Petrochemical Engineering-Lect-(01)

Murid Hussain, PhD

Department of Chemical Engineering, CUI, Lahore Campus

04.09.2019.
Text/Reference Books

 Petrochemical Production Processes by Navid Naderpour

(SBS Publisher)

 Petrochemicals by Dr. A. Srivastava (S.K. Kataria

& Sons)

 Fundamentals of Petroleum and Petrochemical Engineering

by Uttam Ray Chaudhuri (CRS Press)

 Basics of Petrochemical Engineering: Santino Quinn/Editor

Contents
 Introduction

 Primary Raw Materials

 Hydrocarbon Intermediates

 Different Petrochemicals (Processes)

 Miscellaneous Processes

 Catalysts Used in Various Petrochemicals

 Recent Research Trends

Introduction

• Petrochemicals
• The major commercial petrochemicals and their derivatives
• Primary petrochemicals
• Intermediates and derivatives
• Major end use products
• Petrochemical Industry
• Process description
• Chemical processes
Distillation
Fractional and vacuum distillation
Reforming
Cracking
Alkylation
Polymerization
Coking
• Feedstocks; classification
• Effects on environment
Petrochemicals
 Petrochemicals are chemicals derived from petroleum products.
 Examples of pet- rochemicals are plastics, rubbers, fibres, paints, Natural Gas
solvents, and detergents.

 Raw materials for petrochemicals are pure hydrocarbons

separated and converted to desirable products, such as polymers, Petrochemicals
solvents, and surfactants, usually in several stages and may be
grouped as
(1) feedstocks (first-generation petrochemicals),
(2) intermediates (second-generation petrochemicals), and Petroleum Coal
(3) finished products (third-generation petrochemicals).

 Products similar to petrochemicals derived from non-petroleum

sources are not strictly petrochemicals. For example, cellulose,
natural rubber, natural resins, nylon 11, and ethanol of plant
origin are strictly non-petrochemicals.

 Coal distillation is also a source of varieties of coal chemicals, e.g., Clothing

benzene, toluene, xylene, and naphthalene. In fact, before
petroleum sources were known, coal chemicals were used to
produce a variety of products.
 Many of the chemicals from non-petroleum sources are co-
processed with petrochemicals to the finished product. Non-
hydrocarbons obtained from petroleum, e.g., hydrogen, carbon Food Petrochemicals Shelter
monoxide, carbon dioxide, sulfur, and carbon, are also loosely
called petrochemicals. Hydrogen, nitrogen and oxides of carbon
manufactured from steam reforming and partial oxidation of
naphtha are also petrochemicals. These are used for production
of ammonia, urea, melamine, fertilizer, etc. Leisure
Petrochemical Raw Materials

Petrochemicals
(Raw Materials)

Olefins Aromatics

Catalytic Catalytic
Steam cracking
cracking reforming
Primary Petrochemicals
Intermediates and Derivatives
Major End Use Products
 Petrochemical Industry
Basic raw
materials

Key Petrochemical Minor

intermediates Industry intermediates

End products

2500 organic chemical products

(plastics & resins; synthetic fibers;
Elastomers; plasticizers;explosives;
Surface active agents;dyes;surface coatings;
Pharmaceuticals;pesticides)
 Process Description

By-products;
Waste
RAW MATERIALS Products intermediate
streams
products

Associated processes in Petrochemical Industry

• Olefins production
• Butadiene production
• BTX production
• Naphthalene production
• Production of cresols and cresylic acids
• Separation of normal paraffins
Aromatics and Derivative Flow scheme
 Chemical Processes
Distillation

• Removal of impurities from crude oil

and separation of the chemicals
• Boiling point based separation
• Desalination/electrical fields in
desalting drum-first step
• Fractional or vacuum distillation
• Role: separation of impurities and
petrochemicals(in groups rather
individuals, e.g. ethane/propane on
same tray)
Reforming
• Process that converts straight-chained hydrocarbons into branched-
chained, cyclic and aromatic hydrocarbons
• Aromatics obtained are used in plastics, medicines, agriculture etc.
Thermal Reforming
• Developed in late 1920s,
• High T(510-565C),P(55-70 atmospheric) using Naphtha as feedstock
• Problems e.g. in gasoline formation, storage of extra chemicals, high
conditions etc.
Catalytic Reforming

• Endothermic process
• Low T(450-510C),P(10-35 atmospheric) using Pt as catalyst and naphtha
feedstock.
• The main products are aromatics.
Steam Reforming
• N2 and H2 to produce ammonia; CO and H2 to produce CH3OH etc.
• Reversible and endothermic reaction, use Ni based catalysts
Cracking

• The process in which long molecules are broken down into smaller
molecules
• In petrochemical Industry: this is the process by which heavy oils are
converted into lighter and more valuable gasoline products.
• THERMAL CRACKING (heating) vs. CATALYTIC CRACKING(catalysts) vs.
HYDROCRACKING (hydrogen)
Cracking reactions
• The most difficult and dangerous reaction in petroleum refining(high T,
P) ; The most important key process in the refining of petrochemicals.
• Feedstocks: ethane, propane, naphtha, gas oil
e.g. ethane into ethene
C2H6 C2H4 + H2
Hydrocracking
• One of the greatest devlopment of the refining industry was the use of
hydrogen in various processes especially cracking.
• The process is similar to catalytic cracking, gives more flexible product
yield. e.g. producing gasoline or jet fuels from heavy gas oil; or producing
high quality lubricant oils
• The process is performed at lower T but higher P
Alkylation
• In petroleum, it is found that there is an excess of lighter hydrocarbons
when heavier ones are needed. e.g. heating oil in furnaces consists of
heavier hydrocarbons than the gasoline(for cars).
• In this situation; ALKYLATION is used to convert the smaller chains into
larger ones. OPPOSITE OF CRACKING!!!

• “ A process in which a light hydrocarbon with smaller carbon chains is

turned into a heavier hydrocarbon with longer carbon chains”.
C3H6+C4H10 C7H16

Polymerization
• This is a process in which relatively small molecules, called monomers,
are combined together to form an extremely long chainlike or network
molecule called a polymer
• Monomer: could be all alike or could be 2 or 3 different compounds
• Characteristics of polymers are determined by its length; for example,
starch, a natural polymer in plants, consists of over half million
monomers called monosaccharide.
Coking
• This is a severe thermal cracking
• The feedstock is heated to about 475-520 C in a furnace for a short time
and then transferred to the bottom of a large vessel called a coke drum.
• The lighter cracked product rise to the top of drum is separated, which
are used in fractionation column for separation into naphtha, diesel oils,
and heavy gas oils for further processing in catalytic cracking.
• The heavier product remains behind in the drum and eventually cracks to
coke (a solid carbon-based substance similar to coal).
• Coke drum is replaced after filling.

Feedstocks
• Important aspects of reactions involving petrochemicals are products
called feedstocks.
• These are raw materials which are processed into other substances and
finished products in a petrochemical plant.
• Classification of feedstocks:
Olefins(alkanes)
Aromatics
Syngas and inorganic containing group
others(NAPHTHA, cycloalkanes, cracker gases, organic compounds etc.)
Common feedstock

• Alkanes from straight-chained unsaturated compounds, and the most

important alkene feedstocks are ethene, propene, and butadiene.
(plastics contain ethene)
• Common aromatic feedstocks include benzene, toluene, xylene, and
naphthalene (e.g. benzene to styrene).
• Ammonia is another commonly know feedstock (formed by reforming
reaction involving syngas as feedstock) which has great agricultural
importance across the world.
Effects on Environment

CO poisoning

1. CH4(g) + 2O2(g) 2CO(g) + 2H2O(l)

2. 2CO(g) + O2 2CO2(g)

If the petrochemical is not burned properly (not high enough or constant T),
CO will be formed, which could cause problem for humans
(CO in lungs instead of O2)

Plastics

• Plastics are one of the most important products of petrochemicals which are
durable, long lasting and moldable into various shapes
• The long lasting part is a huge problem!!!!!
• Plastics after use are thrown into the dump, where they sit,sit,sit……….take
thousands of years to degrade, unlike the other food items to degrade.

SOLUTION: ?????????

RECYCLING
Acid Rains

• One of the most often heard about problems with petrochemicals are their
part in in the production of acid rain.
• All petrochemicals contain some %age of sulfur and nitrogen, which on burning
produce sulfur and nitrogen dioxide, react with rain water to produce sulphate
and nitrate ions, leading towards an acid in the rain water.
• Acid rain causes many problems both in our society and natural world:
Reacts with building to slowly erode the surface
Fish and other water life could die due to more acidic conc.