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Removes Olefins
Removes Olefins
100%
100%
H2 Consumption
H2 Consumption
170
170
-
-
422 Nm3/m3
422 Nm3/m3
Operating Pressure
Operating Pressure
70
70
-
-
210 kg/cm2G
210 kg/cm2G
Operating Temperature
Operating Temperature
315
315
-
-
430
430
C
C
HYDROCRACKER MERITS &
HYDROCRACKER MERITS &
DEMERITS
DEMERITS
Merits:
i) upgrades heavier fraction of feed to superior quality products.
1. LN has RON, 78-85 - blending stock for the MS pool.
2. HN is excellent feed to reformer. Yields high RON, MS.
3. Jet fuel / SK low in aromatics & has high smoke point.
4. Diesel - high cetane No, low aromatics, sulfur content
5. Bottom products UCO Good feed to FCCU and LUBE
plant.
ii) Environmental regulations have imposed limits on the
aromatic and sulfur content of the diesel in order to reduce
emissions of carcinogens and sulfur oxides into the
atmosphere.
iii) More favorable for production of middle distillates when
compared to a FCC unit.
HYDRO
HYDRO
-
-
CRACKER MERITS &
CRACKER MERITS &
DEMERITS
DEMERITS
Demerits:
High investment cost.
Frequent mechanical problems with
equipments.
High energy consumption.(H2 requirement)
NOTE: With the catalyst development, utilization of
suitable metallurgy & experience gained,
Hydro-cracking has become a very reliable
process world-wide.
History of Hydro
History of Hydro
-
-
cracking
cracking
Early Hydro-cracking (liquid fuel from Coal):
Used Iron-Based Catalysts
Very High Pressures (352 kg/cm
2
G), 426C
Temperature.
Used by Germany in WW-II.
High Gas Make, Low Octane Naphtha, Poor
Quality Diesel (High in Aromatics)
History of Hydro
History of Hydro
-
-
cracking (contd.)
cracking (contd.)
First Modern Hydro-cracking
1959: Chevron Demonstrates Modern High Pressure
Process in Richmond Refinery-iso-cracking.
Union Oil Co Unicracking.
UOP lomax hydro-cracking process.
Employed Amorphous Silica-Alumina Catalysts.
Rapid growth of hydro-cracking after development of
new, Zeolite based hydro-cracking.
1962: Chevron Starts-Up the First Hydro-cracker in
the Then Sohio Refinery in Toledo, Ohio
1966: Chevrons Richmond Hydro-processing
Complex Starts-Up.
First Modern Hydro-cracking
1959: Chevron Demonstrates Modern High Pressure
Process in Richmond Refinery-iso-cracking.
Union Oil Co Unicracking.
UOP lomax hydro-cracking process.
Employed Amorphous Silica-Alumina Catalysts.
Rapid growth of hydro-cracking after development of
new, Zeolite based hydro-cracking.
1962: Chevron Starts-Up the First Hydro-cracker in
the Then Sohio Refinery in Toledo, Ohio
1966: Chevrons Richmond Hydro-processing
Complex Starts-Up.
History of Hydro
History of Hydro
-
-
cracking (contd)
cracking (contd)
State-of-the-Art Hydrocracking
1. Zeolitic Catalysts.
2. Lower Pressures, 70 200 kg/cm2G.
3. Moderate Temperatures 340 - 410C.
State-of-the-Art Hydrocracking
1. Zeolitic Catalysts.
2. Lower Pressures, 70 200 kg/cm2G.
3. Moderate Temperatures 340 - 410C.
Hydrocracking Licensors
Hydrocracking Licensors
Until Early 1990s, the Market (~120 HCRs) Was
Divided Roughly 1/3 Each Between UOP, Unocal
and Chevron.
In 1995, UOP Bought Unocal Technology, and
Now Have 2/3 of the Worlds HCRs.
Other Licensors (Minor Players).
IFP (Subsidized by French Government)
MAKFina (Mainly Compete in Mild HCR)
Shell Global (Several Captive Shell Units,
Criterion Cats)
Until Early 1990s, the Market (~120 HCRs) Was
Divided Roughly 1/3 Each Between UOP, Unocal
and Chevron.
In 1995, UOP Bought Unocal Technology, and
Now Have 2/3 of the Worlds HCRs.
Other Licensors (Minor Players).
IFP (Subsidized by French Government)
MAKFina (Mainly Compete in Mild HCR)
Shell Global (Several Captive Shell Units,
Criterion Cats)
Chemistry of
Chemistry of
Hydro
Hydro
-
-
cracking
cracking
Chemistry of Hydrocracking
Chemistry of Hydrocracking
Typical Hydro-processing & Hydro-cracking
Reactions:
1. De-metallization.
2. De-sulphurization.
3. Denitrification.
4. Olefin Saturation.
5. Aromatics Saturation
6. Hydro-Cracking
7. Sulphiding
8. De-methalization - Thermalcracking
9. Heat Release
Desulfurization reactions convert thiols or thiophenes to
straight-chain or branched paraffins and H2S. The heat of
reaction for desulfurization is about 560 kcal/Nm3 (60 Btu/SCF)
of hydrogen consumed.
R C CH
CH HC
S
+ 4H
2
Catalyst CH
3
CHCH
2
CH
3
Branched Paraffin
Thiophene
R
R
CH SH
R
+ H
2
Catalyst
Thiol
R
CH
2
R
Straight-Chain
Paraffin
+
H
2
S
+
H
2
S
Desulphurisation Reaction
Desulphurisation Reaction
RCH2 CH2 CH2 NH2 + H2 RCH2 CH2 CH3 + NH3
CATALYST
AMINE PARAFFIN AMMONIA
Typical hydrotreating reactions with nitrogen
compounds include hydrogenation of pyridines to form
paraffins and ammonia, quinolines to form aromatics
and ammonia, and pyrroles to form paraffins and
ammonia. The heat of reaction of the denitrification
reactions is about 660 kcal/Nm3 (70 Btu/SCF) of
hydrogen consumed.
R-CH2CH =CH2 + H2
RCH2CH2CH3
CATALYST
OLEFIN PARAFFIN
Hydrogenation of olefins is one of the most rapid of the
reactions taking place. All olefins are saturated very
early. The heat of reaction for these reactions is about
1320 kcal/Nm3 (140 Btu/SCF) of hydrogen consumed.
Because the olefin content of the Hydrocracker feed is
significant and because the saturation reactions are
rapid and release a large quantity of heat.
Olefins saturation
H
H
H
H H
\ /
R C==== C-H
\\ //
C---------C
/ \
H H
+ 3H2
C--------C
/ \
C ----------C
\ /
C --------- C
/ \ / \
H H H H
R
H
H H
H
AROMATIC
NAPHTHENE
Hydrogenated to naphthenes heat of reactions vary from about 380-
750 kcal/Nm3 (40-80 Btu/SCF) of hydrogen consumed depending
on the type of aromatic being saturated. In general, higher
pressures and lower temperatures result in a greater
degree of aromatic saturation
LARGE HC MOLECULES -------> SMALLER MOLECULES
Paraffin of paraffin of
high carbon no. Catalyst (Ni3S2) less carbon no.
CnH
2n+2
+ (x-1) H
2
x C
n/x
H
2n/x +2
+ Heat
Where x = no. of fragments ( low carbon no. Paraffin molecules),
Cracked from the high carbon no. Paraffin molecule.
The heat release from the hydro-cracking reactions
contribute appreciably to the total heat requirement.
H
2
+RCH
2
CH
2
CH
2
CH
3
---------> CH
3
CH
2
CH
3
+RCH
3
Catalyst
Chemistry of Hydrocracking
Chemistry of Hydrocracking
Hydro-Cracking Reactions:
Large Side Chains Easily Removed From
Rings
Saturated Rings Crack Easily.
Paraffins Hard to crack.
Paraffin Products Are Highly Isomerized.
Hydro-Cracking Reactions:
Large Side Chains Easily Removed From
Rings
Saturated Rings Crack Easily.
Paraffins Hard to crack.
Paraffin Products Are Highly Isomerized.
Chemistry of Hydro
Chemistry of Hydro
-
-
cracking
cracking
Hydro-Cracking Reactions (CON):
In the reactors, sulphur and nitrogen are removed from the
feedstock. In general, the carbon skeleton of the feed
molecule is not altered by heteroatom removal; however,
the boiling point of the molecule decreases by 27-54C for
sulphur compounds and up to 104C for nitrogen
compounds. Alkyl aromatics also react in the reaction stage
to give three types of products:
Aromatic- saturation to give a naphthene.
Aromatic- dealkylation to give a paraffin and
aromatic- piece.
Aromatic- condensation to give a polycyclic aromatic.
NOTE:The amounts of each type of product depend on
processing conditions (temperature, catalyst, and hydrogen
partial pressure) and feed composition.
Chemistry of Hydrocracking
Chemistry of Hydrocracking
Other Important Reactions
Thermal Hydrocracking or De-methylation
Undesirable Side Reaction Occurring at >465C
Can Occur at Lower Temperatures With Reduced,
Unsulfided Metals
Produces Light Gases, Mainly Methane
High H2 Consumption, Uncontrollable Heat
Release
Other Important Reactions
Thermal Hydrocracking or De-methylation
Undesirable Side Reaction Occurring at >465C
Can Occur at Lower Temperatures With Reduced,
Unsulfided Metals
Produces Light Gases, Mainly Methane
High H2 Consumption, Uncontrollable Heat
Release
Catalyst Sulfiding
Catalyst Sulfiding
Fresh catalyst as well as regenerated catalyst need to be
sulfided so that the optimum catalyst stability and activity
can be obtained before oil feed is introduced.
The sulfiding process consists of catalyst pretreatment with a
sulfiding agent in the presence of hydrogen. When heated
and passed over the catalyst, the sulfiding agent breaks down
into H2S which reacts with the metal oxides on the catalyst,
thereby generating active metal sites (metal sulfides).
The reactions taking place during sulfiding are as follows:
(1) Cracking of DMDS (The Sulfiding Agent)
CH
3
-S-S-CH
3
+ 3H
2
2CH
4
+ 2H
2
S
This occurs at temperatures between 218232C for
DMDS.
(2) Conversion of metal oxide to metal sulfide
2H
2
S + 3NiO + H
2
Ni
3
S
2
+ 3H
2
O
Heat Release/H
Heat Release/H
2
2
Consumption
Consumption
From Hydro
From Hydro
-
-
crackers
crackers
Reaction H
2
Consumption
Heat Release,
(Kcal/ Nm3
H
2
)
HDS 3 mols H
2
/mol S
(17-25 Nm
3
/m
3
Per 1% S Removed)
565
HDN ~5 mols H
2
/mol N
(5-7 Nm
3
/m
3
Per 1000 ppm N Removed)
610-705
Olefin
Saturation
~1 mol H
2
/C=C Bond 1200-1500
HDA ~ 3 mols H
2
/Ring Saturated
(2-5 Nm
3
/m
3
Per 1% Rings Reduced)
660-800
Cracking 2-5 Nm
3
/m
3
Per 1 LV% Conv. 470-565
Process Configurations
Process Configurations
Process Configurations
Process Configurations
Process Configurations
Single Stage - for 100% conversion of feed
into products.
Single stage - Once-Through operation
CPCLs design configuration
Single Stage Recycle
- CPCLs initial operation configuration
Two Stage Recycle
Single Stage
Single Stage
-
-
for 100% conversion of feed
for 100% conversion of feed
into products.
into products.
Single stage
Single stage
-
-
Once
Once
-
-
Through operation
Through operation
CPCL
CPCL
s design configuration
s design configuration
C D 86 D 86 D 86 D 86 D 1160
ST 23 102 142 229 337
10 36 107 161 268 394
50 49 114 193 302 473
90 79 128 238 348 548
EP 91 147 266 376 562
Sulfur, ppm <5 <5 <50 (Max.)
Mercaptan Sulfur, ppm 10 (Max.) 10 (Max.)
Nitrogen, ppm <1 <1 <1 (Max.)
Paraffins, LV % (Estimated) 66 30
Naphthenes, LV %
(Estimated)
32 62
Aromatics, LV % (Estimated) 2 8 22
Flash Point,
C 38 (Min.) 35 (Min.)
Smoke Point, mm 21
Cetane Index (D 613) 55 (Min.)
Freeze Point,
C (-)51
Pour Point,
C 3 (Max.)
Viscosity @ 40
C, cSt 2 to 5
Viscosity @ 100C, cSt 4.2
Viscosity @ -20C, cSt 8
Water, ppm 500 (Max.)
Metals, ppm <0.1
Octane Number, Estimated
RONC/MONC 75/76 64/62
RVP, kg/cm
2
0.8 (Max.) 0.8 (Max.)
10 (Max.) 10 (Max.)
Process Variables
Process Variables
H
H
2
2
Effects
Effects
Hydrogen Partial Pressure.
Recycle gas purity
Mack-up H2 purity
Recycle gas rate (Gas/Oil Ratio)
Catalyst Temperature.
Catalyst life.
Process Variables
Process Variables
Reactor temperature profile.
Catalyst Average temperature.
Process variables
Process variables
-
-
Make up H
Make up H
2 2
Purity
Purity
Make-up hydrogen consists of a mixture of hydrogen
and methane. Methane is also produced in the
hydrocracking reaction. The hydrogen is consumed in
the hydrocracking reactions and lost.
To maintain the desired hydrogen partial pressure and
maintain the purity of the make-up hydrogen (99.5
mole%H2).
If the make-up hydrogen purity falls below the design
value, a bleed may be required to maintain an
acceptable hydrogen partial pressure.
H
2
partial press can be increased by
Increasing total system pressure (operate as close as the relief
valve set press located on the CHPS).
Increasing Make-Up Hydrogen Purity.
Increasing Recycle Gas Purity (Bleed, Treating)
Recycle Gas Rate.
Decreasing CHPS temperature.
Higher PH
2
Effects
Improves Product Properties (J et Smoke Point, Diesel
Cetane Number).
Increases Cycle Length.
H
2
partial press can be increased by
Increasing total system pressure (operate as close as the relief
valve set press located on the CHPS).
Increasing Make-Up Hydrogen Purity.
Increasing Recycle Gas Purity (Bleed, Treating)
Recycle Gas Rate.
Decreasing CHPS temperature.
Higher PH
2
Effects
Improves Product Properties (J et Smoke Point, Diesel
Cetane Number).
Increases Cycle Length.
Process variables:
Hydrogen Partial Pressure (pH
2
)
Process variables:
Process variables:
Hydrogen Partial Pressure (pH
Hydrogen Partial Pressure (pH
2 2
)
)
MAKE
MAKE
-
-
UP HYDROGEN QUALITY
UP HYDROGEN QUALITY
Parameter Hydrogen Specifications
Hydrogen Purity, Mole % 99.5(Min.)
CO + CO2, Mole 20 ppm (Max.)
Nitrogen, Mole 50 ppm (Max.)
Water, Mole 50 ppm (Max.)
Chlorine + Chlorides, Mole 1ppm (Max.)
Note: Co- more than 30ppm and reactor temp less than 200c, the
chances of nickel corbonyl formation is more. Which is highly toxic
Example: Effect of Increased Make-Up
Hydrogen Purity on Product Properties
and Cycle Length
Example: Effect of Increased Make
Example: Effect of Increased Make
-
-
Up
Up
Hydrogen Purity on Product Properties
Hydrogen Purity on Product Properties
and Cycle Length
and Cycle Length
SSOT Operation, System Pressure=169 kg/cm2
2 2 2
Make -Up Purity, % 85 96 99.9
Recycle Gas Purity, % 75 86.5 90
Hydrogen Partial Pressure,
kg/cm
2
G
125 136 140
Jet Smoke, mm 18 20 21
Diesel Cetane Number 50 53 55
Cycle Length, Months 14 24 29
Effects of High Recycle Gas rate (Gas/Oil Ratio)
Decreases Catalyst Fouling
Maintains High Hydrogen Partial Pressure in Reactors.
Providing a heat sink for high heat of reaction in the
bed.
Helps Distribution of Reactants Over the Catalyst
Bed.
Limits Bed Temperature Rise.
Increases Catalyst Activity
Minimizes "Overcracking" of Products by carrying
them out of the reactors before they can re-crack.
(Higher Liquid Yields)
Effects of High Recycle Gas rate (Gas/Oil Ratio)
Decreases Catalyst Fouling
Maintains High Hydrogen Partial Pressure in Reactors.
Providing a heat sink for high heat of reaction in the
bed.
Helps Distribution of Reactants Over the Catalyst
Bed.
Limits Bed Temperature Rise.
Increases Catalyst Activity
Minimizes "Overcracking" of Products by carrying
them out of the reactors before they can re-crack.
(Higher Liquid Yields)
Process variables: Recycle Gas Rate (Gas/Oil
Ratio)
Process variables
Process variables
:
:
Recycle Gas Rate (Gas/Oil
Recycle Gas Rate (Gas/Oil
Ratio)
Ratio)
Typical Design Guideline
Four to Five Times Chemical Hydrogen
Consumption
Recycle Gas Rate Should Be Maximized
Within Plant Mechanical Constraints.
minimum of 845 Nm3 reactor inlet gas per
m3 of fresh feed.
Typical Design Guideline
Four to Five Times Chemical Hydrogen
Consumption
Recycle Gas Rate Should Be Maximized
Within Plant Mechanical Constraints.
minimum of 845 Nm3 reactor inlet gas per
m3 of fresh feed.
Process variables: Recycle Gas Rate
(Gas/Oil Ratio)
Process variables
Process variables
:
:
Recycle Gas Rate
Recycle Gas Rate
(Gas/Oil Ratio)
(Gas/Oil Ratio)
Process variables
Process variables
-
-
Recycle Gas Purity
Recycle Gas Purity
Effects of Recycle Gas Purity:
1. Yields high hydrogen partial pressures.
2. Minimizes catalyst fouling.
Depends mainly on:
1. Make-up hydrogen purity.
2. The yield of methane in the reactors.
3. Gas bleed from CHPS.
4. CHPS inlet temperature.
ACTION TO BE TAKEN:
Taking a bleed, which results in an increase in the make-up hydrogen
rates, lowers the methane content of the recycle gas and improves hydrogen
rates, lowers the methane content of the recycle gas and improves hydrogen
partial pressure. Lowering the CHPS temperature will improve purity
because more light hydrocarbons will condense out of the recycle gas and
because less hydrogen dissolves at lower levels.
NOTE;
The design purity of the recycle gas is approximately 90.7 mole % H2 at
SOR and 85.6 mole % H2 at EOR. The recycle gas purity
1. Level Average Temperature (LAT)
2. Bed Average Temperature (BAT)
3. Catalyst Average Temperature (CAT)
Temperature Profile:
1. The LAT is the simple arithmetic average for a set of thermocouples at one
level in a catalyst bed.
2. The BAT is the simple arithmetic average of the bed inlet and outlet LATs.
3. The CAT is the weighted average of the BATs.
There are three types of profiles:
1. A flat temperature profile means the BATs are equal.
2. An ascending profile means that each successive BAT is higher than the bed
above.
3. A descending profile means that each successive BAT is lower than the bed
above. This profile is rarely used (or achievable).
Note: BAT, CAT, and temperature profiles are all used to monitor reactor
performance. The CAT determines how hard the catalyst is working and the
temperature profile describes how the work is distributed over the reactor.
1. Level Average Temperature (LAT)
2. Bed Average Temperature (BAT)
3. Catalyst Average Temperature (CAT)
Temperature Profile:
1. The LAT is the simple arithmetic average for a set of thermocouples at one
level in a catalyst bed.
2. The BAT is the simple arithmetic average of the bed inlet and outlet LATs.
3. The CAT is the weighted average of the BATs.
There are three types of profiles:
1. A flat temperature profile means the BATs are equal.
2. An ascending profile means that each successive BAT is higher than the bed
above.
3. A descending profile means that each successive BAT is lower than the bed
above. This profile is rarely used (or achievable).
Note: BAT, CAT, and temperature profiles are all used to monitor reactor
performance. The CAT determines how hard the catalyst is working and the
temperature profile describes how the work is distributed over the reactor.
Process variables; Reactor Temperature
Profile
Process variables
Process variables; ;
Reactor Temperature
Reactor Temperature
Profile
Profile
Catalyst Average Temperature (CAT )
Indicates How Hard Catalyst is Working.
Reactor Temperature Profile
Indicates How Work is Distributed Through the
Reactor.
Catalyst Average Temperature (CAT )
Indicates How Hard Catalyst is Working.
Reactor Temperature Profile
Indicates How Work is Distributed Through the
Reactor.
Process variables- catalyst
effects
Process variables
Process variables
-
-
catalyst
catalyst
effects
effects
Higher Catalyst Average Temperature Allows
Higher Feed Rates at Constant Product Qualities.
Better Product Qualities at Constant Feed Rate.
More Difficult Feeds (Higher S, N) at Constant Product
Qualities and Feed Rate.
But There is No Free Lunch
Higher CATs Increase Coking Rate.
Higher CATs Reduces catalyst Life due to increased
Fouling Rate.
Catalyst Average Temperature
Catalyst Average Temperature
Process variables
Process variables
-
-
catalyst life
catalyst life
The table below summarizes the effects of changing each
of the process variables on catalyst life.
Variable Change Effect on
Catalyst
Life
Feed Rate Increase Decrease
Conversion Increase Decrease
Hydrogen Partial
Pressure
Increase Increase
Make-Up Gas Purity Increase Increase
Reactor Pressure Increase Increase
Recycle Gas Rate Increase Increase
Recycle Gas Purity Increase Increase
WASH WATER INJ ECTION
WASH WATER INJ ECTION
Wash water is continuously injected into fin coolers to remove
ammonium salts.
Although incolloy tubes were selected for the reactor air
cooler, they may be subject to corrosion by deposition of
ammonium bisulfide (NH4HS) salts formed from the
combination of NH3 and H2S in the reactor and/or ammonium
chloride (NH4Cl) salts formed by the combination of NH3 and
HCl (from the chlorides in the feed).
The sublimation range for ammonium bisulfide is generally
about 66-93C. The sublimation range for ammonium chloride
begins at higher temperatures generally about 191-204C.
Therefore, NH4Cl will begin to sublime upstream of the
reactor air cooler.
Reactor air cooler corrosion is minimized by limiting the
chlorides in the feed in the make-up hydrogen, by use of high
alloy material, by balanced flow, and by continuous injection
of water at the air cooler inlet.
Process Variables have a significant impact on
Catalyst Life, Yields, and Product Properties
Understanding Process Variable Effects and
how these are related coupled with the
recognizing the constraints is critical to
maximizing Hydrocracker and Refinery
Profitability
Process Variables have a significant impact on
Catalyst Life, Yields, and Product Properties
Understanding Process Variable Effects and
how these are related coupled with the
recognizing the constraints is critical to
maximizing Hydrocracker and Refinery
Profitability
Summary of Process Variables
Summary of Process Variables
Summary of Process Variables
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