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Transcript of Croda 2007 PRIOLUBE, PERFAD, HYPERMER, EMKAROX AND EMKARATE are trademarks of Croda High Performance...
Croda 2007
PRIOLUBE, PERFAD, HYPERMER, EMKAROX AND EMKARATE are trademarks of Croda
High Performance Biodegradable Ester Lubricants
from Sustainable and Non-Sustainable Feedstocks
Andrew P Swallow (Technical Service Manager) John Eastwood (Technical Service Manager)Steven J Randles (Global Applications Director)
Agenda
• European ECO Labels• Renewability• Performance parameters• Natural esters• Oleochemical esters• Petrochemical esters
Existing Eco-labels in Europe
• The European Eco-label has been based largely on the existing eco-labels of individual European countries, specifically:
– Germany (Blue Angel)– Sweden (Swedish Standard)– Nordic Countries (White Swan)– France (NF Environment)– Holland (VAMIL Regulation)– Austria
An Eco-label for Europe
• In December 2004 the European Commission voted in favour of adopting a European Eco-label for Lubricants.
• The document was published in the Official Journal in the summer of 2005.
• A copy of the document is available at:http://europa.eu.int/comm/environment/ecolabel/product/pg_lubricants_en.htm
Renewable Raw Materials
• The lubricant shall have a carbon content derived from renewable raw materials that shall be:– => 50% for hydraulic oils– => 45% for greases– => 70% for chain saw oils, concrete release agents and
other total loss lubricants– => 50% for two-stroke oils
• Additive targets are difficult achieve– Biodegradability, bio-accumulation and toxicity targets are
difficult to achieve while meeting the correct performance
• Few formulations currently meet the criteria– A review of the European Eco-label will take place in 2008– Many of the European Eco-labels will continue in parallel
Lubricant Overview
• Biodegradability tends to decrease with increasing chain length, branching, aromaticity and saturation, and will be influenced by the nature of the structure
% Biodegradability
28 days OECD 301B
% Renewabilitycontent
Vegetable Oil 70 – 100 100
Mineral oil 20 – 40 0
PAO 20 – 60 0
Alkyl Benzene 5 - 20 0
Diesters 40 - 75 0 to 80
Aromatic ester 5 - 60 0
Polyol ester 20 - 90 0 to 85
Complex ester 20 - 90 0 to 85
Polyalkylene Glycol
10 - 70 0
Esters as Lubricant Base fluids
• Three general categories– Natural oils and fats
• Plant and animal derived
– Oleochemical derived esters • Fatty unsaturated esters (e.g. oleates, dimerates)• Fatty saturated esters (e.g. stearates, isostearates)
– Petrochemical esters • Diesters ( e.g. adipates, sebacates, azelates)
Oleochemical Derived Esters
• Broad technology platform enabling the preparation of biodegradable esters with viscosities ranging from approximately 10cSt up to 1000cSt at 40°C
• Not classified as dangerous for the environment, nor are they classified as harmful to aquatic organisms
• Generally do not bio-accumulate in the environment. Typical esters used in the formulation of environmentally acceptable lubricants (EALs) have Log Kow values ranging from 10 to 25
Petrochemical Esters
• Diester advantages are :– Long-life lubricants – High temperature operating conditions– Very low temperature environments– In addition, diesters have a low viscosity. Until recently they
have been the only real option for low viscosity lubricating oils
• Diesters disadvantages are:– Non renewable– Under new Eco-label criteria, petrochemical esters will
become useful only as co-base fluids and the amount that can be used in a formulation will be dictated by the application in which the lubricant will be used based on renewability
The Ester Reaction
Alcohol + Acid Ester + Water
- Catalyst
- Pressure
- Temperature
- Structure
- Acid
- Alcohol
Degree of Hydrolysis
• High levels of water
Degree of Esterification
• Low levels of water
EsterificationHydrolysis
R - O - C - R1
= OH2OR - OH R1 - C - OH= O
Improving Hydrolytic Stability
• Esters are acid catalysed– Higher initial acid value the faster the breakdown– Tightly controlled manufacturing processes
• Careful additive selection– Anti-wear additives (use stable and low acid
value)– Anti-corrosion additives (neutral ones)
• Acid catchers– Epoxides or carbo-imides
Performance Trade-Offs
Degree of branchingor aromaticity
0 100
Biodegradability0
100Hydrolytic Stability
Perf
orm
ance
O – C – C –
= O
H2O
StericHinderance
Polyol Ester
Performance Trade-Offs
Iodine value
Low High
Low Temp Operability0
100Oxidative Stability
Perf
orm
ance
O
O
O
O
O
O
PyrolysisWax formation
Oxidation
Hydrolysis
Natural Triglyceride
Optimizing Pour Point
Ester Pour Point, °C
TMP oleate (unsaturated C18) -51
TMP stearate (saturated C18) +45
TMP isostearate -30
PE branched C9 +30
PE linear C9 +8
PE branched C8 +8
Mixed branched PE -38
Mixed linear and branched PE -48
PE = Pentaerythritol
Low Temp Flow- Molecular weight- Degree of unsaturation- Structural diversity- Degree of branching
“Regular shaped structures” can flocculate and crystallize over time. Pour point is not always a particularly reliable measurement
Low Temperature Fluidity
Viscosity vs Storage time at - 30 °C
02000400060008000
1000012000140001600018000
0 50 100 150 200
Time (h)
Vis
cosit
y (
cS
t)
TMPO
Modified
ISO 46 Ester Comparison
Physical Property Diester + Complex
ester
StandardTMP Oleate
ModifiedTMP
Oleate
Saturated Polyol Ester
Saturated Opt. Ester
Ester A Ester B Ester C Ester D Ester E
Raw material source Petro Oleo Oleo Oleo Oleo
Viscosity at 40°C, cSt 46 48 44 46 45
Viscosity at 100°C, cSt 8.1 9.8 8.7 8 8.8
Viscosity Index 150 196 181 143 180
Viscosity at -30°C, cSt after 72hrs
9,500 5,500 to 16,000
3,800 9,500 4,400
Pour point, °C -42 -51 -54 -42 -45
Iodine value <1 84 72 2 <1
Dry TOST Test hours(+1.5% RC9321)
>>4000 500 540 >>4,000 On test>1,000
Biodegradability28 days OECD 301B, %
61 84 99 85 77
Renewability, % 17 86 85 85 78*Northern Europe would aim for <5,000 cSt at -30°C after 72hrs
Other Viscosities
Oleo.derived
Petro.derived
Oleo.derived
Oleo.derived
Oleo.derived
Oleoderived
Oleoderive
d
Ester F Ester G Ester H Ester I Ester J Ester K Ester L
Viscosity 40°C, cSt 11 26 35 65 138 320 1040
Viscosity 100°C, cSt 3.0 5.3 7.5 13 17.6 35 90
Viscosity Index 136 139 193 208 140 150 167
Pour point, °C -33 -54 -42 -21 -33 -40 -24
Iodine value 1 <1 75 90 3 <1 4
Dry TOST test hours(+2% RC9308)
>4,000 >4,000 500 500 >4,000 >4,000 >4,000
Biodegradability28 days OECD 301B, %
78 74 81 64 70 70 63
Renewability, % 70 0 85 85 85 88 73Commercial high performance renewable esters have been developed for: Chain oils,Greases, Transformer oils, MWFs, 2T, Fuel additives, Marine and Offshore applications
Conclusions
• A wide range of esters commercially available that allow you to achieve optimum balance of– Biodegradability – Renewability– Stability– Low temperature properties– Cost
• Careful selection of additives are required to optimise hydrolytic stability
Contact
[email protected]+44 1642 435356Wilton CentreRedcar TS10 4RFEngland
[email protected]+ please add your details here
Disclaimer
• The information in this publication is believed to be accurate and is given in good faith but no representation or warranty as to its completeness or accuracy is made.
• Suggestions for uses or applications are only opinions. Users are responsible for determining the suitability of these products for their own particular purpose.
• No representation or warranty, express or implied, is made with respect to information or products including without limitation warranties of merchantability or fitness for a particular purpose or non-infringement of any third party patent or other intellectual property rights including without limit copyright, trademark and designs.
• Any trademarks identified herein are trademarks of the Croda group of companies