SULFURIC ACID

Introduction and History

1. It is the agent for sulfate formation and for sulfonation, but more
frequently it is used because it is a rather strong and cheaply priced
inorganic acid.
2. It is employed in the manufacture of fertilizers, leather, and tin plate, in
the refining of petroleum, and in the dyeing of fabrics.
3. The origin of the first sulfuric acid is unknown, but it was mentioned as
far back as the tenth century.
4. Its preparation, by burning sulfur with saltpeter, was first described by
Valentinus in the fifteenth century.
5. In 1746. Roebuck of Birmingham, England, introduced the lead chamber
process.
6. The contact process was first discovered in 1831 by Phillips, an
Englishman, whose patent included the essential features of the modern
contact process, namely, the passing of a mixture of sulfur dioxide and
air over a catalyst, followed by the absorption of the sulfur trioxide in
98.5 to 99% sulfuric aicd.
PROPERTIES OF SULFURIC ACID.
1. Sulfuric acid is a strong dibasic acid.
2. It is also an oxidizing and dehydrating agent; particularly toward organic
compounds.
3. Its dehydrating action is important in absorbing water formed in such
chemical conversions as nitration, sulfonation, and esterification, thus
ensuring high yields.
4. Sulfuric acid is widely sold in the form of various solutions of H2S04 in
water, or of S03 in H2SO4. The latter, called oleum.
5. The specific gravity of sulfuric acid increases gradually to 1.844 at 15°C
for 97% acid, after, which it decreases to 1.839 at 15°C for 100% acid.
6. Acid containing 93.19% H2S04 (66°Be acid) is the normal acid of
commerce in North America.
7. Acid of somewhat higher strength (about 95% H2S04) is normally used in
Europe.
Production and Usage
Fertilizer manufacture, as is the greatest single use of sulfuric acid When superphosphate
was the usual phosphatic fertilizer.
More concentrated fertilizers are now required in order to reduce the costs of
transportation and application, Plants for triple superphosphate are more capital intensive
than ordinary superphosphate plants.
Strong sulfuric acid, 93 to 99%, is utilized in the purification of petroleum products,
preparation of titanium dioxide, alkylation of isobutane, manufacture of many nitrogen
chemicals, synthesis of phenol, recovery of fatty acids in soap manufacture, and
manufacture of phosphoric acid and triple superphosphate. Oleums are needed for
petroleum, nitrocellulose, nitroglycerin, TNT, and dye manufacture as well as for fortifying
weaker acids. There are many other uses; in fact, few chemical products are manufactured
without the use of sulfuric acid.
Manufacturing
• When the sole problem involved was forming H2S04 at a reasonable
concentration from S02 generated by burning sulfur or pyrites and when
energy was cheap, plants were relatively uncomplicated. When energy
prices increased sharply, the high-level energy resulting from the
oxidation of sulfur and sulfur dioxide became a valuable commodity.
• Major changes in plant design were instituted to use this heat to generate
high-pressure steam for generating electrical energy, thereby maximizing
energy recovery while minimizing process energy use.
• This combination of a chemical plant and an electrical (or steam)
generation system is known as cogeneration.
• A modern sulfuric acid plant is, therefore, an electrical generating system.
• This secondary function complicates the plant's operating system, but it
sharply reduces the cost of the acid produced. Plants have become larger
to utilize the economies of large scale; a 2800-t/day plant was brought on
stream in 1982.
THE CONTACT PROCESS
• Until 1900, no contact plant had been built in the United States, although
this process had become very important in Europe because of the need
for oleums and for high-strength acids for sulfonation, particularly in the
dye industry.
• A substantial number of contact plants were built in the period 1900 to
1925, using platinum catalysts.
• In the middle 1920s, vanadium catalysts came into use and have gradually
completely replaced platinum.
• By 1930, the contact process could compete with the chamber process
regardless of the strength of acid desired.
• Since the mid-1920s most new facilities built have used the contact
process with vanadium catalysts.
• Parts of the process vary considerably, depending upon the type of raw
materials.
• Sulfur-burning plants are the simplest and cheapest since special
purification of burner gases to protect the catalyst is not required. In the
single-absorption configuration, which was the normal procedure until
the 1970s.
Reactions
THE CONTACT PROCESS
The contact process has been gradually modified to use double absorption
(also called double catalyst), which increases yields and reduces stack
emission of unconverted S02.
Conversions using the single absorption contact process were typically about
97 to 98 percent.
Although some units use alkali scrubbers on the tail gases to stay within the
limit, most new plants use double absorption.
In this flow configuration, the gases leaving the first absorbing tower are
reheated by heat exchange with the bottom converter gases and re-enter
the final stage of the converter.
Because of the lower content of sulfur trioxide, the reaction is able to
proceed farther in the desired direction and the higher recovery of 99.7
percent can be achieved. The gases leaving this final stage are cooled and
the SO2 is absorbed in final absorber tower.