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Solvent
Gasoline, Naphtha, Middle distillates Heating oil
extraction Hydro-
cracking
Lube base stocks Lube oils Lube oil
Solvent
dewaxing Waxes
Greases
Propane LPG and Gas
deasphalter
Gasoline, Naphtha, Middle distillates
Asphalt
Visbreaker Fuel oil
Asphalt Industrial
Delayed coker / fuels
Gasoline, Naphtha, Middle distillates
Flexicoker
TUDelft Coke
Crude Oil Refining
Distillate fraction Boiling point C-atoms/
(oC) molecule
Gases <30 1-4
Gasoline 30-210 5-12
Naphta 100-200 8-12
Kerosine (jet fuel) 150-250 11-13 Middle
Diesel, Fuel oil 160-400 13-17 Distillates
Atmospheric 220-345
Gasoil
Heavy Fuel Oil 315-540 20-45
Atmospheric >540 >30
Residue
Vacuum Residue >615 >60
TUDelft
Processes
Processes in
in an
an Oil
Oil Refinery
Refinery
TUDelft
Simple
Simple Crude
Crude Distillation
Distillation
Gases
C1 - C4
reflux water
Gasoline
620 K
steam
steam Kerosene
steam
Gas oil
Crude oil
Residue
TUDelft
More sophisticated ???
Higher T distillation ??
Gases
C1 - C4
reflux water
Gasoline
620 K
steam
steam Kerosene
steam
Gas oil
Crude oil
Residue
reflux water
Gasoline
circulating reflux
Slops
vacuum
circulating reflux
steam Intermediate
vacuum
gas oil
vacuum Heavy
residue
gas oil
Kerosene
steam Light
gas oil
How?
Reduction by removal of suitable solvent
propane
butane, pentane
TUDelft
Propane Deasphalting
Condensers
Propane recycle
Steam condenser
Steam
Vacuum
residue Cond. Water
Propane evaporator
310 - 330 K
35 - 40 bar Steam
Make-up Deasphalted oil
propane
Asphalt
TUDelft
Thermal Processes
gas
Feed Furnace oil
T, tres coke
Flexicoking
combination thermal cracking and coke gasification/combustion
Steam Cracking
production lower olefins
TUDelft
Thermal Processes
VISBREAKING
Mild thermal cracking
Reduction of viscosity
DELAYED COKING
Long residence times (24 h)
Heavy feed coke + oil + gas
FLEXICOKING
Combination of thermal cracking and
coke gasification / combustion
TUDelft
Visbreaking
Gasoline ~ 10 wt%
Vacuum
residue
730 K
20 bar
~ 80 wt%
Cracked residue
Light gas oil
TUDelft
Delayed Coking
Gas
710 K
Unstabilized
Naphtha
2 bar
770 K
Gas oil
Coke
Feed
TUDelft
Market
Market Demands
Demands
TUDelft
Crude Oil Refining
Distillate fraction Boiling point C-atoms/
(oC) molecule
Gases <30 1-4
Gasoline 30-210 5-12
Naphta 100-200 8-12
Kerosine (jet fuel) 150-250 11-13 Middle
Diesel, Fuel oil 160-400 13-17 Distillates
Atmospheric 220-345
Gasoil
Heavy Fuel Oil 315-540 20-45
Atmospheric >540 >30
Residue
Vacuum Residue >615 >60
TUDelft
Octane Numbers, Boiling Points
n-pentane 62 309 K
2-methyl butane 90 301
cyclopentane 85 322
n-hexane 26 342
2,2-dimethylbutane 93 323
benzene >100 353
cyclohexane 77 354
n-octane 0 399
2,2,3-trimethylpentane 100 372
methyl-tertiary-butyl-ether 118 328
TUDelft
Product Distribution
Thermal versus Catalytic Cracking
140
100
80
Catalytic
60
40
20
0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
Carbon Number
TUDelft
Catalytic Cracking
World capacity: > 500 million metric ton/year
CH3 CH3
H3C C+ CH2 C CH3 H3C C CH2 + + C CH3 scission
CH3 CH3 CH3 CH3
Reactions:
C-C bond cleavage:
Isomerization
Protonation/deprotonation
Alkylation
Polymerization
Cyclization, condensation coke formation
TUDelft
Cracking Mechanism
Alkenes: H
R CH C H2 + H+ R C H2 C + or R C+ C H3
via carbenium ions H H
Stability: tertiary > secondary > primary > ethyl > methyl
H
Alkanes:
R C H2 C H3 + H+ R C+ C H3 R C+ C H3 + H2
via carbonium ions H H H
H
+
Or, if carbenium ions H 3C C C H2 C H2 C H2 C H3 H 3C C C H2 C H2 C H2 C H3
H H
are present: + +
H 3C C+ C H2 C H2 C H3 H 3C CH C H2 C H2 C H3
C H3 C H3
TUDelft
Cracking Mechanism
H3C CH2 CH2 CH2 CH2 CH2 CH3 n-Alkane
Initation
+
H3C CH CH2 CH2 CH2 CH2 CH3 Classical carbenium ion
+ +
H3C CH CH3 + H2C CH CH3 H3C CH CH CH2 CH2 CH3
CH3 n-Alkene CH3
etc.
hydride transfer
H3C CH CH3
CH3
iso-Alkane
TUDelft
Catalysts for FCC
Mechanism: H+ donor or H- acceptor
acid sites
Originally
AlCl3 solution:
corrosion
waste streams
Subsequently
Clays (acid-treated)
Amorphous silica-alumina
more stable and more selective
better pore structure
better attrition stability
Zeolites
even more active and stable (less
TUDelft coke, higher thermal stability
Catalytic Cracking Capacity in the US
7
5.5
Capacity with
zeolitic catalysts
5
(actual situation)
4.5
1960 1965 1970 1975 1980 1985 1990 1995
Year
TUDelft
Cracking Catalysts
silica: Si Si
O O
Si O Si OH Si O Si O - + H+
O O
Si Si
TUDelft
Zeolites
Large number found and/or synthesized
Total porosity up to 0.5 ml/g
Examples:
SOD
Sodalite
FAU
Y (Faujasite)
LTA
Zeolite A
TUDelft
Production of FCC catalyst
RECl3, NH4Cl
Micro pores < 3 nm
Wash liquor Meso pores 3 - 50 nm
Sodium silicate Macro pores > 50 nm
Sodium aluminate
zeolite
Water
matrix (dp = 2-10 m)
NaOH Ion exchange
Na zeolite Filter Dryer
crystallization Zeolite 50-70 m
Al2O3 source
SiO2 source
Water FCC catalyst
Matrix material particles
NaOH
TUDelft
Product Distribution of Gas Oil Cracking
100 Gas
LPG
80
% wt on feed
40 Catalyst poisoned
0 Coke
1950s 1960s 1970s 1980s
Amorphous Zeolite
Low Al High Al REY USY
TUDelft
FCC: Fluidized-bed Reactor and Regenerator
C + O2 CO / CO2 To fractionation
Flue gas
2-stage
Cyclones Cracking
2-stage 775 K
Cyclones
Fluidized bed
970 K
Fluidized bed
Later
Grid Steam much more
Spent active catalyst
Riser
catalyst
Regenerated
Consequences
Air
catalyst for process?
Feed
Regenerator Reactor
TUDelft
Modern FCC Unit: Riser Reactor
waste
L/L sep.
heat catalyst
boiler fines water
spent
cat. steam
TUDelft
Riser Reactor: Plug flow Reactor??
Residence Time Distribution ?
Total area = 1
0 20
Time (s)
TUDelft
Typical Conditions in Riser FCC
Reactor Regenerator
Temperature (K) 775 973
Pressure (bar) 1 2
Residence time 1-5 s minutes/half hour
TUDelft
Sulfur Distribution in FCC Products
Capacity: 50000 barrels /day
catalyst / oil ratio: 6 kg/kg
Catalyst inventory: 500 ton
Catalyst recirculation rate: 50000 ton/day
feedstock sulfur content: 2 wt%
TUDelft
Removal of SO2 in FCC unit
M: Ce, Mg,..
MO + H2S
or
MS + H2O
Regeneration of metal oxide in
stripper with release of H2S: MS + H2O MO + H2S
TUDelft
Novel Developments in FCC
0.51 - 0.55 nm
TUDelft
Hydrotreating and Hydrocracking
HYDROTREATING
Conversion with hydrogen
Reactions: hydrogenation & hydrogenolysis
Removal of hetero-atoms (S, N, O)
Some hydrogenation of double bonds &
aromatic rings
Molecular size not drastically altered
Also termed hydropurification
HYDROCRACKING
Similar to hydrotreating
But, drastic reduction in molecular size
TUDelft
Objectives Hydrotreating
TUDelft
Hydrotreating Reactions
HDS
2) Thiophenes + 3 H2 + H2S
S
TUDelft
Equilibrium data
100
90
S
80
70
Industrial conditions
60 S 600-650 K
lnKeq
50
40
30
CH3SH
20
10
0
0 1 2 3 4 5
1000/Temperature (1/K)
TUDelft
Typical process conditions
Naphtha Gas Oil
Temperature (K): 590 - 650 600 - 670
Pressure (bar): 15 - 40 40 - 100
H2/oil (Nm3/kg): 0.1 - 0.3 0.15 - 0.3
WHSV (kg feed/(m3 catalyst)/h) 2000 - 5000 500 - 3000
Catalyst: mixed metal sulfides (CoS and MoS2 or NiS and WS2
on Al2O3)
CoMoS
S
Co
Mo
-Al2O3
Gas + liquid
Deflector
Gas
Liquid Distributor
Inert beads
Gas Complete wetting
Catalyst bed
Incomplete wetting
Support grid
Catalyst particle
with liquid film
Product
TUDelft
Hydrotreating Process (trickle bed)
H2S
Cold HP
water separator Naphtha
Sour steam
water
Product
Feed
Furnace Reactor Hot HP Hot LP Stripper Separator
separator separator
TUDelft
Development of maximum Sulfur
Content in automotive Diesel in Europe
3500
3000
3000
2500
2000
Max S in Diesel
1500 ppm
1000
500
500
350
50
0
1 2 3 4
< 1996 1996 2000 2005
Year
TUDelft
Activity of Various Catalysts for HDS of
Pretreated Gas Oil
S
CH3
S
CH3 CH3
S S
C2H5 CH3
260 ppm
CoMo/-Al2O3
230 ppm
NiMo/-Al2O3
200 ppm
NiW/-Al2O3
140 ppm
Pt/ASA
60 ppm
PtPd/ASA (I)
TUDelft
Retention time
Effect of HDS of FCC feedstock
on gasoline sulfur content
10000
FCC gasoline sulfur, ppmw
10
1
0 0.5 1 1.5 2
FCC
FCCfeedstock sulfur,wt.%
feedstock sulfur, wt.%
TUDelft
Hydrocracking
Similar to FCC
but H2 inhibits some secondary reactions
(e.g. coke formation)
Hydrogenation sites
NiS/MoS, NiS/WS2, Pt
NH3 inhibits reaction
H2S inhibits reaction
TUDelft
Reactions during Hydrocracking
H0208 (kJ/mol)
Hetero-atom removal + 6 H2 + NH3
N - 374
H
+ 2 H2 + 3 H2
Aromatics hydrogenation - 326
Hydrodecyclization + 3 H2 +
- 119
Alkanes hydrocracking + H2 + - 44
Hydro-isomerization -4
TUDelft
Process Configurations for
Hydrocracking
Gas
Gas
Naphtha
MD Naphtha
Feed HT/HC MD
Feed HT HC
Hydrowax
Series flow
TUDelft
Two-stage Hydrocracker
Fresh
hydrogen
Hydrogen recycle
Purge
Naphtha
Quench H2 Quench H2
Middle
distillates
Feed
TUDelft
Summary of Processing Conditions
TUDelft