SULFUR AND SULFURIC ACID

by Marialie M. Enecio

SULFUR

WHAT IS SULFUR?
nonmetallic element (about 0.06% of the earth's crust 20 km deep) in a pure crystalline form also called brimstone, it oxidizes and is responsible for the characteristic smell of many volcanoes used in a number of applications including the manufacture of gunpowder, insecticides, and prescription drugs it is also part of the vulcanization process for rubber

HISTORY
said to have been used by caveman to cleanse his blood used by Egyptians, Greeks and Romans as fumigant

used by Chinese inventors as main ingredient of gunpowder

in 1900, sulfur deposits of the Texas and Louisiana provide a new source of high-purity (99.5%) elemental sulfur and the golden age of U.S. sulfur industry

HISTORY
U.S. expertise allowed a considerable development of sulfur mining in Mexico just after World War II

HOW IS IT PRODUCED?
Sulfur from the Frasch Process
Sulfur from the Claus Process

Sulfur from Pyrites

Recovered Sulfur from Fuel Gases

FRASCH PROCESS
invented by Herman Frasch in 1891 process for extracting sulfur from sulfurbearing calcite deposits

three concentric pipes are lowered down a bore-hole to the ore where superheated water at 165C is pumped down the outermost pipe and compressed hot air is blown down the innermost pipe which forces a frothy mixture of molten sulfur up the middle pipe
very pure sulfur is produced

CLAUS SULFUR RECOVERY

PROCESS
2H2S + SO2 ==> 3S + 2H2O H2S is separated from the host gas stream using alkanolamines

it is then fed to the Claus unit, where it is converted in two steps:

Thermal Step. The H2S is partially oxidized with air. This is done in a reaction furnace at high temperatures (1000-1400 deg C). Sulfur is formed, but some H2S remains unreacted, and some SO2 is made.

 Catalytic Step. The remaining H2S is reacted with the SO2 at lower temperatures (about 200-350 deg C) over a catalyst to make more sulfur. This residual quantity, together with other trace sulfur compounds, is usually dealt with in a tail gas unit which can give overall sulfur recoveries of about 99.8%, which is very impressive indeed.

SULFUR FROM PYRITES

Pyrites is the term given to a variety of sulfide ores. The salt dome deposits and sulfur recovered from petroleum and natural gas are much more economical sources. Pyrites are obtained either as run-of-mine or beneficiated ore from straight pyrite deposits or recovered as by-product flotation concentrates during the refining of iron ore.

RECOVERED SULFUR FROM FUEL

GASES
Removal of hydrogen sulfide during purification of sour natural gas, coke-oven gas and from petroleum refinery by dissolving it in potassium carbonate solution or ethanolamine

H2S is converted to sulfur via modified Claus process:

 Other sources include coke-oven gas and synthetic crude oils from tar sands or shale oils.

FURTHER DEVELOPMENT IN INDUSTRY

Waste sulfur can be transformed into a lightweight plastic that may improve batteries for electric cars. The new plastic has other potential uses, including optical uses.

SULFURIC
ACID

WHAT IS SULFURIC ACID?

-an oily, colorless liquid with no odor -a key component in batteries, wastewater treatment, ore production, and fertilizer creation -65% of all fertilizers available on the market today are created from a combination of this acid and other chemicals -created from inorganic materials through a process that utilizes a special type of chemical reaction -more than 40 million tons are produced annually in the United States alone

HISTORY
It was prepared by Johann Van Helmont (c.1600) by destructive distillation of green vitriol (ferrous sulfate) and by burning sulfur A process for its synthesis by burning sulfur with saltpeter (potassium nitrate) was first used by Johann Glauber in the 17th century and developed commercially by Joshua Ward in England (c.1740). It was soon taken over by the lead chamber process, invented by John Roebuck in 1746 and since, improved by many others The contact process was originally developed (c.1830) by Peregrine Phillips in England

HOW IS IT PRODUCED?
Lead Chamber Process
Contact Process

Wet Sulfuric Acid Process

LEAD CHAMBER PROCESS

In the original lead chamber process, sulfur and potassium nitrate are ignited in a room lined with lead foil which was a batch process and resulted in the consumption of potassium nitrate.

In 1835, Joseph Gay-Lussac invented a process for recovering the nitrogen in nitrogen monoxide and recycling it to replace the saltpeter as a source of nitrogen.

In this process, SO2 is oxidized to SO3 by the oxides of nitrogen and the SO3 thus formed is dissolved in steam to form H2SO4.

SO2 + NO2 > SO3 + NO ; 2NO + O2 > 2NO2 SO3 + H2O > H2SO4
The classic lead chamber process consists of 3 stages; Glover tower, lead chambers and Guy-Lussac Tower.

CONTACT PROCESS
In the contact process, SO2 obtained by burning of S or iron pyrities is catalytically oxidized to SO3 in presence of finely divided Pt or V2O5 as catalyst. S + O2 > SO2 or 4FeS2 + 11O2 > 2Fe2O3 + 8SO2

V2O5 or Pt (673-732 K) 2SO2 + O2 2SO3.

WET SULFURIC ACID PROCESS

Combustion - H2S is mixed with 02 (hot air) to form sulphur dioxide (S02) Oxidation - sulfur dioxide is combed with oxygen (oxidised) in order to form sulphur trioxide

Hydration - sulfur trioxide (S03) is mixed with water (H20) to form sulphuric acid in gas form
Condensation - with the use of water cooling, the acid is condensed from gas form to liquid form

FURTHER DEVELOPMENT IN INDUSTRY

Some examples of recent sulfuric acid-related patents summarised in the report include: The use of ruthenium catalysts for the final bed of a contact sulfuric acid plant. The use of certain metals for constructing heat recovery equipment for use in the acid-making circuit of a sulfuric acid plant. Claimed improvements in the materials of construction in handling the acid. Claimed improvements in dealing with spent acid. Removing organic impurities from sulfuric acid with liquid or supercritical carbon dioxide. Process for manufacturing sulfuric acid from a gas containing sulfur dioxide and steam.