dầu mỏ 2

MLRT-LNQ 1 Hanoi University of Technology

____________________________

MODERN LUBE

REFINING TECHNOLOGY ________________________________________

MLRT

Le Ngoc Quang, PhD

HANOI UNIVERSITY OF TECHNOLOGY

MLRT-LNQ Hanoi University of Technology 2

Trends in Lube Refining

Lube Crude Supply

Processing

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Lube Crude Supply Trends

Premium Crudes Declining

Increasing Effort to Obtain

and Approve Replacements

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Future Lube Processing Objectives

Improve Yields of Lube on Crude

Make Acceptable Lubes from Lower Quality Crudes

Replacing Solvent Refining Steps With Catalytic

Processes Can Help Meet These Objectives.

MLRT-LNQ Hanoi University of Technology 5

Major Processing Trends (cont’d)

Mobil Lube Dewaxing (MLDW)

- Catalytic Dewaxing to Replace Solvent Dewaxing

Wax Hydroisomerization (MWI)

- Extra-High VI Base Stocks

- Production of Group III Stocks

Severe Lube Hydrotreating – LHDT

- Replacing Furfural Solvent Extraction

- Group II Stocks Production

Lube Hydrocracking

Group II-III Stocks Manufacture

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M L D W Mobil Lube DeWaxing

Catalytic Replacement for Solvent Dewaxing

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Lube Oil Base Stock Manufacture: MLDW Catalytic Dewaxing Process

FURFURAL

SOLVENT

EXTRACTION 1

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

OIL 4

* Tanks Represent Different Viscosity Grades

MLRT-LNQ Hanoi University of Technology 8

MLDW Flow Diagram

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MLDW Operating Conditions

H2 Partial Pressure: 400 psig

H2 Circulation: 2500 SCF/B

H2 Consumption: 100 – 250 SCF/B

Space Velocity:

HDW 0.3 – 1.0 LHSV

HDT 1.0 LHSV

Operating Temperature:

HDW 520 – 675oF

HDT 450 – 525oF

MLRT-LNQ Hanoi University of Technology 10

MLDW Catalyst: ZSM-5 Zeolite

10-Member Ring Structure

Medium Pore Zeolite

Pore Dimension

5.3 x 5.6 A0 Straight Channel

5.1 x 5.5 A0 Sinusoidal Channel

MLDW Catalyst:

- 65% ZSM-5 on Al2O3

- 1- 4 wt% Ni

Note: Zeolite Synthesized by Mobil (ZSM)

MLRT-LNQ Hanoi University of Technology 11

MLDW Dewaxing Principles

Concept of Shape-Selective ZSM-5 Dewaxing Catalyst

Cracking High-Pour Paraffins into Naphtha and Gas

Reduction Coking Propensity through Reactant-Shape

Selectivity

Resistance to Poisoning of Bulky Nitrogen Compounds

Utilization of Hydrogen Reactivation Method (High

Temperature H2 Reduction)

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MLDW Advantages

over Solvent Dewaxing

Lower Investment (80%)

Lower Operating Cost (15%)

Higher Lube Yields

Cracked By-Products Primarily high Octane Naphtha

Equivalent Base Stock Quality

Low Pour Point Specialty Products (less than

conventional 200F)

MLRT-LNQ Hanoi University of Technology 13

MLDW: Other Considerations

Lower VI from Equivalent Feed

Eliminates Separate Lube Hydrofinisher

Full Range of Charge Stocks to produce LN, HN and BS

Higher Viscosity from Same Boiling Range Feed

Eliminates Wax Production

MLRT-LNQ Hanoi University of Technology 14

Commercial MLDW Performance

3-Bed Reactor: Yield & VI Comparison

MLDW ∆ (MLDW-SDW)

Yield VI Yield VI

200 SUS Automotive 77 101 - 2 - 7

650 SUS Automotive 79 94 +8 - 5

150 SUS Turbine 69 104 - 4 - 4

600 SUS Turbine 78 93 +9 - 6

150 Bright Stock 86 96 +9 0

(Data Based on 1st Cycle Results for Isthmus Crude)

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Lube Unit Operating Costs ( US$/bbL)

Finished Lubes

Unit Charge SDW MLDW

Vacuum Distillation 1.02 4.47 4.32

Propane Deasphalting 4.44 5.52 4.92

Furfural Extraction 2.67 5.63 5.39

Solvent Dewaxing 9.79 12.59

Catalytic Dewaxing 2.94 3.60

Tankage (Inventory) 3.17 3.40

Total 31.38 21.63

Basis: 5,000 B/CD Lube Plant In N.W. Europe (Arab Light Crude)

100” 300” 700” BS

Production (B/CD) 430 2065 1205 1300

Pct of Pool 9 41 24 26

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Improved MLDW Commercialization through

Catalyst & Process Technology

1981

1992 1993

1996

Discovery of ZSM-5 in Late 1960s

ZSM-5 Patent in 1972

MLDW Process Development in 1970s

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Commercial MLDW Performance

TOST Performance on Base Stocks

MLDW SWD Spec, Hr

LN Turbine 4,000 4,000 4,000

LN >2,000 >2,000 1,000

HN >1,000 >1,000 1,000

MLRT-LNQ Hanoi University of Technology 18

LHDT Process Background

Chemistry

Turbine Oil Stability Improves with Reduced

-Polynuclear Aromatics (PNA’s)

-Total Aromatics

-Sulfur and Nitrogen

Operating Conditions

Hydrogen Partial Pressure 2200 psig

Reactor Temperature 600 – 675oF

Liquid Hourly Space Velocity 0.3 – 0.6 Hr -1

MLRT-LNQ Hanoi University of Technology 19

Performance of Lube Hydrotreating Statfjord 300 SUS Arab Light Automotive Turbine 300 SUS Turbine

Charge Product Charge Product Charge Product

Properties

KV at 40oC, cSt 61.2 50.9 56.5 48.2 54.0 37.3

Viscosity Index 97 102 103 107 103 115

Pour Point, oC -12 -11 -12 -10 -13 -9

Sulfur, ppm 1900 3 1200 1 6000 2

Aromatics, Wt% 17.5 4.3 10.8 1.9 25.6 3.6

Performance (XRL-1509)

OCST (3 Days at 150 oC) D8 2.5 - 2.5 D8 2.5

RBOT, Min 325 440 - 390 330 415

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MLDW Turbine Oil Upgrading

Commercial Demonstration

Conditions 650oF

0.3 Hr -1

2300 psig H2 (Outlet)

Isthmus MLDW Turbine

200 SUS

Properties Charge Product

Viscosity, SUS at 100oF 201 165

Viscosity Index 97 104

Pour Point, oF 15 20

Sulfur, ppm 3100 3

Aromatics, Wt % 24 4

Performance (RL-1442)

OCST (3 Days at 150oC) D8 2

RBOT, mm 305 450

TOST, Hrs 2200 On-Going

MLRT-LNQ Hanoi University of Technology 21

Lube Hydroprocessing Comparison

Hydroprocess Severity Comment

Severe Hydrotreating High Replaces Solvent Extraction,

Acid Treating, Finishing

Hydrotreating Medium Augments Solvent Extraction,

Acid Treating, Finishing

Hydrodewaxed Stocks

Hydrofinishing Low Replaces Clay Finishing

MLRT-LNQ Hanoi University of Technology 22

Lube Hydroprocessing Parameters

HYDROTREATING SEVERITY

HIGH MEDIUM HYDROFINISHING

CATALYST

- Metals NiW, NiMo, CoMo CoMo, NiMo CoMo, NiMo,Mo

- Support Silica-Alumina Al203 Al203

Silica Zirconia

OPERATING CONDITIONS

Temperature,oF 650 - 875 500 - 700 400 - 600

H2 Pressure, psig 2000 - 3000 500 - 1500 200 - 500

LHSV 0.2 - 0.8 1 - 2 1 - 4

H2 Circulation SCF/B Oil 5000 - 10,000 1000 - 3000 500 - 1000

H2 Consumption SCF/B Oil 500 - 2500 200 - 500 25 - 50

Lube Oil Yields, % Vol 50- 80 85- 95 100

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Severe Lube Hydrotreating

ADVANTAGES

Less Crude Sources Dependent

Yields on Feed May be Higher

High VI Base Stocks Possible

High Value Byproducts

DISADVANTAGES

Higher Investment & Operating Costs

Larger Viscosity Decrease

UV Light Stability Problem

May Require Product Reformulations

MLRT-LNQ Hanoi University of Technology 24

Comparison of

Solvent vs. Catalytic Lube Refining Basis: 5 TBD Lube Production from Arab Heavy Crude

All Solvent All Catalytic*

VI Improvement: Solvent Solvent Hydrotreat

Dewaxing: Solvent MLDW MLDW

Lube Qualities, VI

100N 97 90 100

300N 96 90 99

700N 93 87 96

150BS 95 95 95

Crude Required

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ADVANCES IN CATALYTIC LUBE

PROCESSING

’ THE EVOLUTION OF

LUBE PROCESSING’

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Conventional Lube Oil Manufacture

FURFURAL

SOLVENT

EXTRACTION 1

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

WAX

ASPHALTS

ATMOS.

RESID

VACUMM

RESID.

Light

Hydrocarbon

CATALYTIC

DEWAXING

DE-ASPHALTED

OIL 4

* Tanks Represent Different Viscosity Grades

BS

HN

LN

LN

MLRT-LNQ Hanoi University of Technology 27

Forces Driving Catalytic Lube Processing

Economics

- Crude Costs

- Operating Costs

- By-Products Value

Quality

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Lube Product Quality Trends

♦ Engine Oils - Lower Viscosity, Higher VI

- Improved Low Temperature Performance

- Improved Volatility, Stability

♦ Hydraulic Oils - Wider Temperature Range

- Reduced VI Improver, Lower Pour Point

- Increased Service Life

♦ Turbine Oils - Increased Oxidation Stability

- Increased Viscosity

♦ Marine Oils - Increased Stability

- Increased Viscosity

MLRT-LNQ 29 Hanoi University of Technology

Catalytic Lube Processes

Process

Mobil Lube Dewaxing (MLDW)

Lube Hydrotreating (LHDT)

Lube Hydrocracking/ MLDW

Lube Hydrocracking/ SDW

Mobil Wax Hydroisomerization

(MWI)

OBJECTIVE

Pour Point, Cost

Stability

Quality, Cost

Yield, VI

VI

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Lube Base Stock Manufacture Technology

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Lube Hydrocracking /MLDW

Processing Integration

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Lube Hydrocracking

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Lube Hydrocracking Process

CATALYST

-NiMo or NiW on Supported Al2O3 or USY

- Pt on Alumina-Silica or USY

PROCESS CONDITIONS

- P = 1,500-3,000 psig

- T = 600-8000F

- LHSV= 0.5-1.0 hr-1

- H2 Circulation: 3,000- 5,000 SCF/Bbl

MLRT-LNQ Hanoi University of Technology 34

LHDC of Statfjord HN Distillate

Liquid Product Yields

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LHDC of Statfjord HN Distillate

MLRT-LNQ 36 Hanoi University of Technology

Lube Yields from Statfjord Crude

100 SUS

300 SUS

700 SUS

150 BS

TOTAL

LHDC/MLDW

2,767

2,827

1,005

1,006

7,605

FURF/MEK

2,051

1,579

809

930

5,369

Basis: 50,359 BPD Whole Crude

32% }

}

26%

MLRT-LNQ 37 Hanoi University of Technology

Comparison of Lube Routes

(Statfjord HN Distillate Feed)

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

120-89

24-20

MLRT-LNQ Hanoi University of Technology 38

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

MLRT-LNQ Hanoi University of Technology 44

Mobil Selective Dewaxing Process

(MSDW)