4.

Other Bulk Chemicals

Production
4.1 Sulfuric Acid synthesis and applications
4.2 Nitric Acid synthesis and applications
4.3Acetic Acid synthesis and applications
4.4 Dimethyl Terephtalate and Terephtalic
Acid synthesis and applications
 COURSE OUTCOME
• At the end of this topic, student should be
able to:
 Explain in details the synthesis process of
sulfuric acid, nitric acid, acetic acid, dimethyl
terephtalate and terephtalic acid.
 Identify their applications.
4.1 Sulfuric Acid synthesis and
applications
 Background
• The process has developed via the “lead chamber” process, which
was used in the eighteenth and nineteenth centuries and used a
homogeneous catalyst (nitrogen oxides), to the modern “contact
process”.
• In the original lead chamber process, sulfur and potassium nitrate
are ignited in a room lined with lead foil
• Potassium nitrate, or saltpeter is an oxidizing agent oxidizes the
sulfur to sulfur trioxide
• The resultant sulfur trioxide was then reacted with water and
sulfuric acid was produced
• The contact process is the current method of producing sulfuric
acid in the high concentrations needed for industrial processes
• This process was patented in 1831 by British vinegar merchant
Peregrine Phillips
• In addition to being a far more economical process for producing
concentrated sulfuric acid than the previous lead chamber process,
the contact process also produces sulfur trioxide and oleum
• Sulfuric acid is commercially produced in various acid strengths,
ranging from 33.33 to 114.6 wt%. Sulfuric acid with a strength of
over 100 wt% is referred to as oleum, which consists of sulfuric acid
with dissolved sulfur trioxide. The concentration of oleum is
expressed as wt% dissolved sulfur trioxide (“free SO3”) in 100 wt%
sulfuric acid.
 Reaction & Thermodynamics
• The reaction involved in production of H2SO4 from elemental sulfur
involved; generation of sulfur dioxide from elemental sulfur,
followed by catalytic oxidation of sulfur dioxide and absorption of
the formed sulfur trioxide in water.
– S (l) + O2 (g) → SO2 (g) Δr H298 = -298.3 kJ/mol
– SO2 (g) + ½ O2 (g) ⇋ SO3 (g) Δr H298 = -98.5 kJ/mol
– SO3 (g) + H2O (l) → H2SO4 (l) Δr H298 = -130.4 kJ/mol
• In practice, excess air is used so that the oxidation of sulfur is
complete
• The oxidation of sulfur dioxide is thermodynamically favored by low
temperature
• The ideal temperature must be a compromise between achievable
conversion (thermodynamics) and the rate at which this conversion
can be attained (kinetics)
• With the current sulfur dioxide oxidation catalysts this means a
minimum temperature of 680–715 K
• Elevated pressure is thermodynamically favorable, but the effect of
pressure is small
 Conversion of Sulfur to SO2
• Molten sulfur is sprayed into a furnace and burnt in excess air at
about 1300 K
• The sulfur burns with a characteristic blue flame
• SO2 could also be produced by heating sulphide ores like pyrite in an
excess of air
• 4FeS2 (s) + 11O2 → 2Fe2O3 (s) + 8SO2 (g)
• Air are in excess, so that the sulfur dioxide produced is already
mixed with oxygen for the next stage
• The oxidation produce large amount of heat. The heat is used to
boil water to produce steam to generate electricity
• The gas mixture which leave the furnace contains SO2 and enough
oxygen for the next stage
 SO2 conversion reactor
• It is important that sulfur dioxide is converted to sulfur trioxide
nearly quantitatively, not only for plant economic reasons but,
more importantly, for environmental reasons.
• For instance, in the US sulfuric acid emissions from newer plants
must be limited to 2 kg SO2 per metric ton of SO2 (as 100% acid)
produced. This is equivalent to a sulfur dioxide conversion of 99.7%
• The catalytic oxidation of SO2 is carried out in adiabatic fixed bed
reactor.
• The bed reactor consist of 4 separate beds of catalyst known as a
converter
The catalyst
• Initially, platinum was used as the catalyst because of its high
activity. However, platinum is expensive and very sensitive to
poisons such as arsenic (often present in pyrite).
• Therefore, nowadays commercial catalysts are based on vanadium
oxide supported on a porous inorganic support.
• The life of vanadium catalyst may be as long as 20 years, typically at
least 5 years for the 1st and 2nd bed, and 10-15 years for the 3rd and
4th bed
• Reason for loss of activity: physical breakdown giving dust (could
plug the bed) and chemical changes within the catalyst itself
 SO3 conversion to H2SO4
• SO3 conversion cant simply be done by adding water- the reaction is
so uncontrollable that it creates a fog of sulfuric acid.
• Instead, the sulfur trioxide is first dissolved in concentrated sulfuric
acid which produced disulfuric acid (also known as oleum)
• H2SO4 (l) + SO3 (g) → H2S2O7 (l)
• Water is then added to the oleum, to produce sulfuric acid
 Industrial usage of Sulfuric acid

others
24%

pulp, paper
1%
Phosphate fertilizers
paints, pigments 50%
2%
hydroflouric acid
2%
fibres
5%
metal processing
10%
phosphates
6%
4.2 Nitric Acid synthesis and
applications
 Background
• From the Middle Ages onwards, nitric acid was primarily produced
from saltpeter (KNO3) and sulfuric acid.
• In the nineteenth century, Chile saltpeter (sodium nitrate, NaNO3)
largely replaced saltpeter.
• At the beginning of the twentieth century new production
technologies were introduced.
• The rapid development of a process for the production of ammonia
made possible a commercial route for the production of nitric acid
based on the catalytic oxidation of ammonia with air.
• This route, although modernized, is still used for all commercial
nitric-acid production.
 Reaction and Thermodynamics
• Nowadays, all nitric acid production processes are based on the
oxidation of ammonia, for which the overall reaction reads
• NH3 + 2O2 → HNO3 + H2O ΔrH298 = -330kJ/mol
• The sequence of reactions are: burning of ammonia to nitric oxide,
oxidation of the nitric oxide, and absorption of nitrogen dioxide in
water
• 4NH3 + 5O2 → 4NO + 6H2O ΔrH298 = -907kJ/mol
• 2NO + O2 → 2NO2 ΔrH298 = -113.8kJ/mol
• 3NO2 + H2O → 2HNO3 + NO ΔrH298 = -37kJ/mol
 Ammonia oxidation
• Ammonia oxidation is highly exothermic and very rapid.
However, the reaction system has strong tendency towards
the formation of nitrogen
• 4NH3 + 3O2 → 2N2 + 6H2O Δr H298 = −1261 kJ/mol
• This can be overcome by using a selective catalyst and short
residence time (10−4 – 10−3 s) at high temperature.
• The catalyst used is Platinum with 10% rhodium
• The catalyst is made into gauze constructed using fine wires
• Under these conditions the oxidation of ammonia to nitric
oxide (NO) proceeds in an exothermic reaction with a range of
93 to 98 percent yield
• Higher catalyst temperatures increase reaction selectivity
toward NO production. Lower catalyst temperatures tend to
be more selective toward less useful products: nitrogen (N2)
and nitrous oxide (N2O)
• Nitric oxide is considered to be a criteria pollutant and nitrous
oxide is known to be a global warming gas
• The nitrogen dioxide/dimer mixture then passes through a
waste heat boiler and a platinum filter.
• Most plants operates with: temperature (1000 K to 1200 K), P
= 10 – 13 atm, Catalyst. 90% Pt, 10% Rh
Figure: A gauze of a
platinum-rhodium alloy
installed in a converter
 Nitric oxide oxidation and water
absorption
• The oxidation of nitric oxide (NO) to nitrogen dioxide (NO2) is a non-
catalyzed reaction
• The conversion of nitric oxide is favored by low temperature and
high pressure.
• The process stream is passed through a cooler/condenser and
cooled to 300K or less
• The absorption process of nitrogen dioxide in water is quite
complex because several reactions can occur, both in the liquid
phase and in the gas phase. For practical purposes the simplified
reaction is satisfactory
• 3NO2 + H2O → 2HNO3 + NO
 Processes
• The optimal conditions for ammonia oxidation are high
temperature, short residence time (in order to minimize side
and following reactions) and low pressure
• In practice, these conditions are realized by employing a
reactor consisting of several layers of a woven catalyst net,
composed of platinum strengthened with rhodium
• The choice of the reactor pressure is not trivial. In practice,
higher pressure plants are most common, because of reduced
equipment size, and lower capital costs, and because the
absorption of nitrogen dioxide is a process that operates best
at high pressure
• However, a higher pressure lowers the oxidation efficiency
(percentage ammonia converted to NO)
• Therefore, a dilemma exists: should a low or a high pressure
be applied?
• In practice, several options are used; both the oxidation and
the absorption are carried out at atmospheric pressure, or a
combination of low pressure for the oxidation reactor and
high pressure for the absorption process is used
 Single-Pressure Process
• Most single-pressure processes operate at high pressure (7–12 bar)
• Both ammonia and air are filtered to remove impurities such as rust
and other particulates present in the feedstocks; rust particles
promote the decomposition of ammonia
• The compressed air and gaseous ammonia are mixed such that
there is excess oxygen (circa 10 vol.% ammonia in mixture) and are
passed over a stack of several gauzes of platinum catalyst to
produce nitric oxide (NO) and water.
• The resulting gases are rapidly cooled, thus generating steam that
can be used to power the steam turbine driving the compressors
• Upon cooling, nitric oxide is further oxidized to form nitrogen
dioxide (NO2) in equilibrium with its dimer, dinitrogen tetroxide
(N2O4)
• In the condenser, condensation of (weak) nitric acid takes place.
The choice of materials is critical because of the highly acidic
conditions
• The weak acid stream is subsequently separated from the gas
mixture and fed to the absorption column
• The gases leaving the separator are mixed with secondary air (from
stripper) to enhance oxidation of nitric oxide, and then fed to the
bottom of the absorber, where the equilibrium mix of nitrogen
dioxide and dinitrogen tetroxide is absorbed into water, producing
nitric acid
• The nitric acid leaving the bottoms of the absorber is contacted
with air in a stripper to strip dissolved NOx (NO and NO2) from the
nitric acid product.
• The gas leaving the top of the absorber column contains residual
nitrogen oxides (NOx), which have to be removed for environmental
reasons before venting to the atmosphere
 Dual-Pressure Process
• The main change in the flow scheme is the addition of a
compressor between the ammonia conversion stage and the
absorption stage. Another difference in this scheme is the way in
which NOx abatement is achieved, that is, by extended absorption
• Note, however, that the NOx abatement methods are
interchangeable between the single-pressure and dual-pressure
processes
• Extended absorption reduces NOx emissions by increasing the
absorption efficiency
• This option can be implemented by installing a single large
absorption tower, extending the height of an existing tower, or by
adding a second tower in series with the existing tower.
• The increase in the volume and the number of trays in the absorber
results in more NOx recovered as nitric acid
Application of Nitric Acid
4.3Acetic Acid synthesis and
applications
 Background
• The first industrial process for the production of synthetic acetic
acid was commercialized in 1916. This process was based on the
liquid phase oxidation of acetaldehyde which proceeds through
radical reactions
• CH3CHO + ½ O2 → CH3COOH Δr H298 = -292 kJ/mol
• Direct liquid phase oxidation of naphtha or n-butane was once the
preferred route to acetic acid because of the low cost of these
hydrocarbons
• A major drawback of this process is that up to 50% of the feed goes
to by-products (e.g.formic acid, higher acids, and aldehydes), many
of which have very limited markets
• CH3CH2CH2CH3 + 5/2 O2 → 2CH3COOH + H2O Δr H298 = −986 kJ/mol
• The manufacture of acetic acid by carbonylation of methanol at
high temperature and pressure was described as early as 1913
• The first commercial methanol carbonylation plant was developed
by BASF in 1963, when a new cobalt/iodide catalyst system was
used.
• In 1968, Monsanto introduced a carbonylation process using a
novel highly active and selective rhodium-based catalyst that could
operate at much lower pressure
• This process was commercialized successfully only two years later.
• Currently, carbonylation accounts for over 75% of the global acetic
acid production
• CH3OH + CO ⇋ CH3COOH Δr H298 = −135 kJ/mol
 CH3OH Carbonylation: Reactions,
Thermodynamics
• Methanol carbonylation is an exothermic reaction and thus is
favored by low temperature
• The reaction is carried out at elevated pressure, however, in order
to keep the reaction mixture in the liquid phase and to generate
and maintain the catalyst in its active form; the catalyst complex is
not stable at low carbon monoxide pressure.
• An essential part of the catalyst system is iodide, usually supplied as
hydrogen iodide, which is very corrosive. Fortunately, essentially no
free hydrogen iodide is present as it rapidly reacts with methanol to
form methyl iodide
• CH3OH + HI →← CH3I + H2O
• The formation of methyl iodide is the start of the catalytic
cycle in which the actual carbonylation takes place
• CH3I + CO → CH3COI
• The formed CH3COI is then converted to acetic acid:
• CH3COI + H2O→← CH3COOH + HI
 Methanol Carbonylation – Processes
• Carbon monoxide and methanol are fed to a sparged CSTR containing
the catalyst. Reaction takes place in the liquid phase under relatively
mild conditions.
• Non-condensable by-products, mainly carbon dioxide and hydrogen,
which are formed by the water–gas shift reaction, are vented from the
reactor
• Liquid is removed from the reactor through a pressure reduction valve
and enters a flash vessel, resulting in a gas and a liquid phase
• The liquid phase, which contains the dissolved catalyst complex, is
recycled to the reactor.
• The gas phase, containing most of the acetic acid product, water,
methyl acetate, and methyl iodide, is sent to a distillation train for
purification.
• In the light ends column, methyl acetate, methyl iodide and part of
the water are removed and recycled to the reactor
• Wet acetic acid is taken as a side stream from this column and fed
to the drying column, where dry acetic acid is removed as bottoms
product. The overheads of the drying column, containing a mixture
of acetic acid (≈35%) and water, are recycled to the reactor.
• Thus, a fixed amount of acetic acid and water is continuously
circulating through the plant.
• The dry acetic acid is fed to the product column from which heavy
by-products, mainly propionic acid, are removed as bottoms
Industrial Used of Acetic Acid
4.4 Dimethyl Terephtalate and
Terephtalic Acid synthesis and
applications
 Processes
• Figure 9.13 shows a simplified flow scheme of the Witten process
for the production of DMT. At the heart of the process are two
reactors, one for oxidation and one for esterification.
• Fresh and recycled p-xylene, recycled p-methyl toluate, and
catalyst (cobalt naphthenate) are fed to the oxidation reactor, in
which mixing takes place by the upward movement of air.
• In this reactor, both p-xylene and p-methyl toluate are oxidized. The
temperature in the reactor is controlled by evaporation and
condensation of the formed water.
• The product from the oxidation reactor is heated and fed to the
esterification reactor, into which excess evaporated methanol is
sparged
• p-Toluic acid and methyl terephthalate are transformed to their
corresponding esters non-catalytically.
• Overhead vapors are condensed, after which methanol is separated
from the water and recycled. The liquid product is flashed to
remove any remaining methanol and water.
• The esterification products are sent to a distillation column. p-
Xylene and p-methyl toluate are collected overhead and returned to
the oxidation reactor.
• The crude DMT, after removal of heavy by-products and catalyst
metal, is purified by crystallization.
• Although the cobalt catalyst used in this process is relatively cheap,
its recovery is necessary since heavy metals cannot simply be
discarded
 TPA process
• p-Xylene, acetic acid, and catalyst (cobalt acetate,
promoted by bromine) are introduced in the oxidation
reactor. The reaction medium is agitated by introducing air
at the bottom.
• Air is added in excess to maximize p-xylene conversion.
Reaction takes place with acetic acid as the solvent for the
catalyst. The heat generated is removed by vaporization of
part of the solvent, and by condensation and reflux to the
reactor.
• The generated steam can be used in the distillation part of
the plant. A scrubber recovers acetic acid from the off-
gases (nitrogen, unused oxygen, and carbon dioxide
resulting from overoxidation).
• Because of its limited solubility in acetic acid (0.13 g/kg at room
temperature, 15 g/kg at 470 K [29]) most of the TPA crystallizes
while it is being formed. A slurry forms, which is removed from the
base of the reactor and sent to a surge vessel* , which operates at
lower pressure than the reactor.
• More TPA crystallizes. The suspension is filtered and the crude TPA
is dried and sent to purification.
• Due to the presence of acetic acid and bromine, highly corrosive
process conditions exist. Therefore, the use of special materials
such as Hastelloy C or titanium is necessary in the reactor and
some other parts of the process.
• The purity of the “crude” TPA is already over 99 wt%
Reaction mechanism of TPA
• The Amoco process produces polymer grade TPA directly by the
oxidation of p-xylene. Figure 9.14 shows a simplified flow scheme.
• Terephthalic acid is the organic compound
with formula C6H4(CO2H)2.
• This white solid is a commodity chemical, used
principally as a precursor to the polyester PET,
used to make clothing and plastic bottles.
Application of DMT & TPA
End of Chapter 4