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MLRT-LNQ 2Hanoi University of Technology

LECTURERS BACKGROUND Professional Experience

- 20 years with Mobil Oil Corporation

- 14 years in Research & Development in Refining and Petrochemical

- 57 U.S. Patents and 6 Publications

Expertise:

- Refining Technology, especially in Hydroprocessing (HDT,HDC, ISOM)

- Clean Fuels, Lube Production Technology, Zeolite Catalysis

Education:

- BS in Chemistry & Math at Illinois State University (1975)

- MS in Chem. Eng. at University of Massachusetts (1977)

- PhD in Chem. Eng. at University of Massachusetts (1980)

At Present:

- President of US-based Pacific Energy Company (PEC),

Oil & Gas Technology Consulting Company (Hanoi & HCMC Offices)

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Introduction

Lube Oil Technology

Trends in Lubricants- Global vs Vietnam Markets Lubrication Science

Chemical Composition of Crude Oil & Lube Fractions

Lube Refining Technology

Conventional Lube Production via Solvent Extraction

- Propane De-Asphalting- Furfural Extraction and MEK Dewaxing

Catalytic Lube Dewaxing Technology using Zeolite Catalysts

- Wax Cracking (MLDW), Wax Hydroisomerization (MWI)

Advances in Catalytic Lube Processing

Lube Product Development Process Additives

Synthetic Lube Base Stocks

Petroleum Wax Orientation

Environmental Effect of Used Lubricants

OUTLINE OF MLRT COURSE

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MLRT-LNQ Hanoi University of Technology 4

LUBE BASE STOCKS

PRODUCTION

TECHNOLOGY

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API Classification of Lube Base Oils

Group Saturate Sulfur Viscosity Indexwt% wt% VI

I < 90 > 0.03 > 80 to

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Markets for Lube Oil Base Stocks

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Global Base Oil Refining Capacity (2002)*REGION No. Lube Refineries/ Total Capacity

Plants BPD

Canada 4 26,500

United States 23 218,900

Latin America 13 59,805

Europe 24 177,444

Former Soviet Union 17 259,600

Middle East & Africa 15 49,245

Asia 34 20,533

Australia 3 12,679

TOTAL 133 1,024,706

* LUBRICANT WORLD 4thANNUAL Edn. 2002, BPD= Barrels Per Day

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Lubricant Demand Forecast in Vietnam

0

50000

100000

150000

200000

250000

300000

1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010

Year

MetricTon/yr

The Market of Vietnam Lubricants

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COMPANY LOCATION CAPACITY, MT

BP-Petco Nha Be 50,000

ExxonMobil-Unique Dong Nai 25,000

Castrol-SaigonPetro Cat Lai 30,000

Shell Codamo Dong Nai 25,000

Petrolimex HCMC 15,000

Vilube Nha Be 25,000

Indochina HCMC 10,000

Mekong Lube Vinh Long 10,000

Bao Thanh HCMC 10,000

PVPDC (PetroVietnam) HCMC 5,000

Tan My Tien Giang 5,000

Capacity in the South (195,000)

Petrolimex Hai Phong 25,000

Caltex Hai Phong 15,000

Total Hai Phong 10,000

APP Hai Phong & Hanoi 10,000

PVPDC (PetroVietnam) Hai Phong 5,000

Van Dao Ha Tay 4,000

12/11-APP Quang Ninh 4,000

Capacity in the North (73,000)

Total Nameplate Capacity 268,000

Vietnam Lube Blending Oil Plants (LOBP)

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Lube Oil Blending Plant (LOBP)

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Drivers for Lubricant Business

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Basic Functions of Lubricants

Preservation Lubrication

CoolingPower Transfer

Lubricant

Functions

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Lubricant Functions:PRESERVATION Maintain Physical Properties

- Pour point, Volatility, Flash Point, Compatibility

- Emulsibility/Demulsibility, Foam Control

Cope with Contaminants and Deterioration

- Dispersancy, Ash Level, Carbon Residue

- Anti-microbial, Oxidative and Thermal Stability Machine Preservation

- Detergency, Corrosion Inhibition, Seal Compatibility

Human Preservation

- Toxicity

Cosmetic- Color, Odor, Taste

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Physics

- Viscosity (T,P and Shear Rate)

- Shear Strength (high P)

- Shear Strength (grease)

- Pour Point (wax form)

Chemistry- Extreme Pressure

- Anti-wear- Anti-fatigue

- Friction Modification

Lubricant Functions:LUBRICATION

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Lubricants Fundamentals: Technology

Lubricants are segmented into Automotive, Industrial,

Marines & Specialties (60% volume for global Automotive

Lubricants)

Products are blended to qualities established by SAE

(Society of Automotive Engineers) and OEMs (OriginalEquipment Manufactures).

Important application in internal combustion engines,

vehicles and industrial gear boxes, compressors, turbines or

hydraulic systems.

Complex tasks to balance the Lube Base Stocks and

Additives.

Between 5,000-10,000 different lubricant formulations.

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Lubrication Science & Technology

Engineering FRICTION

Physics WEARChemistry LUBRICATION

TRIBOLOGY

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Lube Products orLubricantsLube Oil Base Stocks

Additive Package

(>1% to 25% or more)

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Lube Base Stocks- Key PropertiesComplex Mixture of Paraffins, Naphthenes and

Aromatics with Carbon number from 14 to 40+Viscosity from 4-20 cSt @ 1000C for 100-500 SN and

32 cSt for Bright Stock

Viscosity Index(VI) ranging 80 to 140+

Oxidative StabilityCloud Point

Pour Point( typical 200F or70C)

Flash Point

ColorCCR(Carbon Residue after evaporation)

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Viscosity Measurement Kinematic Viscosity

Driving Force Lubricant weight (density)

Kinematic Viscosity = / = cSt /

Dynamic Viscosity

(cP) (Gap x Torque) / (Geometry x Speed)

Both Need Accurate Temperature Control

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Viscosity Units

Viscometer Times (inexact)- Saybolt Universal Seconds (SUS). UK

- Redwood Seconds. UK

- Engler DegreesEurope, USSR

Kinematic Viscosity (Exact, inappropriate)

- (BRI) in2/sec 1 cS = 0.00155 in2/sec

- (CGS) Stoke (S) , centiStoke (cS) 1 cS = 0.01 S

- (SI) mm2/sec 1 cS = 1 mm2/sec

Dynamic Viscosity (Exact, appropriate)

- (BRI) Reyn (Lbf.sec/in2), Reyn 1 cP = 0.145 Reyn

- (CGS) Poise (P), centiPoise (cP) 1 cP = 0.01 P

- (SI) Pascal second (Pa.sec) 1 cP = 0.001 Pa.sec

Common 00F - 180C

Measurement 1000F 400C

Temperature 2100F 1000C

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Viscosity Index Definition & Calculation

100 VI

0 VI

Changes:

- Remove low viscosityIntersection

- Convert SUS to cSt

- Extend down to 2 CS @ 2100F

- New Definition for VI > 100

- Convert from 100/2120F to

40/1000C

- ASTM D 2270

Relationship of VI & Pour Point for

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Relationship of VI & Pour Point for

Hydrocarbon Model Compounds

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VI and Pour Point of Model Hydrocarbons

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Important ASTM Oxidation Testing Methods

American Standard Testing Methods (ASTM)

ASTM D-2272

RBOT

(Rotary Bomb

Oxidation Test)

for short-termtesting

ASTM D-943

TOST(Turbine Oil

Stability Test)

for long-term

testing

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Chemical Compositions

of Crude Oil &

Lube Fractions

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Importance ofComposition

o Refining Processes

- Separation Processes: Distillation, Solvent

Extraction, Solvent Dewaxing

- Conversion Processes: Catalytic Dewaxing,

Hydrotreating, Hydrocracking

o Base Stock Physical and Chemical Properties

- Viscosity, Viscosity Index, Pour Point, Thermal and

Oxidative Stability

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Complex Mixture of Hydrocarbons with Varying

Amounts of Compounds Containing Nitrogen, Sulfur,

Oxygen and Metals.

Components Contain from 1 to over 100 Carbon Atoms.

No Two Crude Oils Exactly Alike from All Aspects.

Range from Light Liquids to Semi-Solids with API

Gravities from 5 to 40

PETROLEUM CRUDE OILS

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Complexity of Crude Oils

Carbon Atoms

1025

40

Possible

Paraffinic Isomers

7537,000,000

62,000,000,000,000

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Carbon Number vs. Boiling Point

LN & HN BS

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CHEMICAL COMPONENTS OF CRUDE OIL

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Aromatics in Crude Oil Lube Fractions

Good Solvency for Additivesand Deposits, Poor VI andExcellent Oxidative Stability

Higher Ring Structures withpartial Saturation LessDesirable as Lube Base StockComponents due to Very PoorOxidation Stability

Mono-Aromatics

Polynuclear Aromatics (PNA)

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Components with Complex Structures

Resins-Red, Dark, Colored Components

-Enriched in S, N, O

-Chemically Unstable, High CCRAsphaltenes-Precipitated from Crude Oils by

Aliphatic Solvents (C3-C5). Soluble

in Benzene, 1000-3000 MW-Very High in S, N, O, and Metals(V, Ni). Asphaltenes Structure

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Influence of Heteroatom Compounds on

Lube Base Stock Characteristics and Processing

Boiling Point/Yield Relationship

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Boiling Point/Yield Relationship

LUBE FRACTIONS

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Introduction to Lube Processing

Properties of Lube Base Stocks

Crude Evaluation

Processing

Costs

Processing Trends

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LUBE BASE STOCKSCRUDE TYPE

NaphthenicParaffinic

API Gravity 28 32

Viscosity, SUS at 100oF 100 100Pour Point, oF - 45 0

Viscosity Index (VI) 45 100

Flash Point, oF 340 390

ASTM Color 1 1/2

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LUBE BASE STOCK TYPESViscosity Quality

100 SUS Turbine (Spec 4,000 Hr TOST)

150 SUS300 SUS Auto (Spec 1,000 Hr TOST)

450 SUS

700 SUS Regular (Spec 1,000 Hr TOST)

2700 SUS 2700 SUS

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Products from Crude Oil

LIGHT

FUELS

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Complex Refinery Configuration(280,000 b/d)

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Lube Oil Base Stock ManufactureFURFURAL

SOLVENT

EXTRACTION1

2

3

4

MEK

SOLVENT

DEWAXING

4

CLAY

OR

HYDROGEN

FINISHING

1

2

3

4

1

2

3

1

2

3

Propane

De -

asphalt

NEUTRAL

DISTILLATES

WAXYRAFFINATES

DEWAXEDOILS

LUBE BASESTOCKS

VACUUM

DISTILATTION

FURFURAL

EXTRACT

WAX

ASPHALTS

ATMOS.

RESID

VACUMM

RESID.

Light

Hydrocarbon

CATALYTIC

DEWAXING

DE-ASPHALTED

OIL4

* Tanks Represent Different Viscosity Grades

BS

HN

LN

LN

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Key Features of ConventionalLube Base Stocks ManufactureBlock Operation- Requirement of Many Storage TanksHigh Operational Cost- Combination of Several Solvent

Extraction Technology

Energy intensive- Requirement for refrigeration, high

Volume of Solvent, Solvent Recovery, Separation

Expensive Process (Cost of Solvents, Energy, etc)

New Trend- Replacing Solvent Technology withCatalytic Technology

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Typical Lube Vacuum Tower Design

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Properties Set by DistillationViscosity

Flash Point

Volatility

Demulsibility

Color

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Crude Oil Composition - Simplified100

0

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Viscosity-Yield Curve Arab Light Crude

MID VOLUME on crude

100"

300"

700"

OVFL

RESID

60 65 7075

80 9085 95

100000

10000

1000

100

10

viscositykvat1000C

.cst

Undesirable Constituents of

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Undesirable Constituents of

Lube Oil Fractions

CONSTITUENTS EFFECT REMOVED BY

Acids (Naphthenic Acids) - Reduced Storage Stability - Refining

- Corrosion Hazard

Sulfur - Reduced Storage Stability - Refining

- Corrosivity

- Unpleasant Smell

Unstable Compounds - Reduced Storage Stability - Refining

- Olefins, Nitrogen

- Unstable Aromatics

Paraffin Wax - Poor Flow Properties - Selective Precipitation

at Low Temperature

Asphaltenes & Resins - Sludge Formation - Refining

- Selective Precipitation

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Propane De-Asphalting

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Propane De-Asphalting ProcessPropane Extraction of Oil in Vacuum Residuum

Asphalt Production by Precipitation of Asphaltenes

Solubility of Oil in Propane increases with Pressure

and decreases with increased Temperature

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Lube Oil Base Stock Manufacture:PROPANE DE-ASPHALTING

FURFURAL

SOLVENT

EXTRACTION1

2

3

4

MEK

SOLVENT

DEWAXING

4

CLAY

OR

HYDROGEN

FINISHING

1

2

3

4

1

2

3

1

2

3

Propane

De -

asphalt

NEUTRALDISTILLATES

WAXYRAFFINATES

DEWAXEDOILS

LUBE BASESTOCKS

VACUUM

DISTILATTION

FURFURAL

EXTRACT(FOOT OIL)

WAX

ASPHALTS

ATMOS.

RESID

VACUMM

RESID.

Light

Hydrocarbon

CATALYTIC

DEWAXING

DE-ASPHALTED

OIL (DAO)4


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Propane De-Asphalting SchemeDe-Asphalted

Oil (DAO)

Asphalt

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Propane De-asphalting Unit

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Propane De-asphalting Unit

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Propane De-asphalting: Compositions

NAPHTHENES

PARAFFINS

AROMATICS

RESINS

ASPHALTENES

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Performance ofPropane De-Asphalting ProcessFEED* De-Asphalted Oil** ASPHALT

Yield, vol% 30 70

Product Properties:

Density @150C, g/mL 1.024 0.932 1.063

Viscosity @ 400C, cSt ---- 1040 -----

@1000C, cSt 1500 34 20000

Carbon Residue, wt% 20 1.4 -----

Sulfur, wt% 4.9 2.7 -----

Nickel, ppm 29 0.2 -----

Vanadium, ppm 100 0.4 -----

Softening Point,

0

C ---- ---- 65.5Penetration @ 250C, 0.1 mm ---- ---- 12

* Feed: Vacuum Residue

** De-Asp halted Oil for B right Stock Product ion

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Solvent Extraction

with FURFURAL

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Lube Oil Base Stock Manufacture:Furfural Solvent Extraction

FURFURAL

SOLVENT

EXTRACTION1

2

3

4

MEK

SOLVENT

DEWAXING

4

CLAY

OR

HYDROGEN

FINISHING

1

2

3

4

1

2

3

1

2

3

Propane

De -

asphalt

NEUTRALDISTILLATES

WAXYRAFFINATES DEWAXEDOILS LUBE BASESTOCKS

VACUUM

DISTILATTION

FURFURAL

EXTRACT(FOOT OIL)

WAX

ASPHALTS

ATMOS.

RESID

VACUMM

RESID.

Light

Hydrocarbon

CATALYTIC

DEWAXING

DE-ASPHALTED

OIL4


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Properties Set by FurfuralExtractionViscosity Index

Oxidation Stability

Thermal Stability

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Objectives of Solvent Extraction Process

Liquid-liquid extraction of Lubricating OilDistillates

Production of Waxy Raffinates

Removal of Aromatics

Removal of other Undesirable Constituents Suitable Extractants are Furfural, Phenol,

SO2, N-Methyl Pyrrolidone (NMP), Aniline,Nitrobenzene

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Characteristics of Ideal Solvent forExtraction of Lubricating Oils High Selectivityfor Desirable Components

Good Solvent PowerLow Solvent to Feed Ratio

High Extraction Temperaturefor Good Mass Transfer

Easy Recoveryby Simple Distillation

Low Vapor PressureAvoid Use of High Pressure Vessels

High DensityRapid Separation of Oil and Solvent Phases

No EmulsificationRapid Separation of Oil and Solvent Phases StabilityNo Chemical or Thermal Degradation

AdaptableEffective for Wide Range of Feed Stocks

AvailableReasonable Cost Non-Corrosiveto Conventional Metals of Construction

Non-ToxicEnvironmentally Safe

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Commercial Extraction SolventsFurfural, N-Methyl 2-Pyrrolidone (NMP) and Phenol

Furfural is preferred because of:

- High Selectivity- Moderate Toxicity

- Low Cost

- Availability

Excellent for Paraffinic Oil

(high extraction Temperature)

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Furfural Extraction Process

RAFFINATE PHASE

Rotating

Disk

extractor

RAFFINATE

recovery

furfural RAFFINATE

Extract phase

DISTILLATE FEED

furfural

furfural extract

Extract

Recovery

furfural

furfural

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Furfural Extraction: Composition

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Properties of Distillate ComponentsOxidation

VI Stability

Paraffins Excellent Good

1-Ring Naphthenes Good Fair

2+ Ring Naphthenes Fair Fair

1-Ring Aromatics Good Fair2+Ring Aromatics Poor Poor

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Performance ofFurfural Extraction ProcessFEED* RAFFINATE

Yield, vol% --- 82.3

Product Properties:

Density @150C, g/mL 0.884 0.865

Refractive Index @ 210C 1.4769 1.4603

Viscosity @ 400C, cSt 68.9 52.5

@1000C, cSt 8.8 7.9

Pour Point, 0C 35 43

Sulfur, wt% 0.70 0.24

ASTM Color >8.0 2.0

Viscosity Index 99 118

VI (after Dewaxing to-180C Pour Point) 84 100

* Feed: 350 LN Dis tillate

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Monitoring VI and Quality byRaffinate Refractive IndexArab Light

150 SUS LN

I t f Vi it I d

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Importance of Viscosity Index

Indicator of Lube Quality, Stability for Constant

- Feed

- Processing

Minimum VI of 95 for Marketing

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Solvent Extraction Process Variables

Oil CompositionSolvent Dosage (Solvent/Oil Ratio)

Extraction Temperature

Number of Extraction Stages (Extraction Efficiency)

Solvent Contaminants

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Effects of Oil Composition onSolubility in Furfural

Effects of Dosage

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Effects of Dosage

a. Solubility in Furfural b. Extraction Products

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Typical Commercial Furfural Dosages

Furfural Dosage, Vol%

Viscosity Grade Arab Light Statfjord

100 SUS 150 220300 SUS 175 240

850 SUS 240 290

Bright Stock 260 300

Effects of Temperature on

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a. Solubility Furfural b. Extraction Products

Effect of Temperature Profile in Extractor

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Concept Intercooling Application

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Effect of Extraction Temperature onOxidation Stability

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What is an Equilibrium Stage?

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Factors Affecting Extraction Efficiency

General: Depends on Mixing/Settling Characteristics of System

Unit Construction

Throughput

Viscosity/Gravity of Oil/Solvent Solvent Dosage

Temperature, Temperature Gradient

Deposits

Degraded Oil or Solvent

Rotor Speed

Effect of Stages on

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Raffinate Quality and Yield

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High Efficiency ExtractionCommercial Experience

100 SUS

300 SUS

700 SUS

PackedTower

53

54

50

High EfficiencyRDC

58

59

54

5

5

4

Furfural Raffinate Yield (Vol %) Improves Significantly

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Effect of Furfural Quality onExtraction

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Solvent Recovery Objectives Recover Furfural from Product Mix Streams

Purify Furfural for Recycle

Maximize Energy Efficiency

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Solvent ContaminantsContaminant SourceWater Steam Stripping in

Solvent Recovery

Oil Incomplete Solvent-Oil

Separation (Usually Extract)

Effect of Water Contamination in

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Effect of Water Contamination in

Furfural Extraction

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Solvent Recovery Constraints

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Methyl Ethyl KetoneSOLVENT DEWAXING

Lube Oil Base Stock Manufacture:

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MEK SOLVENT DEWAXING

FURFURAL

SOLVENT

EXTRACTION1

2

3

4

MEK

SOLVENT

DEWAXING

4

CLAY

OR

HYDROGEN

FINISHING

1

2

3

4

1

2

3

1

2

3

Propane

De -

asphalt

NEUTRALDISTILLATES

WAXY

RAFFINATES

DEWAXED

OILS

LUBE BASE

STOCKS

VACUUM

DISTILATTION

FURFURAL

EXTRACT(FOOT OIL)

WAX

ASPHALTS

ATMOS.

RESID

VACUMM

RESID.

Light

Hydrocarbon

CATALYTIC

DEWAXING

DE-ASPHALTED

OIL4


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Properties Set by DewaxingPour Point

Cloud PointFilterability

Low Temperature Fluidity

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Solvent Dewaxing: Composition

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Lab Dewaxing using MEK/Toluene

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Dewaxing for Lubes - MEK Process

Improvement MEK Dewaxing ProcessE M bil DILCHILL C t lli

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ExxonMobil DILCHILL Crystallizer

AMORPHOUS WAX SPHERIAL WAX

(CONVENTIONAL) (IMPROVED)

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Improved MEK Dewaxing Process

Improved MEK Dewaxing Process:

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ExxonMobilsMembrane Separation Technology

Propane Dewaxing ProcessE M bil S l t D i T h l

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ExxonMobil Solvent Dewaxing Technology

Propane Dewaxing Advantage:-4-6 time faster Filter Rate

-50-77% less Oil in Wax

-40-50% less Solvent Dilution

-40% less Investment

-Beneficial for Heavy Lube

Base Stocks

-Grass-Roots Plant built in 1997

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MEK Dewaxing ProcessMain Sections of Plant

- Solvent Dilution and Wax Crystallization

- Filtration

- Dewaxed Oil Solvent Recovery

Auxiliary Systems

- Solvent Decantation and Water Removal

- Refrigeration- Inert Gas Circulation

MEK Dewaxing Cycles : Four Steps

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WAX CAKE

DISCHARGE

FILTRATIONWASH.

FLUE

GASBLOW

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Solvent DewaxingProcess Principles

Solvent Dewaxing Overview

Charge Stock

Solvent Composition

Solvent Utilization

Repulping / DeoilingDewaxing Trends

Typical Lube Yields via MEK Dewaxing

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yp g

Arab Light Crude

Commercial Laboratory

Lube Slack Wax Lube Slack Wax

Pour Point Yield Oil Content Yield Oil Content

BASE STOCK oC % Vol. % Vol. % Vol. % Vol.

100 SUS Auto/Turbine -18 78 15 83

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Effect of Feed Composition onDewaxing YieldArab Light 700 SUS Raffinate

Automotive TurbineTreat Treat

Dewaxed Oil Yield 86 83

@ 20oF/-7oC Pour

COMPOSITION, wt%

Paraffins 28.7 30.6

Mono-Naphthenes 18.3 18.5Poly-Naphthenes 20.5 25.1

Aromatics 32.5 25.8

Effect of Oil Viscosity on

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Dewaxing Filter Rate

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Effect of Crude Source on Dewaxing Yield

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Arab Light Statfjord

Pour Lube Slack Wax Lube Slack WaxPoint Yield Oil Content Yield Oil Content

oF/oC % Vol. % Vol. % Vol. % Vol.

100S US Auto* 0/-18 76 0.25 70 0.2

300 SUS Auto* 15/-9 78 0.45 74 0.3

700 SUS Auto 20/-7 75 40 68 38Bright Stock 20/-7 79 30 69 28

* Inclu des IN-LINE WAX DE-OIL ING

Raff inate Composit ionParaff in s, w t% 35 45

iso /n paraff in Ratio 1.95 1.55

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Solvent DewaxingProcess Principles

Solvent Dewaxing Overview

Charge StockSolvent Composition

Solvent Utilization

Repulping / Deoiling

Dewaxing Trends

Desired Dewaxing Solvent

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CharacteristicsSolubility and Selectivity

Boiling Point Lower Than Oil

Low Sensible Heat

Provides Good Filtration Rates

Non-Toxic and Non-Corrosive

Low Freezing Point

Cheap and Available

Selection of Dewaxing Solvent

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Preferred Solvents

- Ketones(Di-Methyl Ketone, Methyl Ethyl Ketone,Methyl Isobutyl Ketone)

- Chlorinated Hydrocarbons(Di Chloro Methane,

Di Chloro Ethane)

- Toluene

- Blends of the these Compounds

Dual Solvent System

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Dual Solvent System

MEK

- Selectively rejects Paraffins from Solution

- Reduces Crystallization Refrigeration Duty

- May Cause Oil Phase Separation TOLUENE

- Maintains Oil in Solution

- Inhibits Oil Phase Separation

Effect of Solvent Composition

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Solvent, MEK/Toluene

Dewaxing Temp.,0F/0C

Pour Point, 0F/0C (Dewaxed Oil)

% Change in Filter Rate

25/75

0/-18

35/2

--

40/60

2/-17

20/-7

+43

75/25

10/-12

20/-7

+200

FEED: MCS150 SUS LN

Three-Phase Solvent Dewaxing

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Effect of Solvent Composition on Oil

Ph S ti T t

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Phase Separation Temperature

Solvent Dilutions for Dewaxing

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Primary

Secondary

Tertiary

Recirc. Filtrate

Cold Wash

Total Fresh Solvents

100

Raffinate

0.5

0.5

1.0

--

1.0

3.0

(Vol. Solvent / Vol. Charge)

300

Raffinate

0.5

0.5

1.0

--

1.0

3.0

700

Raffinate

1.0

0.75

1.0

--

1.0

3.75

Bright Stock

Raffinate

3.5

--

--

--

1.0

4.5

Effect of Solvent Dilution Ratio

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Filtration

Rate

Oil Content in

Wax

Lube Yield

Wash Ratio

Effect of Temperature of Dilution

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Solvent on Dewaxing Light NeutralsFEED: Arab Light 150 SUS LN

Slurry Temp. , oC 13 13 13

Dilution Solvent Temp.,o

C 13 -1 -12Filtration Temperature, oC -18 -18 -18

% Change in Filtration Rate -- -35 -57

Impact of Repulping/Deoiling onDewaxing Performance

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Operating Conditions

Solvent MEK Content, %

Total Dilution Ratio

Filtrate Recycle Ratio

Wash Ratio

Filter Feed Temp., oC

Yields, Vol %

Dewaxed Oil

Wax

Foots OilProduct PropertiesDewaxed Oil VI at -7oC

Wax Oil ContentWax Penetration at 25oC

CASE 1Dewaxing

54

2.6

1.0

1.7

-15

Commercial Statfjord 700 SUS HN Feed

Dewaxing

69

1.9

0.4

1.3

-12

Repulping

69

0.6

--

0.5

-12

Dewaxing

69

2.3

0.7

1.5

-12

Deoiling

69

0.6

--

2.5

16

Deoilin

69

2.7

--

3.0

16

CASE 2 CASE 3

68

32

0

96

38

--

73

27

0

96

26

--

68

13

19

96

0.9

14

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Composition of Various Slack WaxesArab Light Crude

100A/T 300A 700A BS

COMPOSITION, wt%

Paraffins 94.2 81.8 70.5 51.4

Mono-Naphthenes 2.6 11.0 6.3 16.5

Poly-Naphthenes 2.2 3.2 7.9 9.9

Aromatics 1.0 4.0 15.3 22.2

Lube Oil Base Stock Manufacture:LUBE HYDROFINISHING

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LUBE HYDROFINISHING

FURFURAL

SOLVENT

EXTRACTION1

2

3

4

MEK

SOLVENT

DEWAXING

4

CLAY

OR

HYDROGEN

FINISHING

1

2

3

4

1

2

3

1

2

3

Propane

De -

asphalt

NEUTRAL

DISTILLATES

WAXY

RAFFINATES

DEWAXED

OILS

LUBE BASE

STOCKS

VACUUM

DISTILATTION

FURFURAL

EXTRACT(FOOT OIL)

WAX

ASPHALTS

ATMOS.

RESID

VACUMM

RESID.

Light

Hydrocarbon

CATALYTIC

DEWAXING

DE-ASPHALTED

OIL4


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Objectives of Lube HydrofinishingRemove Color Bodies

Decrease Odor

Reduce Acids

Improve DemulsibilityImprove Oxidation Stability

Remove Residual Solvent

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Lube Hydrofinishing Process

Typical Operating Conditions of

L b H d fi i h

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Lube Hydrofinishers

Reactor Temperature 450550oF

Total Pressure 350500 psig

H2 Pressure 250 psig

LHSV, Hr -1 13

H2 Circulation 5001000 SCF/B

Catalyst Mo Supported on Al203

Cycle Life 23 Years

Hydrofinishing Process Variables

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Effect of Temperature and Space Velocity

Effect of Hydrofinishing on Turbine OilsLIGHT NEUTRAL HEAVY NEUTRAL

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LIGHT NEUTRAL HEAVY NEUTRAL

Properties Charge Product Charge Product

Viscosity at 100oF, SUS 146 145 379 377

Viscosity Index 108 108 105 105

Pour point, oF 5 5 20 20

Sulfur, Wt % 0.52 0.45 0.68 0.68

Nitrogen, ppm 19 19 33 33

ASTM Color

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WAX HYDROFINISHING

FURFURAL

SOLVENT

EXTRACTION1

2

3

4

MEK

SOLVENT

DEWAXING

4

CLAY

OR

HYDROGEN

FINISHING

1

2

3

4

1

2

3

1

2

3

Propane

De -

asphalt

NEUTRAL

DISTILLATES

WAXY

RAFFINATES

DEWAXED

OILS

LUBE BASE

STOCKS

VACUUM

DISTILATTION

FURFURAL

EXTRACT(FOOT OIL)

WAX

ASPHALTS

ATMOS.

RESID

VACUMM

RESID.

Light

Hydrocarbon

CATALYTIC

DEWAXING

DE-ASPHALTED

OIL4


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Typical Wax Hydrofinishing Unit

Typical Wax Hydrofinisher (HDF)

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Operating ConditionsCatalyst CoMo /Al2O3

Temperature 500600oF

H2Circulation 5001500 SCF/B

H2Consumption 5075 SCF/B

Paraffin Wax Microwax

H2Parital Pressure, psig 700 -1500 7002000

LHSV, Hr -1 0.51.0 0.250.50

Effect of Hydrofinishing on Waxes

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PARAFFIN WAX MICROCRYSTALLINE

WAXProperties Charge Product Charge Product

Viscosity at 100oF, SUS 109 95 820 600

at 210oF, SUS 44 42 100 86

Melting point, oF 140 140 170 171

Oil Content, Wt % 1.5 0.5 4.5 1.5Needle Penetration at 77oF 45 13 110 30

ASTM Color

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BASIS: 1000 Bbl Arab Light Crude

BRIGHT

NEUTRALS STOCK

100 SUS 300 SUS 700 SUS 165 SUS TOTAL

Distillate / Resid 84 80 56 165 385

Propane Deasphalting

- Deasphalted Oils - - - 69 69- Tar - - - 96 96

Furfural Extraction

- Raffinate 51 47 29 50 177

- Extract 33 33 27 19 112

Solvent Dewaxing

- Dewaxed Oil 41 37 23 39 140- Slack Wax 10 10 6 11 37

Yields Will Vary for Different Crudes

Comparison of Lube Routes(Statfjord HN Distillate Feed)

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Yield, wt%

LUBE

PROPERTIES

VI

Sus at 1000F

Sulfur, wt%

Nitrogen, ppm

Aromatics, wt%

LHDC

69-43

89-128

519-130

.004-.006

9-6

17-5

*

Solvent

Refined

41-35

90-94

710- 673

0.2-0.17

120-8924-20

Mobil Wax Hydroisomerization0 +

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(30 650 F Conversion)Zeolite BetaIntersecting 6.5x5.6 and 7.5x5.7A0

12-Member Ring Large Pore Zeolite

Very Selective Paraffin Isomerization

Discovered by Mobil in 60s

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Effect of Wax Oil Content on VI for

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MLRT-LNQHanoi University of Technology 129

MWI Process

Performance of MWI Process

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MLRT-LNQ Hanoi University of Technology130

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MLRT-LNQ Hanoi University of Technology131

Performance of MWI-2

Improved Zeolite for Higher VI over

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MLDWZSM-23

Medium Pore High-Silica Zeolite

One Dimensional Structure

4.5x5.2 A0 Channel

10-Member Ring

Mobil Selective Dewaxing Process

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(MSDW)

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