Gasoline Finishing: Gasoline Finishing:

Catalytic Reforming, Isomerization, & Alkylation Catalytic Reforming, Isomerization, & Alkylation
Chapters 10 & 11
Light Naphtha
Crude
Oil
Desalter
Atmospheric
Distillation
Vacuum
Distillation
Gas
Separation &
Stabilizer
Solvent
Deasphal-
ting
Coking
Visbreaking
Fluidized
Catalytic
Cracking
Hydro-
cracking
Naphtha
Reforming
Isom-
erization
Sat Gas
Plant
Polymer-
ization
Alkylation
Naphtha
Hydro-
treating
Treating &
Blending
Coke
Fuel Gas
LPG
Aviation
Gasoline
Automotive
Gasoline
Solvents
Jet Fuels
Kerosene
Solvents
Heating Oils
Diesel
Residual
Fuel Oils
Lubricant
Greases
Waxes
Asphalts
Heavy
Naphtha
Kerosene
Distillate
AGO
LVGO
HVGO
Vacuum
Residuum
Cat
Distillates
Gas Oil
Hydro-
treating
DAO
Isomerate
Gas
Alkyl
Feed
Alkylate
Polymerization
Naphtha
Gases
Butanes
LPG
Reformate
Naphtha
Fuel Oil
Bottoms
Distillates
Distillate
Hydro-
treating
Cat
Naphtha
Cycle Oils
SDA
Bottoms
Coker
Naphtha
Heavy
Coker
Gas
Oil
Light Coker
Gas Oil
Sulfur
Plant
Sulfur
Naphtha
Fuel Oil
Solvent
Dewaxing
Lube Oil
Waxes
Purpose
Purpose
Previous conversion processes
Feed stocks higher boiling than gasoline
Break apart large molecules to form smaller molecules
Gasoline finishing processes
Feed stocks same boiling range as gasoline or slightly lower
Start with low-octane gasoline blend stocks
Catalytic Reforming
Converts naphthenes to aromatics
Produces hydrogen
Isomerization
Re-arranges straight chains to branched isomers
Very little change in boiling points
Increase molecular size
Alkylation
Use olefins produced in other processes (primarily FCCU)
Characteristics of Petroleum Products
Characteristics of Petroleum Products
Contributions to Gasoline Blending
Contributions to Gasoline Blending
Pool
Pool
15 vol% Isomerization
20 vol% Alkylation
30 vol% Reformer
35 vol% FCCU
U.S. Refinery Implementation
U.S. Refinery Implementation
Top 20 Atmospheric Distillation Capacity
Company State Site
Atmospheric
Crude Distillation
Capacity (barrels
per stream day)
Cat Reforming:
High Pressure
Downstream
Charge Capacity,
Current Year
(barrels per
stream day)
Cat Reforming:
Low Pressure
Downstream
Charge Capacity,
Current Year
(barrels per
stream day)
Isomerization(Is
ooctane)
Production
Capacity,
Current Year
(barrels per
steam day
except sulfur
and hydrogen)
Isomerization
(Isobutane)
Production
Capacity,
Current Year
(barrels per
steam day
except sulfur
and hydrogen)
Isomerization
(Isopentane/Iso
hexane)
Production
Capacity,
Current Year
(barrels per
steam day
except sulfur
and hydrogen)
Alkylates
Production
Capacity,
Current Year
(barrels per
steam day
except sulfur
and hydrogen)
ExxonMobil Refining Texas BAYTOWN 596,400 0 126,000 0 0 0 37,000
Hovensa LLC Virgin Islands KINGSHILL 525,000 25,000 85,000 0 0 20,000 19,000
ExxonMobil Refining Louisiana BATON ROUGE 524,000 0 78,000 0 0 0 39,700
BP Texas TEXAS CITY 475,000 75,000 63,000 0 18,000 24,000 46,000
PDVSA Louisiana LAKE CHARLES 440,000 52,800 58,000 0 0 28,000 18,000
BP Indiana WHITING 420,000 71,500 0 0 0 26,000 36,000
Chevron USA Inc Mississippi PASCAGOULA 360,000 34,000 62,000 1,400 0 0 18,600
ExxonMobil Refining Texas BEAUMONT 359,100 0 146,000 0 11,200 24,500 16,300
Sunoco Pennsylvania PHILADELPHIA 355,000 86,000 0 0 8,000 0 26,000
Deer Park Refining Ltd Partnership Texas DEER PARK 340,000 25,000 44,000 0 0 0 18,500
Koch Industries Minnesota SAINT PAUL 330,000 13,800 37,500 0 0 0 12,500
WRB Refining LLC Illinois WOOD RIVER 322,000 17,700 78,800 0 0 0 21,800
Valero Energy Corp Texas PORT ARTHUR 320,000 0 55,000 0 0 0 19,900
Koch Industries Texas CORPUS CHRISTI 305,000 18,000 49,500 0 4,900 2,500 14,700
Motiva Enterprises Texas PORT ARTHUR 300,000 0 48,000 0 0 0 20,000
Access Industries Texas HOUSTON 299,300 0 0 0 0 0 11,250
Chevron USA Inc California EL SEGUNDO 294,000 0 49,000 0 7,700 22,300 33,500
Marathon Petroleum Louisiana GARYVILLE 275,000 0 48,000 0 23,000 21,000 28,000
BP California LOS ANGELES 265,500 43,000 10,000 2,500 3,500 23,000 17,000
ConocoPhillips Texas SWEENY 260,000 0 37,500 0 0 10,100 21,700
ConocoPhillips Statistics
ConocoPhillips Statistics
Company State Site
Atmospheric
Crude
Distillation
Capacity
(barrels per
stream day)
Cat Reforming:
High Pressure
Downstream
Charge
Capacity,
Current Year
(barrels per
stream day)
Cat Reforming:
Low Pressure
Downstream
Charge
Capacity,
Current Year
(barrels per
stream day)
Isomerization
(Isooctane)
Production
Capacity,
Current Year
(barrels per
steam day
except sulfur
and hydrogen)
Isomerization
(Isobutane)
Production
Capacity,
Current Year
(barrels per
steam day
except sulfur
and hydrogen)
Isomerization
(Isopentane/Is
ohexane)
Production
Capacity,
Current Year
(barrels per
steam day
except sulfur
and hydrogen)
Alkylates
Production
Capacity,
Current Year
(barrels per
steam day
except sulfur
and hydrogen)
WRB Refining LLC Illinois WOOD RIVER 322,000 17,700 78,800 0 0 0 21,800
ConocoPhillips Louisiana BELLE CHASSE 260,000 44,600 0 0 2,000 0 38,000
ConocoPhillips Texas SWEENY 260,000 0 37,500 0 0 10,100 21,700
ConocoPhillips Louisiana WESTLAKE 252,000 0 44,000 0 0 0 6,000
ConocoPhillips New Jersey LINDEN 250,000 0 32,000 0 4,000 0 18,000
ConocoPhillips Oklahoma PONCA CITY 210,381 52,704 0 0 8,000 0 15,758
ConocoPhillips Pennsylvania TRAINER 190,000 0 50,000 0 0 0 12,000
WRB Refining LLC Texas BORGER 154,000 31,690 0 0 15,000 29,300 14,000
ConocoPhillips California WILMINGTON 147,000 36,000 0 0 3,100 12,800 9,900
ConocoPhillips California RODEO 128,000 32,000 0 0 3,500 9,400 0
ConocoPhillips Washington FERNDALE 107,500 0 17,400 0 2,600 0 9,500
ConocoPhillips Montana BILLINGS 62,000 13,550 0 0 4,000 0 7,250
ConocoPhillips Alaska PRUDHOE BAY 16,000 0 0 0 0 0 0
Dependency of Octane on Chemical Structure Dependency of Octane on Chemical Structure
BPT [F] RON MON BPT [F] RON MON
Paraffins Naphthenes
n-butane 31 94 89.6 cyclopentane 121 100 84.9
isobutane 11 102 97.6 cyclohexane 177 82.5 77.2
n-pentane 97 62 62.6 m-cyclopentane 161 91.3 80
i-pentane 82 92 90.3 C7 naphthenes 203 82 77
n-hexane 156 24.8 26 C8 naphthenes 253 55 50
C6 monomethyls 143 76 73.9 C9 naphthenes 309 35 30
2,2-dimethylbutane 122 91.8 93.4
2,3-dimethylbutane 136 105.8 94.3 Aromatics
n-heptane 209 0 0 benzene 176 102.7 105
C7 monomethyls 196 52 52 toluene 231 118 103.5
C7 dimethyls 183 93.76 90 C8 aromatics 283 112 105
2,2,3-trimethylbutane 178 112.8 101.32 C9 aromatics 327 110 101
n-octane 258 -15 -20 C10 aromatics 365 109 98
C8 monomethyls 245 25 32.3 C11 aromatics 402 105 94
C8 dimethyls 233 69 74.5 C12 aromatics 439 102 90
C8 trimethyls 229 105 98.8
n-nonane 303 -20 -20 Olefins/Cyclic Olefins
C9 monomethyls 290 15 22.3 n-butenes 30 98.7 82.1
C9 dimethyls 273 50 60 n-pentenes 94 90 77.2
C9 trimethyls 267 100 93 i-pentenes 95 103 82
n-decane 345 -30 -30 cyclopentene 112 93.3 69.7
C10 monomethyls 332 10 10 n-hexenes 152 90 80
C10 dimethyls 40 40 i-hexenes 143 100 83
C10 trimethyls 95 87 Total C6 cyclic olefins 175 95 80
n-undecane 385 -35 -35 total C7d 193 90 78
C11 monomethyl 5 5 total C8d 244 90 77
C11 dimethyls 35 35
C11 trimethyls 90 82 Oxygenates
n-dodecane 421 -40 -40 MTBE 115.2 97.2
C12 monomethyl 5 5 TAME 115 98
C12 dimethyls 30 30 EtOH 108 92.9
C12 trimethyls 85 80
Dependency of Octane on Chemical Structure Dependency of Octane on Chemical Structure
-60
-40
-20
0
20
40
60
80
100
120
140
0 50 100 150 200 250 300 350 400 450 500
Boiling Point [F]
R
e
s
e
a
r
c
h

O
c
t
a
n
e

N
u
m
b
e
r
Aromatics
Naphthenes
Olefins & Cyclic Olefins
Iso-paraffins
Normal Paraffins
Light Naphtha
Crude
Oil
Desalter
Atmospheric
Distillation
Vacuum
Distillation
Gas
Separation &
Stabilizer
Solvent
Deasphal-
ting
Coking
Visbreaking
Fluidized
Catalytic
Cracking
Hydro-
cracking
Naphtha
Reforming
Isom-
erization
Sat Gas
Plant
Polymer-
ization
Alkylation
Naphtha
Hydro-
treating
Treating &
Blending
Coke
Fuel Gas
LPG
Aviation
Gasoline
Automotive
Gasoline
Solvents
Jet Fuels
Kerosene
Solvents
Heating Oils
Diesel
Residual
Fuel Oils
Lubricant
Greases
Waxes
Asphalts
Heavy
Naphtha
Kerosene
Distillate
AGO
LVGO
HVGO
Vacuum
Residuum
Cat
Distillates
Gas Oil
Hydro-
treating
DAO
Isomerate
Gas
Alkyl
Feed
Alkylate
Polymerization
Naphtha
Gases
Butanes
LPG
Reformate
Naphtha
Fuel Oil
Bottoms
Distillates
Distillate
Hydro-
treating
Cat
Naphtha
Cycle Oils
SDA
Bottoms
Coker
Naphtha
Heavy
Coker
Gas
Oil
Light Coker
Gas Oil
Sulfur
Plant
Sulfur
Naphtha
Fuel Oil
Solvent
Dewaxing
Lube Oil
Waxes
Naphtha Reforming
Naphtha Reforming
Almost every refinery in the world has a reformer
Purpose to enhance aromatic content of naphtha
Feed stocks to aromatics complex
Improve the octane rating for gasoline
Many different commercial catalytic reforming processes
Hydroforming
Platforming
Powerforming
Ultraforming
Thermofor catalytic reforming
Primary reactions
Dehydrogenation naphthenes aromatics
Isomerization normal paraffins branched isoparaffins
Hydrogen as by-product
Ultimately used in hydrotreating
Catalytic reforming 2
nd
to FCC in commercial importance to refiners
Reformate desirable component for gasoline
High octane number, low vapor pressure, very low sulfur levels, & low olefins concentration
US regulations on levels of benzene, aromatics, & olefins
Air quality concerns
Feedstocks
Feedstocks
& Products
& Products
Hydrotreated heavy naphtha feedstock
Light straight run naphtha tends to crack to butanes & lighter
Gas oil streams tend to hydrocrack & deposit coke on the reforming catalyst
Catalyst is noble metal (e.g. platinum) very sensitive to sulfur &
nitrogen
Feed stocks hydrotreated for sulfur & nitrogen removal
Control of chloride & water also important
Severity
High severity used to maximize aromatics
Sent to BTX separation for aromatic feedstocks
Low severity used for gasoline blend stocks
Produces the majority of the hydrogen used for hydrotreating
Reforming Chemistry
Reforming Chemistry
Uses a solid catalyst to convert naphthenes to the
corresponding aromatics & isomerize paraffinic structures to
isomeric forms
Both reactions lead to a marked increase in octane number
Both reactions lead to volume shrinkage
Correlations permit the use of a PONA analysis of the feed for
prediction of yield and quality of the product
Originally feed qualities measured in terms of Watson "K" Factor
a rough indication of amount of paraffins
Aromatics largely untouched by reactions
Reforming Chemistry
Reforming Chemistry
CH
3
CH
3
+ 3 H2
Dehydrogenation
+ H2
Dehydrocyclization
CH
3
CH
3
CH
3
CH
3
+ H2
Isomerization
CH
3
CH
3
CH
2
CH
3
CH
3
Hydrocracking
CH
2
CH
3
CH
3
+ H2 +
Use of Yield Charts
Use of Yield Charts
100% Total
Ratio

Fig 10.4 C5+ Gasoline

Pure Ratio
58.5%
NC4
Pure Ratio
41.5%
Fig 10.5
IC4
C4s
Pure Fig 10.6 Ratio C3
Fig 10.6 C1 + C2
Fig 10.7 Hydrogen
Density Wt% Vol%
Notes:
Y-axis of Fig 10.4 is C5+ gasoline yield
Typically use the Watson K Factor of feed in Fig 10.4.
Effects of Process Variables
Effects of Process Variables
Primary control for changing conditions or qualities is
reactor temperature
Normally about 950F at reactor inlet
May be raised for declining catalyst activity or to
compensate for lower quality feedstock
Higher reactor temperature increases octane rating but
reduces yield and run length
Effects of Process Variables
Effects of Process Variables
Design considerations for improvement in quality will
include pressure, recycle ratio, reactor residence
time, & catalyst activity
Low reactor pressure increases yield & octane but increases
coke make
Increased hydrogen partial pressure due to hydrogen recycle
(hydrogen to hydrocarbon ratio) suppresses coke formation,
hydrogen yield & octane gain, but promotes hydrocracking
Low space velocity favors aromatics formation but also
promotes cracking by operating closer to equilibrium
conditions
Higher activity catalysts cost more but increases run
lengths and or yields
Effects of Process Variables Effects of Process Variables
High temperature High pressure Hydrocracking
Slight dependence Slight dependence
Isomerization of normal paraffins
to isoparaffins
High temperature Low pressure
Dehydrogenation of naphthenes
to aromatics
High temperature Low pressure
Dehydrocyclization of paraffins to
naphthenes
Indeterminate Indeterminate Isomerization of naphthenes
Temperature Pressure Reaction
Specific Catalytic Reforming Processes
Specific Catalytic Reforming Processes
Hydroforming
Early cyclic process used to produce toluene for TNT during
World War II
Molybdenum oxide on alumina catalyst
Rapid coking of the catalyst, requiring a cyclic regeneration
of reactors about every four hours
Timing mechanism used for lawn sprinkler systems used to
switch from reforming to regeneration service
Reactor system included one extra "swing" reactor
Facilitate periodic removal & regeneration of a reactor
Specific Catalytic Reforming Processes
Specific Catalytic Reforming Processes
UOP Semi-Regenerative Platforming
Low platinum
Regeneration once a year
Made naphtha octane improvement accessible to all refiners
UOP Continuous Regeneration of Reforming Catalyst
Moving bed process
Continuously regenerating a portion of a moving bed of catalyst to remove coke
& sustain activity
Operating pressures lowered to 50 psig
Three reactors stacked one on top of the other
Gravity flow of the catalyst from top to bottom
Reactants pass radially through the catalyst to the inner conduit and then to the
next bed
Mode of regeneration is proprietary probably employs air or oxygen burning of
the coke followed by reduction & acidification
UOP
UOP
Platforming
Platforming
Refining Overview Petroleum Processes & Products,
by Freeman Self, Ed Ekholm, & Keith Bowers, AIChE CD-ROM, 2000
Light Naphtha
Crude
Oil
Desalter
Atmospheric
Distillation
Vacuum
Distillation
Gas
Separation &
Stabilizer
Solvent
Deasphal-
ting
Coking
Visbreaking
Fluidized
Catalytic
Cracking
Hydro-
cracking
Naphtha
Reforming
Isom-
erization
Sat Gas
Plant
Polymer-
ization
Alkylation
Naphtha
Hydro-
treating
Treating &
Blending
Coke
Fuel Gas
LPG
Aviation
Gasoline
Automotive
Gasoline
Solvents
Jet Fuels
Kerosene
Solvents
Heating Oils
Diesel
Residual
Fuel Oils
Lubricant
Greases
Waxes
Asphalts
Heavy
Naphtha
Kerosene
Distillate
AGO
LVGO
HVGO
Vacuum
Residuum
Cat
Distillates
Gas Oil
Hydro-
treating
DAO
Isomerate
Gas
Alkyl
Feed
Alkylate
Polymerization
Naphtha
Gases
Butanes
LPG
Reformate
Naphtha
Fuel Oil
Bottoms
Distillates
Distillate
Hydro-
treating
Cat
Naphtha
Cycle Oils
SDA
Bottoms
Coker
Naphtha
Heavy
Coker
Gas
Oil
Light Coker
Gas Oil
Sulfur
Plant
Sulfur
Naphtha
Fuel Oil
Solvent
Dewaxing
Lube Oil
Waxes
Gasoline Isomerization
Gasoline Isomerization
Major process for octane improvement
Improve the octane rating of straight run gasoline
N-paraffins isomerized to branched isoparaffins
Also converts normal butane to isobutane used in
alkylation
High RVP (about 17 psi) limits its use in gasoline
pool
Dependency of Octane on Chemical Structure Dependency of Octane on Chemical Structure
BPT [F] RON MON BPT [F] RON MON
Paraffins Naphthenes
n-butane 31 94 89.6 cyclopentane 121 100 84.9
isobutane 11 102 97.6 cyclohexane 177 82.5 77.2
n-pentane 97 62 62.6 m-cyclopentane 161 91.3 80
i-pentane 82 92 90.3 C7 naphthenes 203 82 77
n-hexane 156 24.8 26 C8 naphthenes 253 55 50
C6 monomethyls 143 76 73.9 C9 naphthenes 309 35 30
2,2-dimethylbutane 122 91.8 93.4
2,3-dimethylbutane 136 105.8 94.3 Aromatics
n-heptane 209 0 0 benzene 176 102.7 105
C7 monomethyls 196 52 52 toluene 231 118 103.5
C7 dimethyls 183 93.76 90 C8 aromatics 283 112 105
2,2,3-trimethylbutane 178 112.8 101.32 C9 aromatics 327 110 101
n-octane 258 -15 -20 C10 aromatics 365 109 98
C8 monomethyls 245 25 32.3 C11 aromatics 402 105 94
C8 dimethyls 233 69 74.5 C12 aromatics 439 102 90
C8 trimethyls 229 105 98.8
n-nonane 303 -20 -20 Olefins/Cyclic Olefins
C9 monomethyls 290 15 22.3 n-butenes 30 98.7 82.1
C9 dimethyls 273 50 60 n-pentenes 94 90 77.2
C9 trimethyls 267 100 93 i-pentenes 95 103 82
n-decane 345 -30 -30 cyclopentene 112 93.3 69.7
C10 monomethyls 332 10 10 n-hexenes 152 90 80
C10 dimethyls 40 40 i-hexenes 143 100 83
C10 trimethyls 95 87 Total C6 cyclic olefins 175 95 80
n-undecane 385 -35 -35 total C7d 193 90 78
C11 monomethyl 5 5 total C8d 244 90 77
C11 dimethyls 35 35
C11 trimethyls 90 82 Oxygenates
n-dodecane 421 -40 -40 MTBE 115.2 97.2
C12 monomethyl 5 5 TAME 115 98
C12 dimethyls 30 30 EtOH 108 92.9
C12 trimethyls 85 80
History of Isomerization
History of Isomerization
Aviation gasoline for World War II
Butane isomerization was developed to create the needed
isobutane feedstock
Aluminum chloride catalyst
Many of these units were shut down after the war
Tetra Ethyl Lead Phase-Out in 1970s
Straight Run Gasoline (SRG) relied on TEL for octane improvement
Research Octane Number (RON) of only 70
SRG mostly paraffinic pentanes & hexanes with some heptanes and
octanes
Isomerization could provide needed octane boost
Equivalent Isoparaffins have higher RON
Isomerization Processes
Isomerization Processes
Vapor phase process
Hydrogen used to suppress dehydrogenation & coking
High yields & high selectivity to high-octane isomeric forms
Provides moderate (but important) contribution to the gasoline
pool
Catalyst types
Chloride alumina catalyst
Organic chloride deposited on active metal sites
High temperature treatment with carbon tetrachloride
Chlorides sensitive to moisture drying of feed & hydrogen make-up
essential
Acidic zeolite with noble metal catalyst
Platinum catalyst
Does not require activation by hydrogen chloride
Isomerization Processes
Isomerization Processes
Pros
Reforming conditions not appropriate for the paraffinic
components in SRG
Essentially zero benzene, aromatics, & olefins
Very low sulfur levels
Cons
High vapor pressure
Moderate octane levels (R+M)/2 only 85
Isomerization Technologies
Isomerization Technologies
Provider Features
Axens
Either once-through or Ipsorb Isom with normal
paraffin recycle to exinction.
CDTECH ISOMPLUS zeolite-based catalyst.
UOP (1)
Par-Isom process uses high-performance
nonchlorided-alumina catalysts
UOP (2)
HOT (hydrogen-once-through) Penex process
eliminates need of recycle-gas compressor. Fixed
bed using high-activity chloride-promoted catalyst.
UOP (3)
HOT (hydrogen-once-through) Butamer process
eliminates need of recycle-gas compressor. Two
series reactors provide high onstream efficiency.
Feedstocks
Feedstocks
Lightest naphtha feed stock (SRG) with pentanes,
hexanes, & small amounts of heptanes
Feed often debutanized Debutanized Straight Run
Sulfur & nitrogen must be removed since catalysts
employ an acid site for activity
Merox
Clay treating
Hydrotreating
Common for Straight Run Gasoline & Naphtha to be
hydrotreated as one stream & then separated
Products
Products
Products
Isoparaffins & cycloparaffins
Small amounts of light gasses from hydrocracking
Unconverted feedstock
Increased severity increases octane but also
increases yield of light ends
Yields depend on feedstock characteristics & product
octane
Poor quality feeds might yield 85% or less liquid product
Good feeds might yield 97% liquid product
Isomerization Chemistry
Isomerization Chemistry
Primary reaction is to convert normal paraffins to
isomeric paraffins
Olefins may isomerize and shift the position of the
double bond
1-butene coluld shift to a mixture of cis-2-butene & trans-2-
butene
Cycloparaffins (naphthenes) may isomerize & break
the ring forming an olefin
Cyclobutane to butene
Effects of Process Variables
Effects of Process Variables
Low temperature, moderate hydrogen partial pressure, low space
velocity promote long run lengths
Isomerization yields controlled by chemical equilibrium
Removing isoparaffins from feedstock can shift the reactor equilibrium &
increase the final product octane
Temperature primary process control variable
Higher temperatures increase processing severity (including hydrocracking)
Other process variables
Higher pressures increase catalyst life but increases undesirable
hydrocracking reactions
Increased hydrogen partial pressure promotes hydrocracking but prolongs
catalyst life
Space velocity balanced against capital cost, temperature, run length &
yields
Process Improvements
Process Improvements
Number of combinations of fractionation and isomerization
Removing isopentane from feed increases the products RON to 84
Addition of a depentanizer on product stream recycle of n-pentane
recycle increases products RON to 86
Separation using molecular sieves increases the products RON to
89
UOP combines Penex with Molex
Separation carried out entirely in vapor phase no reflux utilities but
cyclic operation
Total recycle with a deisohexanizer increases the products RON to
89
Suitable for blending into premium at no octane penalty
Isomerization With & Without Isomerization With & Without Isopentane Isopentane
Removal Removal
Refining Overview Petroleum Processes & Products,
by Freeman Self, Ed Ekholm, & Keith Bowers, AIChE CD-ROM, 2000
Catalytic Reforming Technologies
Catalytic Reforming Technologies
Provider Features
Axens (1)
Catalyst regenerated in-place at end of cycle. Operates in
pressure range of 170 - 350 psig.
Axens (2)
Advanced Octanizing process, uses continuous catalyst
regeneration allowing pressures as low as 50 psig.
UOP
CCR Platforming process. Radial-flow reactors arranged in
vertical stack.
Light Naphtha
Crude
Oil
Desalter
Atmospheric
Distillation
Vacuum
Distillation
Gas
Separation &
Stabilizer
Solvent
Deasphal-
ting
Coking
Visbreaking
Fluidized
Catalytic
Cracking
Hydro-
cracking
Naphtha
Reforming
Isom-
erization
Sat Gas
Plant
Polymer-
ization
Alkylation
Naphtha
Hydro-
treating
Treating &
Blending
Coke
Fuel Gas
LPG
Aviation
Gasoline
Automotive
Gasoline
Solvents
Jet Fuels
Kerosene
Solvents
Heating Oils
Diesel
Residual
Fuel Oils
Lubricant
Greases
Waxes
Asphalts
Heavy
Naphtha
Kerosene
Distillate
AGO
LVGO
HVGO
Vacuum
Residuum
Cat
Distillates
Gas Oil
Hydro-
treating
DAO
Isomerate
Gas
Alkyl
Feed
Alkylate
Polymerization
Naphtha
Gases
Butanes
LPG
Reformate
Naphtha
Fuel Oil
Bottoms
Distillates
Distillate
Hydro-
treating
Cat
Naphtha
Cycle Oils
SDA
Bottoms
Coker
Naphtha
Heavy
Coker
Gas
Oil
Light Coker
Gas Oil
Sulfur
Plant
Sulfur
Naphtha
Fuel Oil
Solvent
Dewaxing
Lube Oil
Waxes
Alkylation & Polymerization
Alkylation & Polymerization
Processes to make gasoline components from materials that are
too light to otherwise be in gasoline
Alkylation
Form a longer chain highly branched isoparaffin by reacting an alkyl
group (almost exclusively isobutane) with a light olefin
(predominately butylene)
Produces high-octane gasoline
Polymerization
Formation of very short chains
Product is nearly all olefinic high research octane but moderate
motor octane number
Alkylation Technologies
Alkylation Technologies
Provider Features
CDTECH (1) CDAlkyl low-temperature sulfuric acid alkylation.
CDTECH (2)
CDAlkylPlus low-temperature sulfuric acid alkylation
coupled with olefin pretreatment step.
DuPont
Uses STRATCO Effluent Refrigeration Alkylation
process using sulfuric acid
Lummus Technology
AlkylClean process using solid acid catalyst.
Demonstation unit only.
Refining Hydrocarbon
Technologies LLC
RHT-Alkylation process uses sulfuric acid. Eductor
mixing device.
ExxonMobil Research &
Engineering
Sulfuric acid alkylation using autorefrigerated
reactor.
UOP (1) Modified HF Alkylation to reduce aerosol formation.
UOP (2)
Indirect Alkylation (InAlk) uses solid catalyst. Olefins
polymerize & higher molecular weight material
hydrogenated.
Olefin Alkylation & Polymerization
Olefin Alkylation & Polymerization
1920s & 1930s other methods used to improve gasoline octane
Tetra Ethyl Lead in Straight Run Gasoline
Thermal reforming of naphtha
Thermal polymerization of olefinic light ends to hexenes, heptenes, &
octenes
In late 1930s & early 1940s, alkylation of olefins was developed
to improve the octane of aviation gasoline
Vladimir Ipatieff had discovered aluminum chloride catalysis in 1932
FCC significantly increased the production of light ends
High concentration of the C3, C4, & C5 isomers, both olefinic & paraffinic
Led to development of both catalytic polymerization & alkylation
Sulfuric Acid Alkylation
Sulfuric Acid Alkylation
A consortium of major refiners & contractors developed process
with sulfuric acid as the catalyst
Anglo-Iranian Oil, Humble Oil & Refining, Shell Development, Standard Oil
Development, & the Texas Company
First alkylation unit at the Humble Baytown Refinery in 1938
Many alkylation plants were built at the same time as the
catalytic cracking units
Operated during World War II for aviation gasoline production
Sulfuric acid alkylation required access to acid regeneration on a
large scale
Most sulfuric acid alkylation plants were located on deep water for barge
transport of spent acid to regeneration at acid plants & return of fresh acid
Economic handicap for inland midwestern refineries
HF Acid Alkylation
HF Acid Alkylation
Phillips Petroleum & UOP developed process using hydrofluoric
acid as a catalyst
HF could be readily regenerated in alkylation plant facilities
No need to transport catalyst in large quantities for regeneration
HF alkylate in general was not quite as high quality as sulfuric
acid alkylate
Alkylation vs. Polymerization
Alkylation vs. Polymerization
Following end of the Korean conflict (1953) refiners investigated
use of their catalytic polymerization and alkylation capacity for
production of higher-octane motor fuels
Both polymerization & alkylation were adapted alkylation
became the dominant process
By the 1960s, polymerization units were being phased out and
new plants utilized alkylation technology
Chicken & egg increasing octane production capacity &
higher performance engines in automobiles led to the octane
race in mid 1950s
Feedstocks
Feedstocks
Olefinic stream from the catalytic cracker
Butylene is the preferred olefin since it produces the highest octane
number & yields
isobutane & isopentane can be reacted with the olefin
Isopentane not usually used since it is a good gasoline blend stock
High octane number & low vapor pressure
Catalytic cracker feed contains significant sulfur
Treating unit often precedes alkylation unit
Products
Products
Alkylate desirable component for high performance automotive
fuels
Very high octane index (R+M)/2 of 95
Low vapor pressure
Vapor pressure is adjusted for final boiling point
IBP adjusted for addition of normal butane
Low sulfur levels
Essentially no olefins, benzene or aromatics
Contributes large volume to the gasoline pool (19% vol)
Catalytic cracker (34% vol)
Reformer (28% vol)
Isomerization unit (15% vol)
Process Chemistry
Process Chemistry
Acid catalyzed alkylation combines isoparaffins & olefins to
form alkylate, highly branched alkanes
Usually only isobutane is used
Isopentane is a good gasoline blend stock
Friedel-Crafts reaction Lewis acid (HF or H2S04) promotes
carboniumion on a tertiary isoparaffin that rapidly reacts with
any double bond it encounters (propylene, butylenes, or
pentylenes)
The reaction carried out in the liquid phase with an acid/reactant
emulsion maintained at moderate temperatures
Process Chemistry
Process Chemistry
Propylene, butylene, & pentenes are olefins used butylene
preferred
High octane isooctane alkylate produced
Lower reactant consumption
Alkylation reactions have complex mechanisms & may produce
many different varieties
Process Chemistry Examples
Process Chemistry Examples
Isobutylene & isobutane form 2,2,4-trimethylpentane
(isooctane)
Propylene & isobutane form 2,2-dimethylpentane as primary
product with 2,3-dimethylpentane & 2,4-dimethylpentane as
secondary products
C CH
2
C H
3
C H
3
+
H
+
C
+
CH
3
C H
3
C H
3
C
+
CH
3
CH
3
C H
3
CH
CH
3
CH
3
C H
3
+
H
+
C
CH
3
CH
3
C H
3
CH CH
3
CH
3
CH
2
+
Operating Variables & Their Effects
Operating Variables & Their Effects
Capacity expressed in terms of alkylate product, not feed
capacity
Most important variables
Type of olefin
Propylene, butylene, or pentene
Isobutane concentration
Olefin injection & mixing
Reaction temperature
Catalyst type & strength
Critical measures for success
Alkylate octane number
Volume olefin & isobutane consumed per volume alkylate produced
Degree of undesirable side reactions
Acid consumption
Type of Olefin
Type of Olefin
Butylene preferred
Produces the highest isooctane levels
Resulting Research Octane Numbers of 93-95 (with isobutane)
RON and MON are about equal for alkylation
Amounts of butylene consumed per alkylate produced is the lowest
Side reactions are limited
Propylene worse
Octane numbers are low (89-92 RON)
Propylene & acid consumption are high
Pentene results are mixed
Side reactions frequent
Isobutane
Isobutane
concentration
concentration
Excess isobutane required normal volume ratio of isobutane
to olefin in the feed is 6-10
Limited isobutane solubility in acid phase
Olefins need to be surrounded by isobutane exposed to acid if
not, olefins will polymerize instead of alkylate
Newer plants have multi-injection & vigorous mixing systems
Effect of isobutane is expressed in terms of concentration in the
reaction zone
Isobutane to olefin ratios maintained at 10,000 to 1
Isobutane
Isobutane
/Olefin Injection & Mixing
/Olefin Injection & Mixing
More important in sulfuric acid systems
Acid viscosity at operating temperatures
Provide optimal reaction conditions for the very fast reaction
Inject olefin feedstock in incremental fashion to increase
isobutane/olefin ratios
Newer plants designed for multi-injection locations into an agitated
emulsion to disperse olefin as rapidly as possible
Systems with single point injection can easily have an overload
of olefin in the emulsion
Leads to lower quality & higher acid consumption from
esterification reactions
Reaction Temperature
Reaction Temperature
Most noticeable variable in both reaction systems
Increasing temperature reduces octane number
HF systems run at 95F
Sulfuric acid systems run at 45F
Often employ auto refrigeration of the reactant mass to provide
coolant for the reactors
Acid Type & Strength
Acid Type & Strength
HF acid strength is not an important variable in the range of 80%
to 95%
Sulfuric acid strength is somewhat a function of the diluent
Water lowers acid activity 3 to 5 times as fast as hydrocarbon
diluents
Acid is considered "spent" at around 88% sulfuric acid
Sulfuric vs. HF Acid Alkylation
Sulfuric vs. HF Acid Alkylation
Principal difference is operating temperature
Sulfuric acid alkylation refrigeration required
HF alkylation can operate at cooling water temperatures
Sulfuric acid alkylation is dominant process
Sulfuric acid plants require extensive recuperation of the spent acid
generally done off-site
Larger coastal refiners tend to have sulfuric acid alkylation plants
with barge or short haul transportation to acid regeneration
facilities
HF plants generally smaller & catalyst regeneration is done in-
plant with a small acid makeup
Urban community concerns to hazards of HF escape
Sulfuric Acid Alkylation
Sulfuric Acid Alkylation
Refining Overview Petroleum Processes & Products,
by Freeman Self, Ed Ekholm, & Keith Bowers, AIChE CD-ROM, 2000
Time Tank Reactors
Time Tank Reactors
Refining Overview Petroleum Processes & Products,
by Freeman Self, Ed Ekholm, & Keith Bowers, AIChE CD-ROM, 2000
Autorefrigerated
Autorefrigerated
Reactor Sulfuric Acid
Reactor Sulfuric Acid
Alkylation (EMRE)
Alkylation (EMRE)
Refining Overview Petroleum Processes & Products,
by Freeman Self, Ed Ekholm, & Keith Bowers, AIChE CD-ROM, 2000
STRATCO Reactor Sulfuric Acid
STRATCO Reactor Sulfuric Acid
Alkylation (DuPont)
Alkylation (DuPont)
Refining Overview Petroleum Processes & Products,
by Freeman Self, Ed Ekholm, & Keith Bowers, AIChE CD-ROM, 2000
HF Alkylation System
HF Alkylation System
Differences to sulfuric acid systems
Feed driers essential to minimize catalyst consumption
Water forms an azeotrope with HF leading to acid loss
HF stripper required on depropanizer overhead to clean up propane for LPG
HF regenerator operating on a slip stream from acid settler
Many acid soluble organic compounds decompose but some must be rejected as
acid soluble oil
Spent acid requires special neutralization
Convert HF to calcium fluoride & burnable waste
Overall acid loss should be less than one pound per barrel of acid produced
Elaborate HF venting, neutralization & recovery system
Considered by the public to be a threat in terms of large releases of HF
New designs minimize the inventory of HF in the unit far below earlier
designs
Risk is minimized, not eliminated
Phillips Alkylation Process
Phillips Alkylation Process
Handbook of Petroleum Refining Processes
Robert Meyers
McGraw-Hill, Inc, 1986
Phillips Alkylation Process
Phillips Alkylation Process
Component Olefin Feed
Saturated
Butanes
Propane Yield
Motor-Fuel
Butane Yield
Motor-Fuel
Alylate Yield
Acid Oils
Ethane 0.49 0.49
Propylene 21.04
Propane 17.42 0.30 18.77
Isobutane 191.81 13.48 0.34 3.13 0.19
Butenes 169.10
n-Butane 63.17 10.11 63.35 9.93
Pentanes 4.90 0.42 3.67 1.65
Alkylate 390.17
Acid Oils 0.55
Total 467.93 24.31 19.60 70.15 401.94 0.55
Stream Totals 492.24 492.24
RVP [psi] 6.0
Specific Gravity 0.70
RON, clear 95.0
MON, clear 93.5
FBP [

C] 195
FBP [

F] 383