
§ Carriers: zeolite or other base exchange substance
§ Advantages:
ü Higher conversion efficiency maintained for a longer period
ü Immunity to poisoning
ü Mass is less troublesome during operation à easier to handle
ü Lower initial cost
§ Disadvantages:
o Handle lower sulphur dioxide content gas
o No salvage value when worn out

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Manufacture: Contact Process
q Manufacturing Procedure

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Manufacture: Contact Process
q Manufacturing Procedure
Ø Melting of sulfur
Ø Pumping and atomizing of melted sulfur
Ø Burning of sulfur (or sulfide)
Ø Drying of combustion air
Ø Cooling and purification of S02 gas
Ø Oxidation of S02 to SO3 in converters
Ø Heat transfer to secure good yields of S03
Ø Absorption of SO3 in strong acid (98.5 to 99%)
Ø Cooling of acid from absorbers
Ø Pumping of acid over absorption towers

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Manufacture: Contact Process
q Manufacturing Procedure

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Manufacture: Contact Process
q Manufacturing Procedure

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Manufacture: Contact Process
q Manufacturing Procedure

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Manufacture: Contact Process
q Manufacturing Procedure

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Manufacture: Contact Process
q Manufacturing Procedure

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References:
1) Shreve, R.N., The Chemical Process Industries, 2nd Ed., McGrawHill, 1956.
2) Njenga, H. N, Industrial Chemistry Lecture Module Ver 2.5, African Virtual university,
http://creativecommons.org/licenses/by/2.5/

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