PROCESSES

INVOLVED IN
THE
PRODUCTION
OF
PRECURSORS
 Precursor
In Chemistry
s
-Is a compound that participates in a chemical reaction that
produces another compound.

- example : ethane

In Biochemistry

– refer more specifically to a chemical compound preceding another in

a metabolic pathway

- example : protein
 PETROCHEMICAL PRODUCT
TREE
Building Block Intermediate Downstream Products

EDC PVC

Ethylene Polyethylene
(Ld/Hd) Glycol Ethers
EDC - Ethylene dichloride EO/EG Enthaloamines
EO - Ethylene oxide
EG - Ethylene glycol Isopropyl Alcohol/ Dye Stuff and
DMT - Dimethyl terephathalate Acetone Chemicals
PVC - Polyvinyl chloride Intermediate
Propylene
PBR - Polybutadiene rubber Polypropylene
SBR - Styrene butadiene rubber Acrylonitrile
Acrylic Fiber
Plasticisers
2 Ethyl Hexanol
A B S Plastics
Olefins PBR
Butadiene SBR
Cumene/Phenol Pharmaceuticals

Thermoset Resins
Cyclohexane/

Naphtha Caprolactum Nylon

Benzene
Detergents
Alkylate Detergent

Polyester
Aromatics Maleic Anhydride
Alkyd Resins

Phthalic
Anhydride Plasticisers
Xylene Polyester
DMT Fibre
 Petrochemical Feedstocks
The refinery products are: naphtha; gas oil and
catalytic cracker gases.
NOTE:
In oil industry: gasoline fraction
In petrochemical industry, naphtha is the petroleum
fraction that boils between 20-80oC.
Naphta has: mix of alkanes, cycloalkanes and
aromatic hydrocarbons.
Gas oils are mix of have the same components but
with higher molecular weights.
Gas oils are used in place of naphtha as a feedstocks
for ethylene manufacture.
 In USA, large scale cracking : cracker gases are the precursors
for production of propylene and butenes.

In Europe and Japan, small scale cracking: cracker gases are

sources for ethylene.

Kerosine: chemical feedstock, manufacture of ethylene

The Basic building Block Processes

• Petrochemical industry is based on intermediates.
• Known Petrochemical Processes: Thermal cracking; catalytic
cracking and steam reforming.
 Petrochemical Process
Technology
Petrochemical processes are normally Continuous
Processes; the raw materials are continuously fed into the
plant so as the products.

Petrochemical plant would have one or more reaction

systems. C6H6 + C2H4  C6H5C2H5  C6H5CH=CH2 + H2

 Introduction
Hydrocarbon intermediates are obtained by subjecting crude oil
to various processing schemes.

Primary distillation  simple fractions  used as fuels

Small % of these fractions  2ry raw materials

(intermediates) for production of olefins, diolefins and
aromatics.

Further reaction may be required for other transformations.

This chapter deals with the production of intermediates in

correlation to different crude oil treatment schames.
 Physical Separation processes
Separating the components of crude oil without changing
the chemical nature.

Separation is based on the differences of certain

physical properties of the constituents.

e.g. boiling points, melting points,

..etc. Example of the processes :-

- Crude distillation (atmospheric & vacuum distillation), solvent
extraction, solvent deasphalting, solvent dewaxing, clay
treatment, absorption, adsorption, etc
 Atmospheric Distillation
• Separates crude oils into fractions with narrow boiling
points.
• One or more fractionating columns are used.
• Starts by preheating the feed by exchange with the hot
product streams.
• Feed is further heated to 320 oC by heating the stream
pipes.
• Feed inters the fractionator (30-­‐50 fractionation tray).
• Steam is introduced from the bottom to strip light components.
• Efficiency  number of theoretical plates and the reflux ratio.
• Reflux Ratio: The ratio of vapor condensing back to the distillate.
• The higher the RR, the better separation of the mixture
Flow diagram of atmospheric and vacuum distillation units:1 (1,3) heat exchangers;
(2) desalter, (3,4) heater; (5) distillation column, (6) overhead condenser, (7–10)
pump around streams, (11) vacuum distillation heater; (12) vacuum tower.
 VACUUM DISTILLATION
Increases the amount of the middle distillates
Produces lubricating oil base stocks and asphalt.

Superheated steam  Decreases Phydrocarbons and Coke formation in furnace tubes.

Temp: 400–440°C
Absolute pressure: 25–40 mmHg.

Products: Vacuum gas oil (VGO), lube oil base stocks, and asphalt.

Asphalt may be used for paving roads or may be charged to a delayed coking unit.

Crude Oil Distillation Process https://

www.youtube.com/watch?v=vscX_zawdQw
 ABSORPTION PROCESS
Selectively removes a certain gas from a gas mixture using
liquid adsorbent.

Used in removal of acid gases.

ADSORPTION PROCESS
• Using a large surface area adsorbent to selectively adsorb a
gas or a liquid.
e.g. Silica (SiO2), anhydrous alumina and zeolite molecular
sieves (crystalline microporous alumino silicates.
- Can be used to separate liquid mixtures.
- Zeolite 5A selectively adsorb liquid paraffins from Low
octane naphtha.
- Normal paraffins are important for detergent industry.
•
Adsorption also used to separate liquid mixtures. E.g. zeolite 5A
selectively adsorbs n-paraffins from a low-octane naphtha
fraction.

Branched paraffins and aromatics in the mixture are not adsorbed.

Desorption  displacement with another solvent.

C10-C14 paraffins adsorbed from a kerosine or a gas oil is done in
a liquid or a vapor phase adsorption process.

The IsoSiv process is an isobaric, isothermal adsorption

technique used to separate n-paraffins from gas oils @ 370°C
and 100 psi.

Desorption is achieved using n-pentane or n-hexane. The solvent

is easily distilled from the heavier n-paraffins and then recycled.
 SOLVENT
EXTRACTION
Liquid solvents are used to extract either
undesirable compounds from a liquid mixture.
desirable or

Uses a solvent with high solvolytic power for certain

compounds. e.g. ethylene to extract aromatic hydrocarbons
from a reformate mixture (a liquid paraffinic and aromatic
product from catalytic reforming).
The raffinate, which is mainly paraffins, is freed from traces
of ethylene glycol by distillation.
Others: liquid sulfur dioxide and sulfolane (tetramethylene
sulfone).
The sulfolane process is a versatile extractant for producing
high purity BTX aromatics (benzene, toluene, and xylenes). It
also extracts
aromatics from kerosines to produce low-aromatic jet fuels.
Solvent extraction used to reduce asphaltenes and metals from
heavy fractions and residues before using them in catalytic
cracking.

The IFP deasphalting process:4 (1,2) extractor, (3-6) solvent

recovery towers.
 PRECURSORS
BY
CONVERSION
Raw materials by distillation

Paraffins and cyclic

Precursors (basic chemicals) by conversion

Olefins, diolefins, acetylene, aromatics

Natural gas
Sulfides H2S

Hydrogen
Methane
Refinery gases Acetylene, Isobutene
Ethane Ethylene
Propane Propylene
N-Butane N-Butenes
Hexane
Heptanes
Refinery naphthas
Naphthenes Cyclopentadiene
Benzene Toluene
Toluene Toluene
Xylenes O-, m-, p-Xylene, toluene
 CONVERSION PROCESSES
Purpose :
To upgrade lower-value materials
To improve the characteristics of a fuel.
lower octane  to a higher octane reformate product.
To reduce harmful impurities in petroleum fractions and
residues. To avoid poisoning certain processing catalysts.
Conversion processes are either thermal, or
Catalytic Example conversion processesn:-
- Catalytic reforming, hydrotreating, hydrocracking, catalytic
cracking, alkylation, isomerization, delayed coking,
flexicoking, visbreaking, etc..
Catalytic Reforming – used to process low grade
(octane number) fraction. Dehydrogenation,
isomerization, hydrocracking may occur during this
process.

Hydrotreating – carried out to remove impurities such

as sulfur, nitrogen, halides, etc

Alkylation – addition of C branch to produce high

grade products, eg addition of isobutane to butenes.

Isomerization – isomerized process to branched alkanes

to produce a high octane rating product.
Coking – refinery unit operation that upgrades
material called bottoms from the atm/vacuum
distillation into higher-value products. Eg
Delayed Coking & Fluid coking
Flexicoking is a fluid coking process in which the
coke is gasified with air and steam. The resulting gas
mixture partially provides process heat.
Visbreaking – used to reduces the viscosity of the
residual oil from the atm/vacuum distillation of crude
oil & increase the yield of more valuable products
 THERMAL CONVERSION
PROCESSES
Coking Processes
Thermal cracking process designed to handle heavy residues
with high asphaltene and metal contents. These residues
contain impurities which deactivate and poison the catalysts.
Thermal Cracking Reactions
 Cracking
Process
Thermal Cracking

Catalytic
Cracking

Hydro

Cracking

Steam Cracking
Exercise :-

Differentiate these four cracking processes by watching this

video https://www.youtube.com/watch?v=VofKBcdZtjo
 Thermal
cracking
Simplest & older process
Operating Temp – 750-900C, Operating Pressure
– 700kPa
Feedstocks: ethane, propane, naphtha and gas
oils. When ethane is cracked  ethylene
Propane  propene + co-product
Naphtha and gas oil  propylene, butene, butadiene
and aromatic compounds.
 Catalytic
cracking
T =500C with absent of O2

Catalyst – Zeolite (aluminium, silicon,

Oxigen) Products – propane, butane, pentane

till octane
 Hydrocrackin
g
High Pressure – 5000kpa,

Present of Hydrogen & catalyst (platinum,

nickel) Source of Kerosene, gasoline, LPG

 Steam
cracking
Steam cracking is in which saturated hydrocarbons are broken
down into smaller, often unsaturated, hydrocarbons.
Operate at 850C with no Oxigen
Methods for producing the lighter alkenes (or commonly
olefins), including ethene (or ethylene) and propene (or
propylene).
Steam cracker units are facilities in which a feedstock such as
naphtha, liquefied petroleum gas (LPG), ethane, propane
or butane is thermally cracked through the use of steam in a
bank of pyrolysis furnaces to produce lighter hydrocarbons.
The products obtained depend on the composition of the feed,
the hydrocarbon-to-steam ratio, and on the cracking temperature
and furnace residence time
 Delayed Coking
two or more large reactors, called coke drums, are used to
hold, or delay, the heated feedstock while the cracking
takes place.
Coke is deposited in the coke drum as a solid.
This solid coke builds up in the coke drum and is removed
by hydraulically cutting the coke using water.
In order to facilitate the removal of the coke, the hot feed
is diverted from one coke drum to another, alternating the
drums between coke removal and the cracking part of the
process.
 Fluid Coking
With fluid coking, the feed is charged to a heated
reactor, the cracking takes place, and the formed
coke is transferred to a heater as a fluidized solid
where some of it is burned to provide the heat
necessary for the cracking process.

The remaining coke is collected to be sold

 Reforming
Reaction
Processing technique by which the molecular structure of a
hydrocarbon is rearranged to alter its properties. The process
is frequently applied to low-quality gasoline stocks to improve
their combustion characteristics.
Produces reformate that is one of several blending components
in finished gasoline. It contains significant amounts of BTX.

Thermal reforming alters the properties of low-grade naphthas by converting

the molecules into those of higher octane number by exposing the materials to
high temperatures and pressures. Produce reformate with octane numbers 65-
80

Catalytic reforming uses a catalyst, usually platinum, to produce a similar result.

Mixed with hydrogen, naphtha is heated and passed over pellets of catalyst in a
series of reactors, under high pressure, producing high-octane gasoline. Produce
reformate with octane numbers 90-95.
 Catalytic
reforming
Catalytic reforming is a chemical process used to convert
petroleum refinery naphthas with usage of catalyst, typically
having low octane ratings, into high-octane liquid products called
reformates which are components of high-octane gasoline (also
known as high-octane petrol).
Basically, the process re-arranges or re-structures the hydrocarbon
molecules in the naphtha feedstocks as well as breaking some of the
molecules into smaller molecules. The overall effect is that the
product reformate contains hydrocarbons with more complex
molecular shapes having higher octane values than the hydrocarbons
in the naphtha feedstock.
In so doing, the process separates hydrogen atoms from the
hydrocarbon molecules and produces very significant amounts of
byproduct hydrogen gas for use in a number of the other processes
involved in a modern petroleum refinery. Other byproducts are small
amounts of methane, ethane, propane, and butanes.
Catalytic
reforming
Thermal/Steam Reforming
 Synthesis
Gas
Also known as syngas.

Is a fuel gas mixture consisting primarily of

Hydrogen, Carbon Monoxide and very often some
Carbon Dioxide.

Product that can be made : - Ammonia, Hydrogen,

Methanol, Synthetic hydrocarbon, gasification for
electricity generation & internal combustion
engines
 Synthesis
Gas
Production processes ;-

1. Steam Reforming of Natural Gas

2. Steam Reforming of liquid Hydrocarbon(petroleum)

3. Gasification of Coal

4. Partial oxidation of natural gas & petroleum

5. Biomass Catalytic partial oxidation

6.Carbon Dioxide & Hydrogen – Microwave

technology, solar, wind, co-electrolysis
Safety in Petrochemical
Plants
The intrinsic safety for the petrochemical plant
should use technological measures to eliminate or
control risks and to prevent accidents.

Health and safety in the petrochemical industry

is best tackled from two different perspectives:
process safety and occupational health and
safety
 Incident
https://www
.youtube.com/watch?v=QiILbGbk8Qk

Propylene Gas https://www.youtube.com/wa

tch?v=-_ZLQkn7X-k
 HAZOP/SAFET
Y Risk Assessment /
Risk analysis
type

Health Risk Safety Hazard

Assessment (human Analysis (human safety
health focus) High focus) low probability,
probability, low high consequence,
consequence, ongoing, accidental, acute,
chronic, delayed effect immediate effect

Ecological Risk
Assessment
(habitat/ecosystem focus)
Subtle changes, latency,
complex interaction, macro
impacts
 THE 4-STEP RISK ASSESSMENT PROGRAMME

Hazard
Identification
What health problems are
caused by the pollutant?

Exposure Dose-Response
Assessment Assessment
How much of the pollutant What are the health
do people inhale during a problems at different
specific time period? How exposure?
may people are exposed?

Risk Characterization
What is the extra risk of
health problems in the
exposed population?
 Reduction of Effects of
supporting assimilative
capacity capacity

Polluted water
Water resource resources

Wast
Withdrawn of e
raw material water
Haz. waste
Industry Land

Effect flora
fauna Emission Health
Economi
c value
Air pollution
Effect human
settlement Flora &
fauna
 PICTORIAL REPRESENTATION OF
BALANCE
Gaseous Emissions
Raw materials

Catalyst Product
PLANT
Water / Air PROCESS By-product
OR
Power UNIT Catalyst
OPERATION

Recovery from waste

Recycle
Wastewater

Liquid wastes for storage

Reusable waste in and / or
off site disposal
another operation Solid wastes for
storage and /
or off site
disposal
PRINCIPALS OF WASTE MINIMISATION

1. Control of raw material losses

2. Recovery and recycle / reuse

3. Recycling and reuse of wastewater

4. In-plant control
 BACKGROUND
Responses of businesses to pollution

PASSIVE REACTIVE
Ignore pollution Dilution and dispersion

1 2

CONSTRUCTIVE PROACTIVE
End-of-pipe Cleaner Production
treatment
3 4

ACME - Session 2 - Basics of Cleaner

Production
 CLEANER PRODUCTION
Definition by UNEP
“ Cleaner Production is the continuous application of an
integrated, preventive environmental strategy towards
processes, products and services in order to increase
overall efficiency and reduce damage and risks for
humans and the environment.”

Continuous Processe Humans

s

Preventiv ENVIRONMENTA Products RISK

e L STRATEGY REDUCTION

Integrated Service Environment

s

ACME - Session 2 - Basics of Cleaner

Production
CONTROL OF RAW MATERIAL LOSSES

1. Optimisation of reactions and raw material use

2. Elimination of sources of leaks and spills

3. Installation of close system

4. Equipment standardisation

5. Installation of DCS.
 RECOVERY AND RECYCLE / REUSE
 The solvents used in the manufacture of various products can be recovered and
recycled / reused.

 In most of the chemical reactions, there are more products formed than the
required products. These unwanted products form wastes if left un-recovered.
These can be recovered as valuable by-products by employing a suitable
technique such as condensation, distillation, absorption etc.

 Condensate water can be collected and recycled / reused.

 Floor washing, at times, can be collected, treated if necessary and recycled /

reused.

 Seal pot water, vacuum pump water and cooling water can be recycled and
reused in operations such as neutralisation, washing etc.
 RECYCLING AND REUSE OF WASTEWATER
 From the investigation of material balance and unit operations of a particular process, it will
be possible to characterize the waste and identify the possibilities of recycling or recovery of
useful products. The process of identification of recoverable matter and recycling of
wastewater can be made effective through ‘environmental audit’.

 Treating some or all process wastewater to make it suitable for plant process, cooling water
make-up, floor wash etc.

 Re-circulating the same water within an unit operation several times before it becomes unfit.

 Sequential use of effluent from one process with treatment, if necessary, as input into
another.

 Usage of wastewater from a process to a lesser duty usage where an inferior quality of water
will do. For example, it can be used for coal ash quenching in boiler house, for making lime
solution used for neutralisation in ETP etc.

 The 4-R concept – ‘Recycle’, ‘Renvoate’, ‘Recharge’, and ‘Reuse’ should be employed
wherever possible.
 IN-PLANT CONTROL
 Good house keeping is the least expensive means to reduce the overall
burden on treatment and disposal.

 Loss of raw material, solvent and product can be restricted by installing

monitoring devices.

 The steam jet ejectors and barometric condensers can be replaced in

some cases by vacuum pumps and surface condenser systems.

 Waste segregation and treatment also form an important step in in-plant

control of pollution.
 TWO KEY WORDS

REUSE is applied to wastewaters that are discharged and

then withdrawn by a user other than the discharger.
Wastewaters potentially available for reuse include
discharges from municipalities, industries and the
agricultural irrigation.

RECYCLING is frequently defined as the internal use of

wastewater by the original user prior to discharge to a
treatment system of other point of disposal. The wastewater
is recovered, treated or untreated, and then recycled for
repetitive use by the same user.
RENOVATION THE PREREQUISITE
WATER
MATERIALS PROCESS
RECYCLING

WASTEWATER

TECHNOLOGY
RENOVATION
RECHARGING THE OTHER ARM

PROCESS

WASTEWATER

TECHNOLOGY
RENOVATION

RECHARGING

REUSE
 EMISSION PROFILE
Classification of pollutants urces of air pollutants

So
Cracking units
Combustion Incineration

Point Gen set etc.

Sources Flare
Channelised emissions
Emissions

Process
Vent off

Purge gases
Equipment leaks
Fugitive VOCs
Loading
Storage tanks
ETP
SOURCES OF EMISSIONS
 (All figures are in tonnes / Annum)

S.No Feed Naphtha/ Gas Naphtha

Gas Oil (C2+C3)
1. Type of the Olefin Olefin Aromatics
Complex
2. Capacity (1000 400 – 400 -500 300
TPA as 500
Ethylene)
3. Uncontrolled 6000 to 3000 - 2500 -3700
organic release 8000(+) 4000(+)
(C2 -C6 HC) from
complex
4. Sulphur Oxides 25 -40 (+) 18 -20 15 -25 (+)
(SO2) (+)
5. Nitrogen Oxide 80 -450 100 -350 -
(Nox) (+)
6. Carbon 22 -47 (+) 15 -25 12 -18 (+)
Monoxide (CO) (+)

Notes: 1) Excludes balance of Plant Facilities viz. Power etc.

TYPICAL PERCENT SHARE OF EMISSIONS
DOMINANT VOC EMISSION SOURCES AND ITS TYPICAL DISTRIBUTION FROM
A PETROCHEMICAL COMPLEX
SUSTAINABLE
DEVELOPMENT
PRODUCTIVITY

POLLUTION
SAFET
Y SUSTAINABLE CONTROL
DEVELOPMEN
T

HEALT CONSERVATION
H
 EQUAL OBJECTIVES

Objective of environment = Objective of production

management

Conservation of Cost effective

Raw materials
Energy
Water

Loss prevention and

control of production Reliability & variance
control
Standardization and
optimization of Quality of product
unit process Loss of man days

SUSTAINABLE
DEVELOPMENT