UEMK4253

Petroleum
Chemistry and
Petrochemicals
Petrochemical Products from
Methane

1
Petrochemicals

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Petrochemicals

• A petrochemical is any
chemical manufactured or
derived from petroleum (and
natural gas).
• Grouped into:
• Feedstocks
• Intermediates
• Finished products

3
Petrochemicals

4
Petrochemical
Industry
Wide Range of Products from
Petrochemical Industry

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Methane
Value Chain

6
Syngas

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Ethylene
Value Chain

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Propylene

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Aromatics

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 Methane/ Syngas

Ethane/Ethylene
Petrochemical
Building
Blocks Propane/Propylene

Butane/Butenes

11
Natural Gas Processing

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Natural Gas Processing

LPG is produced by fractionation of natural gas

liquids and from crude oil by distillation, catalytic
cracking, delayed cokers, and hydrocrackers.
Natural Gas
Constituents

14
LPG

• Generic name for

hydrocarbons containing C3
and C4 constituents. Mainly
Propane and Butane.
• Also known as Auto Gas.

15
Natural Gas
Processing
Natural Gas Processing-
Acid Gas Removal

• Raw gas from the well head is received in

knock-out drums to separate gas and liquid
phases.
• The oil field gases contain corrosive acid
gases like CO2 and H2S. Removal of these
gases is necessary to further process the
gas for LPG production or more products.
• These acid gases are removed by Amine
treatment, Benfield process, Sulfinol
Process and PSA Unit.
• After this, acid gases’ free natural gas is
sent to extraction unit.
Natural Gas Processing-
Amine Gas Treating

• The absorption of acid gases (H2S, SO2, CO2) in amine

solution is conducted with a two columns operation.

• The first column is used to absorb the acid gas into the
absorbent amine,

• The second column is used to regenerate the amine.

• The process relies on counter current flow to achieve

optimum mixing.

• A lean solution (low acid gas) enters the top of the

absorber and flows to the bottom; acid gas enters the
bottom of the absorber tower and bubbles to the top.

• The rich amine (high acid gas) enters the stripper or

regenerator where the acid gases are released and the
“clean” amine is returned to the absorber.

• The acid gases exit from the top of the stripper.

Natural Gas
Processing -
Amine Gas
Treating
Glycol Dehydration
Unit

• To prevent hydrate formation

• To prevent corrosion
• To prevent slugging(two phase
flow) and erosion
• To prevent freezing in downstream
plants
• To maintain heating value of the
gas

20
Natural Gas Processing-Extraction Unit
• The feed of the extraction unit is
the combination of associated
gases and condensate.
• The product streams are divided
into three steps.
• One stream, having the liquid
stream rich in propane, butane,
and gasoline, is sent to the
fractionation tower for LPG
production;
• the other two streams go to the
product gas unit for further
processing.
Natural Gas Processing-
Fractionation Unit
• Liquid stream consisting of ethane,
propane, butane, and pentane is
treated in the fractionator trains to
separate them and sold as LPG. The
fractionation tower consists of three
columns: de-ethanizer, depropanizer,
and debutanizer
Natural Gas
Processing-
Fractionation
Unit
methane
CH4

24
 • Methane (CH4) is the simplest alkane, and it is not very
reactive under normal conditions.
• It is also known as marsh gas or methyl hydride and is
easily ignited. It burns efficiently without many by
products.
• It is the principal component of Natural gas, a mixture
containing about 75% CH4, 15% ethane (C2H6), 5%
other hydrocarbons, such as propane (C3H8) and
butane (C4H10).
Methane • Under prolonged exposure to fire or intense heat the
containers may rupture in a violent explosion.
• Methane is used in making other chemicals and as a
constituent of the fuel, natural gas.
• Only a few chemicals can be produced directly from
methane under relatively severe conditions.
• It is colorless, odorless, lighter than air.

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Methane

• The first hydrocarbon in

alkane series

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Methane
Properties of Methane

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AM1

Chemicals Based
on Direct
Reaction of
Methane
• Hydrogen cyanide, HCN
• Chloromethanes
• Carbon disulfide, CS2
• Synthesis gas mixture
(Steam Reforming of
Natural Gas)

28
Slide 28

AM1 Arif Musa, 2/14/2021

Chemicals From Methane

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Carbon disulfide

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 • Also called Carbon Bisulfide,
• It is a clear, colourless liquid with boiling point
of 161K
• It is toxic, highly volatile and flammable with
flammability limit of 1.06%-50.0% v/v.
Carbon • Used in the manufacture of viscose rayon,

Disulfide-CS2 cellophane, carbon tetrachloride, and

ammonium thiocyanate.
• Other uses include applications in solvent
extraction processes or converted into other
chemical products, particularly accelerators of
the vulcanization of rubber or agents used in
flotation processes for concentrating ores.

31
 • Commercial manufacture of Carbon Disulfide –
Hydrocarbon Sulfur Process:
•
• Endothermic process with Activated
Alumina/Clay catalyst.

Carbon • Requires activation energy of approximately

150 kJ/mol
Disulfide - CS2 • Separated into 3 main systems:
• Sulfur Preparation (melting and
purification)
• Production and Purification of Carbon
Disulfide
• Sulfur Recovery

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 Carbon Disulfide -CS2

Sulfur is prepared
and fed to the
furnace tubes
followed by
methane

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Carbon Disulfide -CS2

Products sent to
Claus process for
recovery of sulfur

34
Carbon Disulfide – Other Processes
• Charcoal Sulfur Process
• Sulfur vapor reacts with charcoal at temperatures of
750–900 oC to form carbon disulfide.
•
• The overall reaction is endothermic and theoretically
consumes 1950 kJ/kg (466 kcal/kg) of carbon
disulfide when the reactants are at 25 oC and the
products are at 750 oC.

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Hydrogen Cyanide

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Hydrogen Cyanide - HCN
• Also known as Prusic Acid or Promonitrile
• Listed in the Chemical Weapons Convection as Schedule 3 Chemical
by the OPCW
• Used as intermediate to produce:
 Acrylonitrile
 Methyl Methacrylates (from acetone)
 Adiponitrile
 Sodium cyanide
 Oxamide (a long-lived fertilizer that releases nitrogen steadily
over the vegetation period)

37
Hydrogen Cyanide - HCN
• Two dominant commercial processes to
manufacture HCN via reaction of Methane and
Ammonia:
• Andrussow Process
• Blausa¨ure-Methan-Ammoniak (BMA) Process
• The major difference between these two processes
are that the Andrussow Process operates in the
presence of Oxygen while the BMA or Degussa
Process operates in the absence of air.

38
Hydrogen Cyanide -
Andrussow Process

• Chemical Reaction:
• 2𝐶𝐻 + 2𝑁𝐻 + 3𝑂 →
2𝐻𝐶𝑁 + 6𝐻 𝑂
• Overall Reaction in Exothermic
releasing about 480 kJ/mol
energy.
• Reaction between Methane and
Ammonia is Endothermic
requiring about 251 kJ/mol of
energy
• Catalyst : Platinum, alumnium-
ruthenium alloy

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Hydrogen Cyanide -Andrussow Process

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Hydrogen Cyanide - HCN
• Degussa Process:

•
• Reaction between Methane and Ammonia is
Endothermic requiring about 251 kJ/mol of energy
• Catalyst : Platinum, alumnium-ruthenium alloy

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Chloromethanes

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Chloromethanes

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Chloromethanes-
Physical
Properties

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 • To produce silicon polymer
• Synthesis of tetramethyl lead as
a gasoline octane booster
Chloromethanes • As methylating agent in methyl
-Methyl Chloride cellulose production
Uses • As solvent, refrigerant, paint
remover, egreasing solvent,
blowing agent for polyurethane
foams, solvent for cellulose
acetate

45
 • To produce chlorodifluoromethane
(Fluorocarbon22) by the reaction with
hydrogen fluoride.
Chloromethanes- • Chlorodifluoromethane end use:
Chloroform • As a refrigerant
(CHCl3) Uses • As an aerosol propellent
• Used to synthesize tetrafluoroethylene,
which is polymerized to a heat resistant
polymer (Teflon)

46
Chloromethanes -Carbon TetraChloride Uses
• To produce chlorofluorocarbons (CFC) used as
aerosols and refrigerants.
• Trichlorofluoromethane (Freon-11)
• Dichlorofluoromethane (Freon-12)
• Catalyst : Antimony pentachloride (SbCl5)

47
Chloromethanes
• Manufactured by chlorination of methane.
• Chlorination of methane yields other chlorinated
hydrocarbons in substantial amounts; methylene
chloride, chloroform, and carbon tetrachloride.
• Methane can be chlorinated thermally,
photochemically, or catalytically.
• Thermal chlorination, the most difficult method, may
be carried out in the absence of light or catalysts.

48
Chloromethanes

• Exothermic Reactions:
• 𝐶𝐻 + 𝐶𝑙 → 𝐶𝐻 𝐶𝑙 + 𝐻𝐶𝑙
• 𝐶𝐻 𝐶𝑙 + 𝐶𝑙 → 𝐶𝐻 𝐶𝑙 + 𝐻𝐶𝑙
• 𝐶𝐻 𝐶𝑙 + 𝐶𝑙 → 𝐶𝐻𝐶𝑙 + 𝐻𝐶𝑙
• 𝐶𝐻𝐶𝑙 + 𝐶𝑙 → 𝐶𝐶𝑙 + 𝐻𝐶𝑙
• Methane and Chlorine ratio is
about 1:1.8 (Adjusted according
to product demand)
• Reaction temperature about 280
– 300 oC).

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Chloromethanes

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Synthesis gas

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Synthesis Gas Mixture
• Also known as Producer Gas, Town Gas, or Blue
Water Gas
• Mixture of Carbon Monoxide and Hydrogen in
various ratios

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Syngas Uses
• Ammonia
• urea, nitric acid, hydrazine, acrylonitrile,
methylamines

• Methanol
• formaldehyde, acetic acid, and
methylamines

• Fischer-Tropsch Process

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Syngas Uses

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 Syngas Process

• Produced by
• Steam Reforming of
hydrocarbons,
• Partial Oxidation of
hydrocarbons,
• Electrolysis of water
• Coal Gasification.

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Syngas Process

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Syngas Process – Sulfur Removal
• Sulfur is a poison for metal catalysts because it can block
active sites by the formation of rather stable surface sulfides.
• In steam reforming and downstream uses in many reactors,
transition-metal-based catalysts are used.
• When sulfur is present as hydrogen sulfide (H2S),
adsorption on activated carbon, reaction with an oxide (eg.
zinc oxide), or scrubbing with a solvent may be employed.
• If the feed contains more stable sulfur compounds,
hydrotreating may be required.

57
Steam Reforming of
Natural Gas
Natural Gas (methane) reacts
with steam at 750-800°C (1380-
1470ºF) and 3–25 bar pressure
to produce synthesis gas
(syngas), a mixture primarily
made up of hydrogen (H2) and
carbon monoxide (CO).
• CH4 + H2O (+heat) →
CO + 3H2

58
Steam Reforming of Natural
Gas
Subsequently, in "water-gas shift reaction,", the carbon
monoxide produced in the first reaction is reacted with
steam over a catalyst to form hydrogen and carbon
dioxide (CO2). This process occurs in two stages,
consisting of a high temperature shift (HTS) at 350ºC
(662ºF) and a low temperature shift (LTS) at 190-210ºC
(374-410ºF).
• CO + H2O → CO2 + H2 (+small amount of heat)

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Syngas – • Steam to carbon ratio is too low
Common Issue in
• Low catalyst activity
Steam Reformers
• Presence of higher hydrocarbons
Carbon (Coke) formation:
• Tube walls too high
Conditions.
• Catalyst has poor heat transfer
characteristics

60
Coke Formation
• Must be prevented for the following reasons:
• Coke deposition on the active sites of the catalyst leads to
deactivation of catalyst.
• Deactivation of catalyst due to coke deposition leads to reduced
selectivity
• Coke deposition on reactor tubes insulates the heat transfer area
and hence reduces the heat transfer rates.
• Coke deposition on reactor tubes causes an increase in pressure
drops and lower the plant capacity.
• Carbon deposits grow so large that they can cause total blockage
of the reformer tubes, resulting in the development of “hot spots”.

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Coke Formation - Prevention
• Hence, the reforming conditions must be chosen such
that carbon formation is strictly limited:
• Suppressing the carbon forming reactions by
adding excess steam. It is common practice to
operate the reformer at steam-to-carbon ratios of
2.5-4.5 mol H2O per mol C, the higher limit
applying to higher hydrocarbons such as naphtha.
• Compared to methane, higher hydrocarbons
exhibit a greater tendency to form carbonaceous
deposits.
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Coke Formation - Prevention
• Continued…
• The cracking tubes are pre-treated so that an inert barrier is
created on the internal surface, preventing the catalytic
influence of the tubes.
• The tubes can also be passivated by chemical treatment
prior to start-up or during operation. The advantages of this
process are that it is less costly and that dosing can be
adjusted during operation. A disadvantage is that the
chemicals used for passivation could end up in the cracking
products.
• An alternative approach is to apply a catalytic coating to the
cracking tubes, which enables the removal of the deposited
coke while the cracking furnace is in operation.

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Ammonia

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Ammonia-NH3
•Colorless gas
•Pungent (Irritating) odor
•Very soluble in water
•Forms a weakly basic solution
•Easily Liquefied under pressure

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 Ammonia- Derivatives

Fertilizer,
plastics,
drugs

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 Ammonia- Derivatives

Ammonium
nitrate

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Ammonia- Derivatives

fertilizer

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Ammonia- Derivatives

Plastics
Rubbers
chemicals

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Ammonia –
Production
Routes

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Ammonia
• Ammonia was first isolated by English Chemist
Joseph Priestley in 1774.
• It was found that ammonia can be synthesized
by reacting calcium carbide with nitrogen to
produce calcium cyanamide and hydrolizing
calcium cyanamide with water:
•
•

71
Ammonia
• Commercial production did not take off until Fritz Haber
discovered that ammonia can be synthesized from nitrogen
and hydrogen.
• The earlier processes were conducted by passing nitrogen
and hydrogen across iron catalyst at 1000 oC and 75 barg.
However, the conversion rates were very low.
• Haber managed to improve the conversion and his patent
was purchased by BASF who developed the commercial
process.

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Ammonia-NH3

• Simplified Flow Diagram of

Haber Process
• The first plant was built in
1913 with a capacity of 30
mt/day.

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Ammonia-NH3
• Haber Process
•
•
• Catalyst:Iron oxide with other oxides such as
potassium and aluminium oxides.
• Increasing the temperature increases the reaction rate
but decreases the equilibrium.
• According to LeChatelier’s principle, the equilibrium is
favored at high pressures and at lower temperatures.

74
Ammonia – Haber
Process

• H and N (3:1) is compressed

to the desired pressure (150–
1,000 atm)
• Reaction occurs over the
catalyst bed at about 450°C.
• Exit gas (ammonia) is passed
through a cooling chamber
where ammonia is condensed
to a liquid, while unreacted
hydrogen and nitrogen are
recycled.

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Typical Block Flow Diagram

Purification Steam Reforming Shift Conversion

•Natural Gas Feed • Steam Injection • H2O reacted with CO to
•Removes Impurities (S, • Conversion H2, CO,CO2 give CO2 and H2
Cl, metals) • Unreacted CH4, H2O • Followed by H2O
removal

Ammonia Synthesis Syngas Compression Hydrogen

•Converts N2 and H2 to • Injection of N2 Purification
NH3 • Removal of CO, CO2 and
CH4

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 Ammonia - NH3

• KBR Process
• Syngas production
runs at 25 to 35 bar
• Ammonia synthesis
runs at 150 to 200 bar

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Steam Reformer
• Natural gas is treated to remove hydrogen sulfide
• The purified gas mixed with steam and fed to the
first reactor which operates at temperature of
700-800 oC and pressure of 30-50 atmospheres
with promoted nickel catalyst.
• The reaction is favored at high temperature, low
pressure and high steam to carbon ratio.

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Steam Reformer
•Two main Reaction:
•
•

•Mixture of unreacted
, and (steam) will be
fed into the secondary reformer.

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Shift Conversion
• The function of shift conversion is to remove
Carbon Monoxide which if not removed will
poison the catalyst.
•
• Reaction is exothermic and independent of
pressure
• Catalyst: iron catalyst promoted with CrO
• Temperature: 425-500 oC
80
Hydrogen Purification
•The effluent from the shift conversion
section is passed through the hydrogen
purification section to remove the CO2.
• Absorption by chemical solvent or
molecular sieves
•CO2 is normally sent to Urea plant for
further processing.
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Methanation
•
•
• The reactions are exothermic and are favored at
Lower T and higher P
• Temperature: 200 – 300 oC
• Pressure = ~10 atm
• Catalyst : Raney Nickel
• Product: Gas mixture of hydrogen and nitrogen
(approx. 3:1 ratio) for ammonia production.
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Ammonia-ICI Process

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 Ammonia Loop Arrangement

a) Pure and dry feed gas

b)Ammonia recovery after
recycle compression
c) Ammonia recovery
beforerecycle compression
d)Two stage product
condensation

84
Ammonia Loop Arrangement

85
Ammonia Loop
Arrangement

• Figure (a) represents the most

favorable arrangement from a
kinetic and an energy point of
view because it results in the
lowest ammonia content at the
entrance of the reactor and
the highest ammonia
concentration for
condensation.

86
Ammonia Loop
Arrangement

• Figure (b) shows the simplest

arrangement. It has the
disadvantage that the
ammonia produced in the
reactor has to be compressed
together with the recycle gas.

87
Ammonia Loop
Arrangement

• This disadvantage is avoided

by using the scheme in Figure
(c), in which the recycle gas is
compressed after ammonia
separation.
• However, ammonia is
condensed at lower pressure,
resulting in a higher ammonia
concentration in the gas
stream, and thus at the reactor
inlet.

88
Ammonia Loop
Arrangement

• Figure (d) shows another way

to avoid compression of
ammonia by splitting the
ammonia condensation.
• However, the disadvantage is
the need for an additional
condenser.

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Urea

CH4N2O

90
 Urea was first synthesized in 1828
from ammonia and cyanic acid. This
Urea was the first synthesis of an organic
compound from an inorganic
compound.

Commercially, urea is produced by

reacting ammonia and carbon
dioxide where carbon dioxide is a
by-product of the ammonia
production process.

91
Urea - Uses
• Fertilizer
• Solid urea containing 0.8–2.0 wt% biuret is primarily used for direct application
to the soil as a nitrogen-release fertilizer.
• Mixed with additives, urea is used in solid fertilizers of various formulations,
• urea–ammonium phosphate (UAP),
• urea–ammonium sulfate (UAS),
• and urea–phosphate (urea + phosphoric acid).
• Concentrated solutions of urea and ammonium nitrate (UAN) solutions (80–85
wt%) have a high nitrogen content but low crystallization point, suitable for easy
transportation, pipeline distribution, and direct spray application.
• Adhesives and plastics
• Animal Feed
• Used as feed supplement for ruminants, where it assists in the utilization of
protein.
• Used in the preparation of lysine, an amino acid widely used in poultry feed

92
 • The formation of urea occurs through two uncatalyzed
equilibrium reactions.

• 2𝑁𝐻 + 𝐶𝑂 ↔ 𝐻 𝐶𝑂𝑂𝑁𝐻 𝑓𝑎𝑠𝑡 , ∆𝐻 = −159

• 𝐻 𝐶𝑂𝑂𝑁𝐻 ↔ 𝐶𝐻 𝑁 𝑂 + 𝐻 𝑂 𝑠𝑙𝑜𝑤 , ∆𝐻 = 31.4 𝑘𝐽/

𝑚𝑜𝑙
Urea - • The first reaction, the formation of ammonium

CH4N2O carbamate (liquid at reaction conditions, solid at

standard temperature and pressure) is exothermic.
• The second reaction, the dehydration of the carbamate,
is endothermic.
• Since more heat is produced in the first reaction than is
consumed in the second reaction, the overall reaction is
exothermic.

93
Urea - CH4N2O
• Thermodynamically, both the carbon dioxide conversion
and the urea yield as a function of temperature go through
a maximum, which usually lies between 450 and 480 K at
practical conditions.
• Increasing the NH3/CO2 ratio leads to a higher carbon
dioxide conversion.
• The yield on urea has a maximum at an NH3/CO2 ratio of
somewhat above the stoichiometric ratio.
• A large excess of ammonia results in a reduced yield.
• In current practice, an NH3/CO2 ratio of 3–5 mol/mol is
used.
94
Urea - CH4N2O
• From a kinetic viewpoint, both carbamate formation and
urea formation proceed faster with increasing temperature.
• The carbamate to urea conversion is much slower than
carbamate formation; temperatures of over 420 K are
required for a sufficiently high reaction rate.
• At these temperatures, pressures of over 130 bar are
required to prevent dissociation of carbamate into ammonia
and carbon dioxide, that is, the reverse of the first reaction.
• At economically and technically feasible conditions, the
conversion of carbon dioxide to urea is only between 50
and 75%.

95
Urea- CH4N2O

96
Urea Processes - Challenges
• Solutions containing ammonium carbamate are very
corrosive.
• Because of the equilibrium, the reactor effluent will always
contain a considerable amount of carbamate which needs
to be separated from the urea solution.
• To be able to separate the carbamate, it is decomposed
back into carbon dioxide and ammonia to separate it from
the urea solution.

97
Urea Processes - Challenges
• Some of the measures to limit corrosion of the construction
materials are:
• proper selection of construction materials, at least stainless steel.
• addition of a small amount of air to the carbon dioxide feed – by
reaction of oxygen with the stainless steel, the protective metal
oxide layer is kept intact.
• minimal exposure of materials to the corrosive carbamate solution
–by using stripping process.

98
Urea – Toyo Engineering

99
Urea - CH4N2O
• Since urea synthesis reaction takes place in
Toyo Engineering two steps, different N/C ratios are employed
for the reactor and carbamate condenser
(VSCC).
• The reactor N/C ratio is selected at 3.7 to
maximize CO2 conversion with appropriate
excess pressure to that of equilibrium.
• Reactor operates at 152 barg and 182 - 184
°C with CO2 conversion of 63 - 64%.
• The higher CO2 conversion at lower
synthesis pressure requires less
decomposition heat in HP stripper and less
energy for CO2 compression and liquid
ammonia and carbamate solution pumping.

100
Urea - CH4N2O
• VSCC is operated at N/C ratio of 2.8 – 3.0.
Toyo Engineering • This optimum N/C selection allows VSCC be operated at a
temperature of 180 – 182 °C and pressure 152 barG.
• Efficient heat transfer between the shell and the tube is
achieved.
• This leads to higher reaction rate of ammonium carbamate
dehydration to form urea : about 45% conversion from CO2.
• Carbamate is decomposed in three stages at different
pressures:
• In the stripper at the same pressure as the reactor,
• in the medium-pressure decomposer at 18 bar
• and in the low-pressure decomposer at 4.5 bar.

101
Urea - Saipem

102
Urea (CH4N2O) - Saipem
• Ammonia and carbon dioxide react at 155
bar to synthesize urea and carbamate.
• The reactor conversion rate is very high
under the N/C ratio of 3.7 with a
temperature of 182°C–185°C.
• Unconverted materials in synthesis solution
are separated by CO2 stripping.
• Gas from the stripper is condensed in a
vertical submerged carbamate condenser
• The urea solution from synthesis section is
sent to a medium-pressure (MP)
decomposer at 17 bar and a low-pressure
(LP) decomposer at 2.5 bar for further
purification.
• No pure ammonia recycle is required due
to the high separation efficiency in the
stripper

103
Nitric acid

104
Nitric Acid - HNO3
•Colorless to a yellow liquid
•Very corrosive.
•A strong oxidizing acid that can attack
almost any metal.
•Used to produce ammonium nitrate
fertilizer

105
Nitric Acid - HNO3
•Primary use -Production of ammonium
nitrate for fertilizers
• Explosives
•Nitrating agent for aromatic and
paraffinic compounds
•Steel refining
•Uranium extraction

106
Nitric Acid - HNO3
• Ammonia is mixed with air and
having an excess of oxygen, is
passed over a platinum catalyst
to form nitric oxide and water
•
•
•
•
•
•

107
Nitric Acid - HNO3
•High pressure reactors are common
because absorption of nitrogen oxide
operates best at high pressure.
•Setback is that higher pressure lowers
the oxidation efficiency.
•Options:
• Oxidation and absorption operates at low
pressure
• Oxidation at low pressure while absorption
at high pressure
108
Nitric Acid –
Single Pressure
Process
Most single-pressure processes
operate at high pressure (7–12
bar) for both the reactor and the
absorber.

109
Nitric Acid –
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.

110
Hydrazine

N2 H 4

111
Hydrazine - N2H4
•Rocket fuel
•As a blowing agent
•Pharmaceutical
•Fertilizer industries
•Polymerization initiator (weak N-N
bond)
•As a reducing agent (an oxygen
scavenger for steam boilers)
112
Hydrazine -N2H4
•Colorless
•Fuming liquid miscible with water
•Weak base but a strong reducing
agent
•Used as a rocket fuel because its
combustion is highly exothermic and
produces 620 KJ/mol
•
113
Hydrazine - N2H4
• Most hydrazine is produced by some variation of the
Raschig process, which is based on the oxidation of
ammonia using alkaline hypochlorite.
• Ketazine processes are modifications in which the oxidation
is carried out in the presence of a ketone such as acetone or
butanone.
• Another variation involves the oxidation of ammonia by
hydrogen peroxide in the presence of butanone .

114
 • First reaction:
Hydrazine -
•
N2H4 • Second reaction:
Raschig Process •
Based on the oxidation of
ammonia with hypochlorite.
This is a stepwise process. • Overall reaction:
•

115
 • The oxidation of ammonia by
Hydrazine - chlorine or chloramine in the
N2H4 presence of aliphatic ketones
Ketazine Process yields hydrazones, ketazines, or
diaziridines.
• After complete consumption of
the oxidizing agents (Cl2, NaOCl,
NH2Cl), intermediates can be
concentrated and then hydrolyzed
to hydrazine.
116
Hydrazine
N2H4

Raschig Process

117
Hydrazine
N2H4

Ketazine Process

118
Differences (Raschig/Ketazine Process)
Raschig
• Lower efficiency as hydrazine
can be further oxidized
• No requirement for disposal of
additional organic byproducts
Ketazine
• Ketazine is not attacked by
chloramine, hence hydrazine is
not destructed – results in
higher yield
• Lower evaporative load
resulting in less energy intensive
process
• Requires further treatment
(distillation/adsorption/activate
d carbon)
119
Methanol

120
Methyl Alcohol
• 1st member of the aliphatic alcohol family.
• Highly polar (hydrogen bonding)
• Evidenced by:
• relatively high boiling temperature (65°C)
• high heat of vaporization
• low volatility
• Due to the high oxygen content of methanol (50 wt%),
it is being considered as a gasoline blending
compound to reduce carbon monoxide and
hydrocarbon emissions in automobile exhaust gases.

121
Methanol Value Chain

122
Methanol Value Chain

123
 • Oxidized to formaldehyde
•
• Carbonylated to acetic acid
Methyl Alcohol •
High reactivity of • Dehydrated and polymerized to
Methanol has hydrocarbons in the gasoline range (MTG
allowed the various process)
processes: • CH3OH + isobutene  MTBE
• CH3OH + isoamylenes  TAME
• Both MTBE & TAME are important gasoline
additives for raising the octane number
and reducing carbon monoxide and
hydrocarbon exhaust emissions.
124
Methanol
• Produced by the catalytic reaction of CO and H2
(synthesis gas) obtained from steam reforming of
natural gas.
•
• Catalyst: Oxides of Zn, Cr, Mn, Al.
• The strongly endothermic reforming reaction is
favored by high temperatures and low pressures.
• Methanol plant reformers typically operate with
exit temperatures within the 840–880oC range,
the upper limit being determined by the tube
metallurgy.
• An energy-efficient alternative to adjusting the
CO:H2 ratio is to combine the steam reforming
process with autothermal reforming.

125
Methanol Typical Process
• When synthesis gas is subjected
to high pressure and moderate
temperature conditions, it
converts to methanol.
• Desired Reaction:
•
• Undesired Reactions:
•
•
• Catalyst: Oxides of Zn, Cr, Mn,
Al.

126
Methanol - Typical Process
• Hydrogen and Carbon Monoxide is
adjusted to a molar ratio of 1:2.25
• Then eventually the mixture is fed to a
reactor. Steam is circulated in the
heating tubes to maintain a
temperature of 300 – 375 oC.
• After reaction, the exit gases are
cooled and passed through phase
separation where methanol and other
high molecular weight compounds
enter the liquid phase and unreacted
feed is produced as the gas phase.
• The gas phase stream is purged to
remove inert components and most of
the gas stream is sent as a recycle to
the reactor.

127
Methanol Typical Process
• The liquid stream is depressurized
to about 14 atms and fed to a
second phase separator.
• The liquid stream then enters a
mixer fed with KMNO4 so as to
remove traces of impurities such as
ketones, aldehydes etc.
• Eventually, the liquid stream enters
a distillation column that separates
dimethyl ether as a top product.
• The bottom product from the first
distillation column enters a
fractionator that produces
methanol, other high molecular
weight alcohols and water as three
different products.

128
Methanol-Davy Process Technology
• Gas feedstock is compressed ,
desulfurized (1) and sent to the saturator
(2) where most of the process steam is
generated.
• Process steam is added, and the mixture
is preheated and sent to the pre-
reformer (3).
• The partially reformed mixture is
preheated and sent to the reformer (4).
• High-grade heat in the reformed gas is
recovered as high-pressure steam (5),
boiler feedwater preheat, and for
reboiler heat in the distillation system (6).
• After final cooling, the synthesis gas is
compressed (7) and sent to the synthesis
loop. The loop can operate at pressures
between 50 bar to 100 bar.

129
Methanol -Davy Process Technology
• The converter operates around 200°C to
270°C.
• A purge is taken from the synthesis loop
to remove inerts (nitrogen, methane), as
well as surplus hydrogen associated with
non-stoichiometric operation. Also, the
purge is used as fuel for the reformer.
• Crude methanol from the separator
contains water, as well as traces of
ethanol and other compounds. These
impurities are removed in a two-column
distillation system (6).
• The first column removes light ends such
as ethers, esters, acetone and dissolved
non-condensable gases.
• The second column removes water,
higher alcohols and similar organic
heavy ends.

130
Methanol - Haldor Topsoe
• The gas feedstock is compressed
(if required), desulfurized (1) and
sent to a saturator (2) where
process steam is generated.
• The mixture of natural gas and
steam is preheated and sent to the
primary reformer (3).
• Exit gas from the primary reformer
goes directly to an oxygen-blown
secondary reformer (4).
• The primary reformer is relatively
small and the reforming section
operates at about 35 kg/cm2g.

131
Methanol - Haldor Topsoe
• The flue gas’ heat content preheats
reformer feed. Likewise, the heat content
of the process gas is used to produce
superheated high-pressure steam (5),
boiler feedwater preheating, preheating
process condensate going to the
saturator and reboiling in the distillation
section (6).
• After final cooling by air or cooling water,
the synthesis gas is compressed in a one-
stage compressor (7) and sent to the
synthesis loop (8), comprised of three
adiabatic reactors with heat exchangers
between the reactors.
• Raw methanol is separated and sent
directly to the distillation (6).

132
 • Problems - Issues
Methyl Alcohol
Methanol as alternative fuel
for gasoline cars.
• Corrosive properties.
• Material compatibility
• High Vapor pressure.
• Increase in evaporative emissions
• Lower heating value, half that of gasoline.
• Higher volume of fuel required
• Cold engine startability
• High flash point
• High heat of vaporization is 3.5 times that of gasoline
• High amount of formaldehyde emission

133
Changes on a Flexible Fuel Vehicle

134
Effect of Oxygenates in Gasoline Blend

135
Formaldehyde

136
Formaldehyde
CH2O
• colorless gas
• pungent, and suffocating odor.
• readily soluble in water, alcohols, and other polar
solvents.
• readily reduced to methanol by hydrogen over many
metal and metal oxide catalysts.
• It is oxidized to formic acid or carbon dioxide and
water.

137
 • Amino and Phenolic Resin
• used as adhesives for binding wood products
that comprise particle board, fiber board, and
plywood.

• 1,4-Butanediol
Formaldehyde • It is used to produce tetrahydrofuran (THF),
- Uses which is used for polyurethane elastomers

• Polyols
• use in the alkyd resin and synthetic lubricants
markets, urethane coatings, polyurethane
foams, and multifunctional monomers.

138
 Decomposition

• At 150 ◦C, formaldehyde undergoes

Formaldehyde heterogeneous decomposition to form mainly
methanol and CO2
- Reactions • Above 350 ◦C, it tends to decompose into CO
and H2

Reduction and Oxidation

• Formaldehyde is readily reduced to methanol

with hydrogen over a nickel catalyst.
• Formaldehyde is oxidized by nitric acid,
potassium permanganate, potassium
dichromate, or oxygen to give formic acid or
CO2 and water.

139
Formaldehyde - CH2O
• Main industrial route is through catalyzed air oxidation
of methanol.
• Two major processes
• Silver Catalyst Process
• Atmospheric pressure
• Silver catalyst, T = 600-720 oC
• Conversion =75% -85%
• Metal Oxide Catalyst Process
• Iron-Molybdenum-vanadium oxide catalyst
• T=400-425 oC, P= 1 atm
• Conversion = 99%

140
Formaldehyde Synthesis
•
•
•
•
•
•
•
•

141
Formaldehyde

Silver Catalyst
Process

142
Formaldehyde
Silver Catalyst Process

• Catalyst Silver or Zinc Oxide

• Operating temperature and
pressure: Near about
atmospheric pressure and 500
– 600 oC
• The reactor inlet temperature
is 54 oC.
• The feed ratio is about 30 – 50
% for CH3OH: O2
• Reactor exit temperature is
450 – 900 oC

143
Formaldehyde -
Haldor Topsoe

• Air and recycled gas are compressed by

the blower (1) and mixed with liquid
methanol.
• Mixture is preheated to 200 oC and fed
to the Reactors (3 and 4) where
methanol reacts with oxygen to produce
formaldehyde.
• Reactor effluent is cooled and sent to the
absorber (7) where formaldehyde is
absorbed in water or urea solution.

144
End of Presentation

145