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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 3
Lube Crude Supply Trends
Premium Crudes Declining
Increasing Effort to Obtain
and Approve Replacements
MLRT-LNQ Hanoi University of Technology 4
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
MLRT-LNQ Hanoi University of Technology 6
M L D W Mobil Lube DeWaxing
Catalytic Replacement for Solvent Dewaxing
MLRT-LNQ Hanoi University of Technology 7
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 9
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)
MLRT-LNQ Hanoi University of Technology 12
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)
MLRT-LNQ Hanoi University of Technology 15
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
MLRT-LNQ Hanoi University of Technology 16
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
MLRT-LNQ Hanoi University of Technology 17
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
MLRT-LNQ Hanoi University of Technology 20
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
MLRT-LNQ Hanoi University of Technology 23
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
MLRT-LNQ Hanoi University of Technology 25
ADVANCES IN CATALYTIC LUBE
PROCESSING
’ THE EVOLUTION OF
LUBE PROCESSING’
MLRT-LNQ Hanoi University of Technology 26
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
MLRT-LNQ Hanoi University of Technology 28
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
MLRT-LNQ Hanoi University of Technology 33
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 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
MLRT-LNQ Hanoi University of Technology 43
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