PRESENTATION MATERIAL FOR

ISOMERISATION,
PLATFORMING, AND ALKYLATION

Bandung, 20 April 2011

Crude Distillation Column

Desalter
Vacuum Distillation Column

Desalter

Vacuum
Gas Oils
Vapor Recovery Units
Saturate Vapor
Recovery

Sulfur Removal

Sulfur Removal

Unsaturate Vapor
Recovery

Desalter

Vacuum
Gas Oils
Hydrotreating Units
Saturate Vapor
Recovery

Sulfur Removal

Hydrotreating
Unit

Sulfur Removal

Hydrotreating
Unit

Hydrotreating
Unit

Hydrotreating
Unit

Unsaturate Vapor
Recovery

Hydrotreating
Unit

Desalter

Vacuum
Gas Oils
Catalytic Reformer
Saturate Vapor
Recovery

Sulfur Removal

Hydrotreating
Unit

Sulfur Removal

Hydrotreating Catalytic
Unit Reformer

Hydrotreating
Unit

Hydrotreating
Unit

Unsaturate Vapor
Recovery

Hydrotreating
Unit

Desalter

Vacuum
Gas Oils
Isomerization Unit
Saturate Vapor
Recovery

Sulfur Removal

Hydrotreating C5/C6
Unit Isomerization

Sulfur Removal

Hydrotreating Catalytic
Unit Reformer

Hydrotreating
Unit

Hydrotreating
Unit

Unsaturate Vapor
Recovery

Hydrotreating
Unit

Desalter

Vacuum
Gas Oils
Fluid Catalytic Cracking Unit
Saturate Vapor
Recovery

Sulfur Removal

Hydrotreating C5/C6
Unit Isomerization

Sulfur Removal

Hydrotreating Catalytic
Unit Reformer

Hydrotreating
Unit

Hydrotreating
Unit

Fluid Catalytic Unsaturate Vapor

Cracking Unit Recovery

Hydrotreating
Unit

Desalter

Vacuum
Gas Oils
Hydrocracking Unit
Saturate Vapor
Recovery

Sulfur Removal

Hydrotreating C5/C6
Unit Isomerization

Sulfur Removal

Hydrotreating Catalytic
Unit Reformer

Hydrotreating
Unit

Hydrotreating
Unit

Hydrocracking
Unit

Fluid Catalytic Unsaturate Vapor

Cracking Unit Recovery

Hydrotreating
Unit

Desalter

Vacuum
Gas Oils
Alkylation Unit
Saturate Vapor
Recovery

Sulfur Removal

Hydrotreating C5/C6
Unit Isomerization

Sulfur Removal

Hydrotreating Catalytic
Unit Reformer

Hydrotreating
Unit

Hydrotreating
Unit

Hydrocracking
Unit Alkylation

Catalytic
Condensation
Fluid Catalytic Unsaturate Vapor
Cracking Unit Recovery

Hydrotreating
Unit

Desalter

Vacuum
Gas Oils
Residual Units
Saturate Vapor
Recovery

Sulfur Removal

Hydrotreating C5/C6
Unit Isomerization

Sulfur Removal

Hydrotreating Catalytic
Unit Reformer

Hydrotreating
Unit

Hydrotreating
Unit

Hydrocracking
Unit Alkylation

Catalytic
Condensation
Fluid Catalytic Unsaturate Vapor
Cracking Unit Recovery

Hydrotreating
Unit

Desalter
Visbreaking
Vacuum Thermal Cracking
Gas Oils

Asphalt
Asphalt
Oxidation
Coking Unit
Saturate Vapor
Recovery

Sulfur Removal

Hydrotreating C5/C6
Unit Isomerization

Sulfur Removal

Hydrotreating Catalytic
Unit Reformer

Hydrotreating
Unit

Hydrotreating
Unit

Hydrocracking
Unit Alkylation

Catalytic
Condensation
Fluid Catalytic Unsaturate Vapor
Cracking Unit Recovery

Hydrotreating
Unit

Desalter

Coking
Vacuum
Gas Oils
Focus of Discussion
Saturate Vapor
Recovery

Sulfur Removal

Hydrotreating C5/C6
Unit Isomerization

Sulfur Removal

Hydrotreating Catalytic
Unit Reformer

Hydrotreating
Unit

Hydrotreating
Unit

Hydrocracking
Unit Alkylation

Catalytic
Condensation
Fluid Catalytic Unsaturate Vapor
Cracking Unit Recovery

Hydrotreating
Unit

Desalter

Coking
Vacuum
Gas Oils
Paraffin
Isomerization
Paraffin Isomerization Background
• WWII requirement for iso-butane for alkylation
• 1941 – 1st unit based on Friedel-Craft chemistry
– Used corrosive aluminum chloride catalyst
– High costly maintenance
– 38 units fulfilled needs of the time
• 1950s – Development of high temperature dual function,
reforming-like catalyst systems
• 1959 – 1st C4 unit based on low temperature dual
function catalyst systems
• 1969 – 1st C5/C6 unit;
• 1970s - Industry-wide lead reduction created need to
upgrade C5-C6 octane.
• 2000s – Benzene reduction added benefit
Paraffin Isomerization
• Conversion of normal paraffins to iso-paraffins is
one type of isomerization
• Principal application of isomerization is the
conversion of normal C4, C5 and C6 material
• Butane (C4) Isomerization provides iso-butane
feed to an alkylation process or MTBE Complex
• Pentane (C5) – Hexane (C6) Isomerization
provides higher octane (82-91 RONC)
components to the gasoline pool
– Gasoline is less aromatic when C5/C6 isomers are added
– Benzene saturation side reaction helps meet aromatic
concentration standards
Component Blended Octane Values
Co mpo ne nt RONC MONC
iC4 100 .2 97 .6
nC4 95.0 93 .5
iC5 93.5 89 .5
nC5 61.7 61 .3
Cyc lo pe ntane 102 .3 85 .0
22 DMB 94.0 95 .5
23 DMB 105 .0 10 4.3
2 MP 74.4 74 .9
3 MP 75.5 76 .0
nC6 31.0 30 .0
MCP 96.0 85 .0
Cyc lo he xane 84.0 77 .2
Be nze ne 120 .0 11 4.8
Fe e d C7 - 55.0 55 .0
C5 - C6 Isomerization Terms

• Product Ratios, wt% or mol%

– iC5/C5P = iC5/(iC5+nC5) x 100%
– 2,2DMB/C6P = 2,2DMB/C6 Paraffins x 100%
– 2,3DMB/C6P = 2,3 DMB/C6 Paraffins x 100%
– C6 Paraffins = 2,2DMB + 2,3DMB + MP + MCP + CH + nC6

• PIN (Paraffin Isomerization Number), wt%

– Σ (iC5/C5P + 2,2DMB/C6P + 2,3DMB/C6P)

• Feed X-factor, wt%

– Σ (MCP + CH + BZ + C7+)
Component Iso Ratios

Lt SR Naphtha Product
Octane 72 RONC 83 RONC

iC5/C5P 40 77
22 DMB/C6P 2 32
23 DMB/C6P 5 10
2 MP/C6P 31 30
3 MP/C6P 19 17
nC6/C6P 43 11
C5 - C6 Isomerization Process Benefits

• High C5+ product yields (99-100 volume%)

• 100% benzene saturation
• Low severity reactor operations
– Typical: 450 psig (31.5 kg/cm2(g))
– 250-400°F (120-204C)
• Excellent catalyst stability
– Up to 10-15 year catalyst lives
• Capable of processing wide range of feedstocks
Isomerization Feedstocks

• C4 Isomerization
– Vapor Recovery Unit Butane
– Alkylation Product Butane
• C5/C6 Isomerization
– Light Straight Run Naphtha
– Feed Fractionation
• Feed should consist of C5 and C6
material
• C7 material should be kept to a
minimum
Chemistry

• Isomerization
• Benzene Saturation
• Ring Opening
• Hydrocracking

Reactions take place over a dual function catalyst

- Metal function (platinum)
- Acid function (chloride)
Isomerization Reactions
C
C-C-C-C C-C-C
n-Butane (nC4) Isobutane (iC4)

C
C-C-C-C-C C-C-C-C
n-Pentane (nC5) Isopentane (iC5)
61.7 RON 93.5 RON

Cyclohexane (CH) Methylcyclopentane

84.0 RON (MCP)
96.0 RON
Isomerization Reactions
C C
C-C-C-C-C C-C-C-C-C
2-Methylpentane (2MP) 3-Methylpentane (3MP)
74.4 RON 75.5 RON

C-C-C-C-C-C
n-hexane (nC6)
31.0 RON
C C
C-C-C-C C-C-C-C
C C
2,2-Dimethylbutane (2,2DMB) 2,3-Dimethlybutane (2,3DMB)
93.5 RON 105.0 RON
Isomerization Reactions

• Requires metal and acid functions

• Equilibrium limited
• Slightly exothermic
• No hydrogen consumed
• Increases octane
Benzene Saturation
• Benzene saturates to cyclohexane
• Cyclohexane (CH) in equilibrium with
methylcyclopentane (MCP)

100% 40-60% C
3H2 +
Pt
Benzene Cyclohexane MCPentane
120.0 RON 84.0 RON 96.0 RON
Benzene Saturation Reaction

• Immediate with platinum sites and presence of hydrogen

• No acid sites required
• 100% complete
• Highly exothermic (25x isomerization, 5x hydrocracking)
• Consumes 3 moles H2 per mole of benzene
• Reduces octane (120 Bz  84 CH & 96 MCP)
• Limit Bz in feed to ~5 vol%
– ~20ºF (11ºC) rx bed deltaT / 1 vol% Bz
– ~100ºF (55ºC) total deltaT / reactor
DT 1
DT 2
Lead Rx DT 3
DT 4
Ring Opening Reactions

• CH and MCP open to C6 paraffins

• Cyclohexane (CH) in equilibrium with
methylcyclopentane (MCP)

C-C-C-C-C-C

30% 30%

100% 40-60% C
3H2 +
Pt
Benzene Cyclohexane MCPentane
120.0 RON 84.0 RON 96.0 RON
Ring Opening Reactions

• Competes for the platinum sites

• Moderately exothermic
• 20-40 wt% opening
• Consumes 1 moles H2 per mole of ring opened
• Reduces octane
• Necessary to prevent cyclic buildup with DIH
• Increases with lead reactor temperature increases
• Higher temperatures favor MCP
Hydrocracking

• Longer chain molecules break to smaller ones

C C
R-C-C-C + H2 R-H + C-C-C
H
Hydrocracking
• Triggered by high reactor temperatures and catalyst
acid sites
• Exothermic
• Consumes 1 moles H2 per mole of cracked material
• C5 and C6 paraffin hydrocracking is minimal
• About 50% of C7+ paraffins hydrocrack to C4 and C3
paraffins
• C5+ yield loss
• Caused by:
– Higher C7+ in feed
– Higher rx temperatures pushing equilibrium
– Temperature excursion
Isomerization Catalyst
• Dual function catalyst (metal/acid)
– Metal is always platinum
– Acid is always chloride
• Metal impregnated on a high surface area alumina-oxide
• Active sites are bound alumina-chloride
• Gray extrudate or gray trilobe extrudate
Pt
Pt

Cl Cl

• Dual function balance is maintained by:

– Perchloroethylene injection
• Sensitive to contaminants and non-regenerable
Catalyst Promotor - Chloride
• Continuous chloride injection required to maintain
activity.
- Hydrogen and hydrocarbon can strip bound chlorides
from the catalyst if the partial pressure of chloride
surrounding the catalyst is too low.
• Low or loss of chloride injection will permanently
deactivate the catalyst.

H+Cl- C5
C6 H2

Cl- Cl-
Cl Cl-
Cl-
Cl-
C5, C6, H2, HCl
Reactor Feed Contaminants
Contaminant Effect Limit

Total sulfur Attenuates metal activity, reduces 0.1 wtppm max.

benzene saturation, reversible

Nitrogen Neutralizes acid sites, deactivates 0.1 wtppm max.

Organic/Basic catalyst, irreversible; NH4Cl fouling

Water Removes bound chloride, blocks 0.1 wtppm max.

active sites, plug flow, irreversible
1 lb H2O kills 100 lb catalyst
Oxygenates OH groups displace Cl, neutralizes 0.1 wtppm max.
acid site, irreversible

Fluorides Displaces chloride, less acidic, 0.1 wtppm max.

irreversible (very rare)

Metals Block active sites, attach Pt, plug ppb

flow, irreversible (Mercury, Co, Ni)
Makeup Gas Contaminants
Contaminant Effect Limit

Sulfur (H2S) Attenuates metal activity, reduces 1 molppm

benzene saturation, reversible

Nitrogen Neutralizes acid sites, deactivates 0.5 molppm

Organic catalyst, irreversible; NH4Cl fouling

Water Removes bound chloride, blocks 0.1 volppm

active sites, plug flow, irreversible
1 lb H2O kills 100 lb catalyst
CO + CO2 CO2 irreversibly adsorbs on drier 10 molppm max.
sieve hence higher spec, less
reactive than CO on catalyst
CO Attaches to metal, similar to sulfur, 1 molppm max.
eventually methanates with H2,
somewhat reversible
Chloride (HCl) Adsorbs on drier sieve, irreversible 0.5 molppm

Note: Limits at drier inlet except water spec

Contaminants – Final Words
• CO/CO2 & HCl are the most common makeup gas
problems
• Cyclics can act as temporary poison
– Adsorbs on the catalyst
– Inhibits isomerization equilibrium & hence conversion
– Monitor X-factor

WATER, WATER,
WATER!
Water Ingress Mitigation Techniques
• Acidizing of all equipment in the reactor circuit
• Dry nitrogen blanketing of reactor circuit equipment
– If exposed to air during maintenance, must be re-acidized
• Tube rolling and strength welding to charge heater
exchanger tubesheet
• Catalyst handling & loading under inert atmosphere
• All liquid feed MUST be charged directly from NHT
stripper bottoms or naphtha splitter overhead after NHT
• Regenerative driers on makeup gas and feed streams
• Moisture analyzers between lead & lag driers.
• Dry hydrogen as feed surge drum pressure medium
Prevention is much easier than curing the problem
Isomerization Unit Basics
• Feed and makeup hydrogen driers
• Switchable lead/lag reactors
• Reactions under nominal hydrogen atmosphere
– Isomerization reaction hydrogen neutral
• Exothermic equilibrium and saturation reactions
require inter-reactor cooling
• To maintain product quality, severity (temperature)
must be gradually increased
– Performance gradually deteriorates
– Catalyst non-regenerable
• Fractionation (stabilizer) to remove acid gas
Butane Isomerization Process
(UOP Hydrogen Once Through Butamer)

MU Gas
Driers

Make-up
Hydrogen Gas to Scrubbing
and Fuel
Steam
Reactors Condenser

Receiver

C2Cl4

Stabilizer

Liquid
Driers Reboiler

Isomerate
Treated Butanes
Pentane-Hexane Isomerization
(UOP Hydrogen Once Through Penex)

MU Gas
Driers

Make-up
Steam Hydrogen Receiver
Heater
Reactors Scrubber
Gas
to Fuel

C2Cl4

HCFE
Stabilizer
CCFE

Reboiler

Liquid Fresh/Spent
Driers Caustic
Surge
Drum
Isomerate
Light
Naphtha
Pentane-Hexane Isomerization
(UOP Recycle Gas Penex)

MU Gas
Driers

Make-up
Steam Hydrogen Receiver
Heater
Reactors Scrubber
Gas
to Fuel

C2Cl4

HCFE
Stabilizer
CCFE

Reboiler

Liquid Fresh/Spent
Driers Caustic
Surge
Drum
Isomerate
Light
Naphtha
Pentane-Hexane Isomerization with DIH
MU Gas
Driers H.O.T. Penex Deisohexanizer (DIH)
Make-up
Steam Hydrogen Receiver Overhead
Heater C5p, DMB
Reactors Scrubber
Gas
to Fuel
LP Stm
C2Cl4
Product
Side Draw
HCFE CCFE Stabilizer MPs, n-C6

Reboiler
Liquid Fresh/Spent
Driers Caustic Bottoms
Surge
C7+, min n-C6
Drum Isomerate
Light
Naphtha

Increased Octane – More C6 isomers produced

Better for RVP limits
Increases LHSV – recycle offsets
Light Naphtha - Fractionation
Component Boiling Point F [C] Relative
Volatility
iC5 82 [28] 3.18
nC5 97 [36] 2.71
22 DMB 122 [50] 1.90
23 DMB 136 [58] 1.59
2 MP 140 [60] 1.53
3 MP 146 [63] 1.42
nC6 156 [69] 1.26
MCP 161 [72] 1.21
Bz 176 [80] 1.25
CH 177 [81] 1.00
Process Variables

C4 Unit C5/C6 Unit

Pressure 500 psig 250-500 psig
(34 bars) (17-34 bars)
Temperature 300-350F 280-330F
(150-175C) (138-166C)
H2/HCBN Ratio 0.05 mol/mol 0.05 mol/mol
At Outlet At Outlet
LHSV, hr-1 2-4 1-4
Chloride Promotor ~150 wt ppm ~150 wt ppm
Paraffin Isomerization
Process Variables

• Reactor Temperature
– Main process variable
– Higher iso ratio (octane) possible at lower temperature
– Reaction rate faster at higher temperature
– Higher temperature increases cracking and reduces
catalyst life
– Lead reactor outlet temperature runs higher than lag
reactor outlet temperature
 Equilibrium Curves
100

Lead Rx
Lag Rx
iC5/C5P
80
Product Ratios (mol%)

iC4/C4P

60 P + C H)
C
M CP/(M (2MP+3MP)/C6P

40
2 - 2 D M B /C 6 P

20 nC6/C6P
2-3 DMB/C6P

0 121 C 149 C 177 C

200 250 300 350 400
Temperature (F)
Octanes of Equilibrium Mixtures

90

Lead Rx
Lag Rx
88
86 C5 Para
ffins
84
82 Total C
RON

-C6
80 5

78
C6 Pa
76 raffin
s
74
72 302ºF 392ºF
70
100 150 200 250 300
Temperature, °C
IC5/C5 PARAFFINS PRODUCT RATIO, Wt% Lead and Lag Rx IC5 Product Ratio

IC5
77
Pro duct
Rati
SOR o Equi
li br i u
72 EOR
m
SOR

45 EOR

Feed (Minimum)
116 C 167 C 204 C
240 330 350 400
Reactor Outlet Temperature, F
Reactor Temperature Profile
Example
160

150
Temperature, C

140

130

120

110

100
t

t
t

le
le
le

le
In

In
ut

ut
O

O
A

B
A

B
Paraffin Isomerization
Variations

© 2006 UOP LLC. All rights reserved.

 Isomerization Octane Portfolio

95 91
88 89
90
85
85 81
80
RONC

75 Re c ycle
60-70 ocar bon
Hy dr
70 hr ough
T
65 Once

60
55
Light Par Isom Penex Penex Penex DIP Penex
Naphtha DIH Molex DIH
Feed
Relative Erected Costs
Isomerization Flow Schemes

3.0

2.5
Relative Erected Cost

2.0

1.5

1.0

0.5

0
Par- Penex Penex Penex DIP/Penex/
Isom / Molex DIH
DIH
Catalytic Reforming

© 2006 UOP LLC. All rights reserved.

History
• Development during and after WWII
• Commercialized in 1949 to meet increase demand for
motor fuel post-WWII
– Mono-metallic catalyst (platinum)
• Bi-metallic catalyst introduced in 1969
• Continuous catalyst regeneration (CCR) introduced in
1970
• Licensees have different names but all are reforming
processes
Catalytic Reforming

• Catalytic reforming upgrades low octane naphthas to

higher octane motor fuel by promoting specific groups
of chemical reactions, primarily to produce high octane
aromatics
• Reforming is the mainstay of almost all fuels refineries
• Originally, reformate was used to upgrade the gasoline
pool
• Today the reforming process is also designed to
produce specific aromatic hydrocarbons for use in the
petrochemical industry
• High purity hydrogen and LPG are important and
valuable byproducts
Process Feedstocks
Processes feed stocks from various sources

Contaminates Hydrogen

S.R. Naph. Lt. HCBN

FCC Naph. Hydrotreater

Reformer
T.C. Naph.
Coker Naph. Reformate
H.C. Naph.
Feedstock Properties

• Feed is normally a C6 to C11 fraction for motor fuel

applications
– 170-400F (77-204C) D-86 Distillation Range
– Sulfur 0.25-0.5 wt-ppm min
– Nitrogen less than 0.5 wt-ppm
– No olefins, metals, halides or oxygenates
• Narrow range, e.g. C6-C8, for petrochemical applications
• Difficulty of reforming basically set by distillation and
PONA (paraffins, olefins, naphthenes, aromatics)
– Lean naphtha
• High paraffin, low naphthene content
– Rich naphtha
• Low paraffin, high naphthene content
Feed Type Impact on Product Yield

• Conversion of lean and rich naphthas to moderate octane

reformates at constant operating conditions

Lean Rich
Naphtha Reformate Naphtha Reformate

} Loss
P
} Loss
P P
P N
N } From P

N
A
} From P
} From N
N A } From N

A } From A A } From A
Legend
P = Paraffins Loss: Due to both cracking and
N = Naphthenes shrinkage
A = Aromatics
Reforming Chemistry
• Aromatics
– Pass essentially unchanged through the reactors
• Naphthenes
– Almost complete conversion to aromatics, above 90 RONC
– Cyclohexanes easier to convert than cyclopentanes
• Paraffins
– Some conversion to aromatics
– Some isomerization to more highly branched isomers
– Some cracking
– Many remain in product as paraffins
• Difficulty generally increases with decreasing number
of carbon atoms

RONC = Research Octane Number, Clear

Reforming Catalyst
• Dual function catalyst (metal/acid)
– Metal is always platinum
– Acid is almost always chloride
• Other metals usually added for stability and/or yield
improvement
• Metals impregnated on a high surface area alumina-
oxide base. Bases are usually 1/16-1/8 inch (1.6-3.2
mm) diameter spheres or extrudates of various
configurations and lengths.
• Regenerable
• Dual function balance maintained by:
– Water-chloride control
– Regeneration technique
Reforming Reactions

• Naphthene dehydrogenation
• Naphthene isomerization
• Paraffin isomerization
• Paraffin dehydrocyclization
• Hydrocracking
• Demethylation
• Aromatic dealkylation
Naphthene Dehydrogenation

R R
S + 3H2

• Formation of an aromatic from cyclohexanes

• Reaction is easy and very rapid
• Reaction is very endothermic (consumes heat)
• Hydrogen is produced
• Reaction is promoted by the catalyst metal function
• Reaction favored by high temperature and low pressure
Naphthene Isomerization

R R'
S S

• Enables N5 napthenes to convert to aromatics

• Naphthene isomerization converts branched
alkylcyclopentanes to alkylcyclohexanes, then to aromatics
• Ring opening occurs, so paraffins may be produced
• Reaction is promoted by both acid and metal functions
• Reaction favored by low temperatures; little pressure influence.
Paraffin Isomerization

C
R-C-C-C-C-C-C R-C-C-C-C-C

• Paraffin isomerization occurs readily

• Branched isomers are higher in octane than straight chained
molecules
• Reaction is slightly exothermic and equilibrium limited
• Hydrogen neutral
• Reaction is promoted by both acid and metal functions
• Reaction favored by low temperatures; little pressure influence.
– Low temperatures favor higher iso-/normal ratios
– Higher temperatures increase the reaction rate
Paraffin Dehydrocyclization
S R'
+ H2

R-C-C-C-C-C-C
R"
S
+ H2
• Ring closure - conversion of paraffins to naphthenes
– Required for conversion of paraffins to aromatics
• Slowest and most difficult reforming reaction to promote
• Reaction is endothermic
• Hydrogen in produced
• Reaction promoted by both acid and metal functions
• Reaction favored by high temperature and low pressure
Hydrocracking

C C
R – C – C – C + H2 RH + C – C – C
H
• Splitting of longer, chained molecules into shorter, lighter
compounds
– Reduces reformate yield
– Increases light ends yield
– Serves to concentrate aromatics; therefore, increases octane
• Reaction is exothermic and hydrogen is consumed
• Reaction is promoted by the catalyst acid function
• Reaction favored by high temperatures and pressures
Demethylation
R–C–C–C–C + H2 R–C–C–CH + CH4
and
R-C RH
+ H2 + CH4

• Removal of methyl groups from branched compounds

• Only occurs in severe operations or on initial startup
• Reaction is exothermic and consumes hydrogen
• Promoted by the catalyst metal function
• Reaction favored by high temperature and pressure
Aromatic Dealkylation

R R'
+ H2 + R"

• Removal or splitting of alkyl groups from aromatic

compounds
• Reaction is exothermic and consumes hydrogen
• Promoted by the catalyst acid and metal functions
• Reaction favored by high temperature and pressure
 Reaction Scheme

N-Paraffins
M or A M/A
A M M or A Lighter
Cracked A Cyclopentanes Cyclohexanes Aromatics Aromatics
Products

M or A M/A Dealkylation
Naphthene and
Isoparaf fins Dehydrogenation
Isomerization Demethylation
I II III Predominant Active Sites: A = Acid M = Metal

Legend:

I = Hydrocracking and Demethylation (M) II = Paraf fin Isomerization III = Dehydrocyclization

Metal/Acid Sites – for dehydrocyclization, hydrocracking, dealkylation

Properly Balanced Catalyst

Desired
Metal-Acid
Balance
(Pt) (Cl)
Increasing Metal Increasing Acid
Function Function
Demethylation Cracking

Dehydrogenation
Dehydrocyclization
Isomerization
Reactor Feed Contaminants
Contaminant Effect Limit

Total sulfur Attenuates metal activity, suppresses 0.25-0.5 wtppm min

dehydrogenation, reversible

Total Nitrogen Neutralizes acid sites, deactivates 0.5 wtppm max

catalyst, irreversible; NH4Cl fouling

Water Affects water/chloride balance ~1 wtppm

Oxygen (Dissolved Forms water, affects water/chloride 2 ppm as oxygen

and Combined) balance

Fluorides Displaces chloride, less acidic, <0.5 wtppm

irreversible

Metals Block active sites, attach Pt, plug ppb

flow, irreversible (Arsenic, Pb, Cu)
Catalytic Reforming Basics
• Multiple reactors in series
• Reactions under hydrogen atmosphere
– Hydrogen producer
• Endothermic reactions require inter-reactor heaters
• To maintain product quality, severity (temperature)
must be gradually increased
– Performance gradually deteriorates
– Catalyst regeneration periodically required to return catalyst
quality back to acceptable levels
• Fractionation (stabilizer or debutanizer) to ‘stabilize’
products
– Gasoline RVP adjustment
Types of Reforming Process Units

• Fixed Bed (semi-regen unit)

– Unit must be shut down and complete catalyst
inventory is regenerated
• Cyclic Reformer
– Catalyst is regenerated one reactor at a time
– Unit is on stream continuously
• CCR Platforming Unit
– Continuous Catalyst Regeneration
– Unit is on stream continuously
Fixed-Bed
Semi-Regeneration Reforming

• Catalyst is stationary in separate reactors

• Reactors are normally separate and in series
• A high H2/HC ratio is used
– Typically between 6-9 mol/mol
• Moderate to high pressure
– 300 to 600 psig (21 to 42 bars)
• Water/chloride injections used to balance
catalyst performance
Fixed-Bed
Semi-Regeneration Reforming

Reactors Combined Net Gas

Feed
Fuel Gas
Exchanger

Separator

H2O/Cl-
LPG
H H H
Injection Debutanizer

Feed
H
Reformate
Cyclic Catalytic Reforming

Flue Gas

H2-Rich Gas
Swing Reactor Reactor Reactor
Reactor
Overhead

Air

Inert Gas
Furnace
Separator
Pretreated
Naphtha
Furnace Furnace Furnace
Reformate
UOP CCR Platforming Unit
• Catalyst is circulated through the reactor and
regenerator sections
– Reactors are stacked with free flowing piping between them
– Special equipment used to transport catalyst
• Constant regeneration means a constant catalyst
performance throughout most of its life
• Operations at more severe conditions
– Lower pressure, less catalyst, higher
temperatures, less hydrogen circulation,
higher octane
• Reformate product is high quality and
consistent
– More hydrogen produced and at higher purity
 UOP CCR Platforming Unit
with Two-Stage Counter-Current Recontact

Fresh Net Gas

Catalyst Combined
Feed
Exchanger
R R
C C
S
E
P

Stacked
Reactors

REC
H H H Feed
Spent LPG
Catalyst Debutanizer

Legend
RC = Recontact Drum
REC = Receiver
CON = Convection Section Reformate CON H
UOP CCR Platforming Unit
Atmospheric Catalyst Regeneration Section
Fines Dust
Removal Collector
Blower
Lift Gas
Blower
Reduction Disengaging
Zone Hopper
Regeneration
Platforming Tower Flow
Reactors Control
Catalyst Catalyst Hopper
Lift Lines Catalyst
Collector Addition
Surge Hopper
Hopper Lock
Lock Hopper
Hopper No. 2
No. 1 Lift
Engager
Nitrogen No. 2
Lift Lift Gas Hydrogen Lift Gas
Engager
No. 1
UOP CCR Platforming Unit
CycleMax Regeneration Section
Dust
Special
Collector
Elbows

Reduction Disengaging
Zone Hopper

Regeneration
Tower
Reactors

Nitrogen N2 Seal Drum

Isolation
Valves
Lock
Catalyst
Hopper
Collector
Catalyst
Isolation
Addition Valves
Hopper
N2 Lift Gas Booster
Gas
L-Valve Assemblies Lift Gas
Process Variables
• Feed Stock Quality
– Boiling range – 170-400F (77-204C) D-86
– Paraffin/naphthene/aromatic content (PNA)
• Catalyst Type
• Reactor Temperature
– 890-1020F (477-550C)
– Mostly endothermic reactions
• Space Velocity
– 0.8-3.0 hr-1
• Reactor Pressure
– 50-600 psig (3.4-42 bars)
• H2/HC Ratio
– 2-9 mol/mol
Feed Type Impact on Product Yield

• Conversion of lean and rich naphthas to moderate

octane reformates at constant operating conditions

Lean Rich
Naphtha Reformate Naphtha Reformate

} Loss P
} Loss
P P
P N
N } From P

N
A
} From P
} From N
N A } From N

A } From A A } From A
Legend
P = Paraffins Loss: Due to both cracking and
N = Naphthenes shrinkage
A = Aromatics
 Octane-Barrel Yield Response to
Product Octane and Feed Composition

8,500
Octane - Barrel Yield

N + 2A = 80
per 100 BBL Feed

8,000

7,500 N + 2A = 60

7,000

(Pressure = Constant) N + 2A = 40
6,500
90 92 94 96 98 100 102 104
RONC
Reactor Temperature Profile

Inlet
-20
Temperature , °C(°F)

(-38)
-40
(-72)
-60
(-108)
-80
(-144)

0 0.1 0.25 0.5 1.0

Fraction of Total Catalyst
Hydrocarbon Types Conversion
Reactor Profile

60
Moles per 100 Moles of Feed

A
50

40 P
30

20

10 CP
CH
0
0.0 0.10 0.25 0.50 1.0
Fraction of Total Catalyst
Effect of Pressure on Yield Structure

100
Hydrogen
Product Yield, wt-%

90
C1 + C2 + C 3 + C 4

80

C5+ Reformate

70
0 143 285 428 570
(10) (20) (30) (40)
Pressure psig (kg/cm2)
Liquid Yield Variations with Pressure
Continuous vs. Fixed-Bed Reforming
Lean Middle East Naphtha 100 RONC
10
9 Continuous Reforming
Reactor C5 + ΔLV-% Yield

8
7
6
FB Reforming
5
4
3
2
1
0
100 150 200 250 300 350 400 450
(10.5) (14.1) (17.6) (21.1) (24.8) (28.1) (31.6)
Average Reactor Pressure, psig (kg/cm2)
“Perfect” Reformer
• Low pressure to max yields
• High catalyst activity to max octane and aromatics
• High on-stream factor
• CCR > cyclic > semi-regen
Catalyst Issues

• Contaminants
• Feedstock boiling range
• Water-chloride balance
• High temperatures
• Low space velocity
• Low H2/HC ratios
Summary – Reforming
• Complex high temperature process
• 3 types of reformers
• Mechanical issues include compressors,
heaters, fractionators, catalyst handling /
regeneration
• Critical to refinery profitability octane pool,
hydrogen system, aromatics sales
Alkylation Processes
Background

• Alkylation was developed during WWII to make aviation

gasoline
• Today its main purpose is to convert light ends into
gasoline
• The gasoline is ideal for ultra low sulfur and RFG
premium
– high MON
– low emissions – very low in sulfur, olefins, and aromatics
What is Alkylation?
• Alkylation combines C3-C5 olefins with iso-butane to
produce highly-branched, high-octane C7-C9
isoparaffins

• Reaction is catalyzed by strong acids

– HF
– H2SO4
– Solid catalysts (UOP Inalk, Alkylene)
– Superacids (BF3, HSO3F, HSO3CF3)
Alkylation Feeds

Mixed Propane
Butanes from
Hydrocracking, Reforming
n-Butane
And Crude Units

C3/C4 Olefin Alkylation Alkylate

Coker
Unit Product

C3/C4 Olefin
Rich Stream

FCC Feed FCC Butamer

FCC Products
(Gasoline, etc.)
Alkylate Product
• Ideal RFG Blending Component
– High Octane (RON & MON)
• C3=/C4= Feed
– 91-94 RON / 90-93 MON
• C4= Feed
– 94-96 RON / 92-94 MON
– No Aromatics
– No Olefins
– Low RVP
• 3 - 6 psig
• Highly Dependant on Fractionation (nC4,iC5)
– Low Sulfur
• 10-15% of Gasoline Pool
Primary Products and Octanes
Olefin Primary Products Research Motor
Propylene 2,3-Dimethylpentane 91 89
2,4-Dimethylpentane 83 84

Isobutylene 2,2,4-Trimethylpentane 100 100

Butene-2 2,2,3-Trimethylpentane 109 100

2,2,4-Trimethylpentane 100 100
2,3,3-Trimethylpentane 106 99
2,3,4-Trimethylpentane 103 96

Butene-1 2,2-Dimethylhexane 72 77
2,4-Dimethylhexane 65 70
2,3-Dimethylhexane 71 79

Pentenes 2,2,3,4-Tetramethylpentane
2,2,4-Trimethylhexane
2,2,5-Trimethylhexane 92 90
2,2,3-Trimethylhexane
2,3,4-Trimethylhexane
2,3-Dimethylheptane
2,4-Dimethylheptane
Chemistry

Alkylation Reaction:
C
C-C=C-C + C-C-C iC7-9 Alkylate
Olefin isobutane Acid

Hydrogen Transfer Reaction:

Olefin + 2 isobutane iC8 Alkylate + C3-C5 paraffins

• Olefins highly soluble in acid, isobutane sparingly so

• Reaction requires 6-15 fold excess isobutane for selectivity
• Two liquid phases (emulsion) in reactor, reaction occurs in acid phase
• Hydrogen transfer reaction makes iC8, which has higher octane
• However, it consumes more isobutane and makes light paraffins
• In HF alkylation, hydrogen transfer occurs for all olefins
• In H2SO4 alkylation, only for C5 and heavier olefins
Catalyst Selection

• The current commercial catalysts HF and H2SO4 each

have advantages and disadvantages
• Main difference in processes is reactor cooling
– HF uses cooling water
– H2SO4 uses integral refrigeration
• Feedstock, economics and safety control selection
Acid Selection Criteria

• Feedstock
HF better on C3= and iC4 =
H2SO4 better on C5 = and dirty feeds
• Size and Location
HF cheaper for small units
HF requires 1/40 as much acid shipping
H2SO4 more favorable with on-site acid plant
• Community Safety
H2SO4 does not form aerosols at alkylation conditions
HF safety requirements reduce its capital advantage
Alkylate RON for Feed Olefins

H2SO4 HF
C3= 89 91

1-C4= 96 91

2-C4= 96 97

iso-C4= 92 95

91 89
C5 =
Alkylation Yields

Sulfuric Acid Alkylation

C3Alkylate C4Alkylate C5Alkylate
iC4con/olefin (v/v) 1.27-1.32 1.1-1.16 0.96-1.14
Alkylate yield (v/volefin) 1.75-1.78 1.7-1.78 1.55-1.60
R+M/2 88-91 93-95 91-92
Acid con (#/bbl alky) 34-42 13-25 25-34

HF Acid Alkylation
C3Alkylate C4Alkylate C5Alkylate
iC4con/olefin (v/v) 1.33-1.41 1.14-1.16 1.17
Alkylate yield (C5+) 1.78 1.76 1.85
R+M/2 90-91 92-94 90-91
Acid con (#/bbl alky) 0.2 0.1 0.2
HF Acid Unit Features

• Good feedstock flexibility

• Low operating cost
• Lowest capital cost
• Low catalyst usage (0.1-0.2 lb/bbl product)
• 95F (35C) reactor temperature
• HF acid requires special attention
HF Processes

• Accounts for most of the recent new units

• Higher iC4 solubility in acid (2.7%)
• Does not require refrigeration, can use cooling water (T o=100oF)
• Mixing easy due to low interfacial tension
• Favored by small remote refiners because of poor availability of cheap
sulfuric acid
• Acid recovery by distillation at unit (rerun)
• Lower acid costs. Higher yield
• Consumes more iC4; makes propane, n-butane
• Requires dry feed (HF + H2O corrosive)
• Stripper column needed to separate HF from hydrocarbon products (HF is
1% soluble in hydrocarbon)
• Economically favored
• More toxic, corrosive
• Area dominated by safety issues
Sulfuric Acid Features
• C4 feeds make best alkylate
• Acid is handled more easily
• 50F (10°C) reactor temperature requires
refrigeration cooling
• Catalyst usage is higher and generally requires offsite
regeneration (13-42 lb/bbl product)
• Catalyst costs are usually higher
• Large quantities of acid are handled
Acid Properties

Sulfuric Acid HF Acid

• Boiling point 640oF at 1 atm
• Specific gravity 1.83
• Higher surface tension and
viscosity
• Isobutane only slightly soluble in
acid (0.1%)
• Less corrosive
• Sulfuric acid insoluble in
hydrocarbon phase
• $15-120/ton, depending on
location
• Boiling point 67oF at 1 atm
• Specific gravity 0.93
• Low surface tension and viscosity
• Isobutane solubility about 30 times
higher (2.7%)
• HF+water extremely corrosive
• HF acid about 1% soluble in
hydrocarbon phase
• $1,700/ton + processing costs
Advantages and Disadvantages of the Acids

Sulfuric Acid HF Acid

+ Higher Octane, less iC5 from
Pentenes
+ Non aerosoling
+ Less corrosive
+ Less product treating
+ Tolerates dirty feedstocks
- More Expensive to Build
- Requires refrigeration
- High Mixer HP Requirement
- Higher Catalyst Use and Cost
- Large Acid Requirement
- Higher Energy Use - Must remove HF, Fluorides from LPG
- Higher CO2 Make
+ Higher Octane and Yield from
Propylene, Isobutylene
+ Recoverable
Lower net catalyst cost
+ Cheaper to build
No refrigeration
Easier to mix
Favored for smaller units
- Forms Toxic Aerosols
(dominated by safety issues)
- More corrosive
Alkylation Processes
 Alkylation Process Concept

iC4

Olefin Effluent Propane

Reactor Settler
iC4
Distillation n-butane
Acid
Alkylate
H2SO4 Processes

• Exxon/Kellogg Cascade reactor, Kellogg Jet reactor,

and Stratco Contactor reactor.
• Accounts for 65% of the worldwide capacity
• Accounts for 60% of U.S. capacity
• Requires refrigeration (compressors)
• More mixing required
• Acid is less toxic
• Simpler feed treating
• Acid is insoluble in hydrocarbon product
• Acid recovery in acid plant (off-site or on-site)
 H2SO4 Processes

• Stratco Contactor reactor

- Refrigerated by flashing effluent through tubes in the
reactor
• Exxon/Kellogg and Amoco Cascade reactor
- Auto-refrigerated by allowing the reactor contents to
flash into compressor suction in multiple stages
• Older Kellogg Jet and Time Tank reactors
- Auto-refrigerated by one-stage flashing of reactor
contents
 Stratco Process
with Effluent Refrigeration
Propane 110 MBSD

3 MBSD
Suction Settler
Trap
Compressor Emulsion Acid Recycle
Depropanizer

170 MBSD

31 MBSD
Contactor
Effluent
Flash Drum
Pressure
Control Valve

60 MBSD Recycle Isobutane 28 MBSD

Refrigerant
Product Treating

DIB
and Distillation
Fresh Feed 52 MBSD 24 MBSD
H2SO4 Alkylation Process Variables

• Isobutane concentration
– Rx HC effluent > 50% or iC4/Olefin mol ratio > 7
– Higher values are highly desirable
– Might be limited by effluent pump design and condition
– Optimum depends on incremental energy and acid costs versus
octane value

• Temperature
– 35-55°F (2-13°C)
– T <35°F : acid carryover, high acid consumption
– T >55°F : high acid consumption, increased corrosion

• Mixing
– Maximize mixing as limited by acid carryover
H2SO4 Alkylation Process Variables
• Acidity
– Maximum octane occurs at 93-94 wt% for butylene feeds
– Optimum acidity depends on acid costs and octane value
– Keep >89% acidity in tail reactor. Units with excellent feed quality
and low water content can be at 88%
– Risk of acid runaway at <87%

• Olefin Space Velocity

– Olefin feed rate/reactor acid holdup. 0.2 - 0.6 hr-1
– Typically outside the control of the Alky unit
– Low is better. However, the economics of alkylate production
generally overrides.

• Emulsion Quality (Acid Fraction in Rx)

– Keep reactor emulsion at a minimum of 35 vol% acid
– Alkylate quality improves with increasing acid concentration and is at
a maximum at 65%
– Maximize acid recycle rate as limited by acid carryover
 HF Processes

• Phillips
- Gravity Acid Flow
• UOP
- Pumped Acid Flow
- Low Inventory
 UOP HF Alkylation Process
(Propylene & Butylenes)

Reactor Settler Isostripper Depropanizer HF

Stripper

iC4’s
Makeup

Water

Olefin Steam
Feed Acid
Regenerator

Recycle iC4
Acid Alumina
KOH Treaters Treater
Polymer and CBM
To Neutralization
KOH
Saturate C4’s
Treater
Alkylate Butane Propane
HF Alkylation Process Variables
• Reactor Temperature
– Significant influence on the octane number of the product
– All reactors are operated below 100F (38C)
– Higher temperatures lead to lower octane number, higher end points,
and excessive isobutane consumption
– Above 120F (50C) excessive side reactions occur
– Extremely low temperatures (below 60F or 16C) result in incomplete
alkylation

• Acid to Hydrocarbon Ratio

– Normally between 1:1 and 2:1
– Below 0.8:1, excess polymer forms and alkylation stops
– No advantage to operate above 2:1 for HF
 HF Alkylation Process Variables
• Isobutane to Olefin Mol Ratio
– iC4/Olefin > 8-14
– High iso-butane/olefin ratio promotes:
• Higher octane products
• Lower end points
• Suppression of tar products
– High iso-butane/olefin ratio cost energy

• Acid Strength
– Depends on unit design
• Type and quantity of contaminants
• Acid inventory
• Process operations
– Generally 85-90% (wt) HF
– Low acid strengths lead to incomplete alkylation
– Maintain H2O content < 1wt%
Process Contaminants

• Water or water forming compounds

• Sulfur compounds
• Nitrogen compounds
• Ethane, ethylene or non-condensables
• Diolefins
• Amylenes
• Affect acid consumption and regeneration, corrosion and
product quality
Reactor Feed Contaminants
Contaminant Effect Limit

Total sulfur Affects acid strength, polymer 20 wtppm max

production, acid consumption

Total Nitrogen Affects acid strength, polymer 10 wt ppm

production, acid consumption

Water/water Affects acid strength, polymer 3-5 molppm

forming production, corrosion 5 wt% in acid max
compounds
Ethane, ethylene & Affects isostripper pressure 0.5 mol%
non-condensables

Diolefins Affects acid strength, polymer 0.5 mol%

production, acid consumption

Amylenes Affect alkylate octane

InAlk Simplified Process Flow
Alkylation – Hazardous Materials
• HF
– Liquefied gas that forms heavy, toxic
aerosols that can travel downwind for miles
– Causes deep, sometimes delayed burns
that require immediate flushing and medical
treatment to stop tissue destruction
– Most burns occur during equipment
maintenance
– Anything that has contacted HF causes
burn (scale, rags, PPE, equipment, tools …)
Use correct PPE and carefully follow
procedures
Economics
• What is the cost if the unit is not generating?
– Losses are $10/bbl of olefin (fuel vs. gasoline feedstock)
when alky is down
– Losses can reach $20/bbl of olefin (or more) when
feedstock must be flared
• How does it enhance the value of the product?
– Lowers Gasoline Pool emissions as sulfur, aromatics,
olefins increase without Alky
– Improves Gasoline Pool MON, avoids RON Giveaway
– Alkylate can trade for $4/bbl above gasoline
Alkylation Summary
• Alky Keeps the Refinery Out of the Flare
• Alkylate is Great Gasoline
• Don’t Liquidate the Asset
– Keep the genie in the bottle
– Clamps mean something is wrong inside
– Follow PSS and Best Practice Documents
Catalytic
Condensation
Catalytic Condensation
• Also referred to a Polymerization
• Developed in early 1930s because of:
– Excess of thermally cracked olefins
– Need for higher performance gasoline
• Discovered in lab testing cracked gasoline
– Testing for olefin content with H2SO4 acid
– Found increase in gasoline yield.
• 1933 1st commercially viable unit started
Main Applications

• Condensation of light olefins to poly gasoline

- With mixed olefin feed, RONC of poly gasoline and
alkylate are equivalent
- Higher sensitivity than alkylate (∆RONC & MON)
- Particularly relevant where isobutane is not available
• Alkylation of aromatics to cumeme,
ethylbenzene and cymene
Feedstocks

• Unsaturated Vapor Recovery Unit

• FCC, coking and thermal cracking are sources of
light olefins
• C3, C4 or mixed C3/C4 olefin streams
• Feeds are generally treated to remove nitrogen
and sulfur compounds
Chemistry

• Acid polymerization of olefins

C–C=C + C-C=C C=C-C-C-C-C

C C
• Exothermic
Catalyst

• Phosphoric acid on Kieselguhr clay

• Catalyst is attacked by water and basic nitrogen
compounds
• Higher pressure favors longer catalyst life
Catalytic Condensation
Process/Motor Fuel Production
(UOP)

Flash Recycle
Reactor Drum Stabilizer Receiver
Drum
Quench
Streams

C3C4
Olefinic
Feed Feed
Drum C 3C4

Recycle Poly Gasoline

Reactor Types

• Tubular
– Catalyst contained in tubes surrounded by water to
remove excess heat
• Chamber
– Catalyst exists in layers between which there are
quench lines
Operating Conditions
• Pressure
– 450-550 psig (32-39 bars)
• Temperature
– 320-420F (160-216C)
• Space Velocity
– 0.8-1.5 LHSV
• Combined Feed Olefin Content
– 25-30 vol-%