BASE OIL PRODUCTION AND PROCESSING

Michel DAAGE
EXXONMOBIL Process Research
 OUTLINE

• Background
– Base Oil Terminology and Basestock Properties
– Lubricant Quality Drivers

• Base Oil Production

– Feedstocks and Lube Chemistry
– Traditional Lube and “State of the Art” Lube Plant

• Catalytic Refining

• Catalytic Dewaxing

• Conclusion
 BASE OIL TERMINOLOGY

• Lubes are High Value Products with Broad Variety of Uses

– Automotive: Engine oils, Automatic Transmission Fluids (ATF)
– Industrial: Machine oils, Greases, Turbine oils, Electrical oils, Drilling Fluids
– Medicinal: Food Grade oils, White oils,..
• Refineries Produce Base Oils or Basestocks
– Finished Products are Blends of Basestock with(out) Additives
• Basestocks are Called by Various Names:
– Neutrals (100N, 150N, 600N,...)
– Bright Stocks
– Grades (SAE 5, 10, 30, ..; ISO 22, 32,...)
• Most Common Lube Name is Neutral
– Number is the Viscosity @ 100oC
• Bright Stock is Heavy Lube made from Resid
– Name Refers to Appearance and Typical Viscosity is 2,500 SSU @ 100oF
• Grade Names may Refer to Viscosity or to Trademarks
 BASESTOCK PROPERTIES AND DEFINITIONS
• Basestock Composition Determines Performance of Finished Products
– Viscosity Index or 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
• Lower Wax improves Low Temperature Performance
– Pour Point
– Cloud Point
• American Petroleum Institute (API) Basestock Categories
API Group Sats Sulfur VI Typical Manufacturing Process
I <90% >0.03% 80-119 Solvent Processing
II >90% <0.03% 80-119 Hydroprocessing
III >90% <0.03% 120+ Wax Isomerization, H/C, GTL
IV n.a. n.a Polyalphaolefins (PAO)
V All Other Basestocks
 KEY LUBE OIL PROPERTIES

• Viscosity (Measure of Fluidity)

– Range from ~ 4 to 20 cSt @ 100oC for Neutrals up to 32 cSt for Bright Stock
– Brookfield Measures Low Temperature Fluidity on Finished Oils @ -40oC
• Viscosity Index (Inverse Measure of Change of Viscosity with Temperature
– Ranges from ~85 to ~105 for most Basestocks, Higher for Speciality Grades
– (ex: Exxsyn ~140, PAO ~150, XHVI~140+)
• Pour Point (Temperature at Which Fluid Becomes Nearly Solid)
– Typically from -9 to -24oC
– Cloud Point is Temperature at Which Wax Crystals Appear
• Volatility (Measure of Oil Loss Due to Evaporation)
– Noack Volatility Measures Actual Evaporation (Typically 20-35 wt%)
– GCD Volatility Measures Front End of Boiling Curve (e.g 10% @375oC)
• Color (Appearance) and Stability (Measure of Color Change in Light,...)
• Con Carbon (Measure of Carbon Residue Left on Ignition)
• Saturates, Aromatics and Asphaltenes Contents
 LUBRICANT QUALITY DRIVERS

• Passenger Car Engine Oils Shifting to Lower Viscosity and Higher VI

– Lower Viscosity Improves Fuel Economy

– Higher VI Reduces Volatility

• Heavy Duty Engine Oils Shifting to Highly Saturated Baseoils

– NOx Emission Regulations Driving New Engine Designs Which Increase Soot

– Formulation with High Saturates Improved Soot Handling

– Higher Quality Oils Needed to Maintain Service Intervals

• Improvements of Transmission Durability and Performance

– Requires Highest Quality Group II/III Baseoils or Synthetics
 BASE OIL FEEDSTOCKS

• Lube Plant Feedstocks are Typically Obtained by Vacuum Distillation of

Atmospheric Resids
– Preferred Lube Crudes are :
• Paraffinic (W. Texas, Arab Light): High Wax Content
• Naphthenic (S. Louisiana): Low Wax Content
– Atmospheric Resids are Upgraded to Lubes by Combination of:
• Vacuum Distillation
• Deasphalting
• Hydroprocessing
• Hydrocracking
• Dewaxing
• Other Processes or Feedstocks include:
– Synthetics such as PAO, Polyethers and Esters
– GTL Waxes
 LUBE OIL CHEMISTRY

• Complex Relation Between Molecular Composition and Properties Leads

to Large Variety of Process Configurations Comprising Multiple Stages:

– Deasphalting: Remove Condensed Multi-Ring Aromatics

• Improves Con Carbon, Stability and Color
– Solvent Extraction or Hydrocracking
• Removes Aromatics by Extraction, Hydrogenation or Dealkylation
– Hydroprocessing: Remove Sulfur/Nitrogen and Hydrogenate Aromatics
• Lowers Pour, Improves VI and Stability
• Nitrogen Leads to Low Stability, but Sulfur Acts as Antioxidant
• Naphthenics Improves Pour Point
• Removes Napthenic Acids
– Hydroisomerization
• Improves Pour Point of Paraffins
– Dewaxing
• Removes or Converts High Pour Point n-Paraffins
 MULTIPLICITY OF PROCESS OPTIONS

Conventional
Conventional Solvents
Solvents (1930s)
(1930s)

Solvent
Solvent Extraction
Extraction Solvent
Solvent Dewaxing
Dewaxing Group I

All
All Catalytic
Catalytic (1990s)
(1990s)
Catalytic
Catalytic
Lube
Lube Hydrocracking
Hydrocracking Group I, II, III
Hydroisomerization
Hydroisomerization

Hybrid
Hybrid (Mix
(Mix and
and Match
Match to
to Needs)
Needs)

Raffinate
Raffinate Improved
Improved Lube
Lube
Fuels
Fuels Hydrocracking
Hydrocracking Hydroconversion
Hydroconversion Hydrofinishing
Hydrofinishing
Improved
Improved Solvent
Solvent Lube
Lube Group I, II, III
Wax
Wax Hydrofining
Hydrofining
Dewaxing
Dewaxing Hydrosomerization
Hydrosomerization FDA Grade Wax
Membrane
Membrane Assisted
Assisted Advanced
Advanced Catalytic
Catalytic Improved
Improved Solvent
Solvent
Solvent
Solvent Processing
Processing Dewaxing
Dewaxing Extraction
Extraction
 TRADITIONAL BASE OIL PRODUCTION
• Uses Solvent Extraction (Furfural or NMP) and Solvent Dewaxing (MEK)
Waxy Raffinate
Fuels
Solvent I Solvent II
Vacuum
Distillation Light

Solvent Dewaxing

Hydrofinishing
Light

Solvent Extraction
Medium

Atmospheric
Resid Medium
Heavy

Heavy
Bright
Deasphalting

Stock
Propane

Wax Hydro
Deoiling

-finishing
Wax
Bright Solvent
Stock Recovery Wax
Intermediate
Tankage
 STATE OF THE ART LUBE PLANT
• State of the Art is “All-Catalytic Lube Plant”: ExxonMobil Jurong

Lube Hydrocracking MSDW

Fuels Fuels

Hydrogen
Hydrogen
Lube Hydrocracker

HVGO

Hydrotreater
Dewaxer
Vacuum
Stripper
Reactor
Guard

Vacuum Intermediate Base Oil

Distillation Tankage Tankage
 LUBE HYDROCRACKING

• Production of Lube by Hydrocracking may be Carried in Conjunction

with Fuels Production or be Solely Dedicated to Lubes
– Lubes yields tied to yield of 700oF+ (20 to 40+ Carbons)
– VI Uplift Critical to Production of High Quality Lubes
– Conversion to Fuels is Controlled by the Catalyst Acidity

• Hydrocracking Chemistry is Complex and Involves:

– Heteroatom Removal (S, N)
– Aromatics Hydrogenation
– Aromatics Dealkylation
– Naphthene Cracking

• Typical Operating Conditions

– LHSV 0.5 to 1.0 h-1
– Temperature ~ 400oC
– H2 pressure > 100 atm
– Treat Gas Rate 5,000 to 10,000 SCF/bbl
 LUBE HYDROCRACKING (Cont.)

• H/C Catalysts are Bifunctional

– Hydro-Dehydro Function Provided by NiMo or NiW in Sulfided Form
– Acid Function Provided by Amorphous Silica-Alumina or Zeolite
• Large Pore Zeolite such as HY, Composited with a Matrix/Support

• Metal/Acid Balance is Tuned to Selectively React Cyclic Molecules While

Preserving Paraffins
– Results in Significant Increase in VI
• Conversion of Aromatics to Naphthenes to Fuels
• Increased Concentration of Paraffins in Lubes

• Hydrocracking vs Solvent Extraction results in Higher Lube Yields , Rich

in Naphthenic Species
 RAFFINATE HYDROCONVERSION

• Upgrades only Selected Stocks vs Entire Slate

– Increase VI

– Preserves Yield of Lubes and Wax

• Chemistry

– Hydrogenate Aromatics

– Remove Heteroatoms

• Lower Investment Option via Integration with Existing Solvent Lube Plant
 VI ‘HOP’ BY RAFFINATE HYDROCONVERSION

RHC
RHC Group
Group IIII
Basestock
Basestock Thermal
Thermal Diffusion
Diffusion Separation
Separation
•• EHC™
EHC™ 45
•• 116 VI
45 Cold
116 VI Hot Wall
•• -19ºC
-19ºC pour
pour Pt.
Pt.
•• 14%
14% Noack
Noack Volatility
Volatility
200 Low
Density -1
150 -2
-3
100 -4
-5 Collection
Ports
50 -6
-7
VI

0 High -8
-9
-50 Conventional
Conventional Density -10
Group
Group II Basestock
Basestock
-100 •• 100
100 VI
VI
•• -22ºC
-22ºC pour
pour Pt.
Pt.
-150 •• 29%
29% Noack Volatility
Noack Volatility

-200
1 2 3 4 5 6 7 8 9 10
Port No.
RHC PROVIDES FLEXIBILITY TO TAILOR PRODUCTS

11
Noack Volatility, wt%

105 VI
112 VI

9
RHC
7

3
5.4 5.8 6.2 6.6 7

Viscosity, cSt 100ºC

EHC
EHC™™ 45
45 EHC
EHC™™ 60
60
KV@100°C,
KV@100°C, cSt
cSt 4.5
4.5 5.9
5.9
Pour
Pour point,
point, °C
°C -18
-18 -18
-18
VI
VI 116
116 114
114
Noack
Noack Volatility,
Volatility, wt%
wt% 14
14 88
Saturates
Saturates by
by Clay
Clay Gel,
Gel, wt%
wt% 96
96 95
95
 CATALYTIC DEWAXING

• Primary Function is to Improve Cold Flow Properties of Lubes

– By Removing or Converting n-Paraffins
• Decrease Pour Point and Cloud Point

• Development of Catalytic Dewaxing is Tied to the Discovery of Medium

Pore Zeolites :
– 10 Rings Zeolites: ZSM-5, ZSM-11, ZSM-23, SAPO-11*
– Control of Acidity by De-Alumination or Al Substitution
– Steam Treatment
– Acid Extraction
– Shape Selectivity
• Ability to Selectively Reacts Molecules with Smaller Critical Sizes
– Paraffins < Isoparaffins << Naphthenes and Aromatics
• Diffusion/Adsorption Control in Microcrystalline Materials
– Hydro-Dehydro Metal Function
• Impacts Severity of Processing Conditions

* Molecular sieve, not a zeolite

 SHAPE-SELECTIVITY IN ACTION

• Performance Influenced by Choice of Zeolite

– Acidity
– Crystal Size and Morphology
– Pore Size and Shape
 SELECTING THE PROPER CLASS OF ZEOLITES

8-Membered Rings

Adsorption of Linear Paraffins (4-5Å)

Erionite Zeolite A

10-Membered Rings

Isomerization/Cracking of Paraffins (5-6Å)

* Molecular sieve, not a zeolite
ZSM-5 Ferrierite SAPO-11*

12-Membered Rings

Conversion of Heavy Aromatics (6-8Å)

Faujasite Zeolite L Mordenite

 EXAMPLES OF 10-R ZEOLITES

1-Dimensional 2-Dimensional 3-Dimensional

10-R SAPO-11 (3.9x6.3)* NU-87 (4.7x6.0) ZSM-5 (5.3x5.6)

ZSM-22 (4.4x5.5) ZSM-11 (5.3x5.4)
ZSM-23 (4.5x5.2)

10-R x 8-R Ferrierite (4.2x5.4) Wenkite (2.6x4.9)

ZSM-57 (5.1x5.4)

( ) 10-R dimension
* Molecular sieve, not a zeolite
 SELECTING A ZEOLITE FOR DEWAXING

10-Ring, 1-D 8 and 10-Ring, 2-D 10-Ring, 3-D

Channels Intersecting Channels Intersecting Channels
ZSM-23 (MTT) ZSM-35 (FER) ZSM-5 (MFI)
10 4.5 x 5.2 (Å) 10 4.2 x 5.4 10 5.3 x 5.6
8 3.5 x 4.8 (Å) 10 5.1 x 5.5 (Å)

Linear Paraffin Linear Paraffin Paraffin Cracking

Isomerization Isomerization
 MEASURING PERFORMANCE AT THE BENCH

R R'

Choice of Zeolite
?
ZSM-5
R' R R'
R
+

100 Early Technologies

iso-Decane Yield (%)

MSDW-2
80 3-Dimensional ZSM-5
MSDW-1

60
MLDW Selective Cracking
Lower Yield (< 90%)
40

20 Current Technology
Highly-Shape Selectivity
0
0 20 40 60 80 100 Selective Isomerization
n-Decane Conversion (%) High Yield (>90 %)
 MEASURING PERFORMANCE AT THE BENCH (Cont.)

Lowering
Lowering Pour
Pour Point,
Point, yet
yet maintain
maintain high
high VI
VI

• Branching impacts Pour Point • Multiple Branching impacts VI

– Branch Near Center of Chain – Average Branch Number
– Leads to Lower Pour Point measured by 13C NMR
Hydroisomerization of n-C24

160
Melting Points of C9 (oC)
150
-30 nC10 140

VI
-50
130
-70 2MeC8
120
-90
3MeC8 26MeC7
-110 23MeC7 110
4MeC8 234MeC6 1.4 1.6 1.8 2 2.2 2.4
-130 Number Branches

Ref: S.J. Miller, AIChE 1998 Spring National Meeting, New Orleans, LA
 MSDW BASE OIL PRODUCTION

Hydrocracked
Hydrocracked Light
Light Neutral
Neutral Feedstock
Feedstock

100 120

95 116 MSDW-2
MSDW-2
90
MSDW-1 112 MSDW-1
Yield Wt, %

VI
85 108

80 Solvent 104 Solvent

75 100
-50 -40 -30 -20 -10 0 10 -50 -40 -30 -20 -10 0 10
Pour Point, ºC Pour Point, ºC
 Results of Improved MSDW-2 Isomerization

Significantly
Significantly Higher
Higher Lube
Lube Yield
Yield and
and VI
VI

6
150N 500N
5
MSDW-2 Improvement
Over MSDW-1

0
Yield Gain, Vol% VI Gain
 CONCLUSION

• Base Oil Production and Processing is achieved by a Multiplicity of

Extractive and/or Catalytic Processes

• Block Processing is Often used for Optimizing Yield and Quality

• “State of the Art” is an ‘All Catalytic” Lube Plant

• Hydrocracking is Used for Increasing VI

• Dewaxing is Used for Correcting Cold Flow Properties

• Advanced Dewaxing Catalysts, Such as 10-R Zeolites, Well Suited for

Group II/Group III Lube Production
 ACKNOWLEDGEMENTS

J. Beck D. Boate

T. Degnan D. Marler

W. Murphy