Technology solutions for upgrading lube base oil production

Ajit Sapre
Licensing Director, Europe, Middle East & Africa EXXONMOBIL RESEARCH & ENGINEERING

Technology Solutions for Upgrading Lube Base Oil Production

Ajit V. Sapre Tim H. Hilbert Eric D. Joseck Jean P. Andre

History of Lubricants and Basestocks

Lubricants Have Been Used Since Ancient Times The Petroleum-based Lubricants Business Began In The Mid-1800s Initial Processing Was Limited To Separation By Boiling Point

Base Oil Quality Has Evolved With Process Technology

First Generation Process Technology Developed To Remove Aromatics, Other Impurities Solvent Processing Technology Developed Lower cost to operate Dewaxing 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 Hydroprocessing popular 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 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: 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

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 @ 40oC Bright Stock is Heavy Lube Made From Resid Name 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

Solvent Lube Plant
Crude/Vacuum Crude/Vacuum Distillation Distillation Group I

Catalytic Lube Plant

Group II, Group III Fuels by product

Crude

Fuels Plant (HDC or FCC)

Gasoline & Diesel

Overall Refinery Economics Dictate Crude Selection Solvent Lube Plants Often Limit Crude Choices Catalytic Lube Plants Allow More Flexibility In Crude Selection Lube And Fuel Plants Compete For Same Feeds High Crude To Fuel Margins Can: Cause A Lube Refinery To Shutdown Or Lower Throughput Choose To Operate The Catalytic Lube Plant For Fuels Production Solvent Lube Plants Inherently Have High Operating Cash Costs Energy, Solvent Usage, Labor, Size, Etc.

Traditional Base Oil Production

Properties Set by Units Flash Point KV / Noack Viscosity Index Pour Point Color Stability

Waxy Raffinate Fuels Vacuum Distillation Light Solvent I

Solvent
Light

Solvent Dewaxing

Solvent Extraction

Hydrofinishing

Medium

Atmospheric Resid

Medium

Heavy

Propane Deasphalting

Heavy

Bright Stock

Wax Deoiling

Bright Stock Intermediate Tankage

Solvent Recovery

Wax Hydrofinishing

Wax

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

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

Quality Drivers For Modern Basestocks

Basestocks Base Oil

Additives

Finished Lube

Performance Parameter Fuel Economy Low Emissions Drain Interval

Desired Basestock Quality Low Viscosity Low Volatility Good Stability

Base Oil Grouping (API)

Group I 80 < VI < 120 % Sat < 90% % S > 0.03 Group II 80 < VI < 120 % Sat < 90% % S < 0.03 Group III VI > 120 % Sat > 90% % S < 0.03 Group IV PAOs Chemical Rx
Single Component

Catalytic Hydroprocessing Solvent Refining Very Wide Chemical Spectrum

(E.g. Synthetic Esters)

Group V OTHERS

Chemical Rx

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, Low Temperature Performance, Pour Point, Cloud Point

Molecular Type Links VI, Viscosity, Volatility

WAX: n-Paraffin VI > 200, but SOLID

Noack Volatility, wt%

550

(VI)

(170)

(140)

(100)

(80) (40)

500
MABP, C

(0)

15 40

450

400

(-100)

99

350 10 100 1000

Viscosity, cSt at 40C

Source: API Research Project 42, 1966

Volatility Has Become a Driver For Group III

Group I / Group II 95 VI
20

Group II+ Mid Tier Group III Top Tier Group III+

Volatility, %

15

10

Group IV / PAOs
4 5 6 7 8

Viscosity @ 100C, cSt

Primarily for automotive applications

Processing To Reduce Naphthenes and Aromatics

Paraffins
PAO Group III Group II
Viscosity Index

Group I

Gas Oil

Naphthenes

Aromatics

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

Base Oil Manufacturing

Catalytic Dewaxing

Group I/II

Distillation

Solvent Extraction

Solvent Dewaxing

Finishing

Group I/II

Deasphalting

Lube Hydrotreating

Fuels Hydrocracking

Lube Hydrocracking

Isomerization Dewaxing

Group II/III

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

Deasphalting
Required to Produce Bright Stock Base Oils Well-Known, Conventional Technology Commercialized before WWII

Distillation

Solvent Extraction

Solvent Dewaxing

Finishing

Deasphalting

Removes CCR Removes Metals Removes Polars (i.e. Sulfur, Nitrogen) Reduces Viscosity DAO Becomes Viable HDC Feedstock

Asphaltenes: Materials With Complex Structures Asphaltenes Precipitated 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).
O

C84H98N2S2O3 1248 Mol. Wt. 40.4% Aromatic Carbons 80.85 wt%C 7.92 wt%H 2.24 wt%N 5.14 wt%S 3.85 wt%O

O H N S

S N

Typical Contaminant Distribution in ROSE DAO

% COMPONENT IN DAO
100

Propane
80

Butane

Pentane
SULFUR

60

40 NITROGEN 20 CCR

METALS

ASPHALTENES 0 0 10 20 30 40 50 60 70 80 90 100

DAO YIELD, VOL %

DAO Properties

Vac Resid API KV@100C KV@40 C Sats,% Sulfur,wt% Nitrogen,ppm CCR,wt% Ni,ppm V,ppm 2.77 20.6 62 98 3 8.7 1139 410.1 -1.41 21.6 61.22 389.15

DAO

~70 1000 2.5 1.5

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

Distillation

Solvent Extraction

Solvent Dewaxing

Finishing

Deasphalting

Solvent vs. Catalytic Dewaxing:

Solvent Dewaxing Physically Separates Wax from Base Oil

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

Catalytic Dewaxing - Converts Wax to Isoparaffins

Removes Fewer Naphthenes than SDW / Product is Less Paraffinic Preferentially Removes Low Molecular Weight Normal and Near Normal Paraffins Possible to Produce Very Low Pour Point Base Oils

Catalytic Dewaxing- MLDW

Distillate

Extraction 60-80% yield VI uplift 20-100

MLDW

TM

Base Stock

70-90% yield 100-400 scfb

H2 consumption

Compared with Solvent Dewaxing, MLDW has: A Different Dewaxing Mechanism Waxes converted to Naphtha & Distillate Can produce very low pour specialty products Yields better than SDW Less Environmental Concerns Lower Manpower Requirements Lower Operating and Investment Cost

MLDW Characteristics
Waxes are Selectively Cracked to Naphtha and LPG Two Reactor Cascade System Reactor 1: Zeolite catalyst for dewaxing Reactor 2: Commercially available hydrotreating catalyst Low Hydrogen Consumption Cyclic Process Reactor 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 Dewaxing Can make ultra-low pour point basestocks

Especially Attractive Option for Bright-stock Production

Base Oil Manufacturing

Catalytic Dewaxing

Group I/II

Distillation

Solvent Extraction

Solvent Dewaxing

Finishing

Group I/II

Deasphalting

Lube Hydrotreating

Fuels Hydrocracking

Lube Hydrocracking

Isomerization Dewaxing

Group II/III

Hydroprocessing Reduces Sulfur, Nitrogen and Boosts VI

All Catalytic Group II & Group III Lube Plant

Hydroprocessing Hydroprocessing (HDT/RHC/LHDC) (HDT/RHC/LHDC) Catalytic Catalytic Dewaxing Dewaxing Hydrofinishing Hydrofinishing

Group II Group III

80
HDC

VI Increase

60
LHDC

Fuels Manufacture Hydrocracking Lube Manufacture Hydrocracking Raffinate Hydroconversion Raffinate Hydrotreating

40 20 0
HDT

RHC

Base

Conversion to 360O C

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 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

Maximizing Use of Existing Group 1 Equipment

Solvent Dewaxing 70-80% Yield Distillate Extraction 50-70% yield VI uplift 1035 HDT or TM RHC 80-98% yield VI uplift 5-20 300-600 scfb Catalytic Dewaxing 85-97% yield VI uplift 4-10 100-400 scfb Base Stock

Base Oil Manufacturing

Catalytic Dewaxing

Group I/II

Distillation

Solvent Extraction

Solvent Dewaxing

Finishing

Group I/II

Deasphalting

Lube Hydrotreating

Fuels Hydrocracking

Lube Hydrocracking

Isomerization Dewaxing

Group II/III

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 : 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

Catalytic Dewaxing: Shape-Selectivity in Action

Performance Influenced by Choice of Zeolite Acidity Crystal size and morphology Pore size and shape MLDW Primarily cracking No noble metals MSDW Primarily isomerization Noble metals catalyst

iso-Decane Yield (%)

100 80 60 40 20 0 0 20 40 60 80 100

MSDW MLDW

n-Decane Conversion (%)

Lube Hydrocracker with MSDW

Distillate

Lube Hydrocracker 60-80% yield VI uplift 20-100

MSDW 85-97% yield VI uplift 4-10 100-400 scfb

Base Stock

H2 Consumption

800-2000 scfb

Pour Point, C KV @ 100C, cSt Viscosity Index Lube Yield, wt%

MSDW-2 MLDW (Isomerization) (Cracking) -15 -15 5.03 5.57 113 102 94.2 75.9

Historically MSDW preferred for lighter viscosity grades

Flow Diagram For DAO Hydrocracking

Reactor Fractionator Recycle Compressor Gasoline Lean Amine Naphtha Rich Amine Low Temp. Separator Off-Gas High Temp. Separator VGO/DAO Hydrogen Feed Waxy Basestocks or FCC Feed Steam Steam

Kerosene Diesel

Stripper

HDC Reaction Zones

Reactor Configuration

Catalyst Type

HDC Reactions
HDM HDS HDN HDA
selective cracking with low arosat
Sulfur polishing If needed

Treating Zone

Metal

Cracking Zone Post Treat Zone

Bifunctional (Metal + Acid)

Metal

Bright Stock made from Hydroisomerization (MSDW) and Catalytic Dewaxing (MLDW)
MSDW Case 1 Gr II Color 13 saybolt Pour,C -14 Cloud,C -1 KV@100C 29.9 KV@40 C 410.1 API density@70C 0.8508 Sats,% >90 Sulfur 85ppm Nitrogen,ppm <1 VI 102.5 102 Haze no Yield,wt% 75 Extract. yield, wt% 71 MSDW can allows BS Production MSDW Case 2 Gr I+ -9 saybolt -7 3 29.1 389.15 27.7 0.8552 78 639ppm 16 103.4 2.5 astm -6 31.86 486.73 25.3 ~60 1.2wt% 145 96 MLDW Gr I 3.5 astm -6 MLDW (est) Gr I+

no no 83 85-90 71 71 by all Hydroprocessing Route

78 20

MSDW-2 Pilot Study on Hydrocracked DAO

MSDW catalyst is tolerant to poisons and maintains activity
+ 80 160 ppm N, 700 ppm S, 0.57% CCR 22 ppm N, 150 ppm S 0.14% CCR

Dewaxing Temperature, C

+ 60 24 ppm N, 280 ppm S 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 feed 1 -reference HDC DAO feed 2 HDC DAO feed 3 HDC DAO feed 4 HDC DAO feed 5

MSDW-2 Pilot Study on Hydrocracked DAO

DAO A Feed # HDC Severity MSDW Feed kV@100C, cSt Nitrogen, ppm Sulfur, ppm CCR, wt% MSDW Product (Bottoms Fraction) kV@100C, cSt VI Pour point, C 20.7 120 -14 28.9 100 -11 24.1 107 -2 40.1 93 -8 10.3 2 8 0.01 18.9 24 283 0.06 12.8 22 146 0.14 23.5 157 704 0.57 2 High 3 Low 4 High DAO B 5 Low

MSDW Advantage: Bright-Stock Production

Combined HDC/MSDW Performance
Increasing LHDC Severity---->

Increasing LHDC Severity---->

70 60 50 40 KV@100C 30 20 10 0 1000 90 33 Nitrogen,ppm 8 3

100 90 80 70 60 B.S. Yield, wt% 50 40 30 20 10 0 1000 90 33 8 3 Nitrogen,ppm

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

Informatics
Analysis
Mw

2.E+06

1.E+06

8.E+05

4.E+05

Database Management

Experimental Design

0.E+00
G F 1 E D 3 C

Activator

Catalyst

Analytics
High Speed Analysis Automation & Robotics

Robotics
Copyright 2002 Symyx Technologies, Inc. Used with permission.

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

Activity/ Selectivity

Dewaxing: MSDW/ MLDW Hydrofinishing: MAXSAT

Time

Why Hydrofinish?
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 Temperature
Saturates, wt%
600 80 400 psig , H 2

Kinetic control Equilibrium Control Kinetic Control Equilibrium Control

Relative Aromatics

High Activity Catalyst Can Provide Significant Advantage

Estimate of Equilibrium Saturates

100 1800 1200 800

Increasing Pressure
60

200

240

280

320

360

400

Temperature, C

MSDW Base Oil Production

Hydrocracked Light Neutral Feedstock Hydrocracked Light Neutral Feedstock
100 120

Increase Selectivity/ Activity

Increase Selectivity/ Activity

95 90 85 80 75 -50 -40 -30 -20 -10 0 10 116

MSDW-2 MSDW-1

MSDW-2 MSDW-1
VI

Yield Wt, %

112 108 104 100 -50 -40 -30 -20 -10

Solvent

Solvent

10

Pour Point, C

Pour Point, C

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

Slack Wax

HydroIsomerization 50-70% yield 130 to 160 VI

Basestock

H2 Consumption

200 - 400 scfb

GTL Process

Product Upgrading
Natural Gas Steam Oxygen

Syngas Generation

Hydrocarbon Synthesis

Wax

Technology for Converting Methane to Liquid Products Fischer Tropsch Products Have Virtually No Impurities Essentially Sulfur- and Nitrogen-free Very low aromatic content

High-Quality Ultra Clean Products, Incl. Fuels and Lube Basestocks

GTL Basestocks Expected to Be Highly Paraffinic

GTL

Paraffins
PAO Group III Group II
Viscosity Index

Group I

Gas oil

Naphthenes

Aromatics

GTL VI Could be Comparable to PAO of Similar Viscosity

GTL Lube Basestocks

Group I / Group II 95 VI
20

Group II+ Mid Tier Group III Top Tier Group III+ GTL?

Volatility

15

10

Group IV / PAOs
4 5 6 7 8

Viscosity @ 100C, cSt

GTL Basestocks Performance May Approach That of Chemically Derived PAO

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 BS MSDWs Polar Tolerance Allows Excellent Yields Improved Catalysts (Activity/Selectivy on the Horizon) Integrating Catalytic Hydroprocessing/Dewaxing Can Extend the Asset Life of Conventional Solvent Based Lube Base-Oil Plants ExxonMobil Technologies Provide Competitive Advantage in Broad Range of Solutions

70 Years of ExxonMobil Innovation in Catalytic Lube Processing

Lube Hydrocracking 1923 Wax Hydrofining 1953 Lube Hydrofining 1954 White Oils 1973 Lube Dewaxing (MLDW) 1981

Wax Hydrosomerization 1991 MSDW-1 1997 Raffinate Hydroconversion 1999 MSDW-2 1999 MAXSAT 2001 Catalyst Improvements being rolled out

Fuels HDC BTMs to Lubes 1989