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Chapter 9

Petrochemicals

Refinery-ADU

C5-150 C

b.p.150-250 C

Refinery-Types
A topping refinery is equipped with a main Atmospheric
Distillation unit and necessary treating processes for other
products going to storage. They have no capability to alter
the natural yield pattern of the crude oils that they process

Refinery-Types
A hydro-skimming refinery is equipped with a main Atmospheric
Distillation unit, a naphtha reforming unit and necessary treating
processes for other products going to storage. have no capability to alter
the natural yield patterns of the crudes they process

Refinery-Types

Refinery structure
Processing of light crude, even in a complex refinery with FCC,
hydrocracking etc. does not yield a satisfactory product distribution. The
amounts of fuel oil are too high.

CONVERSION OF HEAVY RESIDUES


For heavy oil the situation is even worse with ~ 50% fuel
oil being produced even in a complex refinery.
Fuel oil is worth < original crude. The value of the products
decreases in the order: gasoline> kerosene/gas oil > crude oil > fuel oil.

CONVERSION OF HEAVY RESIDUES


Deep Conversion: Combines carbon extraction with the
addition of hydrogen.
This process is designed to convert the heaviest fractions
(refinery residue or bottoms) into lighter and marketable
products.
Process includes coking, residue catalytic cracking
and de-asphalting.

Refinery-Types

Refinery Margin
The refining margin is the difference in value between
the products manufactured by a refinery and the value
of the crude oil used to produce them.
Refining margins will thus vary from refinery to refinery
and depend on the price and characteristics of the
crude used.
Refinery margins gauge profitability based on the coproduction of the product slate based on specific refinery
configuration, location of the refinery and the
type/specification of the crude oil feedstock.

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Refinery Margin
Margins are influenced by refinery configuration
(simple or complex), the running of a variety of crude
types and the range of products.
Over recent years complex refineries (those with the
ability to crack fuel oil and convert heavy residue) have
achieved consistently higher refining margins than
simple hydroskimming refineries. The key players have
invested extremely large sums in refining upgradesdesulphurisation, hydrocracking and deep
conversion.
Nelson Complexity Index higher the value of
products. US refinery 9.5 and RIL 14
11

Reliance Complex-Refinery

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Petrochemicals
Chemicals derived from petroleum products. Like
plastics, rubber, fibers and solvents.
Raw material for petrochemicals are pure
hydrocarbons separated and converted to desirable
products in several stages and it is grouped as
1. Feed-stocks (First generation PC)
2. Intermediate (Second generation)
3. Finished products (third generation)

Petrochemicals
1. Feed-stocks (First generation PC)
HC obtained from crude oil refining by distillation
and thermal and catalytic process. Ex
HC gases and naphtha from ADU
2. Intermediate (Second generation)
Thermal cracking of ethane, propane , butane and
naphtha produces cracked gases or olefins (C2, C3,
C4 and acetylene) and liquids of BTX
3. Finished products (third generation)
Using above intermediate , a variety of plastics,
rubber, fibre, solvent, paints etc.

CLASSIFICATION
Primary petrochemicals are divided into three
groups depending on their chemical structure:

CLASS 1
Olefins includes ethylene, propylene, and
butadiene. Ethylene and propylene are
important sources of industrial chemicals and
plastics products. Butadiene is used in making
synthetic rubber.

CLASS 2
Aromatics includes benzene, toluene, and
xylenes. Benzene is a raw material for dyes
and synthetic detergents, and benzene and
toluene for isocyanates used in making
polyurethanes. Manufacturers use xylenes to
produce plastics and synthetic fibers.

CLASS 3
Synthesis gas is a mixture of carbon monoxide
and hydrogen used to make ammonia and
methanol. Ammonia is used to make the
fertilizer urea and methanol is used as a
solvent and chemical intermediate.

Naphtha cracking

Naphtha Re-distillation unit


Feed : Stabiliser
bottom.
Products
Lighter : for production
of olefins and
hydrogen.
Heavier : suitable for
high octane gasolene
or BTX petrochemicals

Naphtha cracking
 Major plastics are manufactured from olefins,
produced by cracking of gases (gas-based
petrochemicals) , such as CH4, C2H6 or from Naphtha
(Naphtha based).
 Large availability of Naphtha and low energy
requirement for cracking, it is widely accepted.
 Yield of olefin decreases with increasing Mol. Wt of
HC.
Ethane gives 80% Ethylene
Propane 45%, Butane 37% , Naphtha 30-35%...

The desirable feed stock for Naphtha


cracking is high content of Paraffin
>75% and low boiling range<100 C

Naphtha cracking
Due to thermal cracking, the following cracking
endothermic reaction takes place

Light hydrocarbons obtained from the initial cracking


reactions further crack into lighter olefins and
propagate until the reaction temperature is brought
down (quenched).
If the reaction is continued indefinitely, branched and
cyclised heavy hydrocarbons will be produced and coke
will be generated as the ultimate product.

So the residence time in the furnace is


in milliseconds

Naphtha cracking
Steam is introduced with the feed to remove the coke
layer on the tube surface by converting coke into carbon
monoxide and hydrogen by water gas reaction
C + H2O(steam) = CO + H2.
Furnace Condition

Naphtha cracking
 Cracker furnace operates cyclically between the
cracking and decoking operations.
 Excess steam may also partially convert Naphtha to
CO and H2, reduce the yield of olefins.
 Products from the cracking furnace are quenched and
fractionated.
 Amine or caustic washed to remove H2S and CO2
gases.

Naphtha cracking

Naphtha cracking

Polymers

Epoxy polymer

LDPE

1)Monomers

2)
Initiation:
Initiator added,
bonds break
and radicals
are formed

3) Free radicals +
monomers

4)
Propagation:
monomers
join to radical;
chain grows.

7)Complete polymer

6)
Termination:
Long chain
radicals join.
Polymer
formed. .

5) Long chain
radicals +
monomers

Low Density Polyethylene

In the initiation stage, radicals are made using an organic peroxide catalyst.

Low Density Polyethylene: Initiation

The OO bond is weak and breaks to make RO radicals (alkoxy radicals).

Low Density Polyethylene

An alkoxy radical combines with one of the electrons from the double bond in
ethylene.

Low Density Polyethylene: Propagation

An alkoxy radical combines with one of the electrons from the double bond in
ethylene.

Low Density Polyethylene: Propagation

This forms a new covalent bond and a new radical.

Low Density Polyethylene: Propagation

The new radical reacts with another ethylene molecule.

Low Density Polyethylene: Propagation

This forms another new radical, longer than before.

Low Density Polyethylene

The chain grows longer until two radicals react with each other.

Low Density Polyethylene: Termination

This is called the termination step.

LDPE is used for making films, sheets, tubes,


blocks, insulation, hoses etc.
But, it cannot be used at temperatures above
80C because deformation will occur.
Reaction takes place in solution
Heat of reaction -3650kJ/Kg

Typical Autoclave reactor

HDPE
in Alkyl
aluminium

HDPE has a rigid and translucent property and is


suitable for making electrical goods, bottles, ropes,
etc.
Catalyst is suspended in
Benzene.

HDPE
Benzene

Flash drum

20-35 atm
60-80 C

HDPE
Catalyst consumption is 1 g of Ti per 1500 kg of
polymer. This impurity limit the application of
HDPE.
Modern catalyst yield 6000 kg/gm of catalyst
HDPE high melting point than LDPE.
HDPE is rigid for making electrical goods, bottles
and ropes.
Very Low p as compared to LDPE.

LLDPE
Co-polymer of Ethylene and 1-butene having linear
structure
Temp: 100 C
P : 7-20 atm.
Fluidized condition. Monomers used to fluidise the
polymer granules.
Long residence time 3-5 hr

LLDPE

LLDPE

Uses
plastic bags and sheets (where it allows using lower
thickness than comparable LDPE) plastic wrap, stretch
wrap, pouches, toys, covers, lids, pipes, buckets and
containers, covering of cables, geomembranes and mainly
flexible tubing

Poly-propylene
Used for making pipes, fibres, ropes and chair.
Catalyst : Ti and Aluminium halide , Temp : 60-70 C
Centrifugal
Pressure : 1-2 Mpa.
separator

Stirred Tank
catalyst mixer

Stirred Tank
Reactor

Flash
separation

PVC
Thermoplastic by emulsion polymerisation.
Emulsifier: Ammonium salts of fatty acid
pH : acidic. Polymer in latex.

Polystyrene
Styrene readily polymerizes by free radical chain
mechanism. Egg cantons, plastic cup, plate, foam
M +Initiator---------> Polymer

Rigid thermoplastic.
Homopolymers of styrene referred as general
purpose PS. (GPPS)
Because of brittleness, frequently polymerised in
the presence polybutadiene rubber to improve the
strength. It is high impact PS (HIPS)

Polystyrene
PS polymerised by all process. Mostly by mass
and suspension.
Mass no initiator but control of exothermic is
crucial

Feed

200-220 C
Vacuum

80-85 C
CSTR

or
granules

Polystyrene
Suspension
Solvent : water (45% wt) mixed with suspending
agent (Phosphates of Mg, Ca, Ba)
Initiator/Catalyst: Benzoyl peroxide.
Temp : 90 C and Atm Pressure. Heat removal is
efficient

200-220 C
Vacuum

90 C
CSTR

or
granules

Polybutadiene
Butadiene from Naphtha cracking unit.
Polybutadiene has a high resistance to wear
mainly used in Tire manufacturing. Most golf balls
are made of an elastic core of polybutadiene.

"high cis"-polybutadiene has a high elasticity and is


very popular, whereas the so-called "high trans" is a
plastic crystal with few useful application

Polybutadiene
Catalytic solution polymerisation (Z-Natta catalyst),
Exothermic
Solvent: pentane
Temp : 50 C and Atm P: Time : 30-50 min

S-B Copolymer
HIPS
Polybutadiene is dissolved in Styrene monomer
This graft copolymer improve the impact
strength and toughness.

S-B Copolymer
HIPS
Temp : 50 C
Initiator : Potassium Sulfate in Ammonical soln

SAN and ABS Copolymer


Styrene Acrylonitrile (SAN) Copolymer
Styrene containing 25-35% Acrylonitrile to improve heat
resistance and impact strength

Acrylonitrile-Butadiene-Styrene (ABS) copolymer


High clarity, impact, tensile strength and heat resistance by
blending of SAN (70/30) and SBR (35/65) or PB.

CN

BTX Separation
Feed : Product from Naphtha reforming process
and Naphtha cracking process consist of BTX.
Benzene :
Most valuable petrochemical building blocks as it
serves as the raw materials for cyclohexane
required for nylon industry.
Key intermediate for drugs, dyes, pesticides,
explosives etc.
Toluene:
Mainly as solvent and for making phenols,
benzoic acid, explosives.

BTX Separation
Xylene:
 p-xylene used for manufacture of DMT or TPA.
 o-xylene used to produce phthalic anhydride.
 m-xylene for isophthalic acid and isophthalates.
Not much use.

BTX Separation
The aromatic contains a trace amount of olefin and
sulfur compounds.
This is removed by adsorption in clay.

Xylene Separation
400 trays, 40-60 m height
High reflux ratio 55

Aromatics

Toluene+ML

Pt as catalyst
380- 480 C
O,M to P Xylene

Octafining
Crystalliser temp :
-40 to -50 C
-55 to -70 C

Impure crystals are melted


and recrystallised at -20 C

Recent development
Parex process:
Developed by UOP separation of p-xylene from mixed
xylene by molecular sieve adsorbent. Purity >99%
Aromax process:
Toray industries japan. Separation of p-xylene from mixed
by absorption process.