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Bio-based Hydraulic Fluids

Presented at

STLE Seminar on Environmentally Friendly Tribology 17 April 2008

Dr. In-Sik Rhee Fuels and Lubricants Technology Team U.S. Army Tank Automotive Research, Development and Engineering Center

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17 APR 2008
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Bio-based Hydraulic Fluids

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Dr. In-Sik Rhee

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US Army RDECOM-TARDEC 6501 E 11 Mile Rd Warren, MI 48397-5000
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18809
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TACOM/TARDEC
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18809
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Presented at STLE Seminar on Enivironmentally Friendly Tribology 17 April 2008, The original document contains color images.
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49

Standard Form 298 (Rev. 8-98)
Prescribed by ANSI Std Z39-18

Outline
• Background • Market Survey • Evaluation of Bio-based Hydraulic Fluids • ASTM Biodegradation Tests and Toxicity Test • Field Performance • Summary

17 April 2008

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What is Bio-based Hydraulic Fluid
• Bio-based Hydraulic Fluids (BHFs) are currently formulated with vegetable oils (i.e., rapeseed, sun flower, corn, soybean, canola, coconut, etc.) and synthetic ester, such as polyol ester, and additive packages. Their lubrication properties are very similar to mineral oils and readily biodegradable and low toxic fluids. Some of fluids have a limited operational capability such as a poor low temperature characteristics and oxidation stability. Many oil companies have developed bio-based fluids to eliminate the hazardous pollution caused by accidental oil spillage, which is especially important in environmentally sensitive applications such as construction. Another good reason to use bio-based hydraulic fluids is to develop a market for US grown agricultural feedstock and to reduce reliance on overseas petroleum crude oil.
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17 April 2008

USDA Federal Bio-based Products Preferred Procurement Program
• • Implement Section 9002 of Farm Security and Rural Investment Act of 2002. Provide information about availability , price, performance, environmental and public health benefits, life cycle costs, and recommended biobased content. Require that biobased products must be manufactured with raw materials or wastes from domestic agricultural production or feed stock from trade agreement - farming, ranching, forestry, aquaculture. Certify biobased products Web site: www. biobased.oce.usda.gov

• •

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aquaculture – Minimum content • By category (item) • Verified by ASTM methodology using • • 2. ranching.nist. forestry.CRITERIA FOR PRODUCTS TO BE DESIGNATED BIOBASED • 1. ENVIRONMENTAL PERFORMANCE/LIFE CYCLE – National Institute of Standards and Technology “Building for Environmental and Economic Sustainabilty” (BEES) program www.gov/oae/bees.html 5 14C dating 17 April 2008 . BIOBASED CONTENT – Products must be manufactured with raw materials or wastes from domestic agricultural production – farming. PERFORMANCE AND SPECIFICATIONS 3.bfrl.

Karlshammn. 17 April 2008O. Sweden 6 .Seed Oils and Their Fatty Acid and Genetic Varieties Source: Leissner. et al (1989) Vegetable Oils and Fats.

vacuum.Bio-based Oil Process CRACK. H3PO4) ALKALI REFINE (NaOH) BLEACH (acidic clay) DEODORIZE (250°C. olive) HEXANE EXTRACTION PRESS HEXANE DISTILLATION CRUDE OIL DEGUM (H2O.1-3% phosphatides 1% fatty acids 1 ppm chlorophyll meal Meal Bio-based Oil 17 April 2008 7 . low oil “Soft seeds” . high oil (e. sunflower. soybean) (e.g. FLAKE “Hard” seeds. DEHULL. canola. steam) (optional) HYDROGENATE / WINTERIZE (chill) Volatile impurities: odor (aldehydes & ketones) fatty acids Waxes & saturated fats lecithin Soap stock 0.g.

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Projected Benefits for Bio-based Hydraulic Fluids • Reduce hazardous waste by natural recycling • Reduce petroleum hydrocarbon contamination in landfill • Preserve ground water and soil • Reduce disposal costs of hazardous wastes • Reduce clean up costs of soil and ground water • Reduce petroleum consumption • Alternative lubrication resource • Others 17 April 2008 9 .

10 17 April 2008 . • US Army had evaluated twenty-six (26) Bio-based hydraulic fluids (BHFs) in accordance with Military Requirements. • Two types of Bio-based Hydraulic Fluids are commercially available (I. Vegetable based. • Potential market for Bio-based hydraulic fluids is expected to grow with the increase of environmental regulations.1996.Market Survey for Bio-based Hydraulic Fluid • A number of lubricant industries have developed BHFs which are less toxic and more biodegradable than currently used hydraulic fluids.e. Ref: “Evaluation of Environmentally Acceptable Hydraulic Fluids”.. NLGI Spokesman Vol 60. Synthetic Ester based).

etc. canola. soybean. sunflower.Vegetable Oil • Excellent lubrication • Nontoxic • Biodegradable • Derived from renewable resources such as rapeseed. corn. • Various chemical and physical properties • Poor low temperature fluidity • Poor oxidation stability • Inexpensive 17 April 2008 11 .

Pentaerythritol Very expensive 17 April 2008 12 . Trimethylolpropane.Bio-based Synthetic Ester • • • • • • • • Excellent lubrication Excellent fluidity Excellent low temperature and aging stability Nontoxic (some products are toxic) Biodegradable Physical and chemical properties varied depend on renewable resource Polyol ester. Diester.

% Viscosity.Comparison of Bio-based Fluids Mineral Oils Biodegradability ASTM D5864. ºC Compatibility with Mineral Oils Oxidation Stability Service life Relative Cost 10-40 15-150 -150 -54 to -15 Good 2 yrs 1 Vegetable Oils Synthetic Esters 40-80 32-68 -20 to 10 Good Poor to Good 6 month to 1 yrs 2 to 3 30-80 20 -300 -60 to -20 Good Poor to Good 3 yrs 4-5 17 April 2008 13 . cSt Pour Points.

Laboratory Chemical and Physical Property Test for Bio-based Hydraulic Fluid • • • • • • • • • • • • • • Viscosity Pour point test Flash point test Oxidation stability test Corrosion protection test Low temperature stability test Elastormer compatibility test Wear test Water stability test Thermal stability test Particle contamination test Biodegradation test Toxicity test Others 17 April 2008 14 .

Determining the Aerobic Aquatic Biodegradability of Lubricants or Lubricant Components in a Closed Respirometer. Predicting Biodegradability of Lubricants Using a Bio-kinetic Model. • ASTM D 7373. Determining Aerobic Aquatic Biodegradation of Lubricants or Their Components.ASTM Biodegradation Tests • ASTM D 5864. • ASTM 6731. • ASTM D 6139. 17 April 2008 15 . Determining the Aerobic Biodegradation of Lubricants or Their Components Using the Gledhill Shake Flask.

• Aromatic compounds are usually slowly degradable due to their structures and toxicity. 17 April 2008 16 .Inferenced factors on lubricants’ biodegradability (1) • Biodegradability of lubricants generally depend on their molecular structure and material. • Straight-chain aliphatic compounds are easily degraded. • Natural bio-based lubricants give higher biodegradability than petroleum based lubricants.

Inferenced factors on lubricants’ biodegradability (2) • High water solubility of lubricants provide higher biodegradability. • Low viscosity lubricants give good biodegradability due to their smaller molecular size. 17 April 2008 17 . • Long polymeric material have a low biodegradability. • Biodegradability depends on microorganism cultures and types of material used for food.

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Express biodegradability of lubricant as percentage of maximum (theoretical) carbon conversion (or carbon dioxide generation) under well-controlled conditions for 28 days. 60 % of biodegradability or above is considered as readily biodegradation. Design to determine degree of aerobic aquatic biodegradation of lubricants on exposure to an inoculum under laboratory conditions. this test method is widely used to measure biodegradability of lubricants.ASTM D 5864 Biodegradation Test (Modified Stun Test) • • • ASTM D 5864 biodegradation test is a version of OECD 301B test and is called as Modified sturn test. • • 17 April 2008 19 . Today.

ASTM D 5864 Biodegradation Test Apparatus 17 April 2008 20 .

Biodegradation Test Apparatus 17 April 2008 21 .

Preparation of Test Solution 17 April 2008 22 .

Cumulative Percen Biodegradation 80 60 40 20 0 0 10 Days 20 30 Rapeseed Corn Canola P-Ester Sunflow er Soybean Petroleum Biodegradation of Bio-based Hydraulic Fluids 17 April 2008 23 .

Pro and Con for Modified Stun Test • Pro – Widely used in Environmental Laboratories. – Long testing time. – Require large laboratory space.). safety problem. – Require manpower due to manual operation (high operation cost). • 17 April 2008 24 . Con – Poor test precision. – Handling microorganisms. – Many data are available in petroleum community. – Operational problems (connecting hose leaking. – Test apparatus is inexpensive (glassware test). – Provide meaningful data and test results agree with field performance. etc.

• Design to determine degree of aerobic aquatic biodegradation of lubricants on exposure to an inoculum under laboratory conditions. • Express biodegradability of lubricant as percentage of maximum (theoretical) carbon conversion (or carbon dioxide generation) under well-controlled conditions for 28 days. 17 April 2008 25 . • Today. this test method is not widely used to measure biodegradability of lubricants.ASTM 6139 Biodegradation Test Method • Same as ASTM D 5864 biodegradation test except for agitating test solution and called as EPA Shake Flask Test. • 60 % of biodegradability or above is considered as readily biodegradation.

EPA Shake Flask Test 17 April 2008 26 .

• Express biodegradability of lubricant as percentage of maximum (theoretical) oxygen consumption of microorganism under well-controlled conditions for 28 days. • Today. 17 April 2008 27 .ASTM D 6731 Biodegradation Test (Respirometer) • ASTM D 6731 biodegradation test is a version of OECD 301F test and is called as Respirometer test. this test method is widely used to measure biodegradability of lubricants. • 67 % of biodegradability or above is considered as readily biodegradation. • Design to determine degree of aerobic aquatic biodegradation of lubricants on exposure to an inoculum under laboratory conditions.

ASTM D 6731Biodegradation Test Apparatus (Respirometer) 17 April 2008 28 .

– Many data are available in petroleum community. – Test apparatus is expensive. – Need calibration often 29 • 17 April 2008 . – Some operational problems associated with test apparatus (sensors may not working). – Provide meaningful data and test results agree with field performance. – Long testing time. – Automatic system Con – Poor test precision. – Handling microorganisms.Pro and Con for Respirometer Test • Pro – Widely used in Environmental Laboratories.

• It was developed based on fundamental microbiology theory and composition of lubricants. • Correlated Conventional ASTM Biodegradation Tests.ASTM D 7373 Biodegradation Test • Biodegradability of Lubricants is calculated using a Biokinetic model and Chemical Composition of a lubricant . 17 April 2008 30 . • This bio-kinetic model does not require any biodegradation test apparatus and inoculums. • It can predict biodegradability of lubricant within a day.

01 17 April 2008 31 .49 B(t ) = B(1) + ln t − 2.Bio-kinetic Model 0.38 ln(6.8 × ECB ) where : ECB = ∑ (η a Ca + ηbCb ) a b B(1) : 0.

ECB Calculation b ECB = Σ (ηa Ca + ηb Cb) a where η : ECB coefficient Ca: Fraction of composition in Step 1 (Pentane) Cb: Fraction of composition in Step 3 (Diethyl Ether) ECB: Effective Composition of Biodegradation 17 April 2008 32 .

01 17 April 2008 33 .ECB Coefficients for Oils Lubricant Mineral oil PAO 2 PAO 4 PAO 6 or above Natural esters Renewable based diester or polyol esters Petroleum based ester types ECB Coefficient (η) 0.6 0.8 0.8 0.3 0.4 1 0.

ASTM D 7373 Composition Analysis Test Apparatus 17 April 2008 34 .

waxes Polar based aromatics 17 April 2008 35 .ASTM D 7373 Composition Analysis Procedure Process Step 1 Composition Analysis Pentane Non-aromatics (saturate. mineral oil. PAO) Step 2 Step 3 Step 4 50 % pentane+50% toluene Diethyl ether Chloroform/Ethyl alcohol Non-polar based aromatics Esters. acid.

Tested Hydraulic Fluids Code A B C D E F G H I Type of base oil Soybean PAO 4 + diester Canola Canola PAO 2 Mineral Oil Rapeseed Polyol ester Canola ISO classification 46 22 46 46 2 100 32 22 Identification Commercial HF∗ MIL-PRF-481708 MIL-PRF-320739 Grade 4 MIL-PRF-32073 Grade 4 Commercial HF SAE 15W-40 Commercial HF MIL-PRF-32073 Grade 2 Cooking Oil 36 *Hydraulic fluid 17 April 2008 .

5 1.2 2.7 3.5 0.53 98. or Wax 67.32 0.55 91.69 0.Composition Analysis of Tested Fluids Code Alkanes or Non-polar Saturate aromatics Ester.5 68.7 Polar aromatics ECB* A B C D E F G H I 24.6 0.5 0. Acid.83 0.32 1.93 0.57 1.38 3.4 0.6 5.5 90.7 5.7 7.4 92.18 2.47 13.7 1.07 17.26 0.82 0.49 17.75 0.91 37 * Effective composition for biodegradation 17 April 2008 .98 3.7 90.05 1.8 82.5 0.56 77.95 77.9 2.45 0.7 3.79 0.00 1.9 27.

7 Bio-kinetic Model 64.8 76.7 61.2 78.2 94.0 32.2 38 A B C D E F G H I 17 April 2008 63.1 77.0 51.0 66 73.0 77.4 51.0 70.4 36.Biodegradation Test Results Code ASTM D 5864 67 51.3 71.1 69.9 72.0 77.3 ASTM 6731 CES CO2 Evolution Test 73.7 71.6 88.7 47.1 80.2 30.3 67.0 .8 69.8 79.3 75.8 74.3 24.3 75.6 84.2 66.

Biodegradation Profile for Canola based BHF 90 80 Biodegradation (%) 70 60 50 40 30 20 10 0 0 10 Days Figure 2. Biodegradation Profile for Canola based BHF 20 30 ASTM D5864 Biokinetic Model CES Test ASTM D 6731 17 April 2008 39 .

89 1 0.95 0.89 0.Correlation Coefficients (r2) Between Biodegradation Tests ASTM D 5864 ASTM D 5864 ASTM D 6731 CES CO2 evolution test 1 0.92 0.8 0.82 CES CO2 Evolution Test 0.87 17 April 2008 40 .82 1 ASTM D 7373 0.8 ASTM D 6731 0.

Soil Biodegradation Test 17 April 2008 41 .

Oil Concentration in Soi (PPM) 120000 100000 80000 60000 40000 20000 0 0 1 2 3 4 5 6 7 Month Canola A Syn-BHF Canola B Soy-BHF Rapeseed Soil Biodegradation Test for BHFs 17 April 2008 42 .

Simple and short test (about one hour) 43 • 17 April 2008 .Use Marine bacterium. .A. Standard Test Method for Assessing the Microbial Detoxification of Chemically Contaminated Water and Soil Using a Toxicity Test with a Luminescent Marine Bacterium. . .S.Modify ASTM D 5660.Toxicity is measured based on analysis of light change on Vibro fisherie. Draft ASTM Microtoxicity Test. and Good Laboratory Practices. Vibro fisherie.. “Assessing the Toxicity of the Water Accomodating Extracts from Lubricants Using Luminescent Marine Bacterium”. trout) as a test specimen – Toxicity is determined based on the number of dead fish – Seven day test – Not many laboratory performs this test in U. .e. Acute Toxicity to Fish. – Widely used in Environmental Laboratory – Use live fishes (i.Toxicity Test • OECD Guideline 203.

Bulldozers.e. 17 April 2008 44 .. • Evaluation criteria used in this demonstration are their field operational performances and environmental performances (i. • Duration of tests was one (1) year.e. dump trucks.Field Performance Test for Bio-based Hydraulic Fluids • US Army conducted two Field tests using ten pieces of construction equipment (i. soybean oil.e. etc.. toxicity). polyol ester. • Five (5) BHFs (i. and diester) selected as field demonstration samples. canola oil. scoop loaders..) at Military installations. biodegradability. rapeseed oil.

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• BHFs had good hydrolytic stability that resists reaction with water. • None of fluids had Low Temperature Operational Problem at Midwest Winter Weather (subzero to -30 ºC). • All samples showed some degree of oxidation. but still have good conditions.Field Test Results (1) • No significant viscosity changes observed in any construction Equipment. seals look good 17 April 2008 47 47 . • Equipment had no leaking problem.

Field Test Results (2) • BHFs did not give any volatility problem during demonstration. 17 April 2008 48 48 . • No incompatibility was observed between bio-based fluids and petroleum based fluids.. biodegradability) did not change throughout demonstration. • Environment property of fluids (i. • No Biodegradation occurred in hydraulic systems. • All BHF samples did not give any abnormal behavior during one year of testing and provided excellent service. • No evidence for incompatibility between BHFs and structural materials used in hydraulic systems.e.

17 April 2008 49 . soybean. etc. canola. • Bio-based hydraulic fluid formulated by renewable resource (i. • Therefore. rapeseed.e. • And they provide same quality of performance compared to petroleum based hydraulic fluids. Bio-based hydraulic fluid can be used in construction or other types of equipment. coconut..Summary • Numerous Bio-based hydraulic fluids are currently available in domestic market and new products are being developed to meet commercial and military requirements.) • This fluid provide a high biodegradability and low toxicity.