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____________________________ MODERN LUBE REFINING TECHNOLOGY

________________________________________

MLRT

Le Ngoc Quang, PhD HANOI UNIVERSITY OF TECHNOLOGY


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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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OUTLINE OF MLRT COURSE


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
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LUBE BASE STOCKS PRODUCTION TECHNOLOGY

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API Classification of Lube Base Oils


Group Saturate wt% Sulfur wt% Viscosity Index VI

I II III IV V

< 90 > 0.03 > 80 to <120 90 0.03 80 to <120 90 0.03 120 All Poly Alpha Olefins (PAOs) All other Base Stocks

NOTE: American Petroleum Institute (API) classifies Base Stocks in 1990 Hydroprocessing has emerged as preferred technology for high quality Hydrocracking/Hydroisomerization produces VHVI or XHVI high paraffinic Group II-III Group V contains Alkylated Aromatics, Naphthenics, Ester Synthetics, Silicons and Polyglycols

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Markets for Lube Oil Base Stocks

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Global Base Oil Refining Capacity (2002)*


REGION Canada United States Latin America Europe Former Soviet Union Middle East & Africa Asia Australia TOTAL No. Lube Refineries/ Plants 4 23 13 24 17 15 34 3 133 Total Capacity BPD 26,500 218,900 59,805 177,444 259,600 49,245 20,533 12,679 1,024,706

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

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The Market of Vietnam Lubricants


Lubricant Demand Forecast in Vietnam
300000 250000

Metric Ton/yr

200000 150000 100000 50000 0 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010

Year
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Vietnam Lube Blending Oil Plants (LOBP)


COMPANY
BP-Petco ExxonMobil-Unique Castrol-SaigonPetro Shell Codamo Petrolimex Vilube Indochina Mekong Lube

LOCATION
Nha Be Dong Nai Cat Lai Dong Nai HCMC Nha Be HCMC Vinh Long

CAPACITY, MT
50,000 25,000 30,000 25,000 15,000 25,000 10,000 10,000

Bao Thanh PVPDC (PetroVietnam) Tan My


Capacity in the South Petrolimex Caltex Total APP PVPDC (PetroVietnam)

HCMC HCMC Tien Giang


Hai Phong Hai Phong Hai Phong Hai Phong & Hanoi Hai Phong

10,000 5,000 5,000


(195,000) 25,000 15,000 10,000 10,000 5,000

Van Dao
12/11-APP Capacity in the North

Ha Tay
Quang Ninh

4,000
4,000 (73,000)

Total Nameplate Capacity


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268,000
9

Lube Oil Blending Plant (LOBP)

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Drivers for Lubricant Business

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Basic Functions of Lubricants

Preservation

Lubrication

Lubricant Functions
Cooling Power Transfer

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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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Lubricant Functions: LUBRICATION

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


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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 (Original Equipment 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 Physics Chemistry

FRICTION WEAR LUBRICATION

TRIBOLOGY

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Lube Products or Lubricants


Lube Oil Base Stocks Additive Package

(>1% to 25% or more)

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Lube Base Stocks- Key Properties


Complex 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 Stability Cloud Point Pour Point ( typical 200F or 70C) Flash Point Color CCR (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)


in2/sec Stoke (S) , centiStoke (cS) mm2/sec 1 cS = 0.00155 in 2/sec 1 cS = 0.01 S 1 cS = 1 mm2/sec 1 cP = 0.145 Reyn 1 cP = 0.01 P 1 cP = 0.001 Pa.sec

- (BRI) - (CGS) - (SI)

Dynamic Viscosity (Exact, appropriate)


Reyn (Lbf.sec/in2), Reyn Poise (P), centiPoise (cP) Pascal second (Pa.sec)

- (BRI) - (CGS) - (SI)

Common Measurement Temperature


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00F 1000F 2100F

- 180C 400C 1000C


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Viscosity Index Definition & Calculation


Changes: Remove low viscosity Intersection 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

100 VI

0 VI

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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-term testing

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 of Composition
o

Refining Processes - Separation Processes: Distillation, Solvent Extraction, Solvent Dewaxing - Conversion Processes: Catalytic Dewaxing, Hydrotreating, Hydrocracking Base Stock Physical and Chemical Properties - Viscosity, Viscosity Index, Pour Point, Thermal and Oxidative Stability

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PETROLEUM CRUDE OILS

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

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Complexity of Crude Oils


Possible Paraffinic Isomers 75 37,000,000 62,000,000,000,000

Carbon Atoms 10 25 40

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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


Mono-Aromatics
Good Solvency for Additives and Deposits, Poor VI and Excellent Oxidative Stability

Higher Ring Structures with partial Saturation Less Desirable as Lube Base Stock Components due to Very Poor Oxidation Stability

Polynuclear Aromatics (PNA)

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Components with Complex Structures


Resins
-Red, Dark, Colored Components -Enriched in S, N, O -Chemically Unstable, High CCR

Asphaltenes
-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

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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 STOCKS


CRUDE TYPE
Naphthenic Paraffinic

API Gravity Viscosity, SUS at 100oF Pour Point, oF Viscosity Index (VI) Flash Point, oF ASTM Color

28 100 - 45 45 340 1

32 100 0 100 390 1/2

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LUBE BASE STOCK TYPES


Viscosity
100 SUS

Quality
Turbine (Spec 4,000 Hr TOST)

150 SUS
300 SUS 450 SUS 700 SUS Regular
(Spec 1,000 Hr TOST)

Auto

(Spec 1,000 Hr TOST)

2700 SUS
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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 Manufacture


VACUUM DISTILATTION

NEUTRAL DISTILLATES
1 2
FURFURAL SOLVENT EXTRACTION

WAXY RAFFINATES
MEK SOLVENT DEWAXING

DEWAXED OILS
CLAY OR HYDROGEN FINISHING

LUBE BASE STOCKS LN


1

1 2

1 2

LN
2

ATMOS. RESID

FURFURAL
EXTRACT

WAX

HN
3 3

BS

Propane De asphalt

DE-ASPHALTED OIL

Light Hydrocarbon
CATALYTIC DEWAXING

ASPHALTS

VACUMM RESID.

* Tanks Represent Different Viscosity Grades

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Key Features of Conventional Lube Base Stocks Manufacture

Block Operation- Requirement of Many Storage Tanks High 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 with Catalytic Technology

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Typical Lube Vacuum Tower Design

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Properties Set by Distillation


Viscosity Flash Point Volatility Demulsibility Color

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Crude Oil Composition - Simplified


100

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Viscosity-Yield Curve Arab Light Crude


100000

10000

viscosity kv at 1000C. cst

RESID 1000

100 OVFL 10 100" 60 65 70 80 85 90 95 700" 300"

75

MID VOLUME on crude


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Undesirable Constituents of Lube Oil Fractions


CONSTITUENTS

EFFECT

REMOVED BY

Acids (Naphthenic Acids)

- Reduced Storage Stability - Corrosion Hazard


- Reduced Storage Stability - Corrosivity - Unpleasant Smell - Reduced Storage Stability

- Refining

Sulfur

- Refining

Unstable Compounds - Olefins, Nitrogen - Unstable Aromatics Paraffin Wax

- Refining

- Poor Flow Properties at Low Temperature - Sludge Formation

- Selective Precipitation

Asphaltenes & Resins

- Refining - Selective Precipitation

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Propane De-Asphalting

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Propane De-Asphalting Process


Propane 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
WAXY RAFFINATES
FURFURAL SOLVENT EXTRACTION MEK SOLVENT DEWAXING

VACUUM DISTILATTION

NEUTRAL DISTILLATES
1 2

DEWAXED OILS
CLAY OR HYDROGEN FINISHING

LUBE BASE STOCKS

1 2

1 2

1 2 3

ATMOS. RESID

FURFURAL
EXTRACT
(FOOT OIL)

WAX

Propane De asphalt

DE-ASPHALTED OIL (DAO)

Light Hydrocarbon
CATALYTIC DEWAXING

ASPHALTS

VACUMM RESID.

* Tanks Represent Different Viscosity Grades

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Propane De-Asphalting Scheme


De-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

PARAFFINS

NAPHTHENES

AROMATICS

RESINS ASPHALTENES

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Performance of Propane De-Asphalting Process


FEED* Yield, vol% Product Properties: Density @150C, g/mL Viscosity @ 400C, cSt @1000C, cSt Carbon Residue, wt% Sulfur, wt% Nickel, ppm Vanadium, ppm Softening Point, 0C Penetration @ 250C, 0.1 mm 1.024 ---1500 20 4.9 29 100 ------De-Asphalted Oil** ASPHALT 30 70

0.932 1040 34 1.4 2.7 0.2 0.4 -------

1.063 ----20000 ----------------65.5 12

* Feed: Vacuum Residue ** De-Asphalted Oil for Bright Stock Production

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Solvent Extraction with FURFURAL

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Lube Oil Base Stock Manufacture:


Furfural Solvent Extraction
WAXY RAFFINATES
FURFURAL SOLVENT EXTRACTION MEK SOLVENT DEWAXING

VACUUM DISTILATTION

NEUTRAL DISTILLATES
1 2

DEWAXED OILS
CLAY OR HYDROGEN FINISHING

LUBE BASE STOCKS

1 2

1 2

1 2 3

ATMOS. RESID

FURFURAL
EXTRACT
(FOOT OIL)

WAX

Propane De asphalt

DE-ASPHALTED OIL

Light Hydrocarbon
CATALYTIC DEWAXING

ASPHALTS

VACUMM RESID.

* Tanks Represent Different Viscosity Grades

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Properties Set by Furfural Extraction


Viscosity Index Oxidation Stability Thermal Stability

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Objectives of Solvent Extraction Process


Liquid-liquid extraction of Lubricating Oil Distillates 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 for Extraction of Lubricating Oils


High Selectivity for Desirable Components Good Solvent Power Low Solvent to Feed Ratio High Extraction Temperature for Good Mass Transfer Easy Recovery by Simple Distillation Low Vapor Pressure Avoid Use of High Pressure Vessels High Density Rapid Separation of Oil and Solvent Phases No Emulsification Rapid Separation of Oil and Solvent Phases Stability No Chemical or Thermal Degradation Adaptable Effective for Wide Range of Feed Stocks Available Reasonable Cost Non-Corrosive to Conventional Metals of Construction Non-Toxic Environmentally Safe

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Commercial Extraction Solvents


Furfural, N-Methyl 2-Pyrrolidone (NMP) and Phenol

Furfural is preferred because of: - High Selectivity - Moderate Toxicity - Low Cost - Availability
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Excellent for Paraffinic Oil (high extraction Temperature)

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Furfural Extraction Process

RAFFINATE PHASE

furfural

RAFFINATE recovery furfural furfural Rotating Disk extractor Extract Recovery furfural RAFFINATE

DISTILLATE FEED

Extract phase

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Furfural Extraction: Composition

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Properties of Distillate Components


Oxidation Stability Good Fair Fair Fair Poor

VI Paraffins 1-Ring Naphthenes 2+ Ring Naphthenes 1-Ring Aromatics 2+Ring Aromatics Excellent Good Fair Good Poor

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Performance of Furfural Extraction Process


FEED* Yield, vol% Product Properties: Density @150C, g/mL Refractive Index @ 210C Viscosity @ 400C, cSt @1000C, cSt Pour Point, 0C Sulfur, wt% ASTM Color Viscosity Index VI (after Dewaxing to -180C Pour Point) --RAFFINATE 82.3

0.884 1.4769 68.9 8.8 35 0.70 >8.0 99

0.865 1.4603 52.5 7.9 43 0.24 2.0 118

84

100

* Feed: 350 LN Distillate

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Quality of Furfural Treated Turbine Oils


East Texas Furfural Dosage, % Vol Temperature, 0C Yield, Waxy Raff., % Vol VI @ 200F (-70C) Pour TOST, Hrs to 2 NN 290 93 60 107 2000 Kuwait 160 91 59 104 4500 Amal 180 93 81 105 1400

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Monitoring VI and Quality by Raffinate Refractive Index


Arab Light 150 SUS LN

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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 Composition Solvent Dosage (Solvent/Oil Ratio) Extraction Temperature Number of Extraction Stages (Extraction Efficiency) Solvent Contaminants

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Effects of Oil Composition on Solubility in Furfural

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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 100 SUS 300 SUS 850 SUS Bright Stock Arab Light 150 175 240 260 Statfjord 220 240 290 300

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Effects of Temperature on
a. Solubility Furfural b. Extraction Products

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Effect of Temperature Profile in Extractor


Concept Intercooling Application

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Effect of Extraction Temperature on Oxidation 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

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Effect of Stages on Raffinate Quality and Yield

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High Efficiency Extraction Commercial Experience


Furfural Raffinate Yield (Vol %) Improves Significantly

100 SUS 300 SUS 700 SUS

Packed Tower 53 54 50

High Efficiency RDC 58 59 54

5 5 4

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Solvent Extraction Process Variables


Oil Composition Solvent Dosage (Solvent/Oil Ratio) Extraction Temperature Number of Extraction Stages (Extraction Efficiency) Solvent Contaminants

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Effect of Furfural Quality on Extraction

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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 Contaminants
Contaminant Water Source Steam Stripping in Solvent Recovery
Incomplete Solvent-Oil Separation (Usually Extract)

Oil

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Effect of Water Contamination in Furfural Extraction

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Solvent Recovery Constraints

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Methyl Ethyl Ketone SOLVENT DEWAXING

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Lube Oil Base Stock Manufacture:


MEK SOLVENT DEWAXING
WAXY RAFFINATES
FURFURAL SOLVENT EXTRACTION MEK SOLVENT DEWAXING

VACUUM DISTILATTION

NEUTRAL DISTILLATES
1 2

DEWAXED OILS
CLAY OR HYDROGEN FINISHING

LUBE BASE STOCKS

1 2

1 2

1 2 3

ATMOS. RESID

FURFURAL
EXTRACT
(FOOT OIL)

WAX

Propane De asphalt

DE-ASPHALTED OIL

Light Hydrocarbon
CATALYTIC DEWAXING

ASPHALTS

VACUMM RESID.

* Tanks Represent Different Viscosity Grades

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Properties Set by Dewaxing


Pour Point Cloud Point Filterability 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

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Improvement MEK Dewaxing Process


ExxonMobil DILCHILL Crystallizer

AMORPHOUS WAX (CONVENTIONAL)

SPHERIAL WAX (IMPROVED)

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Improved MEK Dewaxing Process

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Improved MEK Dewaxing Process:


ExxonMobils Membrane Separation Technology

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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

Propane Dewaxing Process

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MEK Dewaxing Process

Main Sections of Plant - Solvent Dilution and Wax Crystallization - Filtration - Dewaxed Oil Solvent Recovery
Auxiliary Systems - Solvent Decantation and Water Removal - Refrigeration - Inert Gas Circulation

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MEK Dewaxing Cycles : Four Steps

FILTRATION

WASH.

WAX CAKE DISCHARGE

FLUE GAS BLOW

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Solvent Dewaxing
Process Principles
Solvent Dewaxing Overview Charge Stock Solvent Composition Solvent Utilization Repulping / Deoiling Dewaxing Trends

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Typical Lube Yields via MEK Dewaxing


Arab Light Crude Commercial
Lube Pour Point Yield Slack Wax Oil Content
% Vol.

Laboratory
Lube Slack Wax Yield Oil Content
% Vol. % Vol.

BASE STOCK 100 SUS Auto/Turbine 300 SUS Auto 300 SUS Turbine 700 SUS Auto 700 SUS Turbine Bright Stock
Note: 200 F = -70C

oC

% Vol.

-18 -9 -7 -7 -7 -7

78 79 76 78 74 77

15 20 15 35 35 30

83 86 83 86 83 86

<5 <5 <5 <5 <5 <5

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Effect of Feed Composition on Dewaxing Yield


Arab Light 700 SUS Raffinate
Automotive Treat Dewaxed Oil Yield @ 20oF/-7oC Pour 86 Turbine Treat 83

COMPOSITION, wt% Paraffins Mono-Naphthenes Poly-Naphthenes Aromatics

28.7 18.3 20.5 32.5

30.6 18.5 25.1 25.8

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Effect of Oil Viscosity on Dewaxing Filter Rate

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Effect of Dewaxing on Viscosity Index and Yield of Dewaxed Oil


Pour Point
Stock Neutrals Bright Stock Lowering,oF/oC 5/3 5/3 Loss in VI 1 0.5

Yield Loss
%Vol of Charge 1.0 1.0

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Effect of Crude Source on Dewaxing Yield

Arab Light
Pour Point
oF/oC

Statfjord
Lube Yield
% Vol.

Lube Yield
% Vol.

Slack Wax Oil Content


% Vol.

Slack Wax Oil Content


% Vol.

100S US Auto* 300 SUS Auto* 700 SUS Auto Bright Stock

0/-18 15/-9 20/-7 20/-7

76 78 75 79

0.25 0.45 40 30

70 74 68 69

0.2 0.3 38 28

* Includes IN-LINE WAX DE-OILING


Raffinate Composition Paraffins, wt% iso/n paraffin Ratio

35
1.95

45
1.55

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Solvent Dewaxing
Process Principles
Solvent Dewaxing Overview Charge Stock Solvent Composition Solvent Utilization Repulping / Deoiling Dewaxing Trends

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Desired Dewaxing Solvent Characteristics


Solubility 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

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Selection of Dewaxing Solvent

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

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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

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Effect of Solvent Composition


FEED: MCS 150 SUS LN
Solvent, MEK/Toluene 25/75 Dewaxing Temp.,0F/0C 0/-18 Pour Point, 0F/0C (Dewaxed Oil) 35/2 40/60 2/-17 20/-7 75/25 10/-12 20/-7

% Change in Filter Rate

--

+43

+200

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Three-Phase Solvent Dewaxing

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Effect of Solvent Composition on Oil Phase Separation Temperature

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Solvent Dilutions for Dewaxing


(Vol. Solvent / Vol. Charge)
100 300 700 Bright Stock Raffinate Raffinate Raffinate Raffinate 0.5 0.5 1.0 3.5 0.5 0.5 0.75 -1.0 1.0 1.0 -----1.0 1.0 1.0 1.0 3.0 3.0 3.75 4.5

Primary Secondary Tertiary Recirc. Filtrate Cold Wash Total Fresh Solvents

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Effect of Solvent Dilution Ratio


Filtration Rate

Lube Yield

Oil Content in Wax

Wash Ratio

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Effect of Temperature of Dilution Solvent on Dewaxing Light Neutrals


FEED: Arab Light 150 SUS LN
Slurry Temp. , oC Dilution Solvent Temp., oC Filtration Temperature, oC % Change in Filtration Rate 13 13 -18 -13 -1 -18 -35 13 -12 -18 -57

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Impact of Repulping/Deoiling on Dewaxing Performance


Commercial Statfjord 700 SUS HN Feed
Operating Conditions Solvent MEK Content, % Total Dilution Ratio Filtrate Recycle Ratio Wash Ratio Filter Feed Temp., oC Yields, Vol % Dewaxed Oil Wax Foots Oil Product Properties
Dewaxed Oil VI at -7oC

CASE 1 CASE 2 CASE 3 Dewaxing Dewaxing Repulping Dewaxing Deoiling Deoiling


54 2.6 1.0 1.7 -15 68 32 0 96 38 -69 1.9 0.4 1.3 -12 73 27 0 96 26 -Hanoi University of Technology

69 0.6 -0.5 -12

69 2.3 0.7 1.5 -12

69 0.6 -2.5 16 68 13 19 96 0.9 14


113

69 2.7 -3.0 16

Wax Oil Content


Wax Penetration at 25oC
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Composition of Various Slack Waxes


Arab Light Crude
100A/T 300A 700A COMPOSITION, wt% Paraffins Mono-Naphthenes Poly-Naphthenes Aromatics 94.2 2.6 2.2 1.0 81.8 11.0 3.2 4.0 70.5 6.3 7.9 15.3 BS 51.4 16.5 9.9 22.2

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Lube Oil Base Stock Manufacture:


LUBE HYDROFINISHING
WAXY RAFFINATES
FURFURAL SOLVENT EXTRACTION MEK SOLVENT DEWAXING

VACUUM DISTILATTION

NEUTRAL DISTILLATES
1 2

DEWAXED OILS
CLAY OR HYDROGEN FINISHING

LUBE BASE STOCKS

1 2

1 2

1 2 3

ATMOS. RESID

FURFURAL
EXTRACT
(FOOT OIL)

WAX

Propane De asphalt

DE-ASPHALTED OIL

Light Hydrocarbon
CATALYTIC DEWAXING

ASPHALTS

VACUMM RESID.

* Tanks Represent Different Viscosity Grades

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Objectives of Lube Hydrofinishing


Remove Color Bodies Decrease Odor Reduce Acids Improve Demulsibility Improve Oxidation Stability Remove Residual Solvent

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Lube Hydrofinishing Process

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Typical Operating Conditions of Lube Hydrofinishers


Reactor Temperature Total Pressure H2 Pressure LHSV, Hr -1 H2 Circulation Catalyst Cycle Life 450 550oF 350 500 psig 250 psig 13 500 1000 SCF/B Mo Supported on Al203 2 3 Years

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Hydrofinishing Process Variables Effect of Temperature and Space Velocity

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Effect of Hydrofinishing on Turbine Oils


LIGHT NEUTRAL
Properties Charge Product HEAVY NEUTRAL Charge Product

Viscosity at 100oF, SUS Viscosity Index Pour point, oF Sulfur, Wt % Nitrogen, ppm ASTM Color Neutralization. No. Demulsibility, Mins to Break Processing Conditions Reactor Temp., OF LHSV, Hr-1 H2 Pressure, psig H2 Circulation, SCF/B Catalyst
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146 108 5 0.52 19 <1.5 0.08 34

145 108 5 0.45 19 <0.5 0.05 3


450 3 250 500 Mo/Al203

379 105 20 0.68 33 <2.0 0.05 No Break

377 105 20 0.68 33 < 1.0 0.02 6

400 2 250 500 Mo/Al203


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Hanoi University of Technology

Lube Oil Base Stock Manufacture:


WAX HYDROFINISHING
WAXY RAFFINATES
FURFURAL SOLVENT EXTRACTION MEK SOLVENT DEWAXING

VACUUM DISTILATTION

NEUTRAL DISTILLATES
1 2

DEWAXED OILS
CLAY OR HYDROGEN FINISHING

LUBE BASE STOCKS

1 2

1 2

1 2 3

ATMOS. RESID

FURFURAL
EXTRACT
(FOOT OIL)

WAX

Propane De asphalt

DE-ASPHALTED OIL

Light Hydrocarbon
CATALYTIC DEWAXING

ASPHALTS

VACUMM RESID.

* Tanks Represent Different Viscosity Grades

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Typical Wax Hydrofinishing Unit

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Typical Wax Hydrofinisher (HDF)


Operating Conditions
Catalyst
Temperature H2 Circulation H2 Consumption

CoMo /Al2O3
500 600oF 500 1500 SCF/B 50 75 SCF/B

H2 Parital Pressure, psig LHSV, Hr -1

Paraffin Wax 700 -1500 0.5 1.0

Microwax 700 2000 0.25 0.50

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Effect of Hydrofinishing on Waxes


PARAFFIN WAX Properties Viscosity at 100oF, SUS at 210oF, SUS Melting point, oF Oil Content, Wt % Needle Penetration at 77oF ASTM Color Processing Conditions Temperature, OF LHSV, Hr -1 H2 Partial Pressure, psig H2 Circulation, SCF/B Charge Product 109 95 44 42 140 140 1.5 0.5 45 13 <1.0 < 0.5 540 0.5 1500 800 MICROCRYSTALLINE WAX Charge Product 820 600 100 86 170 171 4.5 1.5 110 30 <5.0 <1.0 550 0.4 1800 1200

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Lube Refinery Production Balance


BASIS: 1000 Bbl Arab Light Crude
NEUTRALS
BRIGHT STOCK TOTAL 385 69 96

100 SUS 300 SUS 700 SUS 165 SUS Distillate / Resid Propane Deasphalting - Deasphalted Oils - Tar Furfural Extraction - Raffinate - Extract Solvent Dewaxing - Dewaxed Oil - Slack Wax 84 80 56 165 69 96

51 33
41 10

47 33
37 10

29 27
23 6

50 19
39 11

177 112
140 37

Yields Will Vary for Different Crudes


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Comparison of Lube Routes (Statfjord HN Distillate Feed)


Solvent Refined Yield, wt% LUBE PROPERTIES VI Sus at 1000F Sulfur, wt% Nitrogen, ppm Aromatics, wt% 41-35 90-94 710- 673 0.2-0.17 120-89 24-20 LHDC 69-43 89-128 519-130 .004-.006 9-6 17-5

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Mobil Wax Hydroisomerization


(30% 6500F + Conversion)
Zeolite Beta Intersecting 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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Paraffin Isomerization Mechanism


Bifunctional Catalysis

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Effect of Wax Oil Content on VI for MWI Process

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Performance of MWI Process

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Performance of MWI-2

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Improved Zeolite for Higher VI over MLDW


ZSM-23 Medium Pore High-Silica Zeolite One Dimensional Structure 4.5x5.2 A0 Channel 10-Member Ring

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Mobil Selective Dewaxing Process (MSDW)

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