trends in the base oil landscape- changes and …/file/151007_2_t norrby...trends in the base oil...

Trends in the base oil landscape- changes and opportunities Tribology Days, Nynäs Havsbad, October 7&8 2015 Dr. Luis Bastardo-Zambrano Prof. Thomas Norrby Nynas AB, Naphthenics TechDMS, Nynashamn, Sweden

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, %

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

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

Naphthenic market in Europe

Naphthenics market share (%)

0

5

10

15

20

25

1974 1979 1984 1989 1994 1999 2004 2009 20140

5

10

15

20

25

1974 1979 1984 1989 1994 1999 2004 2009 2014

Vanishing of non-core applications

Growth of specialized products

Growth in the global naphthenic capacity

*Source LNG

Evolution of the global base oil pool

51% 28%

11%

1% 9%

2012

Group IGroup IIGroup IIIPAONaphthenic

44%

34%

11%

1% 10%

2014


26%

48%

13%

1% 12%

2019 f’cast


Source. SBA Consulting

The global base oil demand scenario is here assumed to remain around 36 M mt/pa for the period

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 oils 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

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 oversupply 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

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

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 optimized on industrial lubricant requirements

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

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 oils 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

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

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

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?

Nynas Oils and Group I Replacement – the new speciality base oil range

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

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

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

Gr. III

Group II

Group I Viscosity at 40 °C (SUS)

7 20 40 58 80 100 115 140 500

Nybase range

Heavy Naphthenics

Bright Stock

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 oil 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

Base Oil Carbon Type Chart (ASTM D 2140)

0% 20% 40% 60% 80% 100%

T 22

Gr. I

Nybase

Group II

PAO

ParaffinicMulti-Ring Naphth.Aromatic

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 —

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

The Nybase Range vs. SN reference base oils

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

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) -18 -18 -18 -18 -15 -9 -15 -9 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

PPD Expression in Nybase Range

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

The effect in Nybase of added Pour Point Depressant (0,25 m-% PPD) by MPP ASTM D 7346

Neat

PPD@ 0.25%

-60

-50

-40

-30

-20

-10

0NB 70 NB 100 NB 150 NB 300 NB 500 NB 600 SN 150

Pour

Poi

nt (

ºC)

Naphthenic oils in industrial lubricants - Model Hydraulic Fluids based on Nybase

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

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

Foam testing screening (ASTM D 892)

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 -a ≤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

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) -39 -24 Nz (mg KOH/g) 0,2 0,4 Water (ppm) 20 11

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

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

Physical Properties HM2 46 (Nybase ISO VG) vs ISO 111 58

Test Unit HM2 46 ISO 111 58, HM

Method


Foam I @ 24 ºC ml/ml 0/0 150/0 ISO 6247:1998









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) -39 -24 Nz (mg KOH/g) 0,4 0,4 Water (ppm) 43 11

Physical Properties HM2 46 (Nybase ISO VG) vs ISO 111 58

Test Unit HM2 46 ISO 111 58, HM

Method


Foam I @ 24 ºC ml/ml 0/0 150/0 ISO 6247:1998









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

Elastomer Compatibility of the Nybase Range

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)

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)

NBR 28% AN, Peroxide Cured

-14

-12

-10

-8

-6

-4

-2

0

2

Nybase70

Nybase100

Nybase150

Nybase300

Nybase500

Nybase600

P15-103HM 46

P15-104HV 46

P 15-107M 46

Shell SN150

NBR 28% AN Hardness change, %

NBR 28% AN, Peroxide Cured

0

2

4

6

8

10

12

14

16

18

Nybase70

Nybase100

Nybase150

Nybase300

Nybase500

Nybase600

P15-103HM 46

P15-104HV 46

P 15-107M 46

Shell SN150

NBR 28% AN Mass change, %

HNBR-1, 35% AN, Peroxide Cured

-14

-12

-10

-8

-6

-4

-2

0

2

Nybase70

Nybase100

Nybase150

Nybase300

Nybase500

Nybase600

P15-103HM 46

P15-104HV 46

P 15-107M 46

Shell SN150

HNBR-1, 35% AN Hardness change, %

HNBR-1, 35% AN, Peroxide Cured

0

2

4

6

8

10

12

14

16

18

Nybase 70 Nybase100

Nybase150

Nybase300

Nybase500

Nybase600

P15-103HM 46

P15-104HV 46

P 15-107 M46

Shell SN150

HNBR-1, 35% AN Mass change, %

Chloroprene rubber (CR)

-14

-12

-10

-8

-6

-4

-2

0

2

Nybase70

Nybase100

Nybase150

Nybase300

Nybase500

Nybase600

P15-103HM 46

P15-104HV 46

P 15-107M 46

Shell SN150

CR Hardness change, %

Chloroprene rubber (CR)

0

2

4

6

8

10

12

14

16

18

Nybase70

Nybase100

Nybase150

Nybase300

Nybase500

Nybase600

P15-103HM 46

P15-104HV 46

P 15-107M 46

Shell SN150

CR Mass change, %

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

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

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

Visc

osity

40°

C (c

St)

Aniline Point (°C)

Nynas Group Head Office P.O. Box 10700 SE-121 29 Stockholm Sweden Tel. +46-8-602 12 00 Fax +46-8-91 34 27 [email protected]

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