SLIDE 1 Trends in the base oil landscape- changes and
Tribology Days, Nynäs Havsbad, October 7&8 2015
- Dr. Luis Bastardo-Zambrano
- Prof. Thomas Norrby
Nynas AB, Naphthenics TechDMS, Nynashamn, Sweden
SLIDE 2 World Naphthenic market share: A significant part of the global oil market
The Global lubricant demand is 40 M Ton/y
- Ca. 1% of the total petroleum market
Automotive Lubricants 56% Industrial Lubricants 44 % Global naphthenic potential: About 10% of total base oil demand (3.6 M Ton)
(Source Fuchs Petrolub AG presentation at 18th ICIS- LOR World Base Oils conference Feb 2014 in London)
Naphthenic Usage, %
SLIDE 3
Main applications of naphthenic oils (I)
Lubricant Industry (30%) Lubricating greases Metal Working Fluids (MWF) As a component in other industrial lubricants (hydraulic fluids, gear oils, etc.) Electrical Industry (ELI) (30%) Insulating oils for industrial transformers Finished products for direct end use
SLIDE 4
Main applications of naphthenic oils (II)
Process oils (40%) Adhesives and sealants Printing inks Battery separators Insoluble sulfur (as oil dispersion) Antifoams Tyre Industry Used as extender oil in tyre rubber Oil extended polymers
SLIDE 5 Naphthenic market in Europe
Naphthenics market share (%) 5 10 15 20 25 1974 1979 1984 1989 1994 1999 2004 2009 2014 5 10 15 20 25 1974 1979 1984 1989 1994 1999 2004 2009 2014
Vanishing
applications Growth of specialized products
SLIDE 6
Growth in the global naphthenic capacity
*Source LNG
SLIDE 7 Evolution of the global base oil pool
51% 28% 11% 1% 9%
2012
Group I Group II Group III PAO Naphthenic 44% 34% 11% 1% 10%
2014
Group I Group II Group III PAO Naphthenic 26% 48% 13% 1% 12%
2019 f’cast
Group I Group II Group III PAO Naphthenic
The global base oil demand scenario is here assumed to remain around 36 M mt/pa for the period
SLIDE 8 What is driving the change?
Several supply related factors – external to the lubricant industry – have a negative impact on Group I plants: Mandatory clean fuel investments Clean base oil (low Sulfur, low polyaromatics) Crude oil cost and availability Volatile, long term trend? Refining economics Of scale and of method/technology “Technological paradox” Gr I more expensive to make On the demand side, as Group II and III oils are more suited than Group I
- ils to meet the quality demand of the automotive industry
Thus, the Group II and III market is growing at the expenses of Group I oils, which are required for industrial use
SLIDE 9 However, the demand growth will not match the supply growth
Independently of the way the demand will develop, without closures we are heading towards a period of overcapacity The demand outlook will only determine the size of the
In the most optimistic growth scenario the excess capacity would reach 6 M mt/y In the most realistic growth scenario the excess capacity would be over 10 M mt/y
SLIDE 10
Base oil Market in Europe
No closures of Group I refineries took place in 2014 Europe has 15% of the overall global base oil capacity Europe has 25 % of the overall global Group I capacity Group I closures announcements Europe for 2015: Company Location Capacity (tpa) Shell Pernis, Netherlands 370000 Total Gonfreville, France 480000 Colas Dunkerque, France 290000 Nynas Hamburg, Germany 165000
SLIDE 11 How will this affect the lubricant industry?
Shrinking availability: The Group I production rationalization will push major Group I producers with own in- house lubricant production to focus mainly on production for captive use The product offering will not any longer be
- ptimized on industrial lubricant requirements
SLIDE 12
The majority of Group I producers have an in- house lubricant business to care for….
Lubricant producers, 89% Non -lubricant producers, 11%
89% of the global base oil production thus originates from producers that have an in-house lubricant business
SLIDE 13 The “collateral damage” of the paraffinic quality shift
Group II and III paraffinic oils are excellent base stocks for the formulation of modern engine oils However, Group II and III paraffinic oils display lower solvency compared to Group I paraffinic
Moreover, there is a limitation in the maximum viscosity that can be reached in Group II and III plants Therefore, the shift from Group I to Group II and III paraffinic oils will pose challenges to industrial lubricant formulators, as it will lead to a loss of solvency and viscosity range availability
SLIDE 14
The widening Solvency Gap
Solvency is an important property in most industrial lubricant applications In general, the base oil solvency affects the oil’s capability of dissolving additives, oxidation products and deposits In lubricating greases, the base oil solvency affects the soap yield and the oil-soap interaction In Metalworking fluid emulsions, the base oil solvency affects the emulsion stability
SLIDE 15
The growing high viscosity deficiency
API group Light neutral Medium neutral Heavy neutral Bright stock Group I 38% 13% 33% 16% Group II 55% 25% 20% none Group III 80% 20% none none The ongoing shift in capacity will generate availability issues for heavy neutrals and for bright stocks
SLIDE 16
How is the market going to move away from Group I?
Conversion to Group II or Group III? Conversion to Naphthenics ? Conversion to Group II/III – Naphthenic blends?
SLIDE 17
Nynas Oils and Group I Replacement – the new speciality base oil range
SLIDE 18
Nybase - A new specialty product range
Can be widely applied in industrial lubricant formulations Main advantages Most similar product to Group I oils High degree of flexibility in blending Optional tailor-made blends readily available Superior low temperature performance Main challenges vs Group I base oils Slightly higher volatility Lower flash point Slightly lower VI
SLIDE 19
Basic requirements of the Nybase Range
The Nybase™ range should: Closely match the Kinematic Viscosity and Aniline Point of a representative reference base oil range of Solvent Neutral (SN) Group I paraffinic base oils Allow industrial lubricant manufacturers, to maintain key properties of their products Allow direct replacement, with as little re-formulation and re-working of labels, PDS and other marketing material as possible (drop-in replacement) …Or allow for as easy reformulation work as possible
SLIDE 20 Viscosity Range Limitations Overcome
Viscosity at 40 °C (cSt)
API Group
Group III Group II Group I
50 100 200 300 400 500 600 700 2500
Group II
Group I
Viscosity at 40 °C (SUS)
7 20 40 58 80 100 115 140 500
Nybase range
Heavy Naphthenics Bright Stock
SLIDE 21 Chemical composition of mineral base oils
Mineral base oils consist mainly of naphthenic, paraffinic and aromatic molecules The relative amount of these molecules in the
- il determines whether the oil is considered
naphthenic or paraffinic CP (IR) 42-50% Naphthenic CP (IR) 56-67% Paraffinic Aromatic molecules confer high solvency to the oil, but some aromatics are toxic and harmful to the environment so these are removed or converted during the hydrorefining process
Paraffinic Naphthenic Aromatic
SLIDE 22 Base Oil Carbon Type Chart (ASTM D 2140)
0% 20% 40% 60% 80% 100% T 22
Nybase Group II PAO Paraffinic Multi-Ring Naphth. Aromatic
SLIDE 23 Aniline point
— 90ºC — 80ºC — 70ºC — 60ºC — 50ºC — 40ºC — 30ºC — 20ºC — 10ºC — 0ºC 68ºC — — 90ºC — 80ºC — 70ºC — 60ºC — 50ºC — 40ºC — 30ºC — 20ºC — 10ºC — 0ºC 68ºC — — 90ºC — 80ºC — 70ºC — 60ºC — 50ºC — 40ºC — 30ºC — 20ºC — 10ºC — 0ºC 68ºC — — 90ºC — 80ºC — 70ºC — 60ºC — 50ºC — 40ºC — 30ºC — 20ºC — 10ºC — 0ºC 68ºC —
SLIDE 24 Aniline point
Aniline is a polar solvent The lower the “Aniline Point” temperature: The more ”polar” the oil… The higher the solvent power
— 140ºC — 130ºC — 120ºC — 110ºC — 100ºC — 90ºC — 80ºC — 70ºC — 60ºC — 50ºC — 40ºC — 30ºC — 20ºC
Aromatic oils Naphthenic oils Paraffinic oils Increasing solvent power
SLIDE 25
The Nybase Range vs. SN reference base oils
SLIDE 26 The Nybase Range vs. SN reference base oils
Nybase 70 SN 70 Nybase 100 SN 100 Nybase 150 SN 150 Nybase 300 SN 300 Nybase 500 SN 500 Nybase 600 SN 600 Density (kg/m3) 0,873 0,849 0,867 0,859 0,871 0,868 0,886 0,876 0,889 0,879 0,876 0,880 FP COC (°C) 168 190 196 206 222 224 220 258 242 262 268 278 PP (°C)
- 27
- 12
- 24
- 18
- 24
- 18
- 21
- 18
- 21
- 9
- 15
- 9
Viscosity @40 °C (cSt) 14 12 22 17 30 30 60 58 100 94 120 115 Viscosity @100°C (cSt) 3,1 2,9 4,2 3,7 5,0 5,2 7,3 7,8 10,2 10,7 12,6 12,2 VI 67 92 88 104 89 103 80 98 79 97 98 96 Aniline Pt. (°C ) 90 90 100 98 101 102 103 109 111 115 123 117 Sulfur (m-%) 0,02 0,2 0,01 0,2 0,04 0,2 0,02 0,2 0,03 0,3 0,02 0,3 CA 3 7 2 3 3 3 4 3 3 2 2 3 CN 42 27 36 32 35 33 36 32 36 31 30 29 CP 55 66 62 65 62 64 60 65 61 67 69 68 Refractive index 1,477 1,468 1,475 1,472 1,479 1,477 1,485 1,481 1,487 1,483 1,481 1,483
SLIDE 27 The Nybase ISO VG Range vs. SN reference base oils
Nybase ISO VG 32 SN 150 Nybase ISO VG 46 SN 300 Nybase ISO VG 68 SN 500 Nybase ISO VG 100 SN 600 Density (kg/m3) 0,866 0,868 0,872 0,876 0,874 0,879 0,875 0,880 FP COC (°C) 212 224 224 258 232 262 247 278 PP (°C)
Viscosity @40 °C (cSt) 32 30 46 58 68 94 100 115 Viscosity @100°C (cSt) 5,3 5,2 6,7 7,8 8,75 10,7 11,1 12,2 VI 96 103 97 98 100 97 95 96 Aniline Pt. (°C ) 105 102 110 109 115 115 121 117 Sulfur (m-%) 0,02 0,2 0,02 0,2 0,02 0,3 0,02 0,3 CA 1 3 3 3 2 2 1 3 CN 31 33 31 32 31 31 31 29 CP 68 64 66 65 67 67 68 68 Refractive index 1,476 1,477 1,478 1,481 1,479 1,483 1,480 1,483
SLIDE 28
PPD Expression in Nybase Range
SLIDE 29
What does a PPD additive do?
A PPD additive prevents the wax crystals from agglomerating as they form when the fluid temperature is lowered The PPD additive consists of a polymer backbone, with paraffinic side chains that match those of the paraffin in the wax The PPD co-crystallises with the wax in small units The polymer backbone keeps the small crystalline units apart This improved flow and filterability Positive synergy with naphthenic (CN) and aromatic (CA) oil components
SLIDE 30 The effect in Nybase of added Pour Point Depressant (0,25 m-% PPD) by MPP ASTM D 7346
Neat PPD@ 0.25%
NB 70 NB 100 NB 150 NB 300 NB 500 NB 600 SN 150 Pour Point (ºC)
SLIDE 31
Naphthenic oils in industrial lubricants - Model Hydraulic Fluids based on Nybase
SLIDE 32
Formulation of Model Hydraulic Fluids I
Hydraulic fluids are mainly composed of Base oils (92-99%) An additive package (anti-oxidant, anti-wear, rust & corrosion inhibition, anti-foam) Viscosity Index Improvers (VII) (in HV only) and Pour Point Depressants (PPD) Viscosities (KV@ 40 °C) range from 15 cSt to 100 cSt The largest market volumes are in ISO VG 46 and ISO VG 32
SLIDE 33
Formulation of an Industrial Hydraulic Fluid III
The Industrial Hydraulic fluids HM 46 is composed of Base oils (ca. 99 m-%), Nybase 150 & Nybase 600 An additive package at 0,85 m-% (anti-oxidant, anti-wear, rust & corrosion inhibition, anti-foam) Pour Point depressant at 0,25 m-% It was benchmarked vs a leading global industrial hydraulic fluid, in this study called M 46
SLIDE 34
Foam testing screening (ASTM D 892)
SLIDE 35 Physical Properties HM 46 (Nybase) vs ISO
Test Unit HM 46 ISO 111 58, HM Method
Filterability I/II*
97/94 80/60
ISO 13357-2
Foam I @ 24 ºC
ml/ml
10/0 150/0
ISO 6247:1998 Foam II @ 93 ºC
ml/ml
30/0 80/0
ISO 6247:1998 Foam III @ 24 ºC
ml/ml
10/0 150/0
ISO 6247:1998
Air Release
min
2,0 10
ISO 9120
Demulsibility
min
10 30
ISO 6614 Oil/water/emuls.
ml
40/40/0 40/37/3
ISO 6614 TOST (1000 h)
mg KOH/g
≤2
ISO 4263-1 RPVOT
min
374 300a
ASTM D 2272-11 method A
*= Dry (no added water), Applied Pressure 100 kPa a = SS 15 54 34:2015, Swedish Standard for Hydraulic Fluids, Level A, equal to 1000 h TOST
SLIDE 36 HM 46 (Nybase) vs. M 46 (Commercial)
HM 46 M 46 KV @ 40 ºC 46,8 45,8 KV @ 100 ºC 6,6 6,6 VI 92 96 Density (g/ml @ 15 ºC) 0,877 0,879 Flash point (COC, ºC) 202 244 Pour Point (ºC)
Nz (mg KOH/g) 0,2 0,4 Water (ppm) 20 11
SLIDE 37
HM 46 (Nybase) vs. M 46 (Commercial)
ICP* HM 46 M 46 Ca 39 34 P 327 235 S 849** 2472*** Zn 418 259
* = Elemental Analysis by ICP ASTM D5185 ** = Base oil Sulfur contribution ca 300 ppm *** = Base oil Sulfur contribution significantly higher
SLIDE 38
Formulation of an Industrial Hydraulic Fluid IV
The Industrial Hydraulic fluids HM2 46 is composed of Base oils (ca. 99 m-%), Nybase ISO VG 46 An additive package at 0,85 m-% (anti-oxidant, anti-wear, rust & corrosion inhibition, anti-foam) Pour Point depressant at 0,25 m-% It was benchmarked vs a leading global industrial hydraulic fluid, in this study called M 46
SLIDE 39 Physical Properties HM2 46 (Nybase ISO VG) vs ISO 111 58
Test Unit HM2 46 ISO 111 58, HM Method
Filterability I/II*
98/97 80/60
ISO 13357-2
Foam I @ 24 ºC
ml/ml
0/0 150/0
ISO 6247:1998 Foam II @ 93 ºC
ml/ml
0/0 80/0
ISO 6247:1998 Foam III @ 24 ºC
ml/ml
0/0 150/0
ISO 6247:1998
Air Release
min
3,9 10
ISO 9120
Demulsibility
min
10 30
ISO 6614 Oil/water/emuls.
ml
40/38/2 40/37/3
ISO 6614 TOST (1000 h)
mg KOH/g
≤2
ISO 4263-1 RPVOT
min
420 300a
ASTM D 2272-11 method A
*= Dry (no added water), Applied Pressure 100 kPa a = SS 15 54 34:2015, Swedish Standard for Hydraulic Fluids, Level A, equal to 1000 h TOST
SLIDE 40 HM 46 (Nybase ISO VG) vs. M 46 (Commercial)
HM2 46 M 46 KV @ 40 ºC 46,2 45,8 KV @ 100 ºC 6,75 6,6 VI 100 96 Density (g/ml @ 15 ºC) 0,873 0,879 Flash point (COC, ºC) 226 244 Pour Point (ºC)
Nz (mg KOH/g) 0,4 0,4 Water (ppm) 43 11
SLIDE 41 Physical Properties HM2 46 (Nybase ISO VG) vs ISO 111 58
Test Unit HM2 46 ISO 111 58, HM Method
Filterability I/II*
98/97 80/60
ISO 13357-2
Foam I @ 24 ºC
ml/ml
0/0 150/0
ISO 6247:1998 Foam II @ 93 ºC
ml/ml
0/0 80/0
ISO 6247:1998 Foam III @ 24 ºC
ml/ml
0/0 150/0
ISO 6247:1998
Air Release
min
3,9 10
ISO 9120
Demulsibility
min
10 30
ISO 6614 Oil/water/emuls.
ml
40/38/2 40/37/3
ISO 6614 TOST (1000 h)
mg KOH/g
≤2
ISO 4263-1 RPVOT
min
420 300a
ASTM D 2272-11 method A
*= Dry (no added water), Applied Pressure 100 kPa a = SS 15 54 34:2015, Swedish Standard for Hydraulic Fluids, Level A, equal to 1000 h TOST
SLIDE 42 Conclusion of the Formulation & Miscibility study
- 1. The novel Hydraulic Fluids, HM 46 (Nybase) and HV 46 (Nybase) display the
desired and expected properties, the HM2 46 and HV2 46 versions display higher VI and FP according to expectiatíons; PPs remain low.
- 2. The Oxidation stability result in the harsh RPVOT compares well versus e.g.
Gr I based Turbine oils, with improvements for the Nybase ISO VG based products
- 3. They benchmark well vs. two common industry leading formulations,
called M 46 & V 46
- 4. The tested hydraulic fluids in the miscibility study were pair-wise
compatible: HM 46 versus M 46 HV 46 versus V 46
- 5. No significant differences of the physical properties could be experimentally
determined, i.e. no detrimental effects from the blending of different fluids
- 6. It is therefore likely that the new hydraulic fluids, based on the Nybase Range,
would be compatible with similar systems in the field
SLIDE 43
Elastomer Compatibility of the Nybase Range
SLIDE 44
Elastomer sealant material compatibility study
The Nybase range products, two model Hydraulic fluids and a reference Solvent Neutral Group I base oil were examined for elastomer material compatibility Four commonly utilized materials, found in hydraulic systems, engines etc.s were investigated: NBR, 28% Acetonitrile (AN), Peroxide cured (BAM E008) NBR, 28 % AN, Sulfur cured (BAM E009) HNBR-1, 35% AN, Peroxide cured (BAM E020) CR, Chloroprene Rubber (BAM E021)
SLIDE 45
Elastomer sealant material compatibility study
The test specimen were immersed in oil at 100 °C for 168 h (one week) Changes were recorded for Mass (increasing or decreasing) Hardness (increasing or decreasing) Shore A method (Durometer acc. to ASTM D2240 A)
SLIDE 46 NBR 28% AN, Peroxide Cured
2 Nybase 70 Nybase 100 Nybase 150 Nybase 300 Nybase 500 Nybase 600 P15-103 HM 46 P15-104 HV 46 P 15-107 M 46 Shell SN 150
NBR 28% AN Hardness change, %
SLIDE 47 NBR 28% AN, Peroxide Cured
2 4 6 8 10 12 14 16 18 Nybase 70 Nybase 100 Nybase 150 Nybase 300 Nybase 500 Nybase 600 P15-103 HM 46 P15-104 HV 46 P 15-107 M 46 Shell SN 150
NBR 28% AN Mass change, %
SLIDE 48 HNBR-1, 35% AN, Peroxide Cured
2 Nybase 70 Nybase 100 Nybase 150 Nybase 300 Nybase 500 Nybase 600 P15-103 HM 46 P15-104 HV 46 P 15-107 M 46 Shell SN 150
HNBR-1, 35% AN Hardness change, %
SLIDE 49 HNBR-1, 35% AN, Peroxide Cured
2 4 6 8 10 12 14 16 18 Nybase 70 Nybase 100 Nybase 150 Nybase 300 Nybase 500 Nybase 600 P15-103 HM 46 P15-104 HV 46 P 15-107 M 46 Shell SN 150
HNBR-1, 35% AN Mass change, %
SLIDE 50 Chloroprene rubber (CR)
2 Nybase 70 Nybase 100 Nybase 150 Nybase 300 Nybase 500 Nybase 600 P15-103 HM 46 P15-104 HV 46 P 15-107 M 46 Shell SN 150
CR Hardness change, %
SLIDE 51 Chloroprene rubber (CR)
2 4 6 8 10 12 14 16 18 Nybase 70 Nybase 100 Nybase 150 Nybase 300 Nybase 500 Nybase 600 P15-103 HM 46 P15-104 HV 46 P 15-107 M 46 Shell SN 150
CR Mass change, %
SLIDE 52
Some preliminary conclusions
All the Nybase Range fluids, and the model hydraulic fluids based on these, display the expected behaviour Seal material mass change and hardness change remains low across the NBR test series The compatibility with CR is, expectedly, slightly lower, as CR is better suited for more non-polar fluids with higher Aniline points Seal compatibility equals that of the reference fluids One SN 150 Group I base oil One fully formulated industrial hydraulic fluid This screening serves a s good indication for no-harm also in this respect
SLIDE 53
Summary
Nybase, a new Group I replacement base oil range, has been created The key design parameters were KV @ 40 °C and Aniline Point Also, a second line, Nybase ISO VG, is currently being investigated KV@ 40 °C and VI are the main design parameters Lab trials were conducted to elucidate PPD expression Elastomer compatibility Nybase is mainly targeted to industrial and metalworking fluid needs, but can also be utilized in automotive and engine oil applications Two model hydraulic fluids were created, and: Benchmarked vs leading commercially available fluids Evaluated vs technical standards Evaluated vs elastomer compatibility Our lab trials and evaluations strongly support the utilization of Nybase in hydraulic fluids
SLIDE 54 Nynas lubricant product range
T 3 NS 3 T 9 T 22 BNS 8 BS 8.5 T 110 T 400 BBT 28 NS 100 S 100B S 25B BNS 14 BNS 150 HP 2 HP 4 HP 6 HP 12 SR 400 Base stock 130 Nybase 70 Nybase 100 Nybase 150 Nybase 300 Nybase 500 Nybase 600
1 10 100 1000 40 50 60 70 80 90 100 110 120 130 Viscosity 40°C (cSt) Aniline Point (°C)
SLIDE 55 Nynas Group Head Office P.O. Box 10700 SE-121 29 Stockholm Sweden
Fax +46-8-91 34 27 thomas.norrby@nynas.com
