UNIT 3

❖ CRACKING:
❖ WHAT IS CRACKING?
• Cracking involves the decomposition of heavier hydrocarbon feedstock’s to lighter
hydrocarbon feed stocks.
• Cracking can be carried out to any hydrocarbon feedstock but it is usually applied for vacuum
gas oil (VGO)
• Cracking can be with or without a catalyst.
• When cracking is carried out without a catalyst higher operating temperatures and pressures are
required. This is called as thermal cracking. This was the principle of the old generation
refineries.
• Now a days, cracking is usually carried out using a catalyst. The catalyst enabled the reduction
in operating pressure and temperature drastically.

❖ THERMAL CRACKING
1) Thermal cracking process for up gradation of heavy residue has been used since long and still
it is playing an important role in the modern refinery through upgradation of heavy residue and
improving the economics of the refinery through the production of lighter distillate and other
valuable product like low value fuel gas and petroleum coke.

2) Heavy residues are a mixture molecules consisting of an oil phase and an asphaltene phase in
physical equilibrium with each other in colloidal form.

3) Asphaltenes are high molecular weight, relatively high atomicity molecules containing high
levels of metals. During thermal cracking, the long molecules thus depleting the oil phase in the
residue.

4) Asphaltene cracking is the most difficult component to process and asphaltenes in the feed
remain unaffected, additional asphaltenes may be formed by secondary polymerisation reactions.

5) Eg. Visbreacking, Coking, naphtha Cracking etc.

 ❖ CATALYTIC REFORMING

Catalytic reforming is a major conversion process in petroleum refinery and petrochemical

industries. The reforming process is a catalytic process which converts low octane naphthas
into higher octane reformate products for gasoline blending and aromatic rich reformate for
aromatic production. 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. Naphtha feeds to catalytic reforming include heavy straight run naphtha. It
transforms low octane naphtha into high-octane motor gasoline blending stock and aromatics
rich in benzene, toluene, and xylene with hydrogen and liquefied petroleum gas as a
byproduct. With the fast growing demand in aromatics and demand of high - octane
numbers, catalytic reforming is likely to remain one of the most important unit processes in
the petroleum and petrochemical industry. Various commercial catalytic reforming processes
is given in Table.

Fig. catalytic reforming

Process description:

Liquid feed is pumped up to the reaction pressure (5–45 atm) and is joined by a stream of

hydrogen-rich recycle gas. The resulting liquid–gas mixture is preheated by flowing through
a heat exchanger. The preheated feed mixture is then totally vaporized and heated to the reaction
temperature (495–520 °C) before the vaporized reactants enter the first reactor. As the vaporized
reactants flow through the fixed bed of catalyst in the reactor, the major reaction is the
dehydrogenation of naphthenes to aromatics (as described earlier herein) which is
highly endothermic and results in a large temperature decrease between the inlet and outlet of the
reactor. To maintain the required reaction temperature and the rate of reaction, the vaporized
stream is reheated in the second fired heater before it flows through the second reactor. The
temperature again decreases across the second reactor and the vaporized stream must again be
reheated in the third fired heater before it flows through the third reactor. As the vaporized
stream proceeds through the three reactors, the reaction rates decrease and the reactors therefore
become larger. At the same time, the amount of reheat required between the reactors becomes
smaller. Usually, three reactors are all that is required to provide the desired performance of the
catalytic reforming unit.

Some installations use three separate fired heaters as shown in the schematic diagram and some
installations use a single fired heater with three separate heating coils.

The hot reaction products from the third reactor are partially cooled by flowing through the heat
exchanger where the feed to the first reactor is preheated and then flow through a water-cooled
heat exchanger before flowing through the pressure controller (PC) into the gas separator.

Most of the hydrogen-rich gas from the gas separator vessel returns to the suction of the recycle
hydrogen gas compressor and the net production of hydrogen-rich gas from the reforming
reactions is exported for use in the other refinery processes that consume hydrogen (such as
hydrodesulfurization units and/or a hydrocracker unit).

The liquid from the gas separator vessel is routed into a fractionating column commonly called
a stabilizer. The overhead offgas product from the stabilizer contains the byproduct methane,
ethane, propane and butane gases produced by the hydrocracking reactions as explained in the
above discussion of the reaction chemistry of a catalytic reformer, and it may also contain some
small amount of hydrogen. That offgas is routed to the refinery's central gas processing plant for
removal and recovery of propane and butane. The residual gas after such processing becomes
part of the refinery's fuel gas system.
The bottoms product from the stabilizer is the high-octane liquid reformate that will become a
component of the refinery's product gasoline. Reformate can be blended directly in the gasoline
pool but often it is separated in two or more streams. A common refining scheme consists in
fractionating the reformate in two streams, light and heavy reformate. The light reformate has
lower octane and can be used as isomerization feedstock if this unit is available. The heavy
reformate is high in octane and low in benzene, hence it is an excellent blending component for
the gasoline pool.

Benzene is often removed with a specific operation to reduce the content of benzene in the reformate
as the finished gasoline has often an upper limit of benzene content (in the UE this is 1% volume). The
benzene extracted can be marketed as feedstock for the chemical industry

❖ NAPHTHA /GAS CRACKING

- Olefins are major building blocks for petrochemicals. Because of their reactivity and
versatility, olefins especially the light olefins like ethylene, propylene, butenes,
butadiene, etc., there has been tremendous growth in the demand of the olefins.

- Naphtha cracking is appropriated to produce olefins, mainly ethylene and propylene.

Process Description:
1) Naphtha cracking for olefins is schematically presented in following fig. The HC feedstock is
preheated in presence of steam in tubular furnace (1).

2) The furnace is maintained at high temperature at 800-850 0C, therefore furnace output are
cooled in transfer line heat exchanger (2), which is apart for production of high pressure
steam(1000-200 kg/cm2).

3) The hot products are rapidly quenched by showering with feed stock or with circulating oils.
Direct quenching with oil is also practiced.

4) Quenching with oil is done in pyrolysis fractionator (3), where fractionation is also carried out
simultaneously. The bottom product of this fractionator shall be heavy oil or fuel oil.
5) The lighter fractions are cooled in reflux condenser, separation of gaseous products from
lighter product take place. The gases are always infested with acidic constituents CO2, CO, H2S,
SO2, oxides of nitrogen etc. and these are stripped off by suitable solvents.

6) The acid free gases are now cooled and compressed to a pressure of 30 to 40 atm whereby
propane and higher components are liquefied.

7) The mixture is separated into propane and gases in depropanizer unit. The top gases of
depropanizer mainly contain uncondensables such as H2, CH4 and C2 fractions. Further chilling
will liquefy C2 fraction, from where CH4 and H2 streams can be easily driven off; this is done in
demethaniser (4).

8) The demethaniser bottoms are given mild hydrogen treatment to convert acetylene into
ethylene. Ethane – ethylene fractionation is done in column (5).

Fig. Naptha / gas cracking

❖ Coking
Coking refers to extreme thermal cracking process

Coking is a batch reaction. Feed is heated to 480 – 510 oC and left for some time so that coke and lighter
products form.

Since coking is a batch reaction, there can be different ways to carry out coking.

There are two types of refinery coking processes namely delayed coking and fluid coking.

1] Delayed coking
The heated feed is fed to a coke drum and coke forms in the drum. The lighter products are withdrawn
from the top section of the delayed coker. After coking,the coke drum is full of coke and it is then
removed using water jets. The process is called delayed coking because in this process the coal is heated
using a much more complex system , and it consists of multiple furnaces or coke drums. Usually the coal
is heated at a lower temperature for shorter periods of time , which removes water and other by –
products more slowly than the conventional process, thereby increasing the overall time span.

Figure Delayed Coking

2] Fluid coking

The heated feed is fed to a fluidized bed where coke particles with finer particle sizes would aid
fluidization. After coking, lighter products are withdrawn as overhead vapour and coke thus formed is
removed continuously. The fluid coker also has an additional scrubber which will remove heavier
compounds from the vapors (if any) and send them back with the feed stream. Here, the feed stream
absorbs heavier hydrocarbons from the vapors generated. This is required as it is difficult to keep
heavier hydrocarbons in the feed phase only due to pertinent high temperatures. The coke after coking
reaction is cold coke. Therefore, to generate hot coke, a burner unit is used to heat the coke using
exothermic CO2 reaction. The offgases from the burner are sent to cyclones, scrubbing and then to the
vent. The hot coke thus obtained is recycled back to the fluidized bed or taken out as a net coke
product.

The coker products are fed to a complex distillation column i.e., main column supplemented with side
columns. From the complex distillation column, naphtha, water, light gas oil and heavy gas oil are
obtained.

- Additional complexities in the distillation unit are:

Feed entering the distillation column but not the coker unit: This is to facilitate the removal of light ends
from the feed (if any) and don’t subject them to cracking. This is also due to the reason that light ends
are valuable commodities and we don’t want to loose them to produce cheap coke product. In this case,
the bottom product from the distillation column is fed to the furnace for pre-heating and subsequent
coking operation.

Live steam in distillation: This is to facilitate easy removal of lighter hydrocarbons in various sections.

Circulatory reflux (Pump around units): This is to facilitate good amount of liquid reflux in various
sections of the main column. For Further details, of the above two issues, please refer to the crude
distillation lecture notes.

Figure Fluid Coking

ALKYLATION PROCESS

1) Alkylation is the process of producing gasoline range material light olefins (primarily
propylene and butylene) with isobutane in the presence of a highly acidic catalyst, either
sulphuric acid or hydrofluoric acid. The product (alkylate) contains a mixture of high-octane,
branched-chain paraffinic hydrocarbons.

2) Refinery gases produced from different units are collected and sent to the gas plant. Olefins
and isobutanes are separated and used as a feed to the alkylation plant to produce gasoline which
can be sent to the gasoline pool.

3) Alkylation is catalysed by a strong acid, either sulphuric (H2SO4) or hydrofluoric (HF).

4) In the absence of catalysts, alkylation between isobutene and olefin must be run under severe
conditions such as T = 500 °C (932 F) and P = 200–400 bars (2940–7080 psia). In the presence
of an acid catalyst, the reaction temperature will be lower than 50 °C (122 F), and the pressure
will be lower than 30 bars (441 psia).

5) The major difference in using either acid is that isobutane is quite insoluble in H2SO4 but
reasonably soluble in HF.

1. Sulphuric Acid Alkylation

1) In sulfuric acid (H2SO4) alkylation units, the feeds – propylene, butylene, amylene, and fresh
isobutane – enter the reactor and contact sulfuric acid with a concentration of 85 to 95%. The
reactor is divided into zones.
2) Olefins are fed through distributors to each zone, and sulfuric acid and isobutanes flow over
baffles from one zone to the next. Overall alkylation reaction carried out in reactor.

3) The reactor effluent goes to a settler, in which hydrocarbons separate from the acid. The acid
is returned to the reactor.

4) The hydrocarbons are washed with caustic and sent to fractionation. The fractionation section
comprises a depropanizer, a deisobutanizer, and a debutanizer. Alkylate from the deisobutanizer
can go directly to motor-fuel blending, or it can be reprocessed to produce aviation-grade
gasoline. Isobutane is recycled. A block diagram of the process is shown in Figure below.
 Fig: Sulphuric Acid Alkylation

2. Hydrofluoric Acid Alkylation

1) The process is similar to the sulphuric acid plant. However, additional safety issues make
the process complex.
2) The feed is first subjected to drying followed by pre-cooling.
3) After pre-cooling the reaction mixture the reaction mixture is fed to a reactor.
4) Unlike CSTRs in series here impeller reactors are used. The reactor consists of cooling
tubes to absorb the heat generated.
5) The reaction products enters a settler where oil and the HF are separated.
6) Since there can be traces of HF in the oil rich phase and vice-versa additional processing
is followed.
7) The HF rerun column removes traces of oils from the bulk of the HF. Thus HF purified
will be recycled back to the reactor. The bottom product thus generated in this unit is acid
oils.
8) A HF stripper is used to remove the HF in lower quantities from the alkylate product.
Eventually, the HF stripper produces HF that is sent back to the reactor and the alkylate
product.
 9) The alkylate product is sent to a deisobutanizer and depropanizer units. The final
alkylate product is produced by using a deflourinator which is basically a caustic wash or
adsorption unit. Finally n-butane + alkylate is produced as the bottom product.

Fig: Hydrofluoric Acid Alkylation

PETROCHEMICALS
INTRODUCTION

- Petrochemicals refers to all those compounds that can be derived from the petroleum refinery
products
- Typical feedstocks to petrochemical processes include
o C1 Compounds: Methane & Synthesis gas

o C2 Compounds: Ethylene and Acetylene

o C3 Compounds: Propylene

o C4 Compounds: Butanes and Butenes

o Aromatic Compounds: Benzene

- It can be seen that petrochemicals are produced from simple compounds such as methane,
ethylene and acetylene but not multicomponent products such as gas oil etc.

- Definition : These are the chemicals that are made from petroleum and natural gas. Petroleum
and natural gas are made up of hydrocarbon molecules, which comprises of one or more carbon
atoms, to which hydrogen atoms are attached.
- About 5 % of the oil and gas consumed each year is needed to make all the petrochemical
products. Petrochemicals play an important role on our food, clothing, shelter and leisure.
Because of low cost and easy availability, oil and natural gas are considered to be the main
sources of raw materials for most petrochemicals.

- Classification: Petrochemicals can be broadly classified into three categories

a. Light Petrochemicals: These are mainly used as bottled fuel and raw materials for other
organic chemicals. The lightest of these -- methane, ethane and ethylene -- are gaseous at room
temperature.The next lightest fractions comprise petroleum ether and light naphtha with boiling
points between 80 and 190 degrees Fahrenheit.
b. Medium Petrochemicals: Hydrocarbons with 6 – 12 carbon atoms are called "gasoline",
which are mainly used as automobile fuels. Octane, with eight carbons, is a particularly good
automobile fuel, and is considered to be of high quality. Kerosene contains 12 to 15 carbons and
is used in aviation fuels, and also as solvents for heating and lighting.
c. Heavy Petrochemicals: These can be generally categorized as diesel oil, heating oil and lubricating oil
for engines and machinery. They contain around 15 and 18 carbon atoms with boiling points between
570 and 750 degrees Fahrenheit. The heaviest fractions of all are called "bitumens" and are used to
surface roads or for waterproofing