STLE Eco Friendly Lubes

LUBRICATION FUNDAMENTALSAND

FUTURE DIRECTIONS

Eco Friendly Lubricants

Ken Brown, P. Eng., FSTLEEco Fluid Center Ltd.

February 10, 2009

Old Mill, Toronto

What is a green lubricant?

Environmentally friendly lubricants first came on to the market in the mid 1980’s. It is generally recognized that these lubricants should have two main characteristics; low toxicity and high biodegradability.

For example, if a lubricant washed out into the waterways, it should not be toxic to aquatic life, and it should biodegrade in a short period of time.

In addition, a viable environmentally friendly lubricant has to give an acceptable level of performance compared to existing mineral-based products.

The product must also be satisfactorily long-lasting within the equipment to eliminate both the need for frequent replacement and the problems of disposing of the product.

Reducing environmental impact used to consider just the lubricant itself. Then it became the lubricant life cycle from raw materials to end of life.

Now more focus is being placed on the complete process including facility (plant) construction, raw materials, intermediate compounds during manufacturing, the energy consumed and maintenance activities.

The correct choice might be synthetic lubricants, it might be different additives, and in other cases it could be biodegradable products and/or products with less environmental impact.

A decision matrix has been proposed for a European Community environmental evaluation.

What Is Needed?

Good from start to finish

Try to extend the life so that less waste oil is generated. Mineral oil based industrial oils seldom wore out, so in order to get the best out of the oil and of the oil-lubricated equipment, one goal was to keep the oil clean and dry.

This can be more important with some ‘green’ fluids that can shear down, require fresh additives and/or which are sensitive to water.

For self-contained sumps, this can be as simple as ensuring that make-up oil is added properly, that the breathers are adequate and working, and that any cloudiness, such as from water, is corrected.

Desiccant breathers, sealed reservoirs or dry air purge might be required with some ester based fluids.

For circulating oil systems, it is also important to make sure that the make-up oil is not a source of contaminant.

In most cases, effective use can be made of inexpensive but good equipment to remove dirt and/or water. These can be either off-line or on-line filtration and either continuous or as required.

CONDITION MONITORING

An important aspect of extending the lubrication service life is condition monitoring. This serves a number of purposes. First, it ensures that the right lubricant is in place. When starting a test program it is often found that oil of the wrong viscosity has been used. Such tests can also determine if the right oil type is being used.

What is required can be different with ‘green’lubes.

When testing the oil it can be determined what is required to keep it in good condition. This can be filtration, purification, sweetening, or, with large systems, re-inhibition with additives.

The advantage is that if you do not have to change it, uptime is maximized and waste oil generation is minimized. With less handling of the lubricants you also reduce the risk of leaks.

With premium priced ‘green’ lubes better fluid maintenance can be more cost effective.

The G-7 Countries’ Certification Programsare comprised of six official environmental labeling agencies incorporated by seven countries.

They use rigorous, objective environmental testing without the biases of marketing departments or manufacturers’ associations.

‘Green’ Certification

The official environmental labeling agencies are the following:

Environmental Choice (Canada),

Green Seal (U. S. A.),

Eco Mark (Japan),

Ecolabel (United Kingdom and Italy),

NF Environment (France), and

Blue Angel (Germany).

The Environmental Choice Program was created by Environment Canada in 1988 and is the official environmental labeling agency of Canada.

Canadian Eco Certification

In 1995, a Canadian private sector company called TerraChoice Environmental Services Inc. assumed responsibility for the delivery of the program.

Environment Canada continues to provide ultimate accountability for environmental labeling practices in Canada, while TerraChoice is financially and operationally responsible to Environment Canada.

What is considered ‘green' and by who?

•Wall Paints: ”The Blue Angel because low in emissions“

•Small-scale Cogeneration Units: ”The Blue Angel because energy-efficient“

•Office Printers and Multifunction Devices: ”The Blue Angel because resource-saving and low in emissions“

• The product has a reduced impact on the aquatic environment and the soil during use.• CO2 emissions are reduced.• The product contains high percentage of renewable raw materials.• The product does not contain certain hazardous substances (e.g. R-phases).• The product guarantees a high level of performance.

ISO 15380:2002

Lubricants, industrial oils and related products (class L) -- Family H (Hydraulic systems) -- Specifications for categories HETG, HEPG, HEES and HEPR

a: Water-soluble fluids shall be tested according to the test method cited. Fluids with low water solubility shall be tested using water accommodated fractions, prepared according to ASTM D6081

NOTE: The biodegradability and aquatic toxicity tests should be performed according to Good Laboratory Practice (GLP).

ISO 7346-2

ISO 6341

ISO 8192

100

100

100

mg/l

mg/l

mg/l

Toxicity a

Acute fish toxicity, 96 h, LC50

Acute Daphnia toxicity, 48 h, EC50

Bacterial inhibition, 3 h, EC50

ISO14593 or ISO 9439

60%Biodegradability

Test methods

MinUnitsCharacteristics

Specifications or Report requirements for categories HETG, HEPG, HEES and HEPR

MYSID SHRIMP

(MYSIDOPSIS BAHIA)

WHICH TOX TESTS?WHICH TOX TESTS?

REFERENCE: MIL-PRF-18458C TYPE II GREASE, WIRE ROPE – EXPOSED GEAR, 5 JULY 2002

SECTION 4.4.8 AQUATIC TOXICITY: STATIC NON-RENEWAL, 48-HOUR MYSID (MYSIDOPSIS BAHIA) ACUTE TOXICITY TEST IN SEAWATER PER EPA/600/4-90/027F. LD50 1000 ppm minimum


Viscosity Grade Density

Colour Appearance

Ash Content Flash Point

Viscosity -20, 0, 40 & 100°C

Pour Point Low Temp Fluidity (7days)

Acid No. Copper Corrosion

Rust Prevention Foam

Air Release Water Separation

Elastomer Comp. Oxidation Stability

FZG Load Carrying Vane Pump Wear


Many of the tests are not given limits but are to be reported or “as agreed between the supplier and end user”.

For the standard performance related tests those such as for wear are identical but for some of the physical characteristics tests and the oxidation testing there are differences. These differences are in the tests required and the limits.


Load Carrying CapabilitiesLoad Carrying Capabilities

IP 281, IP 281,

CETPO CETPO

RP67H, RP67H,

DIN 51389DIN 51389--22

120120

3030

120120

3030

120120

3030

120120

3030

mgmg

mgmg

Vane pumpVane pump

RingRing

VaneVane

DIN 51354DIN 51354--22101010101010nanastagestageFZG,A/8, FZG,A/8,

3/90, min3/90, min

6868464632322222UnitsUnits


The specification also contains information on what should be checked when considering changing fluid types and also what should be done after changing fluids.

The latter includes targets for residual fluid (½-2%) as well as the periods between oil and filter changes. With all four fluids they recommend filter changes after the first 50 hours.


To determine the fluid changes they suggest monitoring the fluid by testing for the following; water content and solid particle contamination as well as viscosity, neutralization number, FTIR and spectrographic analysis.

Native oils (vegetable)Native oils (vegetable)

Crop-based or native oils or vegetable oils are the oldest known lubricants and were rediscovered in the early 70’s. These include rapeseed, canola, sunflower and soya oils.

Rapeseed oil is a triglyceride and consists of a fatty alcohol, the tribasic glycerin and three monobasic long-chain carboxylic acids (fatty acids). The fatty acids include oleic, linoleic

and linolenic, palmitic and stearic acids.

Vegetable Oils

Vegetable OilsVegetable Oils

In the ISO classification systems these are In the ISO classification systems these are

known by the abbreviation HETG (hydraulic known by the abbreviation HETG (hydraulic

oil environmental triglyceride).oil environmental triglyceride).

Still used but tend to have poor oxidative Still used but tend to have poor oxidative

stability and poor low temperature stability and poor low temperature

characteristics.characteristics.

Polyglycols

Polyalkylene glycols have been used for almost fifty years because they had good characteristics at very high and low temperatures. There are many types with polybutylene and ethylene oxide/propylene oxide commonly being used for environmental applications.

They can be soluble in water, which is good in some applications but can also restrict their use when spill clean-up is required.

Polyglycols

In the ISO classification systems these are known by the abbreviation HEPG (hydraulic oil environmental polyglycol).

Tend to have good lubricating characteristics and shear stability. You have to consider compatibility with seals, hoses, paints and filter elements as well as preventing any accidental mixing with mineral oil based products.

Unsaturated Esters - These are mainly made from modified animal fats and vegetable oils. Examples include TMP esters or trimethylpropane esters, also known as oleic acid esters or trioleates.

Synthetic esters

Synthetic estersSynthetic esters

In the ISO classification systems these are known by the abbreviation HEES (hydraulic oil ester synthetic).

Show better low and high temperature characteristics than vegetable oils. SG remains high at about 0.918.

Saturated Esters - These have reportedly been available since the mid 80’s and are formed during the reaction of alcohols with carboxylic acids.

Also called HEES but tend to have better oxidative stability.

Synthetic esters

A fourth classification is HEPR. These are hydraulic oil environmental polyalphaolefins and related products. These includes PAO’s and hydrotreated oils. For biodegradability normally only the low viscosity oils are suitable.

In some countries mineral oil based products that have a recycled component or other eco attributes are also allowed.

PAO’s and Others

THE EUROPEAN ECO-LABEL CATALOGUE

LUBRICANTS, HYDRAULIC FLUIDS -CANADA

DIESTERlub 2T PlusDIESTERlub CSL 100 & CSL 150DIESTERlub Hydro 46

NOVANCE France

ECO Lube H46 (200 & 30L) INTERFLON Netherlands

HLP SYNTH E15, E22, E32, E46 & E68TURWADA S 220 LLTURWADA SYNTH E 46

PANOLIN Switzerland

DIESTERlub 2T Plus is a formulated refined vegetable oil for a best lubrication of terrestrial 2 stroke engines.

DIESTERlub CSL 150 is a vegetable lubricant designed for a better lubrication of chain saw formulated from refined vegetable oils,

particularly stable against oxidation.

Canadian EcoLogo M

Bicycle Chain Lubricants must:

• Meet all applicable performance standards, includin g rust protection, wear and tear, and viscosity level s;

• Be safe to use (not labeled as poisonous or infectious);

• Have low aquatic toxicity (LC 50 or EC50 no lower than 1,000 mg/l for fish, crustaceans and algae OR LC 50 or EC50 no lower than 2,500 ppm according to the Microtox™ test);

plus

EcoLogo M, bicycle chain lubricants must:

The former and;

• Be biodegradable; • Not contain more than 5% additives, more than 3% of

non-biodegradable additives, or more than 0.1% petroleum oil additives and

• Not contain organic chlorine or nitrite compounds, lead, zinc, chromium, magnesium or vanadium.

No products available at the moment.

EcoLogo M, Lubricant - industrial, re-refined

To be authorized to carry the EcoLogo M, re-refined industrial lubricating oils must:

• Meet all applicable performance standards; • Contain a minimum of 55% by volume of re-

refined oil; • Not contain more than 5 ppm each of organic

halides, benzo(a)pyrene and benzo(a)anthracene;

• Ensure that all by-products of the re-refining process are diverted from disposal through reuse, recycling, or energy recovery; and

• Be identified as not for automotive use.

Forsythe Lubrication Associates LimitedDow Chemical Canada Inc.H. L. Blachford Ltd./Ltée

EcoLogo M, Lubricant - industrial, re-refined

Must:• Be safe to use (not labeled as poisonous or

infectious, and have a flash point greater than 190°C);

• Have low toxicity to aquatic organisms (LC 50 greater than 1,000 mg/ on fish, crustaceans and algae);

• Not contain more than 5% additives; • Meet all applicable performance standards, includin g

rust protection and viscosity levels;

plus

EcoLogo M synthetic industrial lubricants

The former and;

• Not contain more than 3% of additives that are not biodegradable;

• Not contain more than 0.1 % petroleum additives, organic halides, nitrite compounds, lead, zinc, chromium, magnesium or vanadium; and

• Demonstrate a low tendency for foaming and oxidation stability.


� Magna Chemical Canada Inc.

� LubeCorp Inc.

� Prolab Technolub


Was the first environment related label for products and services. It was created in 1978 and considers itself as a market-conforming instrument of environmental policy designed to distinguish the positive environmental features of products and services on a voluntary basis.

Today, about 10,000 products and services in 80 product categories carry the Blue Angel eco-label.

The Blue Angel – Eco-Label

The Blue Angel-labeled products are readily biodegradable, free from water-endangering substances and, hence, they noticeably ease the impact on soil, groundwater and water bodies.

In the 90’s about 5% of the hydraulic liquids were Blue Angel eco-labeled. In 2005 the percentage of bio-hydraulic oils rose to 9% for stationary applications (primarily hydroelectric power plants, locks, dams, etc.) and to 19% for mobile applications (e.g. agricultural equipment; construction machinery and forest equipment).

RAL-UZ 79Rapidly Biodegradable Hydraulic Fluids

http://www.blauer-engel.de/en/products_brands/vergabegrundlage.php?id=83

The hydraulic fluids must not contain any substances1 which are listed in Annex I to Directive 67/548/EEC2 and which are classified according to Section 4a, Gefahrstoffverordnung3 (Ordinance on Hazardous Substances) as “very toxic“ (T+) or „toxic“ (T) and/or which according to Annexes III and VI to Directive 67/548/EEC must be marked with the following Risk Phrases:

• R 45 (may cause cancer),

• R 46 (may cause heritable genetic damage),

• R 48 (danger of serious damage to health by prolonged exposure),

• R 68 (possible risk of irreversible effects);


3.1.1.2 classified as carcinogenic in accordance with EC Category Carc. Cat.1, Carc.Cat.2 or Carc.Cat.3 or mutagenic according to EC Category Mut.Cat.1,Mut.Cat.2 or Mut.Cat.3 or reprotoxic according to EC Category Repr. Cat.1, Repr. Cat. 2 or Repr.Cat.3;

3.1.1.3 classified in TRGS 9054 as carcinogenic, mutagenic or reprotoxic substances ;

3.1.1.4 classified in the MAK Value List5 as:

- cancerogenic working materials - Category 1, 2 or 3;

- germ cell mutagenic working materials - Category 1, 2, 3A or 3B;

- teratogenic working materials in the column “pregnancy“ in group A or group B;


3.1.2 classified in the „Verwaltungsvorschrift wassergefährdender Stoffe“6 (Administrative Regulation on the Classification of Substances Hazardous to Waters) as amended, in Water Hazard Class 3;

3.1.3 or which according to scientific knowledge must be classified in one of the categories under para. 3.1.1.2 either as carcinogenic, teratogenic or mutagenic or have sensitizing or other chronically damaging properties or which as such or as their impurities or decomposition products are apt to cause considerable risk or considerable disadvantage for the public.


Biodegradability and Eco-Toxicity of the Ingredients

3.5.1 Basic Substances

Ingredients accounting for more than 5 percent by weight are considered as basic substances.

Basic substances of hydraulic fluids must - each by itself - be biodegradable by at least 70%.


Biodegradability

CO2- Evolution Test (OECD 301 B, EC C.4-C)

Manometric Respirometry Test (OECD 301 F, EC C.4-D)

Closed Bottle Test (OECD 301 D, EC C.4-E)

Modified MITI-(I)-Test (OECD 301 C, EC C.4-F)

CO2-Headspace-Test (ISO 14593)

BODIS-Test (ISO 10708)


Ecotoxicity


A substance or a mixture of substances shall be proven by the tests A, B, C, F.

A) Test for acute toxicity on daphnia (OECD 202 Part I, EC C.2)

B) Test for acute toxicity on fish (OECD 203, EC C.1)

C) Algae test (OECD 201, EC C.3)

D) a 21-day daphnia test (OECD 202 Part II)

E) a long term fish test (OECD 204 or 210)

F) a growth test on vascular plants. (OECD 208)

G) a fish embryo test (DIN 38418-6)


Plus, information on bacterial toxicity, an

estimation of the bio-accumulative potential,

and limits on any polymers that might have been

used.

The hydraulic fluids must meet the technical

minimum requirements under ISO 15380.

A check showed that seventy eight products

from twenty six suppliers are approved.

Blue Angel Eco-label Annual fee

Annual Sales(in Million Euros)

Annual Fee(in Euros)*

Fee Category

≤0.25 270.00 1

0.25 up to 1.0 540.00 2

>1.0 up to 2.5 1080.00 3

>2.5 up to 5.0 2110.00 4

>5.0 up to 15.0 3050.00 5

>15.0 up to 25.0 4500.00 6

>25.0 6000.00 7

*plus value-added tax (VAT)

ASTM D 6046 – 02 (Reapproved 2006)

Standard Classification of Hydraulic Fluids for Environmental Impact

1. Scope

1.1 This classification covers all unused fully formulated hydraulic fluids in their original form.

BioaccumulationEcotoxicityEnvironmental

Persistence

Environmental

Compartment

Bw

Bm

Bs

Ba

Tw

Tm

Ts

Ta

Pw

Pm

Ps

Pa

Fresh Water Marine

Soil

Anaerobic

Categories of Environmental Impact

Overview of Extended Classification

1.6 This classification addresses releases to the environment which are incidental to the use of a hydraulic fluid. The classification is not intended to address environmental impact in situations of major, accidental release.

Nothing in this classification should be taken to relieve the user of the responsibility to properly use and dispose of hydraulic fluids.

A SPILL IS STILL A SPILL!

ultimate biodegradation test; a test which estimates the extent to which the carbon in a material is converted to CO2 or methane, either directly by measuring the production of CO2 or methane, or, for aerobic biodegradation, indirectly by measuring the consumption of O2.

ASTM D- D6046 Tests of Biodegradability in Aerobic Aquatic Environments

Ultimate Biodegradation Tests:

ASTM D 5864, Test Method for Determining the Aerobic Aquatic Biodegradation of Lubricants - % theoretical CO2

ISO 9439:1990, Technical Corrigendum 1, Water quality—evaluation in an aqueous medium of the “ultimate” biodegradability of organic compounds—Method by analysis of released carbon dioxide - % theoretical CO2

OECD 301B, CO2 Evolution Test (Modified Sturm Test) -% theoretical CO2

OECD 301C, Modified MITI Test (I) - % theoretical O2

OECD 301F, The Manometric Respirometry Test - % theoretical O2


Ultimate Biodegradation Tests: cont’d

Aerobic Aquatic Biodegradation Test 40 CFR 796.3100 - % theoretical CO2 US EPA

EUC C.4–C: Carbon dioxide (CO2) evolution - % theoretical CO2

EUC C.4–D: Manometric Respirometry - % theoretical O2

primary biodegradation test; a test which follows the disappearance of a test material by measuring some attribute of the material.


Primary Biodegradation Tests:

CEC L-33–A-934, Biodegradability of Two-Stroke Cycle Outboard Engine Oils in Water (Formerly L-33–T-82) - % loss of extractable CH2 groups

<45% in 84 days (12 weeks)

<40% in 84 days (12 weeks)

Pw4

≥ 45% in 84 days≥40% in 84 daysPw3

≥67% in 84 days≥60% in 84 daysPw2

≥67% in 28 days≥60% in 28 daysPw1

For Hydraulic Fluids Containing Less Than 10 Wt % O2

% Theoretical O2% Theoretical CO2

Ultimate Biodegradation Test ResultsPersistence

Designation

Environmental Persistence Classification—Aerobic Fresh Water

<40% in 84 days (12 weeks)Pw4

≥40% in 84 daysPw3



For Hydraulic Fluids Containing 10 Wt % or More O2

% Theoretical CO2 or% Theoretical O2

Ultimate Biodegradation Test ResultsPersistence

Designation


<80% in 21 daysPw4

≥80% in 21 daysPw-C

For All Hydraulic Fluids

% Loss of Starting Material

Primary Biodegradation Test ResultsPersistence

Designation


Acute Ecotoxicity Classification

Tw4

Tw3

Tw2

Tw1

<10<10Ts4

100-10Ts3

1000-100Ts2

>1000Ts1

Loading Rate, wppm LL50, IL50, or EL50

Water Designation

Soil

Designation

Acute ecotoxicity in an aquatic

environment shall be tested with at

least three tests of acute toxicity, one

test being on a plant, one test on a

vertebrate, and one test on an

invertebrate appropriate for the

aquatic compartment.

Acute ecotoxicity in a terrestrial

environment shall be tested in at least two

tests of acute toxicity, one on an

invertebrate and one on a plant.

Tests on terrestrial vertebrates usually fall

under the category of mammalian toxicity

rather than ecotoxicity and so are not

included in this classification.

PLUS 14021Environmental claims: A guide for industry and advertisersDeveloped in partnership with

Published in June 2008 by Canadian Standards Association

Self-declared environmental claims, including any explanatory statement, shall be true not only in relation to the final product but also shall take into consideration all relevant aspects of the product life cycle in order to identify the potential for one impact to be increased in the process of decreasing another.

CAN/CSA-ISO 14021, Clause 5.7 h)

Product Life CycleProduct Life Cycle

Such considerations include;

• design of the product;

• extraction of any raw materials used in the product or process;

• materials (including energy) used in the production process;

• emissions created during production (air, water, solid waste, etc.);

• toxicity of these materials and emissions;

• environmental impacts of the distribution system (including packaging and transportation);

• environmental impacts that occur during use of the product or service;

• durability, reusability, and recyclability of the product;

• consumer packaging and its disposal; and

• final disposal of the product.

Example:

The use of non-ozone-depleting gas for refrigeration can have a negative impact on the energy efficiency of refrigerators. If a claim is made with regards to the use of non-ozone-depleting gas, either the net benefit must be verified or the reduction in efficiency must also be clearly stated.

Environmental Labeling

An environmental claim that is vague or non-specific or which broadly implies that a product is environmentally beneficial or environmentally benign shall not be used.

CAN/CSA-ISO 14021, Clause 5.3

Claims such as “environmentally friendly”, “ecological (eco)”, and “green” are examples of vague claims and should be reserved for products/services whose life cycles have been thoroughly examined and verified.

These imply that a product is environmentally benign or is environmentally beneficial. Without greater specificity such far-reaching claims could be misleading or deceptive.

Free of ….Free of ….

An environmental claim of "... free" shall only be made when the level of the specified substance is no more than that which would be found as an acknowledged trace contaminant or background level.

CAN/CSA-ISO 14021, Clause 5.4

To be biodegradable, degradable, or photodegradable, most substances need either light or oxygen, neither of which is available if the product is placed in a landfill.

If package labeled as such ends up in landfill or in disposal facilities that are deprived of the conditions necessary to the degradation process, the claim of biodegradability or degradability could be false or misleading.

When biodegradable isn’t

If substances that are harmful to the environment are released during the degradation process, the claim of "degradable" should not be made.

Example: Cleaners containing phosphates biodegrade totally and quickly; however, if they reach rivers and lakes, they can have a serious impact on aquatic life and can promote massive algae growths.

Latest Engine Oils Latest Engine Oils -- ‘Green’?‘Green’?

Improved Fuel EfficiencyImproved Fuel Efficiency

Reduced WearReduced Wear

Reduced EmissionsReduced Emissions

Improved VolatilityImproved Volatility

Reduced Heavy MetalsReduced Heavy Metals

Refillable ContainersRefillable Containers

In many situations, it should be relatively easy to make improvements by taking advantage of the many options. This really makes it a ‘win-win’ scenario, because not only can the equipment run better, but there can be less environmental impact.

In addition, going ‘Green’ can cost less in the long-term when all the life-cycle factors are taken into account.

Summary

When considering ‘green’ lubricants there are more factors than just the biodegradability.

The toxicity has to be considered and the specific tests will depend on the application.

The product also has to work!

Summary

The application will also influence the type of fluid used and take into account characteristics such as whether or not the fluid is soluble in water.

For example, if the fluid is soluble in water then any oil skimmer type equipment will have to be changed.

Similarly, if water is soluble in the fluid then any coalescer type equipment will likely not be effective.

Summary

With different products the materials used also have to be reviewed for compatibility and this should take into account material affects but also any different rheological impacts on the equipment, especially the pumps and filters.

Plus, the lubricant has to perform in the application and in some cases if the life is less this might not be suitable.

Summary

In addition, ensure that the fluid changeover is done properly and that the fluid and filter element changes are properly addressed. Changes might be required to the condition monitoring testing and to the limits.

Lastly, ensure that what is done with the fluid at its end of life is appropriate; re recycling, incineration or using in other applications.

Summary

COMMENTSCOMMENTS

� There are a number of ways a product can be ‘green’ and there are almost as many certification programs.

� In Canada our process really just appears to be getting going and to get it right will require more involvement from suppliers and users.

� Canada also appears to one of the few countries where there have been almost no regulatory requirements to use ‘green’ lubes.

THANK YOUTHANK YOU

STLE Eco Friendly Lubes

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