New Trends in Refinery

Processes/Breakthroughs in Refinery
Technology

Tim Hilbert Haldor Tropse

Chris Oliveri Catalyst Forum
August 20, 2010

Research and Engineering

Technology Designed to Meet Global 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)
 H2 purification via Rapid Cycle Pressure Swing Adsorption (RCPSA)
Technology Designed to Meet Global 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)
 H2 purification via Rapid Cycle Pressure Swing Adsorption (RCPSA)
What is MIDW?
 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:
 End-point (T95) reduction
 Improved cetane and density
 Applicable to kerosene and HDC bottoms
Upgrading Diesel via Shape-selective Catalysis
 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 ISOPARAFFINIC DIESEL 
MOLECULE
GO

SHAPE-
SELECTIVE
CATALYST

BULKY ISOPARAFFINIC  LARGE MOLECULE CANNOT UNCHANGED BULKY 

DIESEL MOLECULE ENTER ZEOLITE PORE ISOPARAFFIN
Isomerization has a Significant impact on melting point
Before Isom
Hydrocarbon Melting Point (oC) After Isom

n-Tetradecane 5.0
7-Methyltridecane -37.2

Amount
n-Octadecan 28.2
Methylheptadecane 5.7

n-Nonadecane 32.1
7-Hexyltridecane -28.3

Linear Sequence

 Improvement of cold-flow properties arises from a net

reduction in the linear molecular sequence
Catalyst Operates with Excellent Diesel Selectivity

3rd Generation
100

300 F+ (150 C+) Yield (wt%)

MIDW Operating
90
“Range”

MDDW Operating Line

80 (1st Generation
2nd Generation
Dewaxing Technology)
o

70
o

60

50
0 20 40 60 80 100
CLOUD POINT
Cloud REDUCTION (Fo) (oF)
Point Reduction
Increased Selectivity via Catalyst R&D
 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
 New ULSD units provide potential
MDDW
MIDW
100

opportunities 90

80
 Multi-bed reactors 70

 Feeds treated to low levels of organic S & N 60

50

40

30

D
20

is
til
la
10

te
N
ap
0

ht
ah
MIDW

LP
G
MDDW
Where is MIDW?
MIDW units currently in operation (8)
- ExxonMobil (2)
- USA (2) (one converted to MSDW)
- Canada (3)
- Germany (1)
- Asia (1)
- Russia (one under construction)
MIDW Commercial Operating Experience
2

1.8

1.6
Feed Sulfur (wt%)

SOUR UNITS (TYPICAL)

1.4
10 - 30 oC Delta Cloud = Sweet Unit
Commercial
1.2 Data

0.8 = Sour Unit

Commercial
0.6 Data

0.4

0.2

0
0 100 200 300 400 500 600

Feed Nitrogen (ppm)

MIDW Commercial Operating Experience
2

1.8

1.6
SWEET UNITS (TYPICAL)
Feed Sulfur (wt%)

1.4 20 - 40 oC Delta Cloud

= Sweet Unit
Commercial
1.2 Data

0.8 = Sour Unit

Commercial
Data
0.6

0.4

0.2

0
0 100 200 300 400 500 600

Feed Nitrogen (ppm)

Sour feed MIDW units
 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
1-Reactor Configuration 2-Reactor Configuration

HDT Rxr MIDW Rxr

High Activity Quench
NiMo HDT Beds
High Activity
NiMo HDT MIDW
Quench
Beds Bed

MIDW
Bed
Optional R2
Bypass
Cascade HDT/MIDW commercial data

1.2°F/month aging after 30 DOS

Sweet Unit MIDW Commercial Data
Renewable Diesel Demand
 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
MIDW is an Effective Solution for Renewable
Diesel Dewaxing
•Substantial cold-flow improvement is possible
•MIDW versatility allows for various cloud/pour points depending on regional requirements

Renewable Diesel
Isomerized
Renewable Diesel
What about lubes base oil grouping (API)?
Group I Group II Group III Group IV
80 < VI < 120 80 < VI < 120 VI > 120 PAOs
% Sat < 90% % Sat < 90% % Sat > 90%
% S > 0.03 % S < 0.03 % S < 0.03 Chemical Rx
Solvent Refining Catalytic Hydroprocessing Single
Component
Very Wide
Chemical Group V
Spectrum
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
Lube activity focused on Group II and Group III

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

ExxonMobil
Technologies
Integrated Route to Base Oils
Group I Integrated into Group II & Group III Lube Plant

Group
GroupII Hydroprocessing
Hydroprocessing Catalytic
Catalytic Hydrofinishing
Hydrofinishing Group II
Solvent
SolventPlant
Plant (HDT/RHC)
(HDT/RHC) Dewaxing
Dewaxing(MSDW)
(MSDW) (MAXSAT)
(MAXSAT) Group III

Existing
Existing
Solvent
Group II
SolventDewaxing
Dewaxing

• 8 RHC/RHT units in
80
operation or in design
70 Group III Group III • Group I solvent operation
60 improves VI with a yield
VI Increase

50 loss to aromatic extracts

40 Group II Group II • Removal of 3-4 ring
30 aromatic compounds and
20 complex sulfur and
10 nitrogen compounds
Aromatic Extract
0 allows reduction in
Base Conversion to 360-O C Fuels hydroprocessing severity,
hydrogen consumption
and associated yield loss
Catalytic Dewaxing: Shape-selectivity in action

iso-Decane Yield (%)

Performance influenced by choice of zeolite

 acidity
100
 crystal size and morphology
 pore size and shape 80
MSDW™
MLDW™ (Mobil Lube DeWaxing) MLDW
 primarily cracking iso-Decane Yield (%) 60
 metal-free
40
MSDW™ (Mobil Selective DeWaxing)
 primarily isomerization 20
 noble metal catalyst
0
0 20 40 60 80 100

n-Decane Conversion (%)

Why Hydrofinish?
 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
Kinetic
Relative Aromatics

8 control
6 Equilibrium
Control
4 Kinetic
2 Control
Equilibrium
0
Control
0 20 40 60 80
Relative Temperature
Lube hydrocracker with MSDW™

Lube
Distillate MSDW Base Stock
Hydrocracker
60-80% yield 85-97% yield
VI uplift
20 - 100 4 - 10
H2 Consumption
800 - 2000 100 - 400
(scf/bbl)

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
MSDW Catalyst
 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

Operating or in Design/Construction
Lube Hydrocrackers 6
RHC/RHT 8
MSDW 24
MAXSAT (HDF) 18
MSDW-2 pilot study on hydrocracked DAO
 MSDW catalyst is tolerant to poisons and maintains activity
Dewaxing Temperature (°C) + 80
160 ppm N, 700 ppm
S, 0.57% CCR
+ 60
22 ppm N, 150 ppm S
24 ppm N, 280 ppm S 0.14% CCR
0.06% CCR
+ 40

+ 20 2 ppm N
18 ppm S 2 ppm N
8 ppm S

Base
0 50 100 150 200 250
Time on stream (days)
HDC HVGO HDC DAO HDC DAO HDC DAO HDC DAO
feed 1 -reference feed 2 feed 3 feed 4 feed 5
ExxonMobil Methanol to Gasoline Technology Overview

 Methanol to gasoline (MTG)

reactions de-hydrate methanol
and convert the available Methanol
carbon and hydrogen into
various hydrocarbons

 The “Shape-Selective” MTG

catalyst limits the synthesis
reactions to 10 carbons Water

 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
Gasoline
MTG Reaction Chemistry

2 CH3OH CH3OCH3 + H2O

C5+ Olefins Light Olefins + H2O

Paraffins
Naphthenes Gasoline
Aromatics
ExxonMobil MTG Process Flow Diagram

Methanol MTG Purge Gas C2- LPG

Light
Reactor Gasoline
Blending
System
(Multiple)

Treated
Gasoline
Heavy
Gasoline Finished
Gasoline
Stabilized
H2O Gasoline
Raw HGT
Gasoline Stabilizer Reactor
DeEthanizer Splitter Stabilizer

27
New Zealand Plant Operating Experience

 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%

2nd Generation MTG Technology
 Next-generation design based on 10 years learning's
from New Zealand operation
 Improved heat integration
 Improved process efficiency

Reduced capital cost

Reduced operating cost

ExxonMobil is the world leader In

catalyst development and manufacture
JAMG MTG plant in Shanxi, China
 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
Reducing benzene in gasoline pool

1 vol %
legislation pending 1 vol % 1 - 5 vol %
range

0.62 vol%

1.5 - 4 vol %
range

1 - 2.5 vol % 1 vol %

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

Reformate ~ 30 3-11 ~ 75

FCC Gasoline ~ 36 0.5-2 ~ 16

Hydrocrackate ~3 1-5 ~3

Others ~ 31 0-3 ~6

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

Refiner’s options

Octane
Gasoline Gasoline Hydrogen Light
Volume Pool Balance Olefins
Reduced
Reformer Feed Tailoring -
Production

Benzene Extraction No change -

High
Benzene Saturation consumptio -
n
No Upgrade to
BenzOUT™ consumption Mogas
Simplified BenzOUT process configuration

Benzene Light Olefins
Concentrate Pretreatment

Light end

Full Reformate
Splitter BenzOUT
Reactor
Splitter

Simplified BenzOUT™ process configuration 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
BenzOUT – benzene reduction with increasing product
value
 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 H2 consumption
 provide the flexibility to increase H2 production by allowing refineries to feed
the C6’s to the reformer
Conversion can be achieved according to specific needs

Primary reaction chemistry is alkylation of benzene with olefin

 benzene conversion controlled by olefin/aromatic ratio

100
Benzene Conversion (%)

Olefin/Aromatic Ratio
BenzOUT (example of product volume increase)

benzene  light olefin
pre‐treatment
concentrate

light end
full reformate
Splitter
40 KB/D
splitter

42.3 KB/D

• ~ 5% volume increase based on full reformate

Page 8
BenzOUT product properties

Typical Gasoline End Point

Temperature (oF)
Product
Feed

% 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
Process demonstrated in a North America refinery

Light Olefin
Reformate

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
Commercial trial confirmed pilot plant results

100

Olefin/Aromatic ratio
Benzene Conversion (%)

0
0 10 20 30 40 50 60
Days on Stream

 High Benzene Conversion Demonstrated

 Commercial Results Confirm Pilot Plant Data

Rapid cycle pressure swing adsorption for H2 purification
Conventional PSA Rapid Cycle PSA

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
Commercial demonstration of RCPSA technology
Treat Gas from
H2 purge Design Specification
Reformer FCC NAPHTHA to Fuel Gas
~ 90% H2 NAPHTHA HDT Feed: 8 MMSCFD, 55% H2
HDT
Operating pressure: 230 - 500 psig
GO Operating temperature: 110 F
Hydrofiner RCPSA
GOHF recycle Product purity: 90% H2
Gas compressors
H2 recovery: 71-85%
Amine
scrubber

• Start up went according to plan

Hydrogen (%)
90
• Reliable through first three-months 85
operation 80
– unattended operation w/ no unplanned
shutdowns 75
– seamless integration with refinery treat gas 70
system
65
– tested for full hydraulic load at various speeds
– varied product flows and enriched hydrogen 60
10/25/07 11/4/07 1/13/08
concentration
– demonstrated individual module flexibility via
planned S/D & S/U
RCPSA enables low-cost H2

 Improves capacity & performance by increasing H2 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 H2 recovery
 Reliable operation without tail gas compressor
 Developing technology
designed to meet global needs

 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)
 H2 purification via Rapid Cycle Pressure Swing Adsorption (RCPSA)
thank you