PRESENTATION

ON
CATALYTIC CRACKING OF HEAVY RESIDUE

Presented By: Submitted to:

MD RAIHAN ARFIN Dr. ASHISH SAWARKAR
M.TECH- CHEMICAL ENGINEERING
CONTENTS
INTRODUCTION OF REFINERY PROCESS
CRACKING PROCESSES IN REFINERY
CATALYTIC CRACKING UNIT
LATEST RESEARCH WORK
RESULT AND DISCUSSION
ADDITIONAL INFORMATION
CONCLUSION
REFERENCES
INTRODUCTION
• The Petroleum Refineries are the main sources of production and
marketing of variety of fuels used in daily life.

• Fuel Refineries have common goal of conversion of as much of the

barrel of crude oil into transportation fuels in the most economical
way possible.

• Nowadays, the refinery operations have become very complex, most

especially to meet the environmental regulations.
 Vapour
Recovery

Isomerization
STABILIZER

GASOLINE BLENDING POOL

SECTION

Hydrotreating Reforming

ADU Hydrotreating

FCC
VDU

DCU
Fig-1 Simple Refinery Process Diagram
The different plants in an Oil Refinery
include:
• Atmospheric/Vacuum Distillation Unit.
• FCC/Residue FCC Unit.
• Hydrocracking Unit.
• Catalytic Reforming, Hydrogen Generation Unit.
• Delayed Coking Unit.
• Lube Processing Unit, Vis-breaking Unit.
• Hydro-Desulphurization of Kerosene & Gasoil streams,
Sulphur recovery Unit.
• Diesel hydrotreating, LPG Unit etc.
Cracking:
• Cracking refers to breaking of high molecular weight long-chain
compounds into shorter chain low molecular weight compounds.

• It is usually carried out by application of heat or by using Catalyst.

• It is very important process of refinery as large fractions of the

valuable fuels are produced in this unit.
Cracking Classification:

Cracking

Thermal Catalytic
Cracking Cracking

V
s
b
r
i
Fluidised
Bed
e
V
ai
ks
bi
rn
ge
a
k
i
n
g
Table 1: Comparison between Thermal and Catalytic Process (J H. Gray, G E.Handwerk, Fourth edition, Petroleum
Refining Technology and Economics, 94)
S.NO Components Thermal Cracking (wt.%) Catalytic Cracking (wt.%)
1 Fresh Feed 100 100
2 Gas 6.6 4.5
3 Propane 2.1 1.3
4 Propylene 1.0 2.0
5 Isobutane 0.8 2.6
6 n-Butane 1.9 0.9
7 Butylene 1.8 2.6
8 C5+ Gasoline 26.9 40.2
9 Light Cycle Oil 1.9 33.2
10 Decant Oil -- 7.7
11 Residual Oil 57 --
12 Coke 0 5.0
Total 100.0 100.0
Catalytic Cracking:
• It is the most important and widely used refinery process for
converting heavy oils and residue into more valuable gasoline and
lighter products.

• The feed to catalytic cracking unit has CCR value (Conradson Carbon
Residue) up to 4%.

• In recent years, fluidised catalytic cracking has been preferred over

thermal and other catalytic cracking processes.
Fluidized bed and Moving bed Cracking:

Fig-2 Fluidized bed and Moving bed Reactors (Fixed bed and Moving bed cracking, Applied Chemistry 2, Fuel, 2)
Fluidized Catalytic Cracking:
• The FCC process is carried out in a fluidized bed reactor called riser. It
employs catalyst in the very fine form (average particle size less than
70 microns) to maintain good fluidity.

• It is accompanied by a regeneration system to regenerate and re-use

the spent catalyst during the process.

• The reactor consists of a cyclone separator at the top. It separates the

product vapor from the partially spent catalyst.
 Vapor
product

Reactor temp
Flue gas (450-550 deg. C)
Spent
catalyst

Regenerator
Temp (650-750) deg. C

Feed
(HVCO, LVCO)
Air blower Regenerated
catalyst

Fig-3 Flowdiagram of RFCC Unit

 C1-C2

(C3-C4 )

Product Fractio-
vapours nating C5+Gasoline
from column
RFCCU
LCO and
DHDT
HCO

Coker unit

Fig-4 Fractionation of Product Vapor from RFCCU

Cracking Reactions:
• The product formed in catalytic cracking are result of both primary and
secondary reaction.

• Primary Reactions:
 Paraffin paraffin + olefin
 Alkyl naphthene naphthene + olefin
 Alkyl aromatic aromatic + olefin

• The reactions are found to be follow the carbocation formation

mechanism.
Reaction Mechanism:
• Mild thermal cracking initiation reaction:
nC8H18 CH4 + R-CH CH2
• Proton Shift: +

R-CH CH2 + H2O + Al3OSi R-CH-CH2 + [HO-Al-O-Si]-

• Beta Scission
• Rearrangement toward more stable (tertiary>secondary>primary)
structure.
• Hydrogen Ion transfer:

CH3 +

CH3-C-CH3 + C8H18 i-C4H10 + CH3CHCH2R

+

• Thus another large carbonium ion is formed and the chain is ready to
repeat itself.
Operating Parameters:
• Activity
• Catalyst/Oil Ratio
• Conversion
• Efficiency = (%gasoline)× conversion
• Selectivity
• Cycle Stock
• Within limits of normal operations increase in reaction temperature,
C/O ratio, activity and contact time increases the conversion.
Types of Catalysts used in FCC:
• Commercial cracking catalysts are broadly classified into three classes.
1. Acid-treated natural alumino-silicate.
2. Amorphous synthetic silica-alumina.
3. Crystalline synthetic silica-alumina or Zeolites.

• Most widely used catalyst is zeolite due to number of advantages over

others.
Latest Research Work on FCC technology:
• With growing concern over meeting the stringent environmental
regulations, the quality upgrading, emission reduction and energy
saving have become theme of refining technology.

• So, the double riser technique which very much serves the purpose has
been widely appreciated and adapted in the market.

• The current research deals with decreasing the aromatic content of

gasoline and at the same time meeting the increasing demand of
aromatics.
Research on HLCO entering secondary riser of
FDFCC unit to improve light aromatics production :
• Study on the potential of recycling hydrofining light cycle oil (HLCO) to
a secondary riser to improve light aromatics production has been
done.

• The effect of reaction temperature and degree of hydrogenation has

been explored.

• The Pilot test has been done which mainly focuses on the cracking
taking place in secondary riser of the FDFCC unit.
 LPG Light
Aromatics
Heavy
fraction
Cracked Raffinate
Cutting Aromatics Gasoline
LCO HLCO 2nd Gasoline Hydrogenatio
Hydrofining fractiona Complex
Riser n
tion plant

Cracked Heavy
Diesel Oil Aromatics

Light
fraction
Gasoline
blending

Fig-5 Flowsheet of Pilot Plant of FDFCCU (Shiyuan Sun, et al., 2019, Research on HLCO entering secondary riser of FDFCC unit
to improve light aromatics production, Journal of Petroleum Science and Engineering, 178, 858)
Experimental Scheme:
• The product distribution and gasoline hydrocarbon composition of
HLCO under different reaction temperatures and hydrogen content
were investigated.

• The product distribution and gasoline hydrocarbon composition of

HLCO under the same experimental conditions were investigated.
Results:
Table 2- Product Distribution of FCC under different reaction temperature (Shiyuan Sun, et al., 2019, Research on HLCO entering
secondary riser of FDFCC unit to improve light aromatics production, Journal of Petroleum Science and Engineering, 178, 860)
Table 3- Product Distribution of FCC under different HLCO Hydrogen content (Shiyuan Sun, et al., 2019, Research on HLCO
entering secondary riser of FDFCC unit to improve light aromatics production, Journal of Petroleum Science and
Engineering, 178, 861)
Table-4- Yield and production of aromatics of cracking gasoline by secondary riser (Shiyuan
Sun, et al., 2019, Research on HLCO entering secondary riser of FDFCC unit to improve light
aromatics production, Journal of Petroleum Science and Engineering,178, 862)
Feedstock 1-th HLCO (wt%) 2-th HLCO (wt%) 3-th HLCO (wt%)

Benzene 1.41 1.55 1.74

Methyl-benzene 8.43 9.55 9.89

C6 Aromatics 13.16 14.37 15.77

C9 Aromatics 9.88 10.85 12.10
C10 Aromatics 2.23 2.26 2.00
Aromatics 35.10 38.19 41.49
Raffinate gasoline 10.72 10.70 8.83

Gasoline 45.82 48.49 50.32

Conclusion:
• Cracking technology has become the most important and profitable
part of petroleum refineries.

• Catalytic cracking is comparatively more compatible with the market

demands than thermal cracking, hence more preferred in the
industry.

• The conversion of Heavy Residue to gasoline depends upon a number

of factors which must be set to optimize the process.
• Large amount of aromatics and high quality gasoline can be produced
using double riser FCC.

• The results suggested that at high operating parameters, the

conversion of HLCO is approximately 66.8-72.9%.

• For obtaining large quantity of aromatics, the LCO produced by main

riser needs deep hydrogenation.

• The process of cracking of HLCO entering secondary riser of FDFCC

unit has multi-fold benefits.