Ajit Sapre - ExxonMobil

Technology solutions for upgradinglube base oil production

Ajit SapreLicensing Director, Europe, Middle East & AfricaEXXONMOBIL RESEARCH & ENGINEERING

Technology solutions for upgradinglube base oil production

Ajit SapreLicensing Director, Europe, Middle East & AfricaEXXONMOBIL RESEARCH & ENGINEERING

Technology Solutions forUpgrading Lube Base Oil Production

Ajit V. SapreTim H. HilbertEric D. JoseckJean P. Andre

History of Lubricants and Basestocks

Lubricants Have Been Used Since Ancient Times

Initial Processing Was Limited To Separation By Boiling Point

The Petroleum-based Lubricants Business Began In The Mid-1800’s

Base Oil Quality Has Evolved With Process Technology

First Generation Process Technology Developed To Remove Aromatics, Other ImpuritiesSolvent Processing Technology Developed

Lower cost to operateDewaxing to lower pour point (and recover wax as a byproduct)Simple hydrofining also added to further reduce impurities

Hydroprocessing Technology Changed Base Oil Business From “ Physical Separations” To “Chemical Transformations”

Base oil quality drivers for lighter viscosity grades and refinery economics are making Hydroprocessingpopular option

Wax Isomerization Can Produce Very High Quality Base Oils

GTL wax derived Base oils

Key Lube Oil Properties

Viscosity (Measure of Fluidity)Range from ~ 4 to 20 cSt @ 100oC for Neutrals up to 32 cSt for Bright StockBrookfield 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: PAO ~150, XHVI~140+)

Pour Point (Temperature at Which Fluid Becomes Nearly Solid)Typically from -9 to -24oCCloud 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

Base Oil TerminologyLubes 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 FluidsMedicinal: Food Grade oils, White oils,..

Refineries Produce Base Oils or BasestocksFinished Products are Blends of Basestock with(out) Additives

Basestocks are Called by Various Names:Neutrals (100N, 150N, 600N,...)Bright StocksGrades (SAE 5, 10, 30, ..; ISO 22, 32,...)

Most Common Lube Name is NeutralNumber is the Viscosity @ 40oC

Bright Stock is Heavy Lube Made From ResidName Refers to Appearance and Typical Viscosity is 2,500 SUS @ 40oC

Grade Names May Refer to Viscosity or to Trademarks

Base Oil Production Economic Factors

Overall Refinery Economics Dictate Crude SelectionSolvent Lube Plants Often Limit Crude ChoicesCatalytic Lube Plants Allow More Flexibility In Crude SelectionLube And Fuel Plants Compete For Same FeedsHigh Crude To Fuel Margins Can:

Cause A Lube Refinery To Shutdown Or Lower ThroughputChoose To Operate The Catalytic Lube Plant For Fuels Production

Solvent Lube Plants Inherently Have High Operating Cash CostsEnergy, Solvent Usage, Labor, Size, Etc.

Cru

de/V

acuu

mD

istil

latio

nC

rude

/Vac

uum

Dis

tilla

tion

Solvent Lube Plant

Catalytic Lube Plant

Fuels Plant (HDC or FCC)

Crude

Group I

Group IIIGroup II,

Fuels by product

Gasoline & Diesel

Traditional Base Oil Production

Uses Solvent Extraction (Furfural or NMP) and Solvent Dewaxing (MEK)

Waxy Raffinate

Solv

ent D

ewax

ing

Hyd

rofin

ishi

ng

Prop

ane

Dea

spha

lting

AtmosphericResid

Fuels

IntermediateTankage

VacuumDistillation

Solv

ent E

xtra

ctio

n

Solvent I

Solvent Recovery

Solvent

Wax

D

eoili

ng

Wax

H

ydro

-fin

ishi

ng

Wax

Light

Medium

Heavy

BrightStock

Light

Medium

Heavy

BrightStock

Recent Quality Trends for Automotive Lube Grades is Putting Pressure on Conventional Solvent Based Plants

Properties Set by Units

Flash PointKV / Noack

Viscosity Index Pour Point ColorStability

Quality Drivers For Modern Basestocks

Basestocks Base OilAdditives

Good StabilityDrain Interval

Low VolatilityLow Emissions

Low ViscosityFuel Economy

Desired Basestock QualityPerformance Parameter

Finished Lube

Base Oil Grouping (API)

80 < VI < 120% Sat < 90%% S > 0.03

Group IGroup I80 < VI < 120% Sat < 90%

% S < 0.03

Group IIGroup IIVI > 120

% Sat > 90%% S < 0.03

Group IIIGroup IIIPAOs

Group IVGroup IV

Solvent RefiningCatalytic Hydroprocessing

Chemical Rx

OTHERS(E.g. Synthetic

Esters)

Group VGroup V

Chemical Rx

Very WideChemicalSpectrum

Single Component

Basestock Composition Determines Performance of Finished ProductsViscosity 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, Low TemperaturePerformance, Pour Point, Cloud Point

99

40

15

1

Noa

ck V

olat

ility

, wt%

Molecular Type Links VI, Viscosity, Volatility

Viscosity, cSt at 40°C

350

400

450

500

550

10 100 1000

MA

BP,

°C

(VI) (170) (140) (100) (80)

(40)

(0)

(-100)

WAX: n-ParaffinVI > 200, but SOLID

Source: API Research Project 42, 1966

Volatility Has Become a Driver For Group III

Group I / Group II 95 VI

Group II+

Mid Tier Group III

Top Tier Group III+

Vola

tility

, %

5

10

15

20

Viscosity @ 100°C, cSt

4 5 6 7 8

Group IV / PAO’s

Primarily for automotive applications

Paraffins

Naphthenes Aromatics

Processing To Reduce Naphthenes and Aromatics

Higher Paraffin Content Results in Higher Viscosity Index (VI)VI is a good surrogate for many performance characteristics

Viscosity Index

Group II Gas Oil

Group IGroup III

PAO

Base Oil Manufacturing

GroupI/II

CatalyticDewaxing

GroupII/III

IsomerizationDewaxing

LubeHydrocracking

LubeHydrotreating

FuelsHydrocracking

GroupI/II

SolventDewaxing

SolventExtractionDistillation Finishing

Deasphalting

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 AromaticsImproves Con Carbon, Stability and Color

Solvent Extraction or HydrocrackingRemoves Aromatics by Extraction, Hydrogenation or Dealkylation

Hydroprocessing: Remove Sulfur/Nitrogen and Hydrogenate Aromatics

Lowers Pour, Improves VI and StabilityNitrogen Leads to Low Stability, but Sulfur Acts as AntioxidantNaphthenics Improves Pour PointRemoves Napthenic Acids

HydroisomerizationImproves Pour Point of Paraffins

DewaxingRemoves or Converts High Pour Point n-Paraffins

Deasphalting

Required to Produce Bright Stock Base OilsWell-Known, Conventional Technology

Commercialized before WWII

SolventDewaxing


Deasphalting

Removes CCRRemoves MetalsRemoves Polars (i.e. Sulfur, Nitrogen)Reduces ViscosityDAO Becomes Viable HDC Feedstock

AsphaltenesPrecipitated from Crude Oils by Aliphatic Solvents (e.g. n-C5). Soluble in Benzene. Mol. Wt. 1000-3000. High in S, N, O, and Metals (V + Ni).

S

S

O

H

O O

N

N

C84H98N2S2O31248 Mol. Wt.40.4% Aromatic Carbons

80.85 wt%C7.92 wt%H2.24 wt%N5.14 wt%S3.85 wt%O

Asphaltenes: Materials With Complex Structures

Typical Contaminant Distribution in ROSE DAO

% COMPONENT IN DAO100

80

60

40

20

00 10 20 30 40 50 60 70 80 90 100

DAO YIELD, VOL %

METALS

SULFUR

NITROGEN

CCR

ASPHALTENES

Propane Butane Pentane

DAO Properties

Vac Resid DAO

API 8.7 21.6

KV@100C 1139 61.22KV@40 C 410.1 389.15

Sats,% -- ~70

Sulfur,wt% 2.77 1.41Nitrogen,ppm - 1000

CCR,wt% 20.6 3Ni,ppm 62 2.5V,ppm 98 1.5

Extraction

Removes Aromatics and Polar Components Proper Extraction Unit Operation is Critical to Meet Base Oil VI, Stability and Solvency SpecificationsYields are Crude Dependent but Typical Yields Around 70% for 95 VI. Higher VI Lowers Yields.

SolventDewaxing


Deasphalting

Solvent vs. Catalytic Dewaxing:

Solvent Dewaxing – Physically Separates Wax from Base Oil

Removes Normal and High-Pour Branched Paraffins by Crystallizing WaxAlso Removes Some High-Pour Non-ParaffinsPour Point Reduction Limited by Refrigeration Capabilities

Catalytic Dewaxing - Converts Wax to IsoparaffinsRemoves Fewer Naphthenes than SDW / Product is Less ParaffinicPreferentially Removes Low Molecular Weight Normal and Near Normal ParaffinsPossible to Produce Very Low Pour Point Base Oils

Catalytic Dewaxing- MLDW™

Extraction MLDWTMDistillate

60-80% yieldVI uplift 20-100

70-90% yield

H2 consumption 100-400 scfb

Base Stock

Compared with Solvent Dewaxing, MLDW has:

A Different Dewaxing MechanismWaxes converted to Naphtha & DistillateCan produce very low pour specialty productsYields better than SDW

Less Environmental ConcernsLower Manpower RequirementsLower Operating and Investment Cost

MLDW Characteristics

Waxes are Selectively Cracked to Naphtha and LPG

Two Reactor Cascade SystemReactor 1: Zeolite catalyst for dewaxingReactor 2: Commercially available hydrotreating catalyst

Low Hydrogen Consumption

Cyclic ProcessReactor temperature increased during cycle to meet pour point spec.At end of cycle, catalyst is reactivated to restore activity

Can Process a Full Range of Basestocks

Replaces and/or Supplements Solvent DewaxingCan make ultra-low pour point basestocks

Especially Attractive Option for Bright-stock Production


GroupI/II

CatalyticDewaxing

GroupII/III


LubeHydrocracking

LubeHydrotreating

FuelsHydrocracking

GroupI/II

SolventDewaxing


Deasphalting

Hydroprocessing Reduces Sulfur, Nitrogen and Boosts VI

Group IIGroup III

All Catalytic Group II & Group IIILube Plant

Hydroprocessing(HDT/RHC/LHDC)Hydroprocessing(HDT/RHC/LHDC)

CatalyticDewaxingCatalyticDewaxing

HydrofinishingHydrofinishing

0

20

40

60

80HDC

LHDC

RHC

HDT

Fuels Manufacture Hydrocracking

Lube Manufacture Hydrocracking

Raffinate Hydroconversion

Raffinate Hydrotreating

Conversion to 360O CBase

VI In

crea

se

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 375oC+ (20 to 40+ Carbons)VI uplift critical to production of high quality lubesConversion to fuels is controlled by the catalyst acidity

Hydrocracking Chemistry is Complex and Involves:Heteroatom removal (S, N)Aromatics hydrogenationAromatics dealkylationNaphthene cracking

Typical Operating ConditionsLHSV 0.5 to 1.0 h-1

Temperature ~ 400oCH2 pressure > 100 atmTreat Gas Rate 5,000 to 10,000 SCF/bbl

Lube Hydrocracking (Cont.)

H/C Catalysts are BifunctionalHydro-dehydro function provided by NiMo or NiW in sulfidedformAcid 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 VIConversion of aromatics to naphthenes to fuelsIncreased concentration of paraffins in lubes

Hydrocracking vs Solvent Extraction Results in Higher Lube Yields, Rich in Naphthenic Species

Maximizing Use of Existing Group 1 Equipment

Extraction HDT orRHCTM

Catalytic DewaxingDistillate

SolventDewaxing

70-80% Yield

50-70% yieldVI uplift 10-

35



300-600 scfb 100-400 scfb

Base Stock


GroupI/II

CatalyticDewaxing

GroupII/III


LubeHydrocracking

LubeHydrotreating

FuelsHydrocracking

GroupI/II

SolventDewaxing


Deasphalting

Catalytic Dewaxing

Primary Function is to Improve Cold Flow Properties of LubesBy removing or converting n-paraffins

Decrease pour point and cloud point

Development of Catalytic Dewaxing is Tied to the Discovery of Medium Pore Zeolites :

Control of acidity by de-alumination or al substitutionSteam treatmentAcid extraction

Shape selectivityAbility to selectively reacts molecules with smaller critical sizes

Paraffins < Isoparaffins << Naphthenes and AromaticsDiffusion/adsorption control in microcrystalline materials

Hydro-Dehydro Metal FunctionImpacts severity of processing conditions

Catalytic Dewaxing: Shape-Selectivity in Action

Performance Influenced by Choice of Zeolite

AcidityCrystal size and morphologyPore size and shape

MLDW™Primarily crackingNo noble metals

MSDW™Primarily isomerizationNoble metals catalyst

n-Decane Conversion (%)is

o-D

ecan

eYi

eld

(%)

0

20

40

60

80

100

0 20 40 60 80 100

MSDW™MLDWMSDW™MLDW

Lube Hydrocracker with MSDW™

Lube Hydrocracker MSDWDistillate



H2 Consumption 100-400 scfb800-2000 scfb

Base Stock

MSDW-2 MLDW(Isomerization) (Cracking)

Pour Point, °C -15 -15KV @ 100°C, cSt 5.03 5.57Viscosity Index 113 102Lube Yield, wt% 94.2 75.9

Historically MSDW preferred for lighter viscosity grades

Flow Diagram For DAO Hydrocracking

VGO/DAO

Hydrogen Feed

Low Temp.Separator

Steam

HighTemp.Separator

Reactor

LeanAmine

RichAmine

Off-Gas

Stripper

RecycleCompressor

Fractionator

Gasoline

Naphtha

Kerosene

Diesel

Steam

WaxyBasestocks or FCC Feed

HDC Reaction Zones

Reactor Catalyst HDCConfiguration Type Reactions

Metal

Bifunctional(Metal + Acid)

TreatingZone

CrackingZone

HDM

HDN

selectivecracking

with low arosat

Sulfur polishingIf needed

Post TreatZone Metal

HDS

HDA

Bright Stock made from Hydroisomerization (MSDW) and Catalytic Dewaxing (MLDW)

MSDW MSDW MLDW MLDW (est)Case 1 Case 2Gr II Gr I+ Gr I Gr I+

Color 13 saybolt -9 saybolt 2.5 astm 3.5 astmPour,C -14 -7 -6 -6Cloud,C -1 3 -KV@100C 29.9 29.1 31.86KV@40 C 410.1 389.15 486.73API - 27.7 25.3density@70C 0.8508 0.8552 -Sats,% >90 78 ~60Sulfur 85ppm 639ppm 1.2wt%Nitrogen,ppm <1 16 145VI 102.5 103.4 96

102Haze no no noYield,wt% 75 83 85-90 78Extract. yield, wt% 71 71 71 20MSDW can allows BS Production by all Hydroprocessing Route

MSDW-2 Pilot Study on Hydrocracked DAO

20

40

60

80

0 50 100 150 200 250Time on stream, days

Dew

axin

gT

empe

ratu

re, °

C

22 ppm N, 150 ppm S0.14% CCR24 ppm N, 280 ppm S

0.06% CCR

2 ppm N8 ppm S

2 ppm N18 ppm S

160 ppm N, 700 ppmS, 0.57% CCR

Base

+

+

+

+

HDC HVGOfeed 1 -reference

HDC DAOfeed 2

HDC DAOfeed 3

HDC DAOfeed 4

HDC DAOfeed 5

MSDW catalyst is tolerant to poisons and maintains activity

Feed # 2 3 4 5HDC Severity High Low High Low

MSDW FeedkV@100°C, cSt 10.3 18.9 12.8 23.5Nitrogen, ppm 2 24 22 157Sulfur, ppm 8 283 146 704CCR, wt% 0.01 0.06 0.14 0.57

MSDW Product (Bottoms Fraction)kV@100°C, cSt 20.7 28.9 24.1 40.1VI 120 100 107 93Pour point, °C -14 -11 -2 -8

DAO BDAO A

MSDW-2 Pilot Study on Hydrocracked DAO

MSDW Advantage: Bright-Stock Production

0

10

20

30

40

50

60

70

KV@100C

1000 90 33 8 3

Nitrogen,ppm

Increasing LHDC Severity---->

010

203040

50607080

90100

B.S. Yield, wt%

1000 90 33 8 3

Nitrogen,ppm

Increasing LHDC Severity---->

Combined HDC/MSDW Performance

MSDW can tolerate higher levels of Nitrogen allowing improved yields and blending flexibility

All Hydroprocessing option for Bright-Stock Production

High Throughput Experimentation Accelerating Catalyst Innovation

Analysis

ExperimentalDesign

Automation &Robotics

High SpeedAnalysis

DatabaseManagement

Informatics

Robotics

Analytics

1 2

3 4

5

6

A

B

C D E F G I0.E+00

4.E+05

8.E+05

1.E+06

2.E+06

Mw

Activator Catalyst

Copyright 2002 Symyx Technologies, Inc. Used with permission.

R&D Focus is to Develop More Active/Selective Catalysts

Activity/Selectivity

Time

Dewaxing:MSDW/ MLDWHydrofinishing:MAXSAT™

60

80

100

200 240 280 320 360 400Temperature, °C

Estimate of Equilibrium Saturates

400 psig, H2

600800

12001800

Satu

rate

s, w

t%

Why Hydrofinish?Removes Polynuclear Aromatics (PNA) and Trace Amounts of OlefinsImproves Color, Oxidation and Thermal Stability of Base OilsPNA Equilibrium Concentration Controlled by Reaction Temperature and Pressure

Aromatic Saturation

0

2

4

6

8

0 20 40 60 80

Relative Temperature

Rel

ativ

e A

rom

atic

s KineticcontrolEquilibriumControlKineticControlEquilibriumControl

High Activity Catalyst Can Provide Significant Advantage

Increasing Pressure

MSDW Base Oil Production

Hydrocracked Light Neutral FeedstockHydrocrackedHydrocracked Light Neutral FeedstockLight Neutral Feedstock

Yiel

d W

t, %

Yiel

d W

t, %

MSDW-2MSDW-2MSDW-1MSDW-1

SolventSolvent

75

80

85

90

95

100

-50 -40 -30 -20 -10 0 10100

104

108

112

116

120

-50 -40 -30 -20 -10 0 10Pour Point, ºC Pour Point, ºC

VIVI

MSDW-2MSDW-2

MSDW-1MSDW-1

SolventSolvent

Increase Selectivity/ ActivityIncrease Selectivity/ Activity

Direct Isomerization of Slack Wax to High Quality Lubes (MWI™ - Process)

Hydro-Isomerization

Slack Wax

50-70% yield130 to 160 VI

H2 Consumption 200 - 400 scfb

Basestock

Technology for Converting Methane to Liquid ProductsFischer Tropsch Products Have Virtually No Impurities

Essentially Sulfur- and Nitrogen-freeVery low aromatic content High-Quality Ultra

CleanProducts, Incl. Fuels and Lube

Basestocks

Syngas Generation

Hydrocarbon Synthesis

Product Upgrading

GTL Process

Natural Gas

Steam

Oxygen Wax

GTL Basestocks Expected to Be Highly Paraffinic

GTL VI Could be Comparable to PAO of Similar Viscosity

Paraffins

Gas oil

Group I

Group II

Group III

PAO

Naphthenes Aromatics

Viscosity Index

GTL

Vola

tility

5

10

15

20

Viscosity @ 100°C, cSt4 5 6 7 8

GTL Lube Basestocks

GTL Basestocks Performance May Approach That of Chemically Derived PAO

Group I / Group II 95 VI

Group II+

Mid Tier Group III

Top Tier Group III+

Group IV / PAO’sGTL?

Conclusions

MLDW Catalytic Dewaxing is Excellent for BS Manufacture at Conventional VI Levels for Group I With Yields Equal or Better Than Solvent Dewaxing.Hydroisomerization (MSDW) is Excellent for Higher VI BS and Group II BSMSDW’s Polar Tolerance Allows Excellent YieldsImproved Catalysts (Activity/Selectivy on the Horizon)Integrating Catalytic Hydroprocessing/Dewaxing Can Extend the Asset Life of Conventional Solvent Based Lube Base-Oil PlantsExxonMobil Technologies Provide Competitive Advantage in Broad Range of Solutions

Wax Hydrosomerization1991

MSDW-11997

Raffinate Hydroconversion1999

MSDW-21999

Lube Hydrocracking1923

MAXSAT2001

Lube Dewaxing(MLDW) 1981

Fuels HDC BTMs toLubes 1989

Wax Hydrofining1953

Lube Hydrofining1954

White Oils1973

70 Years of ExxonMobil Innovation in Catalytic Lube Processing –

Catalyst Improvements being rolled out

Ajit Sapre - ExxonMobil

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