Transcript Russia Lubricants 2007

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)
 Croda 2007
PRIOLUBE, PERFAD, HYPERMER, EMKAROX AND EMKARATE are trademarks of Croda
Agenda
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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:
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–
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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/ecola
bel/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
28 days OECD 301B
% Renewability
content
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
Biodegradability tends to decrease with increasing chain length, branching,
aromaticity and saturation, and will be influenced by the nature of the
structure
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
R - OH
R - O - C - R1
R1 - C - OH
Alcohol + Acid
H 2O
Ester + Water
Degree of Hydrolysis
- Catalyst
Degree of Esterification
• High levels of water
- Pressure
• Low levels of water
- Temperature
- Structure
- Acid
- Alcohol
Hydrolysis
Esterification
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
100
Performance
Hydrolytic Stability
H2O
=
O
O–C–C–
Steric
Hinderance
Biodegradability
0
0
100
Degree of branching
or aromaticity
Polyol Ester
Performance Trade-Offs
Pyrolysis
Wax formation
100
Performance
Oxidative Stability
O
O
O
O
O
O
Low Temp Operability
0
Low
High
Iodine value
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 (cSt)
Viscosity vs Storage time at - 30 °C
18000
16000
14000
12000
10000
8000
6000
4000
2000
0
TMPO
Modified
0
50
100
Time (h)
150
200
ISO 46 Ester Comparison
Physical Property
Diester +
Complex ester
Standard
TMP Oleate
Modified
TMP 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
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
>>4000
500
540
>>4,000
On test
>1,000
Biodegradability
28 days OECD 301B, %
61
84
99
85
77
Renewability, %
17
86
85
85
78
Viscosity at -30°C, cSt
after 72hrs
Dry TOST Test hours
(+1.5% RC9321)
*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
Oleo
derived
Oleo
derived
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
1
<1
75
90
3
<1
4
>4,000
>4,000
500
500
>4,000
>4,000
>4,000
Biodegradability
28 days OECD 301B, %
78
74
81
64
70
70
63
Renewability, %
70
0
85
85
85
88
73
Iodine value
Dry TOST test hours
(+2% RC9308)
Commercial 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
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Biodegradability
Renewability
Stability
Low temperature properties
Cost
• Careful selection of additives are required to
optimise hydrolytic stability
Contact
[email protected]
+44 1642 435356
Wilton Centre
Redcar TS10 4RF
England
[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