Hydrocarbons Technology :: SSP

Cracking
Dissociation of high molecular weight hydrocarbons into smaller
fragments.

Thermal Cracking
When, High molecular weight hydrocarbons are heated at > 4000C, they split
into two, almost at middle & producing one saturated and other unsaturated
H.C.
i.e.
One is Unsaturated
C12 → C6 + C6
C6 → C4 + C2 or C3 + C3
Unsaturated crack again
C4H8 → C2H6 + H2
C2H4 + CH4 + C → under severe conditions
CH4 + C3H4 (diolefin/alkyne)

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General formula
CnH(2n+2) → C(n/2)H(n+2) + C(n/2)Hn
Dehydrogenation:

- Upto some extent,

1. Hydrogenation of low mol. wt. & unsaturates
2. Ring opening

Temperature of Thermal Cracking : 450-500 oC

Feed : Heavy gas oil to light vaccum gas oil

Mechanism
Free Radical Mechanism
Radicals are atoms or group of atoms with bare unpaired electrons.

CH4 → CH.3 + H.
H2 → H. +H. Free Radicals
R.CH2.CH3 → R.CH 2 + CH.3
.

Hydrogen charged ions or Hydrogen compound with charged ions

known as the carbonium Ions.
H2 → H. + H.
O2 → O. + O.
C5H12 → C5H.11 +H. Radical
production
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C14H30 + H. → C7H16 + C7H.15

C5H12 + H. → C5H.11 + H2 Propagation
C5H12 +C2H.5 → C5H.11 + C2H6
C3H.7 + C5H12 → C4H10 + C4H.9

C3H.7 + H. → C3H8
C5H.11 + C3H.7 → C8H18 Termination
H . + H . → H2

- Endothermic Nature (Temp.)

High temperature is desirable.
- Pressure:
Low P is desirable but at low ‘P’ coke formation is more (also gas ↑)
therefore, 15 atm P is used
P↑ light fractions ↓
- Time:
Time of cracking ↑ for a given T&P, light fractions ↑ also gas C↑
Optimum time is to be set.
- Recycle Ratio: 2 to 3

CATALYTIC CRACKING
Most widely used process in refinery
 Fluidized bed catalytic cracking (FCC) and
 Moving bed catalytic cracking are in use .
Purpose: heavy oils into gasoline and light olefins.
Feed: Atmospheric gas oil (AGO), vaccum gas oil
(VGO), coker gas oil, vaccum residue (20%).
Catalysts:
 Zeolites (heavy acidic) X&Y type
 ZSM-5
 Pt/zeolites (Pt for CO-CO2 in regeneration)

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Typical process conditions:

 Feed temperature: 150-3700C
 Reactor T: 500-5500C
 Regenerator T: 650-7300C
 Cat./oil ratio: 4-10
 Reactor pressure: 1-3 atm
Typical product yields: (wt %)
 Gasoline: 45-56%
 Light crude oil: 13-20%
 Butanes+ butenes : 9-12%
 X: 70-85%
 Propane: 4-6%
 Coke: 5-6%
 Other gases: 3-5%
Catalytic cracking processes:
1. Fixed bed process: obsolete due to problem in regeneration of catalyst
and heat control.
2. Moving bed process: (Thermofor) 10-20% of cat. Cracking is done using
this process.

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Thermofor moving bed catalytic cracker

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Houdri moving bed catalytic cracker

Advantages:
 Low maintenance cost
 High cost activity
 Flexibility in charged stocks and conversions.

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Fluidized bed (fluid) catalytic cracking (FCC) or FCC Riser-Reactor or

Flexi FCC

FCC
Typical capacity:
Bombay & H.P. Refinery: 7500 B/day.
Cat. Circulation : 8 T/hr.
Cat. Hold up : 15T cracker
19T Cat. in Regenerator
Cat. Particle size : 40-80 m

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S.A. =500m2/g fresh and 200m2g spent.

R.T. 465-5100 C
P=1.5 atm

Catalyst: Zeolite is crystalline Alumino-silicate material.

Al and Si atoms form tetrahedral, which are linked by shared oxidation atoms.
More than 150 zeolites are available Natural and synthetic.
As Alumina increases, Acidity increases.
Zeolites have high adsorption capacity,
High S.A. 300 to 500 m2g.
High acidity.
Favourable for catalytic cracking:
Pore size: 60-80A0. Too low pore size causes the problem in ‘C’ removal,
where as large pore size decreases cracking.
Brosted acid sites are responsible for the cracking.

Bronsted Site Lewis Site

During reaction course and heating

Bronsted acid sites → Lewis site → B.A. sites + H2O (steam) Activation at 7000C
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X & Y Zeolites are used for FCC NaP AlpSi102.pO384.gH2O

P = 96 to 74 for X zeolite
74 to 48 for y zeolite
g= 250 to 270 as Al ↓

Reactor variables for FCC:

Temperature: RT : 450- 520 0C
Regenerator temp: up to 7000C
‘No Net Heat Addition’
Regenerator
C + O2 → CO2 + CO , ΔH= negative
Heated catalyst Particles from regenerator are used to exchange heat with
preheated feed to achieve reactor temperature and heat of cracking reactions.
H.T. → olefins (C3,C4)
M.T. → gasoline
L.T. → Improper cracking

Short contact time → high reactor temperature can be maintained.

Pressure: 1.5 atm or so, As such no effects

L.P ↑ ‘C’ formation
H.P. ↓ light H.C.
Riser contact time: 2 to 6 sec
Short contact time and high temperature give High O.N. compounds.
Catalyst to oil ratio: 2 to 7

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Ratio has to be varied over the period of time due to ↓ in catalytic activity
with usage of it even if regenerating the catalysts. For fresh catalysts keep the
ratio 2 to 3.
Slip velocity:
𝑣𝑎𝑝𝑜𝑢𝑟 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦
𝑠𝑙𝑖𝑝 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦 =
𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦
𝑉𝑎𝑝𝑜𝑢𝑟 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦
=
𝑣𝑎𝑝𝑜𝑢𝑟 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦 − 𝑇𝑒𝑟𝑚𝑖𝑛𝑎𝑙 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒

As slip velocity ↑ contact between vapour and particles is poor → Improper

cracking.

Heat balance:
Breakdown of FCC Heat Requirements
Heat consuming event % of Total
Heat up and vaporize fresh feed 40-50%
Heat for recycled oil 0-10%
Heat of reaction(ΔH= +ve) 15-30%
Heat: steam 2-8%
Heat : losses 2-5%
Heat: air to regeneration temp. 15-25%
Heat: C to from Reactor Temp. to 1-2%
Regeneration Temp.

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Hydrocracking
H2 + Catalyst + heat → Hydrocracking.
Hydrotreating deals with removal of impurities using mild operating conditions
low H2 P.P. and diff. Catalysts then hydrocracking.
Hydrocracking deals with the in addition to removal of impurities, cracking of
highly heavy feed stock to get the products like Diesel, Gasoline, Naphta, &
Fuel oil.
Hydrocracking:
Purpose: heavy H.C. to lighter H.C.
Feed: VGO,HGO, LGO, visbreaker gas oil, FCC residue.
Products: Naphtha (gasoline), Diesel, kerosene, olefins.
Licensors: Axens (IFP) Exxon Mobil
Shell global solution UOP
Catalyst: Ni Mo or Ni W on Zeolite
Ni Mo or Ni W on amorphous silica alumina.
Pd on zeolite
Catalytic Reaction Conditions:
Reactor temp.: 315-4250C
Pressure: 60-70 atm.
Typical Reactions:
Additional reactions: HDS, HDN ,HDO, HDM. Impurity Removal.
Aromatic saturation
Isomerization n-R.H → i-R-H
Hydrocracking of parrafins R-R’ + H2 → RH + R’H
Dealkylation of Aromatic Rings.

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Coke formation:
Due to H2 presence, coke formation is slow or very less. The high pressure of
system also help in reducing coke formation.
Without regeneration catalyst can be used for 1 yr.

Reactors:
Trickle Bed Reactor
Ebullated Bed Reactor

Trickle Bed Reactor: {H.C.(liq.) + H2 (gas) } reactants are pass down over a fixed
bed of catalysts.

Once -Through Trickle Bed Hydrocracker

 Hot water injected to remove NH3 & H2S
 Series of fractionators are used to separate L.N, H.N, middle distillates.
Unconverted oil.
 Feed B.P. range: 340-5500C , API: 22, Sp. g.r. : 0.922, S=2.5%,N:950rpm.
 Product quality: Research O.N. 79-80 (Heavy Naphtha)
Jet fuel: Flash point: 380C , Smoke point: 34mm, Aromatics: 7%.
Diesel: Cetane No: 55, flash point: 520C.

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Ebullating Bed Hydrocracker

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Ebullated Bed Reactor

It can treat Residual oils (ADU, VDU etc)
Hydrocracking is an exothermic Reaction
Ebullated bed provides turbulent mixing of all three phases→ better H.T.,
uniform temp.
Conversion upto 90%
Better quality of products
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Catalytic Reforming
Improvement of low O.N. cut of Heavy Naphtha to high O.N. gasoline.
Done by re-orienting or re-forming the low octane compounds.
Also, produces BTX (feed stock for petrochem) & H2 (can be used for
Hydrotreating).
Catalysts:
MoO3/Al2O3 , Co/MoO3, Pt/Al2O3. Cr2O3/Al2O3 , Pt-Re-Sn or γ-Al2O3 ----most
recent & highly effective.
T: 475-6000C
P: 10-25 atm
Space velocity: 1-7 s.
ΔH= +ve
Type of Reactors: Fixed bed , fluidised bed
Licensors: UOP, Exxonmobil, BP
Reactions: (Endothermic)
 Dehydrogenation of Nahtenes (Aromatic production)

 Dehydrogenation of paraffin (with H2 generation)

 Isomerization

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n-Hexane → 2 methyl pentane

(32) (66)

n-Pentane → 1 methyl butane

(63) (90)

Also, some reaction like, (extent is very less)

 Hydrogeneation of unsaturates
C4H8 + H2 → C4H10

 Paraffin cracking
C8H18 → 2 C4H8 + H2

 Hydrodesulfurization

Catalyst selectivity plays an Important role to inhibit undesirable

reactions.

Process Flows:
There are three major process flows for catalytic reforming:
A. Semi-regenerative
B. Cyclic
C. Continuous catalyst regeneration (CCR)

Semi-regenerative reformer:
It is a fixed-bed unit in which catalyst cycles last from 6 to 12 months. A
catalyst cycle ends when the unit is unable to meet its process objectives –
typically octane and overall C5-plus yields. At the end of a cycle, the entire unit
is brought down and catalyst is regenerated. In a cyclic reformer, catalyst
cycles are shorter – 20 to 40 hours –but they are staggered so that only one
reactor goes down at a time. In a CCR unit, the catalyst is slowly but constantly
moving from the reactor to the regenerator and back again.
In a semi-regenerative unit, desulfurized naphtha is mixed with
hydrogen,
heated to >480°C and passed through a series of fixed-bed reactors. The major
chemical reactions – dehydrogenation and dehydrocyclization – are

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endothermic (heat absorbing), and the reactors themselves are essentially

adiabatic. This means that heat can’t enter or leave except by the cooling or
heating of reaction fluids. Consequently, the temperature drops as reactants
flow through a reactor. Between reactors, fired heaters bring the process fluids
back to desired reactor inlet temperatures.
Some catalytic reformers operate at low pressure (791 kPa), while others
operate at 3549 kPa. Low operating pressure improves yields of aromatics and
hydrogen, but it accelerates catalyst deactivation by increasing the rate at
which coke forms on the catalyst. In a CCR reformer, the catalyst always is
being regenerated, so increased coking is less problematic. Therefore, CCR
units can operate at very low pressures. In most reformers, the feed is spiked
with an organic chloride, which converts to hydrogen chloride (HCl) in the
reactors. The HCl increases catalyst acidity and helps to minimize catalyst
coking. The effluent from the last reactor is cooled and sent to a separator,
from which hydrogen-rich gas is removed and recycled to the reactors. The
liquid product flows to a stabilizer column, where entrained gases are
removed, before going to the gasoline blender or aromatics plant.

Semi-regenerative catalytic reforming

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Continuous catalytic reforming (CCR) or UOP platforming process:

The hydrotreated feed mixes with recycle hydrogen and goes to series of
adiabatic, radial-flow reactors arranged in a vertical stack. Catalyst flows down
the stack, while the reaction fluids flow radially across the annular catalyst
beds. The predominant reforming reactions are endothermic, so heaters are
used between reactors to reheat the charge to reaction temperature. Flue gas
from the fired heaters is typically used to generate steam.
The effluent from the last reactor is cooled and sent to a separator. Part
of the vapor is compressed and recycled to the reactors. The rest is
compressed, combined with separator liquids, and sent to the product
recovery section. Liquids from the recovery section go to a stabilizer, where
light saturates are removed from the C6-plus aromatic products.
Partly deactivated catalyst is continually withdrawn from the bottom of
the reactor stack and sent to the regenerator. As the catalyst flows down
through the regenerator, the coke is burned away. Regenerated catalyst is
lifted by hydrogen to the top of the reactor stack. Because the reactor and
regenerator sections are separate, each operates at its own optimum
conditions. The regeneration section can be temporarily shut down for
maintenance without affecting the operation of the reactor and product
recovery sections.

CCR catalytic reforming

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Alkylation
Alkylation Objectives
Alkylation processes combine light olefins (primarily propylene and butylene)
with isobutane in the presence of a highly acidic catalyst, either sulfuric acid or
hydrofluoric acid. The product (alkylate) contains a mixture of high-octane,
branched-chain paraffinic hydrocarbons. The illustrative reaction between
isobutane and trans-2-butene is shown below. Alkylate is a highly desirable
gasoline blend stock because, in addition to its high octane, it has a low vapor
pressure. The octane of the product depends on the operating condition and
the kinds of olefins used.

Alkylation of trans-2-butene

Process Flow: Sulfuric Acid Alkylation

In the sulfuric acid alkylation units, the feeds – propylene, butylenes,
amylene, and fresh isobutane enter the reactor and contact sulfuric acid with
a concentration of 85 to 95%. The reactor is divided into zones. Olefins are fed
through distributors to each zone, and sulfuric acid and isobutanes flow over
baffles from one zone to the next.
The reactor effluent goes to a settler, in which hydrocarbons separate
from the acid. The acid is returned to the reactor. 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.

Process Flow: HF Alkylation

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Olefins and isobutane are dried and fed to a reactor, where the
alkylation reaction takes place over the HF catalyst. The reactor effluent flows
to a settler, where the acid phase separates from the hydrocarbon phase. The
acid is drawn off and recycled. The hydrocarbon phase goes to a
deisobutanizer (DIB). The overhead stream, containing propane, isobutane,
and residual HF, goes to a depropanizer (DeC3). The DeC3 overhead goes to an
HF stripper. It is then treated with caustic and sent to storage. Isobutane from
the DIB main fractionator is recycled. The bottom stream from the debutanizer
goes to product blending.

HF Alkylation

Coking
Coking processes come in two basic forms – delayed coking, which is a semi-
batch process, and fluid-bed coking, which is continuous.

Delayed Coking:
In a delayed coker, vacuum residue feed is heated to about 487 to 520°C
and sent to a large coke drum. Cracking begins immediately, generating coke

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and cracked, vaporized products. Coke stays behind in the drum while the
vapors rise to the top and flow to the product fractionator. Liquid products
include coker naphtha, light coker gas oil (LCGO), and heavy coker gas oil
(HCGO). All of these require further processing due to direct blending into
finished products. The coker naphtha and LCGO are hydrotreated. The HCGO
can go either to an FCC unit or a hydrocracker

Representative thermal-cracking reaction. The reaction shown here is the sum

of a condensation reaction, which generates hydrogen, and dealkylation, which
consumes hydrogen.

Meanwhile, hot residue keeps flowing into the drum until it is filled with
solid coke. To remove the coke, the top and bottom heads of the drum are
removed. A rotating cutting tool uses high-pressure jets of water to drill a hole
through the center of the coke from top to bottom. In addition to cutting the
hole, the water also cools the coke, forming steam as it does so. The cutter is
then raised, step by step, cutting the coke into lumps, which fall out the
bottom of the drum. Typically, coke drums operate on 18- to 24-hour cycles,
which include preheating the drum, filling it with hot oil, allowing coke and
liquid products to form, cooling the drum, and decoking.
Coke can account for up to 30 wt% of the product. It can be shipped by
rail, truck, or conveyor belt to a calciner, which converts green coke fresh from
the drum into various grades of petroleum coke. Green coke can also be used
for fuel.

Types of Coke:
Sponge Coke. Sponge coke is named for its sponge-like appearance. It is
produced from feeds that have low-to-moderate asphaltene concentrations. If
sponge coke meets certain specifications, it can be used to make carbon
anodes for the aluminum industry. Otherwise, it is used for fuel. “Green”
sponge coke must be calcined before it can be used for anodes. Fuel coke may
not require calcination.
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Needle Coke. Needle coke, named for its needle-like structure, is made from
feeds that contain nil asphaltenes, such as hydrotreated FCC decant oils.
Needle coke is a high-value product used to make graphite electrodes for
electric-arc furnaces in the steel industry.
Shot Coke. Shot coke is an undesirable product because it is inconsistent and in
some cases dangerous. It is produced when the concentration of feedstock
asphaltenes and/or coke-drum temperatures are too high. Excessive feedstock
oxygen content can also induce its formation. Shot coke begins to form as the
oil flows into the coke drum. As light ends flash away, small globules of heavy
tar are left behind. These globs of tar coke rapidly grow due to the heat
produced by asphaltene polymerization, producing discrete mini-balls 0.1 to
0.2 inches (2 to 5 mm) in diameter. In the center of the drum, the mini-balls
can stick together to form clusters as large as 10 inches (25 cm). On occasion, a
cluster breaks apart when the coke drum is opened, spraying a volley of hot
mini-balls in every direction. Adding aromatic feeds, such as FCC decant oil, can
eliminate shot coke formation. Other methods of eliminating shot coke –
decreasing temperature, increasing drum pressure, increasing the amount of
product recycle – decrease liquid yields, which is not desired.

Fluid Coking:
Fluid coking, also called continuous coking, is a moving-bed process for
which the operating temperature is higher than the temperatures used for
delayed coking. In continuous coking, hot recycled coke particles are combined
with liquid feed in a radial mixer (reactor) at about 446 kPa. Vapors are taken
from the reactor, quenched to stop any further reaction, and fractionated. The
coke goes to a surge drum, then to a classifier, where the larger particles are
removed as product. The smaller coke particles are recycled to a preheater,
where they mix with fresh feed. Coking occurs both in the reactor and in the
surge drum. Installation costs for fluid coking are somewhat higher than for
delayed coking, but feeds can be heavier and heat losses are lower.

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Alternative Fuels
Alternative to Gasoline Fuels:
1). LPG:
 Mixture of propane and butane liquefied and stored at 15 atm.
 Propane: 25, Butane: 75% (i &n-butane)
 Used for domestic heating but can also be used for automobiles.
 LPG= Dual cars.
2). CNG:
 Compressed Natural gas.
 Methane=90% others C2-C4 compounds
 O.N. of CNG=130
 Tail pipe emission reduces greatly.
 Very less ‘C’ formation
 NG is almost insoluble in engine oil, consequently lubricating oil retains
its properties longer.
 Vol. required is higher.
 Large amount of N.G. is found world wide.
3). Syn gas
 Synthetic fuels like fuel from coal, oil shale, tar sands etc.

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 “Sasol” world leader in production of liq. Fuel from coal by coal

gasification.
 Also, world leader in gas to liq technology.
Two step process :
1st step= R/M to H2, CO, CH4
2nd step= gas to liquid Fuels in the presence of Iron catalysts.(Fisher Tropsch
synthesis).
4). Alcohols:
 Good burning quality but low calorific values.
All above alternatives are used in the “SI” engine.

Alternative Diesel Fuels:

ADF should preserve global environment, give solution to long term supply for
auto-mobiles.
1). Vegetable oils:
 90-98%: Triglycerides with small amount of mono & Di-glycerides, free
fatty acids etc.
 Veg. Oils from castor, Zethropa, corn, cotton seed, linseed, peanut,
soyabean, palm, sunflower.
 High viscosity compared to diesel fuel due to large molecular structure
and mass (30-40 centi-stoke)
 Mol. Wt. 3 times the diesel.
 Vol. heating value 39-40 mJ/Kg, Diesel 45 mJ/Kg
Problems in engine:
High viscosity leads problem of injection (poor automization), insufficient
mixing, high flash point→ low volatility, more carbon deposits, high gum
formation.
Therefore, to use veg. Oil into conventional diesel engine some modifications
of veg. Oil is to be done.
‘Trans-esterification’ is done to ↓ .

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Tri glyceride + 3 CH3OH → Glycerol + Fatty acid methyl esters

(known as BIODIESEL)
Characteristics are close to Diesel
 C.N. =45 to 64
 Viscosity↓ by a factor of 8 to 10 compared to Triglyceride.
Adv:
 Renewable
 Net emission too low or almost zero
2). Petro crops:
 Several plants with their latex contain petroleum like H.C. which can be
extracted using organic solvents known as ‘Bio crude’.
These plants known as the ‘Petro crops’ plants found in uncultivated areas
cactus plants.
3). Coal:
 Coal gasification
Coal→ CO + H2 + CH4 → liquid fuel.
4). Agricultural wastes:
 Bagasse to Diesel.
 Any waste to fuels (solid, liquid, gas phase). 3rd Generation Fuels

Some other Alternatives being developed:

 Shale Gas and Shale Oil: Mass production started
 Ice Gas (Japan, 2014)
 Fuel cell based Automobiles
H2 + ½ O ↔ H2O
Anode, cathode ≈ electricity → automobile parts.
 Production of ultra pure H2

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- methane, ethanol, glycerol (bio-diesel by-product).

 Sugar to H2 = fuel cell.
 Plastic waste to liq. fuel.
 Methane Decomposition to H2 and Nano-Carbon.
 H2 from water electro-splitting.

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