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Lan Mai-Cao, HCM University of Technology, Vietnam 41

Chapter Outline

▪ Introduction
▪ FCC Process Description
▪ Chemical Reactions in FCC Process
▪ Modeling of FCC Process
Petroleum Refinery Block Flow Diagram

Fluidized
Catalytic
Cracking
What is FCC?

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What is Fluidized Catalytic Cracking?
▪ A secondary unit operation in a refinery process that breaks
long chain hydrocarbons to smaller molecular weight ones
▪ A chemical process that uses catalysts to get more fuel
(gasoline) with high octane number at moderate p and T
▪ Powdered catalyst is fluidized and mixed with hydrocarbon
vapors to adsorb coke formed during the cracking process

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What is Fluidized Catalytic Cracking?
▪ A secondary unit operation in a refinery process that breaks
long chain hydrocarbons to smaller molecular weight ones
▪ A chemical process that uses catalyst to facilite the cracking
reaction at lower p and T
▪ Powdered catalyst is fluidized and mixed with hydrocarbon
vapors to adsorb coke formed during the cracking process

𝑀𝑥 𝐴𝑙𝑂2 𝑥 𝑆𝑖𝑂2 𝑦 . 𝑧(𝐻2 𝑂)

𝑛

Cracking Condition

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What is Fluidized Catalytic Cracking?
▪ A secondary unit operation in a refinery process that breaks C-
C bondings to create new, smaller hydrocarbon fractions
▪ A chemical process that uses catalyst to get more fuel
(gasoline) with high octane number at moderate p and T
▪ Powdered catalyst is fluidized and mixed with hydrocarbon
vapors to adsorb coke formed during the cracking process

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Quiz

▪ Differences between distillation and catalytic cracking?

▪ Differences between thermal cracking
(visbreaking/delayed coking) and catalytic cracking?

▪ Is it ok if the refinery run without FCC? Why?

▪ What is the meaning of fluidized? Which one is fluidized
in FCC process?
FCC Process Description

49
FCC Process Description

50
FCC Process Description

51
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Chapter Outline

▪ Introduction
▪ Hydrotreating
▪ Hydrocracking
Introduction

Hydroprocessing: Use hydrogen for

▪ removing unwanted compounds from petroleum products
▪ converting high boiling constituents into lower ones

Hydroprocessing includes:
- Hydrotreating: to remove sulfur, nitrogen, oxygen and metals
- Hydrocracking: to crack C-C bonds with the presence of
hydrogen

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Hydrotreating

Removing impurities
▪ Sulfur, nitrogen, oxygen

Saturating C-C bonds

▪ Olefinic bonds saturated
▪ Aromatic bonds saturated

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Hydrotreating Unit Reactions

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Main Hydrotreating Units in Refineries

Naphtha Hydrotreater
▪ for light naphtha
▪ for heavy naphtha

Diesel-Oil Hydrotreater
▪ for direct cut from ADU
▪ for mixture of LCO from FCC and HCO from delayed coker

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Hydrotreating for Naphtha
Naphtha: commonly C5-C12 cut

Light naphtha
▪ boiling point: [30oC – 145oC]
▪ between C4 and C6

Heavy naphtha
▪ boiling point: [140oC – 205oC]
▪ between C6-C12

Removing a relatively small amount in naphtha is beneficial for

engine performance and operational longevity.

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Hydrotreating for Naphtha

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Hydrotreating for Diesel Oils
Diesel Oil
▪ a direct cut from ADU
▪ a mixture of LCO from FCC and HCO from delayed coker

Diesel oil may contain 1-2% sulfur (10,000-20,000 ppm), much

higher than the fuel requirement of 10-15 ppm

Hydrotreating is the most important steps of processing diesel

oils, especially for removing sulfur and other impurities

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Hydrotreating for Diesel Oils
Removing sulfur and other impurities is much more complicated
than that of naphtha

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The Amine Gas Treatment (Reminder)

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Absorption Process for Acid Gas Removal

Absorption processes can be separated into 2 main groups:

▪ Physical absorption (physical solvent)

▪ Chemical absorption (chemical solvent)

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Physical Solvent Processes

• Based on the gas solubility within a solvent instead of

chemical reactions.
• May result in significant loss of heavier mole weight
hydrocarbons (gas stream in rich C3+).

• Use cases:
✓ Partial pressure of acid gases higher than 50 psi
✓ Low heavy hydrocarbons concentration
✓ H2S selective removal is required
✓ Only bulk removal of acid gas is required

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Physical Solvent Process Flow

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Chemical Solvent Processes

• An aqueous solution of a weak base is used to react and

absorb the acid gases.

• Aqueous base solution can be regenerated by changing

the system temperature, pressure or both.

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Comparison of Chemical & Physical Processes

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Amine Processes

• Amines are organic compounds with ammonia (NH3). All

commonly used amines are alkanolamines.

• Amines remove H2S and CO2 following in 2 steps:

– The gas dissolved in the liquid (physical absorption)

– The dissolved gas reacts with the weakly basic

amines

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Amine Chemical Formula

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Chemical Reactions

1. Ionization and Hydrolysis of H2S and/or CO2:

- -
H2S + OH = HS + H20
- -
CO2 + OH = HCO3
2. Protonation of the amine
+ +
RNH2 + H = RNH3 (primary amine)
3. Reactions with H2S
+ -
RR’NH2 + H2S = RR’NH2.SH
RR’NH + H2S = RR’NH2.SH
4. Reactions with CO2
+ -
RR’NH2 + HCO3 = RR’NH2.HCO3
-
RR’NH + HCO3 = RR’NH.HCO3

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Quiz for CO2 Absorption Process
1. Why physical absorption? Describe the main flow in an
acid gas removal process using physical solvent.
2. Principles of chemical absorption of CO2?
3. Write chemical reactions occurring in CO2 absorption
processes with the three kinds of amines (primary,
secondary and tertiary)

4. Write chemical reactions occurring in H2S absorption

processes with the three kinds of amines (primary,
secondary and tertiary)

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Hydrocracking

Hydrocracking is the process of converting heavy oil feedstocks

into high quality, lighter fuel products

The main purpose is to obtain more valuable products such as

gasoline, diesel, jet fuel from the residue

Hydrocracking use severe conditions, i.e. exposure of the

feedstock to reactor temperature for a long time period

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Hydrocracking vs Catalytic Cracking
Both have similar feedstocks

Hydrocracking offers higher flexibility in product yields

▪ to produce gasoline or jet fuels from heavy gas oils
▪ to produce high-quality lubricating oils from VDU residue
▪ to produce distillation residues into lighter oils

Hydrocracking requires
▪ lower temperature (500 to 800oF)
▪ much higher pressure (800 to 2500 psi)

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Main Hydrocracker Configurations
▪ Single stage, once through hydrocracker
- uses only one reactor
- uncracked residual is not recycled for further cracking
- feedstock must be hydrotreated to remove NH3 and H2S
▪ Single stage hydrocracker with recycle
- most commonly used configuration
- uncracked residual is recycled back into the reactor
- feedstock must be hydrotreated to remove NH3 and H2S
▪ Two stage hydrocracker
- uses two reactors
- the residual hydrocarbon is recycled back to the 2nd reactor
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Hydrocracking Process

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Quiz for Hydrocracking
1. Explain the similarity and differences between
hydrocracking and catalytic cracking?

2. Mechanism of hydrocracking?
3. Why NH3 and H2S need to be removed before
hydrocracking?

4. Describe the main flow in a hydrocracking process

shown in slide 151

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