Sulfur,

Nitrogen: Sources
and Their Products

Sulfur
•  One of the most important materials in the chemical
process industries
•  An abundant, non-metallic chemical element that has
a bright lemon yellow to yellow brown color and
finds utility in many areas of life
•  A naturally occurring mineral that is found mostly
near hot springs and volcanic craters
•  It has a distinct "rotten egg" smell, caused by sulfur
dioxide gas escaping into the air
ORES
•  Sulfur is found as a free element or in combined state
in nature. Free sulfur is found in at a large depth
below the earth’s surface. Metal sulfides such as Zn,
Fe, Ag, Ca, Pb, Cu are found in abundant quantities.
Mineral ores containing S are :
•  Cinnabar: HgS Argentite(or Silver glance): Ag2S
•  Iron pyrites: FeS2 Galena: PbS
•  Sphalerite (or Zinc blende): ZnS
•  Chalcopyrite (or Copper pyrite): CuFeS2
•  Pyrrhotite: Fe7S8
•  Sulfur also occurs in petroleum crude oil and natural
gas (H2S)
•  In recent years, a major source of elemental sulfur is
H2S, which is a by-product of the desulfurization of
sour natural gas and sour crude oil
•  Other sources expected to be of future importance
are:
a) Shale oil c) Synthetic fuel projects
b) Coal gasification d) Gypsum or anhydrite
USES
•  90% of Sulfur used is converted to Sulfuric Acid
•  The industrial uses of sulfur include use in
manufacture of adhesives, animal feed, cement,
explosives, glass, fumigants, matches and inorganic
chemicals
•  Sulfur powder is used as an active ingredient in many
of the skin creams and lotions. It is used in many of
the skin treatment ointments, bar soaps, lotions and
creams as it is extremely beneficial in the treatment
of acne
•  Magnesium sulfate, which contains sulfur, is used as
a laxative, in bath salts and as a magnesium
supplement for plants.
•  In a finely divided state, it is frequently mixed with
lime to be used as fungicide
•  One of the most important applications of sulfur is in
the form of fertilizers. Sulfur is a major nutrient for
the plants and is required for their overall growth,
formation of root nodules, and protection of plants
from various diseases
•  Sulfur is used to vulcanize rubber. Vulcanization
makes rubber tougher. It ensures that rubber
maintains its shape
 Three main sources of sulfur
1) Sulfur from “sour” natural gas
–  Gas containing H2S is termed “sour” natural gas
–  The gas is treated with either Ethanolamine or
K2CO3 to dissolve the H2S then followed by
heating
H2S (g) + O2(g) à 2S(s) + 2H2O(g)

2) Sulfur from sulfate ores in metallurgical processes
–  Many metals occur in nature as sulfide ores such
as FeS2, Fe7S8, CuFeS2, PbS, and ZnS
–  The first step in preparing a metal from its sulfide
ore is called Roasting which converts sulfides to
SO2
2PbS(s) + 3O2(g) à 2PbO(s) + 2SO2(g)
.... sulfur ores
•  Sulfate ores:
– Gypsum: CaSO4 • 2H2O
– Epsom salt: MgSO4 • 7H2O
– Barites: BaSO4
– Alum: KAl(SO4)2 • 12H2O
3) Mining of Sulfur beneath the earth’s surface (Frasch
Process)
–  Herman Frasch devised this method during the
late 1890’s
–  It utilizes the concept of melting the sulfur
underground or under the sea and then pumping
it up the surface
–  It is the only economic method of recovering
sulfur from elemental deposits
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
to 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.
.....Frasch Process
•  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.
•  The Frasch process can be used for deposits
50–800 meters deep. 3-38 cubic meters of
superheated water are required to produce
every ton of sulfur, and the associated energy
cost is significant.
Other methods of sulfur recovery:
•  Extracted from the oil or gas stream at a
processing plant
•  Scraped from the surface of the earth or dug
out of open pits

Sulfuric acid industry
Sulfuric acid
•  One of the most widely used and most
important technical product in the chemical
process industries
•  A highly corrosive, clear to viscous, colorless
to slightly yellow liquid and is soluble in water
at all concentrations
•  Its corrosiveness is mainly due to its strong
acidic nature, strong dehydrating property
and if concentrated strong oxidizing property
....Sulfuric acid

•  A strong dibasic acid, which serves as an
oxidizing and dehydrating agent
•  It is the agent for sulfate formation and for
sulfonation
•  Dilute solutions of sulfuric acid taste sour,
conduct electricity, neutralize alkalis, and
corrode active metals with formation of
hydrogen gas
•  Concentrated sulfuric acid is a valuable
desiccating agent
....Sulfuric acid

•  Known to medieval European alchemists as oil of

vitriol, spirit of vitriol or simply vitriol
–  Vitriol – latin vitreus (“glass”)
–  Blue vitriol / Roman vitriol – copper (II) sulfate
–  White vitriol – zinc sulfate
–  Green vitriol – iron (II) sulfate
–  Vitriol of Mars – iron (III) sulfate
–  Red Vitriol – cobalt (II) sulfate
....Sulfuric acid
•  When concentrated sulfuric acid mixed with water,
the energy released can be enough to heat the
mixture to boiling. When diluted, always add
sulfuric acid slowly to cold water and stir to
dissipate the heat
•  If sulfuric acid gets on your skin, it immediately
begins to take water out of the
molecules in the skin.
This is what causes an acid
burn.
 ....Sulfuric acid
•  Cutting an onion arouses the gas (propanethiol
S-oxide) contained within the onion. When this
upwardly mobile gas encounters water in our
eyes, sulfuric acid is produced. In response to
the caustic acid, our eyes automatically blink,
and produce tears which irrigate the eye, and
flushes out the sulfuric acid.
Uses of sulfuric aid
•  The major use of sulfuric acid is in the
production of fertilizers, e.g., superphosphate
of lime and ammonium sulfate
•  Widely used in the manufacture of chemicals,
e.g., in making hydrochloric acid, nitric acid,
sulfate salts, synthetic detergents, dyes and
pigments, explosives, and drugs
•  Used in petroleum refining to wash impurities
out of gasoline and other refinery products
 ....uses

•  Used in processing metals, e.g., in pickling

(cleaning) iron and steel before plating them
with tin or zinc
•  Serves as the electrolyte in the lead-acid
storage battery commonly used in motor
vehicles (acid for this use, containing about
33% H2SO4 and with specific gravity about 1.25,
is often called battery acid)
•  Rayon is made with sulfuric acid.
History
•  The discovery of sulfuric acid is credited to the 8th
century Arabian chemist and alchemist Jabir ibn
Hayyan
....History

•  The early alchemists prepared it in large

quantities by heating naturally occurring
sulfates to a high temperature and dissolving
in water the sulfur trioxide thus formed.
•  About the 15th century, a method was
developed for obtaining the acid by distilling
hydrated ferrous sulfate, or iron vitriol, with
sand
•  In 1740, the acid was produced successfully on a
commercial scale by burning sulfur and
potassium nitrate (salt peter) in a ladle
suspended in a large glass globe partially filled
with water (described by Basilius Valentinus)
•  In the 17th century, the German – Dutch chemist
Johann Glauber prepared sulfuric acid by burning
sulfur together with saltpeter (KNO3) in the
presence of steam
•  In 1736, Joshua Ward, a London pharmacist,
began the first large scale production of sulfuric
acid using the method introduced by Glauber
•  In 1746, John Roebuck of Birmingham introduced
production of sulfuric acid in lead – lined chambers,
thus, the Lead Chamber Process, which although
approached only 35 – 40% concentration, remained
the standard method of production for almost 2
centuries
•  French chemist Joseph – Louis Gay – Lussac and
British chemist John Glover refined the lead –
chamber process, thus improving the yield to 78%
•  In 1831, Peregrine Phillips discovered the Contact
Process
•  The Contact Process was not a commercial success
for more than 40 years because:
–  There was a lack of demand for store acid
–  Inadequate knowledge of catalytic gas reactions
–  The slow progress of chemical technology
•  During the 19th century, the German chemist Baron
Justus Von Liebig discovered that sulfuric acid, when
added to the soil, increased the amount of soil
phosphorus available to plants

Grades of sulfuric acid
Mass Fraction Density Concentration Common Name
H2SO4 (kg / L) ( mol / L )
10% 1.07 ~ 1 Dilute sulfuric acid

29 – 32% 1.25 – 1.28 4.2 – 5 Battery acid (used

in lead – acid
batteries)
62 – 70% 1.52 – 1.60 9.6 – 11.5 Chamber acid
Fertilizer acid
78 – 80% 1.70 - 1.73 13.5 – 14 Tower acid
Glover acid
95 - 98% 1.83 ~ 18 Concentrated
sulfuric acid
 Methods of Measuring the Strength
of H2SO4
1) Using a Hydrometer graduated in
degrees Baume’ (⁰Be’)
–  Ordinary H2SO4 solutions are sold
according to their specific gravity or the
⁰Be’ (especially with those with up to
93% acid)
–  The usual temperature to which
specific gravity or ⁰Be’ is referred to
60⁰F
Sp. Gr. = 145 - (⁰Be’ / 145 )
2)  By Titration – for oleums containing more than 50% SO3
(Oleum is made in various strengths and consists of SO3
dissolved in 100% H2SO4. Thus, for example, 20% oleum
contains 20% SO3 and 80% H2SO4 by weight)

3) By electrical conductivity – for solution with 93% and
above H2SO4

 Manufacture of sulfuric acid
There are two processes in which Sulfuric Acid is
manufactured: a) Lead Chamber Process
b) Contact Process
A) Lead Chamber Process
•  The process employs, as reaction vessels, large lead –
sheathed brick towers. In these towers, sulfur dioxide
gas, air, steam and oxides of nitrogen react to yield
sulfuric acid as fine droplets that fall to the bottom of the
chamber. Almost all the nitrogen oxides are recovered
from the out flowing gas and are brought back to the
chamber to be used again. The process produces a weak
acid of only about 62 to 78% strength. It entails high
investment cost.


•  Overall Reaction:
SO2(g) + O2(g) + H2O(l) à H2SO4(soln)
•  Homogenous reaction (gas phase)
2NO(g) + O2(g) à 2NO(g)
•  Heterogeneous Reaction (gas – liquid interface)
SO2(g) + H2O(l) à H2SO3(soln)
H2SO3(soln) + NO2(g) à H2SO4NO(soln)
Sulfonitronic acid
NO(g) + NO2(g) + H2SO4(soln) à 2HO-SO2-ONO(soln) + H2O(l)
Nitrosylsulfuric acid
Sulfonitronic Acid – very loose molecular weight compound which
is present in very small concentration in chamber acid
Nitrosylsulfuric acid – stable compound which can be prepared in
crystalline form


B)  Contact Process
•  The current method of producing sulfuric acid in the high
concentrations needed for industrial processes (98 – 100%)
•  So – called because the reacting molecules meet in contact
with the walls of the solid catalyst which may also be the
walls and pores and micropores of the agent provided.

Reagents used as catalyst (for the oxidation of SO2 to SO3)
•  Iron Oxide – rugged but less expensive
•  Platinum – effective catalyst but very expensive and it is
vitiated by certain impurities in ordinary sulfur dioxide that
reduce its activity
•  Vanadium Pentoxide (V2O5) – most commonly employed
catalyst

Reactions:
•  Burning of raw material
S(S) + O2(g) --à SO2
4FeS2 + 11O2(g) --à 2Fe2O3 + 8SO2
4FeS2 + 15O2(g) --à 2Fe2O3 + 8SO3

•  Conversion of SO2 to SO3
SO2 + 1/2O2 --à SO3

•  Absorption of SO3
SO3 + H2O --à H2SO4



Nitrogen Industries
I. Ammonia
•  A colorless, reactive gas that is lighter than air
(approximately half as heavy) which dissolves readily in
water
•  It has a strong smell, similar to urine, which can be
detected by most people even in small amounts
•  Ammonia gas is nonflammable, but because some
mixtures with air could explode if ignited, it is treated
as flammable
•  Ammonia occurs naturally at low levels throughout the
environment, as it is released from the natural
breakdown of organic waste matter. Intensive
agricultural practices may increase local levels, e.g.
from lots of animal waste (slurry)
Uses
•  Agricultural industries are the major users of ammonia,
representing nearly 80% of all ammonia produced. Ammonia
is a very valuable source of nitrogen that is essential for plant
growth
•  The petroleum industry utilizes ammonia in neutralizing the
acid constituents of crude oil and for protection of
equipment from corrosion.
•  Ammonia is used in the mining industry for extraction of
metals such as copper, nickel and molybdenum from their
ores
•  Ammonia is used in several areas of water and wastewater
treatment, such as pH control, in solution form to regenerate
weak anion exchange resins, in conjunction with chlorine to
produce potable water and as an oxygen scavenger in boiler
water treatment
•  Ammonia is a widely used refrigerant in industrial
refrigeration systems found in the food,
beverage, petro-chemical and cold storage
industries.
•  Ammonia is used in the rubber industry for the
stabilization of natural and synthetic latex to
prevent premature coagulation.
•  The pulp and paper industry uses ammonia for
pulping wood and as a casein dispersant in the
coating of paper.
•  The food and beverage industry uses ammonia as
a source of nitrogen needed for yeast and
microorganisms
Raw Materials used in the Manufacture of
Synthetic Ammonia

1)  Air
2)  Water
3)  Hydrocarbons
4)  Power
•  Coal can replace the hydrocarbons, but the
process is more complex and expensive
Manufacture of ammonia: production
of synthetic ammonia
1)  Manufacture of Reactant Gases
-  Synthesis gas is prepared by high – pressure catalytic
reforming of hydrocarbon feed, usually natural gas
freed of sulfur

2)  Purification
-  Removal of CO and CO2
-  Any residual CO and CO2 is completely converted to
methane in a methanator because methane is an
inert gas with respect to the ammonia catalyst
3)  Compression
-  T h e h y d r o g e n –
nitrogen mixture is
raised to the full
reaction pressure
from 2.75 Mpa to 20
Mpa by means of
turbine – driven
c e n t r i f u g a l
compressors

4)  Catalytic Reaction
-  Occurs in the catalytic converter
Major Reaction: N2 + 3H2 --à 2NH3

•  Since hydrogen and nitrogen alone react together
extremely slowly, catalysis of the reaction is
important
•  Catalyst: Iron with added promoters like oxides
of aluminum, zirconium or silicon at about 3%
concentration and potassium oxide at about 1%
(the promoters prevent sintering and make the
catalyst more porous; Iron catalysts lose their
activity rapidly if heated above 520⁰C)
•  Catalysts are deactivated by contact with copper,
phosphorus, arsenic, sulfur and CO.
5)  Recovery of Ammonia Formed
-  Ammonia is recovered by means of
refrigeration or absorption and handled as an
anhydrous liquid under modest pressure

6)  Recirculation
- Recovery of remaining inert gases
MANUFACTURE OF AMMONIA
 ii. Manufacture of nitric acid (Hno3)

•  NITRIC ACID has a clear colorless appearance when

in its pure form, but the accumulation of oxides of
nitrogen in it over the period tends to give it a yellow
cast. The fumes coming from this hygroscopic liquid
give it a choking smell.
•  The usual method of preparation is the distillation of
saltpeter with sulfuric acid
•  Highly concentrated nitric acid contains 94.5 to
95.5% HNO3
•  Commercial grades: 36 – 42⁰Be’ (53.4 – 68.7%
HNO3)
uses
1)  Chief use of nitric acid is for the manufacture of
fertilizers such as ammonium nitrate and ammonium
sulfate
2)  Used in the manufacture of explosives
- Production of Nitrocellulose
- Production of Nitroglycerine
- Production of Trinitrotoluene
3)  Used in the manufacture of synthetic fibers, films,
dyes and plastics
4)  Used in mining industries (e.g. in parting gold from
silver)


5) In very low concentration, it is used to artificially age
pine and maple wood
6) Its aqueous blend is used for cleaning food and dairy
equipment owing to its ability to remove precipitated
calcium and magnesium compounds with ease

Raw Materials used in the Manufacture of Nitric

Acid
1) Ammonia
2)  Air
Catalyst: Platinum – 10% Rhodium Gauze

 SIMPLIFIED PROCESS
•  Nitric acid is made from the reaction of
ammonia with oxygen.
1) The first stage produces nitrogen monoxide.
•  A hot platinum catalyst is used (about 850 °C).
The reaction is highly exothermic and the heat
given out by the reaction is sufficient to keep
the reaction going.

4NH3(g) + 5O2(g) à 4NO(g) + 6H2O(g)
2) The second stage involves the reaction of nitrogen
monoxide with more oxygen.
nitrogen monoxide + oxygen à nitrogen dioxide
2NO(g) + O2(g) 2NO2(g)
3) Finally, nitrogen dioxide reacts with water and more
oxygen.
nitrogen dioxide + oxygen + water à nitric acid.
4NO2(g) + O2(g) + 2H2O(l) à 4HNO3(aq)

The overall reaction is:
ammonia + oxygen à nitric acid + water.
4NH3(g) + 8O2(g) à 4HNO3(aq) + 4H2O(l)
This is the oxidation of ammonia to produce nitric
acid

Manufacturing Procedure

(1) Ammonia and preheated air are mixed to give a 9.5 –

11% gas, filtered to remove dust and then oxidized in a
reactor (or oxidizer) with platinum as catalyst at 750⁰C.
(2) The exit gases pass through an exchanger, a waste
heat boiler and a primary cooler to condense out the
water in the form of a dilute solution of nitric acid (about
40 – 45%)
(3) The oxides of nitrogen are then sent to a series of
absorption towers to produce an acid of about 61 – 68%.
The tail gases contain 0.2 – 0.3% of NO, and usually must
be scrubbed with an alkaline solution to recover nitrogen
values or to be recycled back to the oxidizer to convert it
to NO2.
(4) The oxidation efficiency is 95 – 96% and
the absorption efficiency is 98 – 99%.
(5) Dehydrating agents aid in the removal of
the water to concentrate the nitric acid
produced. The most used method consists of
mixing 65% nitric acid with strong sulfuric acid
(93%) and then passing through a distillation
system from which concentrated nitric acid
(95 – 98%) and residual sulfuric acid are
obtained.
III. MANUFACTURE OF UREA
Urea
•  First organic compound synthesized from an inorganic
material
•  Most convenient form of fixed Nitrogen
•  Important fertilizer which contains the highest nitrogen
content (46% available N2)
•  First prepared by Wohler (1828) by heating ammonium
cyanate according to the reaction:
NH4CNO à NH2CONH2 + H2O
Ammonium cyanate Urea
•  Urea is a waste product secreted by living organisms as a
result of breaking down the amino acids in consumed
proteins. The breaking-down process creates ammonia,
carbon dioxide and water
Uses:
1)  Manufacture of Fertilizer
Urea is a concentrated source of nitrogen, which consists of
46 percent of the compound. It is primarily sold as a solid in
dried pills, crystals or granules. Liquid urea is combined in
nitrogen solution fertilizers used in industrialized nations
* “Ureaform” – complex between urea and formaldehyde,
it releases the nitrogen slowly
2) Resins
Urea is used in the manufacturing of urea-formaldehyde
resins, which are used to coat textiles, leather and paper. The
resins are also used to make adhesives for plywood, paper,
board, surface coatings and molding resins.


3) Catalytic Reduction
A solution with urea is sprayed into a diesel engine's
exhaust fumes to reduce the amount of nitrous-oxide
emissions, breaking them down to nitrogen and water
4) Sleeping Pills
Barbiturates are formed from a reaction between urea
and a diester of malonic acid in the presence of a
strong base at an elevated temperature. The result is a
salt of barbituric acid, which causes sleepiness in
human beings
Raw Materials used in the Manufacture of Urea
1) Ammonia
2) Carbon dioxide

Process: Carbonation of Ammonia

Reactions:
2NH3 + CO2 --à NH2COONH4
(Ammonium carbamate)

NH2COONH4 ß---à NH2CONH2 + H2O
Urea
IV. Manufacture of Ammonium Nitrate
(NH4NO3)

•  Major explosive ingredient
•  It is a very important nitrogenous fertilizer
because of its:
(a) High nitrogen content
(b) Simplicity and cheapness of its manufacture
(c) Valuable combination of quick acting nitrate
and slower acting ammoniacal nitrogen
•  Its tendency to cake reduced its acceptability
but has been remedied by addition of anti –
hygroscopic agents
•  On explosive decomposition, it rapidly and
violently decomposes
•  NH4NO3 --à 2N2 + 4H2O + O2
Amatol – mixture of TNT and granular
ammonium nitrate, it is a major conventional
military explosive
•  At 200 - 260⁰C, it is safely decomposed to
form anesthetic nitrous oxide
NH4NO3 --à N2O + 2H2O
•  It is produced from the oxidation of ammonia
by nitric acid
NH3 + HNO3 --à NH4NO3