Product Performance Data

Transcription

1 Biosynthetic Technologies is one of many companies developing and commercializing renewable and biodegradable base oil (called Estolides and sometimes referred to herein as SE7B) used as petroleum oil replacements in the formulation of motor oils and other industrial lubricants. Finished motor oils and lubricants are formulated by blending the base oil and additives to make the final product. Biosynthetic Technologies is a supplier of base oil only. How motor oil and lubricant marketers choose to formulate will vary from product to product and from company to company. That process is propriety and will be completely out of the control of Biosynthetic Technologies. We have formulated and tested some finished products in an effort to offer insight into the technical and environmental performance of finished products, but the results may not be indicative of all formulations. Further, the choice of equipment and varying operating conditions out of the control of Biosynthetic Technologies could also create variability in test results of specific formulations. Section 1: Technical Performance Motor Oil - Piston Deposit Test Data Product Performance Data An Estolide formulation containing 35% biosynthetic base oil recently passed a Sequence IIIG piston deposit test in 5w30 motor oil, far surpassing the toughest industry standards for engine cleanliness. The formulation included 35% Estolides to reduce piston deposits while increasing bio-content. In this test, piston deposits are measured on a merit system from 0 to 10, with 10 indicating no deposits are detected. To pass the current standards a minimum rating of 4 is required. Estolides have continually proven to greatly reduce piston deposits per the IIIG test as evidenced in this data set. The 8.46 is a very high rating and surpasses the piston deposit ratings of full synthetic petroleum formulations currently available in the market. Environmental Bottom Line: Cleaner engines last longer and typically get better fuel efficiency

2 Oxidative Stability Estolides offer resistance to oxidation and demonstrate excellent response to antioxidant additives, leading to increased oil longevity and extended drain intervals. Biosynthetic Estolides test on par with the highest performing petroleum base oils. Poly-alpha olefins (PAOs) are the most common petroleum base oil used in synthetic motor oil formulations. High-Oleic Canola is representative of the performance of unmodified vegetable oils. What makes vegetable oils good environmentally prevents their use in challenging technical applications such as motor oil. Oxidative Stability of Biosynthetic SE7B Compared to Common Low Viscosity Base Oils RPVOT - ASTM D2272, minutes Group V Note: Base Oils with 1% Antioxidant (1:1 Aminic/Phenolic) Environmental Bottom Line: Motor oil with good oxidative stability allows for much longer oil drain intervals reducing petroleum consumption and preventing pollution.

3 Low Volatility Estolides exhibit low volatility, resulting in increased flash and fire points and lower evaporative loss (NOACK) as compared to other high performance base stocks. High flash and fire points make Estolides ideal for applications where operating temperatures are high and flammability is a concern. 205 Flash Points of Low Viscosity Base Oils (6-8 cst) ASTM D92, C Group V Estolides have distinguished low NOACK values, meaning less of the oil is lost due to evaporation over the life of the lubricant. When lighter lubricant components vaporize, the overall fluid can thicken, causing reduced energy efficiency, lower fuel economy, and increased oil consumption. Additionally, in motor oil applications, low NOACKs can increase phosphorous retention of the lubricant, reducing the potential for poisoning of catalytic converters. Environmental Bottom Line: It s well understood that synthetic motor oil offers longer drain intervals than conventional motor oils. Estolide base oils offer similar extended drain intervals. However, if oil thickens due to evaporative loss, the drain interval may be longer but fuel efficiency can quickly erode. What good is changing the oil less often if it requires burning more fuel? Biosynthetic motor oils with lower NOACK scores have the potential to maintain fuel economy and offer improved phosphorus retention.

4 Viscosity Index Estolides have higher viscosity indices (VI) than nearly any other base oil in industry and with high VIs come a number of advantages. Higher VI base oils provide increased film thickness at elevated temperatures, resulting in better protection, and potentially lower wear. At lower temperatures, high VI base fluids create reduced viscous drag on moving parts, leading to higher horsepower and increased energy efficiency. The naturally high VI of Estolide base oils also has its benefits to formulators, requiring lower treats of viscosity modifier additives to meet VI specifications. Typical Base Oil Viscosity Indices (6-8 cst) ASTM D2270 Group V Group I Group II Group III Group IV (PAO) Polyol Ester Diester PAG Biosynthetic SE7B Natural Detergency As a polar compound, Estolides have the unique ability to dissolve sludge and varnish, helping equipment stay clean and operate efficiently. This property of natural detergency is a quality inherent to ester base stocks, a molecular class of which Estolides are a subset. When Estolide-based motor oil was compared to a typical mineral oil-based formulation, engines using an Estolide formulation (right) appeared clean and new, while the Group II formulation showed higher levels of varnish (left). Engine Cleanliness Using Estolide Motor Oils Conventional Group II Motor Oil Estolide Motor Oil Environmental Bottom Line: Base oil with higher viscosity indices and excellent natural detergency can be formulated using fewer additives (source reduction).

5 Section 2: Environmental Performance In November 2011 the United States Environmental Protection Agency released a paper titled Environmentally Acceptable Lubricants which focused primarily on lubricants used in vessels. In outlining the properties of Environmentally Acceptable Lubricants (EALs) the agency targeted three primary environmental traits; biodegradability, Aquatic Toxicity and Bioaccumulation. The report concluded that the three most common categories of base oils that meet the requirements are: 1) vegetable oils, 2) synthetic esters, and 3) polyalkylene glycols (PAG). Estolides, while derived from vegetable oils, would most appropriately be categorized as a synthetic ester. The text from the following sections relating to Biodegradability, Aquatic Toxicity and Bioaccumulation is from that report (in purple + tables) unless indicated as specific to Biosynthetic Technologies Estolide. Biodegradability Biodegradability is a measure of the breakdown of a chemical (or a chemical mixture) by micro-organisms. Primary biodegradation is the loss of one or more active groups in a chemical compound that renders the compound inactive with regard to a particular function (Betton, 2009). Primary biodegradation may result in the conversion of a toxic compound into a less toxic or non-toxic compound. Ultimate biodegradation, also referred to as mineralization, is the process whereby a chemical compound is converted to carbon dioxide, water, and mineral salts (Betton, 2009). In addition to primary and ultimate biodegradation, biodegradation is also defined by two other operational properties: inherent biodegradability and ready biodegradability. A compound is considered inherently biodegradable so long as it shows evidence of biodegradation in any test for biodegradability. Readily biodegradable is an operational definition that some fraction of a compound is ultimately biodegradable within a specific timeframe, as specified by a test method. Common test methods, such as those developed by the Organization for Economic Cooperation and Development (OECD), the Coordinating European Council (CEC), and the American Society for Testing and Materials (ASTM), for determining lubricant biodegradability are OECD 301B (the Modified Strum test), ASTM D-5864, and CEC L-33-A-934. Both OECD 301B and ASTM D measure ready biodegradability, defined as the conversion of 60% of the material to CO2 within a ten day window following the onset of biodegradation, which must occur within 28 days of test initiation (Willing, 2001). The table below summarizes biodegradation rates for different lubricant base oils. Ester-based oils have a much greater inherent biodegradation rate due to the presence of carboxylic acid groups that bacteria can readily utilize (Mudge, 2010). These compounds are also more water soluble than compounds that do not contain polar functional groups, the absence of which can reduce their bioaccumulation potential. Summary of Differential Biodegradation Rates by Lubricant Base Oils: Lubricant Base Oil Base Oil Source Biodegradation Mineral Oil Petroleum Persistent/Inherently Polyalkylene Glycols (PAG) Petroleum - synthesized Hydrocarbon Readily Synthetic Esters Synthesized from biological sources Readily Vegetable Oils Naturally occuring vegetable oils Readily Source: Mudge, 2010 While maintaining excellent stability in rigorous lubricating environments, Biosynthetic Technologies Estolide products biodegrade once released into the environment. The graph below shows the results of OECD 310 for both Biosynthetic Technologies SE7B Estolide product as well as a comparable PAO, the most common petroleum base oil used in the formulation of synthetic motor oils.

6 Additional tests were run with formulated motor oils, both before and after use in automobiles. The Estolide-based motor oil formulation contained Estolide base oil plus additives and the conventional motor oil contained Group II petroleum base oil plus additives. As is evident from the graph below, biosynthetic motor oils degrade much faster than conventional Group II motor oils, both before and after use in an engine. Biodegradability of Biosynthetic SE7B vs. Conventional Motor Oils (OECD 301B):

7 Aquatic Toxicity In addition to possessing a certain percentage of readily biodegradable material, an EAL must also demonstrate low toxicity to aquatic organisms. The most common aquatic toxicity tests for assessing EALs are the 72-hour growth test for algae (OECD 201), the 48-hour acute toxicity test for daphnia (OECD 202), and the 96-hour toxicity test for fish (OECD 203). In general, the vegetable oil and synthetic ester base oils have a low toxicity towards marine organisms with the LC50 for fish toxicity reported as being ~10,000 ppm for fatty acid esters and glycerol esters (van Broekhuizen, 2003). Water soluble PAGs may demonstrate increased toxicity to aquatic organisms by directly entering the water column and sediments rather than remaining on the water column surface as a sheen (Habereder et al. 2008). Summary of Comparative Toxicity of Base Oils: Lubricant Base Oil Base Oil Source Toxicity Mineral Oil Petroleum High Polyalkylene Glycols (PAG) Petroleum - synthesized Hydrocarbon Low* Synthetic Esters Synthesized from biological sources Low Vegetable Oils Naturally occuring vegetable oils Low Mudge, 2010 *Solubility may increase the toxicity of some PAGs The petroleum-based oils have a greater toxicity to biota in the marine food chain compared to the other base oil sources (Mudge, 2010). The use of additives is dependent on the choice of base oil and the intended function of the lubricant (Mudge, 2010). However, several of the more toxic compounds in formulations are also the ones with poor degradability. The overall product toxicity may be significantly reduced by switching to biologically-sourced base oil used in conjunction with low toxicity additives. Estolides are a subset of a much broader type of base oil referred to as esters. So, from a chemical perspective, the reactivity of Estolides will be essentially identical to other common ester base stocks. It is widely understood that esters (and thus, Estolides) can be blended with other Group I-V base oils without reacting or derivatizing in such a way that toxicity is increased. Biosynthetic Technologies hired an independent lab to perform OECD 203 Fish, Acute Toxicity Test on the Estolide base oil product, both before and after use in an automobile. The same study included results for Group II based motor oil. In this test, a higher number correlates with lower toxicity levels. The results were as follows: Motor Oil New Oil Used Oil Estolide based motor oil >10,000 mg/l 9,375 mg/l Group II based motor oil >10,000 mg/l 7,500 mg/l Aquatic Toxicity Classifications Scale - LC50 (mg/l or ppm) Classification U.S. Fish & Wildlife US E.P.A. Super toxic > Extremely toxic <0.1 Highly toxic > Moderately toxic > > Slightly toxic > > Practically nontoxic > >100 Relatively harmless > Per the United States Department of Fish and Wildlife, Estolide based motor oil, new or used would be considered relatively harmless and per the United States Environmental Protection agency, the oil is considered practically nontoxic.

8 Bioaccumulation The propensity of a substance to bioaccumulate is another property of a lubricant that is often considered in the qualification of a product as an EAL (Mudge, 2010). Bioaccumulation is the build-up of chemicals within the tissues of an organism over time. The longer the organism is exposed to a chemical and the longer the organism lives, the greater the accumulation of the chemical in the tissues (Mudge, 2010). If the chemical has a slow degradation rate or low depuration rate within an organism, concentrations of that chemical may build-up in the organism s tissues and may eventually lead to adverse biological effects. It is, therefore, desirable to use compounds in formulations that do not bioaccumulate. The bioaccumulation potential of a compound is directly related to its water solubility; chemicals that are not water soluble tend to move into fatty tissues rather than to staying in water. These lipophilic chemicals include most of the compounds used in the manufacture of the base oil in lubricants. The water solubility of a compound is related to the type of atoms in the molecule; compounds comprised solely of carbon and hydrogen tend to have the lowest solubility in water. Compounds of this type include alkanes, which form almost 90% of the current base oil in conventional lubricant formulations. The inclusion of one or more oxygen atoms in a molecule will, in general, increase the water solubility and reduce bioaccumulation. Compounds with oxygen also tend to degrade more quickly in the environment or be excreted faster from organisms. Many naturally-derived base oils used in lubricants are formulated around carboxylic acids, which increase water solubility and degradation; therefore, their bioaccumulation potential is reduced in comparison to alkane-based oils. It has been assumed for some time that larger molecules are not bioaccumulated as they are unable to physically pass through the membranes of cells and be incorporated into the living cells (Arnot et al., 2010). Therefore, when designing lubricant formulations, the molecular size of the components of the base oil are considered as they will directly affect the rate of uptake. Biosynthetic Technologies commissioned independent testing to determine if Estolides are non-bioaccumulative, defined by the EPA as a test material with a log POW of less than 3 or greater than 7 using the OECD 117 and OECD 107 test methods. The test results indicate a log POW >7 meaning it is Not Bioaccumulative. In summary, the level to which a component of the product is bioaccumulated in an organism is dependent on the environmental and biological half-lives of the compounds (some will degrade before being incorporated into an organism and some will be metabolized within the organism), as well as the lipophilic nature of the compounds (as measured by water solubility). Any component that has low water solubility may potentially bioaccumulate in an organism. In the case of lubricants, fatty acid-containing components have reduced bioaccumulation potential due to greater water solubility and higher biodegradation rates. This is one distinct advantage in using esters over the other carbon and hydrogen alone base oil types. Summary of Bioaccumulation Potential by Base Oil Types: Lubricant Base Oil Base Oil Source Potential for Bioaccumulation Mineral Oil Petroleum Yes Polyalkylene Glycols (PAG) Petroleum - synthesized Hydrocarbon No Synthetic Esters Synthesized from biological sources No Vegetable Oils Naturally occuring vegetable oils No Source: Mudge, 2010

9 SUMMARY OF ENVIRONMENTALLY ACCEPTABLE LUBRICANT CHARACTERISTICS A summary of the major factors regarding biodegradation, toxicity and bioaccumulation potential, for each of the base oil types is shown in the following Table. In this table, the three major criteria are presented for each base oil and color-coded to indicate the environmental outcome. The biodegradability of a lubricant reflects that of the lubricant s base oil, while the degree of aquatic toxicity is typically a consequence of the performance enhancing additives (or thickening agents) within the formulation. The base oils that degrade quickly are considered more preferable than those that do not rapidly degrade, although there might be a trade-off with regard to the depletion of oxygen during compound metabolism. The compounds that do not bioaccumulate and are relatively less toxic are considered more preferable than those that bioaccumulate and have higher toxicities. Comparative Environmental Behavior of Lubricants by Base Oil Type: Lubricant Base Oil Base Oil Source Biodegradation Toxicity Potential for Bioaccumulation Mineral Oil Petroleum Persistent/Inherently High Yes Polyalkylene Glycols (PAG) Petroleum - synthesized Hydrocarbon Readily Low* No Synthetic Esters Synthesized from biological sources Readily Low No Vegetable Oils Naturally occuring vegetable oils Readily Low No Source: Mudge, 2010 *Solubility may increase the toxicity of some PAGs Currently, a majority of lubricant base oils (mineral oils) have the lowest biodegradation rate, a high potential for bioaccumulation, and a measurable toxicity towards marine organisms. In contrast, the base oils derived from oleochemicals (vegetable oils and synthetic esters) degrade faster, have a smaller residual, do not bioaccumulate appreciably and have a lower toxicity to marine organisms. PAG-based lubricants are also generally biodegradable and do not bioaccumulate; however, some PAGs may be more toxic due to their solubility in water. On the basis of this simple comparison, lower environmental impacts will arise if a greater proportion of base oils are manufactured from biologically-sourced materials.

10 Additional Environmental Benefits and Characteristics of Estolide Base Oil: Renewable Carbon Biosynthetic Technologies Estolide products have the highest Percent Renewable Carbon (PRC) content of any comparable high-performance base oil in industry. Percent Renewable Carbon (PRC) of common base oils: Base Oil Percent Renewable Carbon Low Viscosity (5-9 cst, 100C) Group I 0 Group II 0 Group III 0 Group IV, PAO 0 PAG 0 Diester 0-30 POE 0-75* Biosynthetic 82 * Typically < 50% In 2013, the USDA included engine crankcase oils to the BioPreferred Program, which designates product categories within which bio-based products will be afforded Federal procurement preferences. The minimum level of bio-based content was set at 25% Greenhouse Gas Emissions as compared to PAO s A Life Cycle Analysis of Greenhouse Gas Emissions (GHG) from Biosynthetic base oil (Estolides) is % lower than the GHG emissions associated with the poly-alpha olefin (PAO), a product of similar function and use. The variability depends on the combinations of feedstock used to make short chain fatty acids and oleic acid that make up the eight pathways analyzed in the study. Miscibility BT s Estolides are fully miscible with Group I-V base oils. Additionally, unlike some synthetic base stocks, Estolides are readily soluble with a broad range of lubricant additives. Re-refinability BT s Estolide based motor oil formulations have no negative effect upon the re-refining process. In fact, stocks of used motor oil that is recycled and rerefined into new motor oil can benefit from this new technology by blending the recycled oil with high performance, bio-based, biodegradable products that have greater environmental impact and public health benefits.