Petrochemicals

• Petrochemicals; a large group of chemicals

obtained from natural gas or cruse by various
processes.
• Such as:
Alcohols, Aldehydes, butylene, aromatics,
ethylene oxide, acetic acid, acrylonitrile and
hundreds of chemicals
 Classification of Petrochemicals
• Petrochemicals are generally divided into 3
categories
STARTING CHEMICALS
Olefins (Ethylene, Propylene and
C4) INTERMADIATES or DERIVAIVES
Aromatics (Benzene, Toluene, Chemicals that are derived form
Xylene) starting chemicals
Methanol Vinyl Chloride, Ethylene Glycol,
Acetone, BPA, Adipic Acid

FINAL PRODUCTS
Generally polymeric groups
Polyethylene, Polystyrene, PC
 PETROCHEMICAL COMPLEX
NATURAL GAS CRUDE OIL
PRODUCTS
METHANE
NATURAL GAS
REFINERY
PROCESSING
Heavy Naphtha

Ethane, Propane, Butane,

Naphtha, Gasoil Chlorine, Caustic

Gasoline
OLEFINS AROMATICS CHLORINE
PLANT PLANT ALKALI PLANT
Aromatics

PRODUCTS PRODUCTS PRODUCTS

Ethylene, Benzene, Chlorine,
Propylene, Toluene, Caustic
Mixed C4 Xylenes,
Ethyl benzne
 A. Syngas and Derivatives
• Syngas can be obtained from coal or natural gas
• Syngas from NG is cheaper than that from coal
Fisher-Tropsch Synthetic fuel Hydrogen
Synthesis LPG
Naphtha, Diesel, Wax
Chemicals MTBE, Acetic acid,
CO + H2
Formaldehyde
Methanol Synthetic fuel LPG, Gasoline, Naphtha,
Diesel, Wax
Propylene
Olefins Ethylene, Propylene
Ethylene gylcol

Ammonia
A.1 Fisher-Tropsch Synthesis

• 1 mol of CO reacts with 2 moles of H2, then

formation of hydrocarbon chain begins

CO + 2H2 --CH2-- + H2O

• min H2/CO is 2

Water-Gas Shift Reaction’s

2CO + H2 --CH2-- + CO2

• min H2/CO is 0.7
Alkanes nCO + (2n+1)H2 → CnH2n+2 + nH2O
Alkenes nCO + 2nH2 → CnH2n + nH2O
Water-Gas CO + H2O ↔ CO2 + H2

Side Reactions

nCO + 2nH2 → H(-CH2-)nOH + (n-1)H2O

2CO → C + CO2
There are lots of chemicals rxn’s during syngas
production. The following rxn’s are related to
methane:
Reforming Reaction’s: (endo)
𝑁𝑖
900°𝐶
𝐶𝐻4 + 𝐻2 𝑂 𝐶𝑂 + 𝐻2 𝑂
𝐶𝐻4 + 𝐶𝑂2 ՜ 2𝐶𝑂 + 𝐻2
Oxidation Reaction’s: (exo)
𝐶𝐻4 + 𝑂2 ՜ 2𝐶𝑂 + 4𝐻2
𝐶𝐻4 + 2𝑂2 ՜ 𝐶𝑂2 + 𝐻2

Water-Gas Shift Reaction’s: (exo)

𝐶𝑂 + 𝐻2 𝑂 ՜ 𝐶𝑂2 + 𝐻2
A.2 Methanol from SynGas
𝐶𝐻4 + 𝐻2 𝑂՜𝐶𝑂 + 3𝐻2
𝐶𝑂 + 2𝐻2 ՜ 𝐶𝐻3 𝑂𝐻
𝐶𝑂2 + 3𝐻2 ՜ 𝐶𝐻3 𝑂𝐻 + 𝐻2 𝑂
A.2.1 Formaldehyde from Methanol
CH3OH HCHO + H2

CH3OH + 1/2 O2 HCHO + H2O

Methanol recycle

Methanol
ADSORPTION METHANOL
CONVERTER WASHING RECOVERY
Air
Water

Formaldehyde
37vol.%
 OLEFIN PLANT

ETHYLENE
• Ethylen oxide MIXED C4
• Vinyl acetate PROPYLENE • n-Butenes
• Ethylene • Cumene • Isobutenes
dichloride • Isopropyl • Budaien
• Ethylbenzene alcohol • Butanes
• Acrylonitrile
ETHYLENE
 It is especially used in the production of plastics,
 By direct polymerization PE is produced
 It is a hormone used in the development of fruits
 Coolant

PROPYLENE
 It is starting material fır plastics and
acrylonitirile, isopropyl alcohol and more..
For gasoline production,
Used in automobile parts and acking material
MIXED C4
 Generally used for the production of
butadiene,
Butadiene is used for producing synthetic
rubber (polybutadiene)
SBR, ABS,
 ETHYLENE
• Produced by;
Steam cracking,
Methanol olefin process (UOP)
Olefin conversion processes
 ETHYLENE

Polyethylene Ethylene Glycols Polyesters

Motor coolant
Ethanol amines
Ethylene Oxide
Glycol eters
Etoxylates
Vinyl acetate
Vinyl chloride PVC
Trichloriethylene
Ethylene dichloride
Perchloroethylene

Ethylbenzene Styrene ABS, SBR

 polyethylene
• Thermoplastic,
• White color,
• Semitransparent
• Polymerization of ethylene
TiCl4
n CH2=CH2 CH CH
Trialkyl n
aluminum
LDPE process flow diagram
 ethylene oxide
• Reaction of ethylene and oxygen at 250-300 °C
under 1-2 Mpa pressure
• Ag based catalyst are employed
• Ethylene oxide is an intermadiate and used for
the production of ethylene glycol, glycol ethers,
polyesters
O
250-300 °C
2CH2=CH2 + O2 H2C CH2
-
1 2 MPa

• Side reaction
2CH2=CH2 + 3O2 → 2CO2 + 2H2O
Ethylene oxide production process flow diagram
 Ethylene glycol (from ethylene oxide)
• Used as antifreezer in motorvehicles
• The reaction of ethylene oxide with water
under T and P produces Ethylene Glycol
O HO CH2

H2C CH2
+ H2O
CH2 OH

Ethylene glycol mono ethylene glycol

MOG + Ethylene glycol → DEG

DEG + Ethylene glycol → TEG
TEG + Ethylene glycol → Tetraethylene glycol
 Light MEG DEG
Water gases
recycle

DISTILLATION

DISTILLATION
DISTILLATION
Multistep
Vaporizer
REACTOR

Ethylene
oxide

TEG
Steam Steam

ETHYLENE GLYCOL PRODUCTION PROCESS

 Glycol Ethers (from ethylene oxide)
• Used in the monoglycol ethers.
Monoglycol ethers → cleaning solvents, paint
coating, ink production, antiacing agent
Di/Triglycol ethers → Hydrolic oil
Reactions
Ethylene Oxide + Ammonia → Monoethanolamine
MEA + Ammonia → EAD
DEA + Ammonia→ TEA

• The above reactions are series reaction scheme

•Reaction is exothermic
• Ammonia is mixed with ammonia recycle stream
from the process and pumped to the CSTR where
liquid phase ammonolysis takes place.
• Ethylene oxide is compressed and fed to the CSTR.
• The CSTR operating pressure will be such that the
feed (and product) mixtures do not vaporize and
good liquid phase reaction can occur.
• The reactor is cooled using water in the cooling
jacket as the reactions are mildly exothermic.
• The product stream is then sent to a flash unit
that separates NH3 + H2O as a vapour stream and
water + ethanolamines as a liquid stream.
• The ammonia + water stream is recycled to mix
with the fresh ammonia and enter the reactor.
ETHYLENE AMINE PRODUCTION PROCESS
 Vinyl acetate (from ethylene)
• Used for the production of
Polyvinyl acetate (paints, glue, surface coatings)

Polyvinyl alcohol (glue, water soluble packing)

Polyvinyl acetale (safety glasses, paints)

+ →

Ethylene Acetic acid Vinyl acetate

 Ethylene dichloride (from ethylene)
Basically it is used to produce PVC
Direct chlorination process

4 atm
+ Cl2 →
60 °C

Ethylene EDC

30 atm
→ + HCl
500 °C
Vinyl chloride