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New Trends in Refinery Processes/Breakthroughs in Refinery Technology

Tim Hilbert Chris Oliveri

Haldor Tropse Catalyst Forum August 20, 2010

in Refinery Technology Tim Hilbert Chris Oliveri Haldor Tropse Catalyst Forum August 20, 2010 Research and

Research and Engineering

Technology Designed to Meet Global Needs

Technology Designed to Meet Global Needs  Developing countries changing gasoline and distillate needs 

Developing countries changing gasoline and distillate needs

Environmental factors changing gasoline and distillate qualities

Focus on four different technology areas that have or may impact fuels and lubes production

Hydroisomerization

MIDW™ for fuels

MSDW™ for lubes

MTG (Methanol-To-Gasoline)

BenzOUT™ (benzene reduction technology via aromatic alkylation)

H 2 purification via Rapid Cycle Pressure Swing Adsorption (RCPSA)

reduction technol ogy via aromatic alkylation)  H 2 purification via Rapid Cycle Pressure Swing Adsorption

Technology Designed to Meet Global Needs

Technology Designed to Meet Global Needs  Developing countries changing gasoline and distillate needs 

Developing countries changing gasoline and distillate needs

Environmental factors changing gasoline and distillate qualities

Focus on four different technology areas that have or may impact fuels and lubes production

Hydroisomerization

MIDW™ for fuels

MSDW™ for lubes

MTG (Methanol-To-Gasoline)

BenzOUT™ (benzene reduction technology via aromatic alkylation)

H 2 purification via Rapid Cycle Pressure Swing Adsorption (RCPSA)

reduction technol ogy via aromatic alkylation)  H 2 purification via Rapid Cycle Pressure Swing Adsorption

What is MIDW?

What is MIDW?  M obil I somerization D e W axing  Improves diesel cold

Mobil Isomerization DeWaxing

Improves diesel cold flow properties:

Pour point

Cloud point

CFPP (cold filtration test)

Selectively converts long chain paraffins to isoparaffins

Enables fuels to flow at low temperatures

Other benefits:

fuels to flow at low temperatures  Other benefits:  End-point (T95) reduction  Improved cetane

End-point (T95) reduction

Improved cetane and density

Applicable to kerosene and HDC bottoms

benefits:  End-point (T95) reduction  Improved cetane and density  Applicable to kerosene and HDC

Upgrading Diesel via Shape-selective Catalysis

Upgrading Diesel via Shape-selective Catalysis  Heavy distillate boiling range streams have increased concentration of

Heavy distillate boiling range streams have increased concentration of n- paraffins

N-paraffins have high cetane value, but poor cold-flow properties

Catalyst (MIDW) technology platform contains a metal capable of dehydrogenation/hydrogenation reactions and a zeolite for shape selective skeletal isomerization of n-paraffins to iso-paraffins

PARAFFINIC DIESEL MOLECULE GO SHAPESHAPE-- SELECTIVESELECTIVE CATALYSTCATALYST
PARAFFINIC DIESEL
MOLECULE
GO
SHAPESHAPE--
SELECTIVESELECTIVE
CATALYSTCATALYST

BULKY ISOPARAFFINIC DIESEL MOLECULE

LARGE MOLECULE CANNOT ENTER ZEOLITE PORE

ISOPARAFFINICISOPARAFFINIC DIESELDIESEL MOLECULEMOLECULE

ISOPARAFFINIC ISOPARAFFINIC DIESEL DIESEL MOLECULE MOLECULE UNCHANGED UNCHANGED BULKY BULKY ISOPARAFFIN ISOPARAFFIN
ISOPARAFFINIC ISOPARAFFINIC DIESEL DIESEL MOLECULE MOLECULE UNCHANGED UNCHANGED BULKY BULKY ISOPARAFFIN ISOPARAFFIN

UNCHANGEDUNCHANGED BULKYBULKY ISOPARAFFINISOPARAFFIN

ISOPARAFFINIC ISOPARAFFINIC DIESEL DIESEL MOLECULE MOLECULE UNCHANGED UNCHANGED BULKY BULKY ISOPARAFFIN ISOPARAFFIN

Isomerization has a Significant impact on melting point

Isomerization has a Significant impact on melting point Hydrocarbon Melting Point (oC) n-Tetradecane 5.0

Hydrocarbon

Melting Point (oC)

n-Tetradecane

5.0

7-Methyltridecane

-37.2

n-Octadecan

28.2

Methylheptadecane

5.7

n-Nonadecane

32.1

7-Hexyltridecane

-28.3

Before Isom After Isom Amount
Before Isom
After Isom
Amount

Linear Sequence

-28.3 Before Isom After Isom Amount Linear Sequence  Improvement of cold-flow properties arises from a

Improvement of cold-flow properties arises from a net reduction in the linear molecular sequence

Linear Sequence  Improvement of cold-flow properties arises from a net reduction in the linear molecular

Catalyst Operates with Excellent Diesel Selectivity

Catalyst Operates with Excellent Diesel Selectivity 3 rd Generation 100 MIDW Operating 90 “Range” MDDW Operating
3 rd Generation 100 MIDW Operating 90 “Range” MDDW Operating Line 80 (1st Generation Dewaxing
3 rd Generation
100
MIDW Operating
90
“Range”
MDDW Operating Line
80
(1st Generation
Dewaxing Technology)
2 nd Generation
70
60
50
0
20
40
60
80
100
CLOUD POINT REDUCTION (F
o
Cloud Point Reduction ( o F)
)
300 o F+ (150 o C+) Yield (wt%)
50 0 20 40 60 80 100 CLOUD POINT REDUCTION (F o Cloud Point Reduction (

Distillate

Increased Selectivity via Catalyst R&D

Distillate Increased Selectivity via Catalyst R&D  MIDW catalyst is compatible with conventional HDT catalysts

MIDW catalyst is compatible with conventional HDT catalysts

“Drop-in” potential as stand-alone or stacked-bed

Wide operating window

Capable of operating in both sweet and sour applications

Highly distillate selective (low naphtha/gas yields) compared to original dewaxing catalyst technology

Naphtha LPG MDDW MIDW 100 90 80 70 60 50 40 30 20 10 0
Naphtha
LPG
MDDW
MIDW
100
90
80
70
60
50
40
30
20
10
0
MIDW
MDDW

New ULSD units provide potential opportunities

Multi-bed reactors

Feeds treated to low levels of organic S & N

ULSD units provide potential opportunities  Multi-bed reactors  Feeds treated to low levels of organic

Where is MIDW?

Where is MIDW? MIDW units currently in operation (8) - ExxonMobil (2) - USA (2) (one

MIDW units currently in operation (8)

- ExxonMobil (2)

- USA (2) (one converted to MSDW)

- Canada (3)

- Germany (1)

- Asia (1)

- Russia (one under construction)

- ExxonMobil (2) - USA (2) (one converted to MSDW) - Canada (3) - Germany (1)
- ExxonMobil (2) - USA (2) (one converted to MSDW) - Canada (3) - Germany (1)

MIDW Commercial Operating Experience

MIDW Commercial Operating Experience 2 1.8 1.6 SOUR SOUR UNITS UNITS (TYPICAL) (TYPICAL) 1.4 10 o
2 1.8 1.6 SOUR SOUR UNITS UNITS (TYPICAL) (TYPICAL) 1.4 10 o 10 - -
2
1.8
1.6
SOUR SOUR UNITS UNITS (TYPICAL) (TYPICAL)
1.4
10
o
10
- - 30 30
o
C
C
Delta Delta Cloud Cloud
1.2
= Sweet Unit
Commercial
Data
1
0.8
= Sour Unit
Commercial
Data
0.6
0.4
0.2
0
0
100
200
300
400
500
600
Feed Sulfur (wt%)
= Sour Unit Commercial Data 0.6 0.4 0.2 0 0 100 200 300 400 500 600

Feed Nitrogen (ppm)

MIDW Commercial Operating Experience

MIDW Commercial Operating Experience 2 1.8 1.6 SWEET UNITS (TYPICAL) 20 - 40 o C Delta
2 1.8 1.6 SWEET UNITS (TYPICAL) 20 - 40 o C Delta Cloud 1.4 1.2
2
1.8
1.6
SWEET UNITS (TYPICAL)
20 - 40 o C Delta Cloud
1.4
1.2
= Sweet Unit
Commercial
Data
1
0.8
= Sour Unit
Commercial
Data
0.6
0.4
0.2
0
0
100
200
300
400
500
600
Feed Nitrogen (ppm)
Feed Sulfur (wt%)
= Sour Unit Commercial Data 0.6 0.4 0.2 0 0 100 200 300 400 500 600
= Sour Unit Commercial Data 0.6 0.4 0.2 0 0 100 200 300 400 500 600

Sour feed MIDW units

Sour feed MIDW units  One or two multi-bed reactor configurations  Ability to quench MIDW

One or two multi-bed reactor configurations

Ability to quench MIDW bed for summer mode to preserve catalyst activity

Experience w/ high-activity NiMo HDT catalyst for increased nitrogen removal

Post-treat catalyst bed to prevent EOC mercaptan reversion

Quench

1-Reactor Configuration

EOC mercaptan reversion Quench 1-Reactor Configuration High Activity NiMo HDT Beds MIDW Bed 2 -Reactor
EOC mercaptan reversion Quench 1-Reactor Configuration High Activity NiMo HDT Beds MIDW Bed 2 -Reactor
EOC mercaptan reversion Quench 1-Reactor Configuration High Activity NiMo HDT Beds MIDW Bed 2 -Reactor
EOC mercaptan reversion Quench 1-Reactor Configuration High Activity NiMo HDT Beds MIDW Bed 2 -Reactor
EOC mercaptan reversion Quench 1-Reactor Configuration High Activity NiMo HDT Beds MIDW Bed 2 -Reactor

High Activity NiMo HDT Beds

MIDW

Bed

Configuration High Activity NiMo HDT Beds MIDW Bed 2 -Reactor Configuration HDT Rxr High Activity NiMo

2-Reactor Configuration

HDT Rxr High Activity NiMo HDT Beds Optional R2 Bypass
HDT Rxr
High Activity
NiMo HDT
Beds
Optional R2
Bypass

MIDW Rxr

MIDW Bed
MIDW
Bed

Quench

Cascade HDT/MIDW commercial data

Cascade HDT/MIDW commercial data 1.2°F/month aging after 30 DOS
1.2°F/month aging after 30 DOS
1.2°F/month aging after 30 DOS
Cascade HDT/MIDW commercial data 1.2°F/month aging after 30 DOS

Sweet Unit MIDW Commercial Data

Sweet Unit MIDW Commercial Data
Sweet Unit MIDW Commercial Data
Sweet Unit MIDW Commercial Data

Renewable Diesel Demand

Renewable Diesel Demand  EU fuels quality directive and renewable energy directive propose to increase renewable

EU fuels quality directive and renewable energy directive propose to increase renewable content in transport by minimum 10% by energy in

2020

French law No. 2004 1484 Article 32 requires 7% by energy (7.7 vol%) in 2010

Some engine manufacturers may not warrant light duty engines above 7 vol% biodiesel

Increment above 7 vol% has to come from a source of renewable diesel

light duty engines above 7 vol% biodiesel  Increment above 7 vol% has to come from
light duty engines above 7 vol% biodiesel  Increment above 7 vol% has to come from
light duty engines above 7 vol% biodiesel  Increment above 7 vol% has to come from
light duty engines above 7 vol% biodiesel  Increment above 7 vol% has to come from
light duty engines above 7 vol% biodiesel  Increment above 7 vol% has to come from

MIDW is an Effective Solution for Renewable Diesel Dewaxing

MIDW is an Effective Solution for Renewable Diesel Dewaxing •Substantial cold-flow improvement is possible •MIDW

•Substantial cold-flow improvement is possible

•MIDW versatility allows for various cloud/pour points depending on regional requirements

Renewable Diesel Isomerized Renewable Diesel
Renewable Diesel
Isomerized
Renewable Diesel
allows for va rious cloud/pour points depending on regi onal requirements Renewable Diesel Isomerized Renewable Diesel

What about lubes base oil grouping (API)?

What about lubes base oil grouping (API)? Group I 80 < VI < 120 % Sat
Group I 80 < VI < 120 % Sat < 90% % S > 0.03
Group
I
80 <
VI < 120
% Sat < 90%
% S > 0.03
Solvent Refining
Very Wide
Chemical
Spectrum
Group II Group III 80 < VI < 120 VI > 120 % Sat <
Group
II
Group III
80
<
VI < 120
VI
>
120
% Sat <
90%
% Sat
> 90%
% S
< 0.03
% S
< 0.03
Catalytic Hydroprocessing
Group IV PAOs Chemical Rx Single Component
Group
IV
PAOs
Chemical Rx
Single
Component
Group V
Group V
Group IV PAOs Chemical Rx Single Component Group V OTHERS (E.g. Synthetic Esters) Chemical Rx 

OTHERS

(E.g. Synthetic Esters)

Chemical Rx

Base stock composition determines performance of finished products

Viscosity Index (VI)

Higher VI improves volatility, fuel economy, and operating range)

Saturate content

Higher saturates improves oxidation stability and soot handling

Wax content

Lower wax improves operating range, low temperature performance, pour point, cloud point

handling  Wax content • Lower wax improves operating range, low temperature performance, pour po int,

Lube activity focused on Group II and Group III

Lube activity focused on Group II and Group III High growth rate for group II and

High growth rate for group II and group III base oils

Demand for improved fuel economy and lower emissions translates to lower viscosity/volatility engine oils

Demand for increased equipment reliability

Extended service intervals/fill for life for engines requires both performance and stability

Grassroots group II/III plants have Cap-Ex and Op-Ex advantages versus Group I plants when integrated with existing fuels hydrocrackers.

Others ExxonMobilExxonMobil TechnologiesTechnologies
Others
ExxonMobilExxonMobil
TechnologiesTechnologies
Group I plants when integrated with existing fuels hydrocrackers. Others ExxonMobilExxonMobil TechnologiesTechnologies
Group I plants when integrated with existing fuels hydrocrackers. Others ExxonMobilExxonMobil TechnologiesTechnologies

Integrated Route to Base Oils

Integrated Route to Base Oils Group I Integrated into Group II & Group III Lube Plant
Group I Integrated into Group II & Group III Lube Plant Group II Group Group
Group I Integrated into Group II & Group III Lube Plant
Group II
Group Group I I
Hydroprocessing Hydroprocessing
Catalytic Catalytic
Hydrofinishing Hydrofinishing
Group III
Solvent Solvent Plant Plant
(HDT/RHC) (HDT/RHC)
Dewaxing Dewaxing (MSDW) (MSDW)
(MAXSAT) (MAXSAT)
Group II
8 RHC/RHT units
in
operation or in
design
80
Group I solvent operation
70
Group III
Group III
improves VI with
a yield
60
loss to aromatic extracts
50
Group II
Group II
40
Removal of 3-4 ring
30
20
10
aromatic compounds and
complex sulfur and
nitrogen compounds
Aromatic Extract
0
allows reduction
hydroprocessing
in
severity,
Base
Conversion to 360- O C Fuels
hydrogen consumption
and associated yield loss
VI Increase

Catalytic Dewaxing: Shape-selectivity in action

Catalytic Dewaxing: Shape-selectivity in action iso-Decane Yield (%) Performance influenced by choice of zeolite 
Catalytic Dewaxing: Shape-selectivity in action iso-Decane Yield (%) Performance influenced by choice of zeolite 
Catalytic Dewaxing: Shape-selectivity in action iso-Decane Yield (%) Performance influenced by choice of zeolite 

iso-Decane Yield (%)

Performance influenced by choice of zeolite

acidity

crystal size and morphology

pore size and shape

MLDW™ (Mobil Lube DeWaxing)

primarily cracking iso-Decane Yield (%)

metal-free

MSDW™ (Mobil Selective DeWaxing)

primarily isomerization

noble metal catalyst

100

80

60

40

20

0

MSDW™ MSDW™ MLDW MLDW
MSDW™ MSDW™
MLDW MLDW

0

20

40

60

80

100

catalyst 100 80 60 40 20 0 MSDW™ MSDW™ MLDW MLDW 0 20 40 60 80

n-Decane Conversion (%)

Why Hydrofinish?

Why Hydrofinish?  High activity catalyst can provide significant advantage  Removes polynuclear aromatics (PNA)

High activity catalyst can provide significant advantage

Removes polynuclear aromatics (PNA) and trace amounts of olefins

Improves color, oxidation and thermal stability of base oils

PNA equilibrium concentration controlled by reaction temperature and pressure

Aromatic Saturation

8 6 4 2 0 0 20 40 60 80 Relative Aromatics
8
6
4
2
0
0
20
40
60
80
Relative Aromatics

Relative Temperature

 

Kinetic

control

Equilibrium

Control

Kinetic

Control

Equilibrium
Equilibrium
Equilibrium
Equilibrium
Equilibrium
Equilibrium
Equilibrium
Equilibrium

Equilibrium

 

Control

  Kinetic control Equilibrium Control Kinetic Control Equilibrium   Control
  Kinetic control Equilibrium Control Kinetic Control Equilibrium   Control

Lube hydrocracker with MSDW™

Lube hydrocracker with MSDW™ Distillate VI uplift H 2 Consumption (scf/bbl) Lube Hydrocracker 60-80% yield 20

Distillate

VI uplift

Lube hydrocracker with MSDW™ Distillate VI uplift H 2 Consumption (scf/bbl) Lube Hydrocracker 60-80% yield 20

H 2 Consumption (scf/bbl)

Lube

Hydrocracker

60-80% yield 20 - 100

800 - 2000

Lube Hydrocracker 60-80% yield 20 - 100 800 - 2000 MSDW 85-97% yield 4 - 10
MSDW
MSDW
Lube Hydrocracker 60-80% yield 20 - 100 800 - 2000 MSDW 85-97% yield 4 - 10

85-97% yield 4 - 10 100 - 400

Base Stock
Base Stock
 

MSDW-2

MLDW

Reactive chemistry

(Isomerization)

(Cracking)

Pour Point, °C

-15

-15

KV @ 100°C, cSt

5.03

5.57

Viscosity Index

113

102

Lube Yield, wt%

94.2

75.9

-15 -15 KV @ 100°C, cSt 5.03 5.57 Viscosity Index 113 102 Lube Yield, wt% 94.2

MSDW Catalyst

MSDW Catalyst  LHDC/MSDW demonstrated as a versatile process for producing group II/III base stocks from

LHDC/MSDW demonstrated as a versatile process for producing group II/III base stocks from a range of crude sources

RHC/MSDW can be considered an economic alternative to LHDC/MSDW when group I facilities exist

MSDW catalysts provide highest dewaxing yields with high VI, and broad feedstock flexibility

Development of MAXSAT HDF catalyst adds significant value to entire lube complex

VI, and broad feedstock flexibility  Development of MAXSAT HDF catalyst adds significant value to entire
OperatingOperating oror inin Design/ConstructionDesign/Construction Lube Hydrocrackers RHC/RHT MSDW MAXSAT (HDF) 6 8 24 18
OperatingOperating oror inin Design/ConstructionDesign/Construction
OperatingOperating oror inin Design/ConstructionDesign/Construction

Lube Hydrocrackers

RHC/RHT

MSDW

MAXSAT (HDF)

6

8

24

18

MSDW-2 pilot study on hydrocracked DAO

MSDW-2 pilot study on hydrocracked DAO  MSDW catalyst is tolerant to poisons and maintains activity

MSDW catalyst is tolerant to poisons and maintains activity

+ 80 160 ppm N, 700 ppm S, 0.57% CCR + 60 24 ppm N,
+
80
160 ppm N, 700 ppm
S, 0.57% CCR
+
60
24 ppm N, 280 ppm S
0.06% CCR
22 ppm N, 150 ppm S
0.14% CCR
+
40
+
20
2 ppm N
18 ppm S
2
ppm N
8
ppm
S
Base
0
50
100
150
200
250
Dewaxing Temperature (°C)

Time on stream (days)

200 250 Dewaxing Temperature (°C) Time on stream (days) HDC HVGO feed 1 -reference HDC DAO

HDC HVGO feed 1 -reference

(°C) Time on stream (days) HDC HVGO feed 1 -reference HDC DAO feed 2 HDC DAO
HDC DAO feed 2
HDC DAO
feed 2
(°C) Time on stream (days) HDC HVGO feed 1 -reference HDC DAO feed 2 HDC DAO

HDC DAO

feed 3

(°C) Time on stream (days) HDC HVGO feed 1 -reference HDC DAO feed 2 HDC DAO

HDC DAO

feed 4

(°C) Time on stream (days) HDC HVGO feed 1 -reference HDC DAO feed 2 HDC DAO
(°C) Time on stream (days) HDC HVGO feed 1 -reference HDC DAO feed 2 HDC DAO

HDC DAO

feed 5

ExxonMobil Methanol to Gasoline Technology Overview

ExxonMobil Methanol to Gasoline Technology Overview  Methanol to gasoline (MTG) reactions de-hydrate methanol and

Methanol to gasoline (MTG) reactions de-hydrate methanol and convert the available carbon and hydrogen into various hydrocarbons

The “Shape-Selective” MTG catalyst limits the synthesis reactions to 10 carbons

Result is sulfur free gasoline with a typical 92 Research Octane

First MTG plant was operated in New Zealand from 1985 to 1997 converting natural gas to gasoline

MTG plant was operated in New Zealand from 1985 to 1997 converting natural gas to gasoline
Methanol Water Gasoline
Methanol
Water
Gasoline

MTG Reaction Chemistry

MTG Reaction Chemistry 2 CH 3 OH C 5 + Olefins CH 3 OCH 3 +
2 CH 3 OH
2 CH 3 OH
MTG Reaction Chemistry 2 CH 3 OH C 5 + Olefins CH 3 OCH 3 +
C 5 + Olefins
C 5 + Olefins
MTG Reaction Chemistry 2 CH 3 OH C 5 + Olefins CH 3 OCH 3 +
CH 3 OCH 3
CH 3 OCH 3

+

H 2 O

Light Olefins
Light Olefins

+ H 2 O

Paraffins Naphthenes Aromatics
Paraffins
Naphthenes
Aromatics
2 CH 3 OH C 5 + Olefins CH 3 OCH 3 + H 2 O
Gasoline
Gasoline
2 CH 3 OH C 5 + Olefins CH 3 OCH 3 + H 2 O

ExxonMobil MTG Process Flow Diagram

ExxonMobil MTG Process Flow Diagram Methanol MTG Purge Gas C 2 - LPG Reactor System (Multiple)
Methanol MTG Purge Gas C 2 - LPG Reactor System (Multiple) Stabilized H Gasoline 2
Methanol
MTG
Purge Gas
C 2 -
LPG
Reactor
System
(Multiple)
Stabilized
H
Gasoline
2 O
Raw
Gasoline
Stabilizer

DeEthanizer

H Gasoline 2 O Raw Gasoline Stabilizer DeEthanizer Light Gasoline Blending Finished Gasoline Treated

Light

Gasoline Blending
Gasoline
Blending
Finished Gasoline
Finished
Gasoline
Treated Gasoline
Treated
Gasoline

Heavy

Gasoline

Splitter

HGT

Reactor

Stabilizer

27

New Zealand Plant Operating Experience

New Zealand Plant Operating Experience  The New Zealand MTG experience demonstrated MTG to be a
New Zealand Plant Operating Experience  The New Zealand MTG experience demonstrated MTG to be a

The New Zealand MTG experience demonstrated MTG to be a robust technology

Daily gasoline yield and octane indicated a very consistent process performance

Unit ran reliably with an on-stream factor of greater than 96%

octane indicated a very consistent process performance  Unit ran reliably with an on-stream factor of

2 nd Generation MTG Technology

2 n d Generation MTG Technology  Next-generation design based on 10 years l earning's from

Next-generation design based on 10 years learning's from New Zealand operation

Improved heat integration

Improved process efficiency

Improved heat integration  Improved process efficiency ExxonMobil is the world leader In catalyst development and
ExxonMobil is the world leader In catalyst development and manufacture
ExxonMobil is the world leader In
catalyst development and manufacture

Reduced capital cost

Reduced operating cost

ExxonMobil is the world leader In catalyst development and manufacture Reduced capital cost Reduced operating cost

JAMG MTG plant in Shanxi, China

JAMG MTG plant in Shanxi, China  JAMG plant has a capacity of 100,00 t/a, successfully

JAMG plant has a capacity of 100,00 t/a, successfully started up in June 2009

JAMG plans to increase coal based gasoline production to 1,000,000 t/a

t/a, successfully started up in June 2009  JAMG plans to increase coal based gasoline production
t/a, successfully started up in June 2009  JAMG plans to increase coal based gasoline production

Reducing benzene in gasoline pool

Reducing benzene in gasoline pool 1 vol % legislation pending 1 vol % 1 - 5
1 vol % legislation pending 1 vol % 1 - 5 vol % range 0.62
1 vol %
legislation pending
1 vol %
1 - 5 vol %
range
0.62 vol%
1.5 - 4 vol %
range
1 - 2.5 vol %
range
1 vol %
1 vol % legislation pending 1 vol % 1 - 5 vol % range 0.62 vol%

Typical gasoline pool benzene in USA

Typical gasoline pool benzene in USA   Average Volume in Gasoline % Typical   Benzene Level
 

Average Volume in Gasoline %

Typical

 

Benzene Level

Benzene

Components

%

Contribution %

Reformate

~ 30

3-11

~ 75

FCC Gasoline

~

36

0.5-2

~ 16

Hydrocrackate

 

~ 3

1-5

~ 3

Others

~

31

0-3

~ 6

  ~ 3 1-5 ~ 3 Others ~ 31 0-3 ~ 6 Reference: EPA-HQ-OAR-2005-0036; FRL-8041-2, Table

Reference: EPA-HQ-OAR-2005-0036; FRL-8041-2, Table VII.F-2

Refiner’s options

Refiner’s options Octane Gasoline Gasoline Hydrogen Light Volume Pool Balance Olefins Reduced Reformer Feed
Octane Gasoline Gasoline Hydrogen Light Volume Pool Balance Olefins Reduced Reformer Feed Tailoring -
Octane
Gasoline
Gasoline
Hydrogen
Light
Volume
Pool
Balance
Olefins
Reduced
Reformer Feed Tailoring
-
Production
Benzene Extraction
No change
-
High
Benzene Saturation
consumptio
-
n
No
BenzOUT™
consumption
Upgrade to
Mogas
Extraction No change - High Benzene Saturation consumptio - n No BenzOUT™ consumption Upgrade to Mogas

Simplified BenzOUT process configuration

Simplified BenzOUT process configuration Light Olefins Light end Benzene Pretreatment Concentrate Splitter BenzOUT

Light Olefins

Simplified BenzOUT process configuration Light Olefins Light end Benzene Pretreatment Concentrate Splitter BenzOUT

Light end

Benzene

Pretreatment Concentrate Splitter BenzOUT Reactor Simplified BenzOUT™ process configuration
Pretreatment
Concentrate
Splitter
BenzOUT
Reactor
Simplified BenzOUT™ process configuration
Reactor Simplified BenzOUT™ process configuration Full Reformate Splitter Products  Fixed bed reactor

Full Reformate

Splitter

BenzOUT™ process configuration Full Reformate Splitter Products  Fixed bed reactor configuration  Adiabatic

Products

Fixed bed reactor configuration

Adiabatic or isothermal

Carbon steel equipment and no compressor needed

Process uses a proprietary catalyst

High activity, high selectivity and a long catalyst life

compressor needed  Process uses a proprietary catalyst  High activity, high selectivity and a long

BenzOUT – benzene reduction with increasing product value

BenzOUT – benzene reduction with increasing product value  BenzOUT process alkylates benzene-containing streams with

BenzOUT process alkylates benzene-containing streams with light olefins to produce alkyl aromatics for gasoline blending

Incentives include:

reducing benzene to meet regulations

upgrading light olefins to high octane gasoline

increasing gasoline volume and reducing RVP

commercially demonstrated

avoid H 2 consumption

provide the flexibility to increase H 2 production by allowing refineries to feed the C6’s to the reformer

 provide the flexibility to increase H 2 production by allowing refineries to feed the C6’s

Benzene Conversion (%)

Conversion can be achieved according to specific needs

(%) Conversion can be achieved according to specific needs Primary reaction chemistry is al kylation of

Primary reaction chemistry is alkylation of benzene with olefin

benzene conversion controlled by olefin/aromatic ratio

100

0

kylation of benzene with olefin  benzene conversion controlled by olefin/aromatic ratio 100 0 Olefin/Aromatic Ratio

Olefin/Aromatic Ratio

kylation of benzene with olefin  benzene conversion controlled by olefin/aromatic ratio 100 0 Olefin/Aromatic Ratio

BenzOUT (example of product volume increase)

BenzOUT (example of product volume increase) full reformate 40 KB/D benzene light olefin pre‐treatment concentrate

full reformate

BenzOUT (example of product volume increase) full reformate 40 KB/D benzene light olefin pre‐treatment concentrate

40 KB/D

benzene light olefin pre‐treatment concentrate light end Splitter splitter 42.3 KB/D
benzene
light olefin
pre‐treatment
concentrate
light end
Splitter
splitter
42.3 KB/D

~ 5% volume increase based on full reformate

concentrate light end Splitter splitter 42.3 KB/D • ~ 5% volume increase based on full reformate

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BenzOUT product properties

BenzOUT product properties Typical Gasoline End Point Product Feed Temperature ( o F) % Evaporated 
Typical Gasoline End Point Product Feed Temperature ( o F)
Typical Gasoline End Point
Product
Feed
Temperature ( o F)

% Evaporated

Final product properties are a function of feed composition and benzene conversion

approximate (R+M)/2 increase of 2 - 5

approximate RVP reduction of 0.5 PSI

composition and benzene conversion  approximate (R+M)/2 increase of 2 - 5  approximate RVP reduction

Process demonstrated in a North America refinery

Process demonstrated in a North America refinery Light Olefin Reformate BenzOUT Catalyst Mogas Blending  BenzOUT

Light Olefin

demonstrated in a North America refinery Light Olefin Reformate BenzOUT Catalyst Mogas Blending  BenzOUT

Reformate

in a North America refinery Light Olefin Reformate BenzOUT Catalyst Mogas Blending  BenzOUT catalyst

BenzOUT

Catalyst

Mogas Blending

BenzOUT catalyst drop-in application

Only minor modification to the polygas unit

BenzOUT demonstration conducted in one of the 3 tubular reactors

BenzOUT and polygas products combined for mogas blending

demonstration conducted in one of the 3 tubular reactors  BenzOUT and polygas products combined for

Olefin/Aromatic ratio

Benzene Conversion (%)

Commercial trial confirmed pilot plant results

(%) Commercial trial confirmed pilot plant results 100 0 0 10 20 30 40 50 60
100 0 0 10 20 30 40 50 60
100
0
0
10
20
30
40
50
60

Days on Stream

High Benzene Conversion Demonstrated

Commercial Results Confirm Pilot Plant Data

30 40 50 60 Days on Stream  High Benzene Conversion Demonstrated  Commercial Results Confirm

Rapid cycle pressure swing adsorption for H 2 purification

cycle pressure swing adsorption for H 2 purification C o n v e n t i

Conventional PSA

RapidRapid CycleCycle PSAPSA

n t i o n a l PSA Rapid Rapid Cycle Cycle PSA PSA RCPSA unit
n t i o n a l PSA Rapid Rapid Cycle Cycle PSA PSA RCPSA unit

RCPSA unit at an ExxonMobil Refinery

RCPSA has inherent advantages over conventional PSA (cPSA)

Structured adsorbent beds - a breakthrough in mass transfer

Up to 100 times higher mass transfer rate than conventional adsorbent

Significantly increased productivity/unit volume of adsorbent bed

Motor driven multi-port rotary plates

Rapid & efficient switch gases between beds (1-100 cycles/min.)

Effectively capture increased capacity of adsorbent bed

efficient switch gases bet ween beds (1-100 cycles/min.)  Effectively capture increased capacity of adsorbent bed

Commercial demonstration of RCPSA technology

Commercial demonstration of RCPSA technology Treat Gas from Reformer FCC NAPHTHA NAPHTHA HDT ~ 90% H
Treat Gas from Reformer FCC NAPHTHA NAPHTHA HDT ~ 90% H 2 HDT GO Hydrofiner
Treat Gas from
Reformer
FCC
NAPHTHA
NAPHTHA
HDT
~ 90% H 2
HDT
GO
Hydrofiner
RCPSA
GOHF recycle
Gas compressors
Amine
scrubber

H 2 purge to Fuel Gas

Design Specification Feed: 8 MMSCFD, 55% H 2 Operating pressure: 230 - 500 psig Operating
Design Specification
Feed: 8 MMSCFD, 55% H 2
Operating pressure: 230 - 500 psig
Operating temperature: 110 F
Product purity: 90% H 2
H 2 recovery: 71-85%

Start up went according to plan

Reliable through first three-months operation

unattended operation w/ no unplanned shutdowns

seamless integration with refinery treat gas

system

tested for full hydraulic load at various speeds

varied product flows and enriched hydrogen concentration

demonstrated individual module flexibility via planned S/D & S/U

individual module flexibility via planned S/D & S/U 90 85 80 75 70 65 60 10/25/07
90 85 80 75 70 65 60 10/25/07 11/4/07 1/13/08 Hydrogen (%)
90
85
80
75
70
65
60
10/25/07 11/4/07
1/13/08
Hydrogen (%)

RCPSA enables low-cost H 2

RCPSA enables low-cost H 2  Improves capacity & performance by increasing H 2 purity 

Improves capacity & performance by increasing H 2 purity

Hydrotreaters, hydrocrackers and naphtha reformers

Key RCPSA features

Low total erected cost - 30 to 50% cheaper than cPSA

Low operating costs - reliability, maintenance, service

Small plot space requirement - as little as ¼ of cPSA

Maximized H 2 recovery

Reliable operation without tail gas compressor

requirement - as little as ¼ of cPSA  Maximized H 2 recovery  Reliable operation

Developing technology designed to meet global needs

Developing technology designed to meet global needs  ExxonMobil has continued to develop and deploy new

ExxonMobil has continued to develop and deploy new catalyst and process technology aimed at helping developing countries meet gasoline and distillate needs Focus on four technologies that have or may impact fuels and lubes production going forward

Hydroisomerization

MIDW for fuels

MSDW for lubes

MTG (Methanol-To-Gasoline)

BenzOUT (benzene reduction technology via aromatic alkylation)

H 2 purification via Rapid Cycle Pressure Swing Adsorption (RCPSA)

reduction technology via aromatic alkylation)  H 2 purification via Rapid Cycle Pressure Swing Adsorption (RCPSA)

thank you

thank you
thank you
thank you