5

Biodiesel
Steve Howell1
FOR PURPOSES OF THIS CHAPTER, THE TERM biodiesel is a fuel comprised of mono-alkyl esters of long chain fatty acids derived from vegetable oils or animal fats meeting ASTM D6751 specifications and is designated as B100. Biodiesel is an ultra-low sulfur, renewable fuel that can be used as a neat (pure) fuel but is most often blended into petroleum diesel (petrodiesel). To distinguish the amount in the blend, the convention prescribed in D6751 is to state the amount of biodiesel in the blend by the volume percentage preceded by the uppercase letter B. Therefore, a 5 % blend of biodiesel in petrodiesel is B5 and a 20 % blend of biodiesel in petrodiesel is B20. Biodiesel blends can be used in many applications where petroleum middle distillate (i.e., diesel fuel) products are used, such as on-road and off-road diesel, home heating oil and boiler fuel, marine diesel fuel, and nonaviation gas turbine fuel. There may be some limitations on the blend percentages used in unmodified diesel engines, and the original equipment manufacturer (OEM) should be consulted, especially if using higher blend ratios. Most biodiesel made today is not suitable for use in kerosene lamps due to its higher viscosity and surface tension, resulting in less than optimum wicking properties, although it can be used in heating applications where wicking is not important. The biodiesel industry focus in the United States over the past 10 years has been the on-road and off-road diesel market and the home heating oil market. Biodiesel is most commonly used as a blend of B5 with conventional petrodiesel in the existing equipment that more traditionally has operated solely on petrodiesel. Blends in the range of B6 to B20 are also in regular usage with heavier duty diesel trucks and buses. Other sections of this manual cover in more detail both general and special engine and burner equipment considerations when using petrodiesel. These same considerations are also valid for the use of biodiesel blends and will not be covered further in this chapter. Biodiesels long straight chain hydrocarbon structure with a limited number of double bonds (directly related to the structure of the natural oils and fats from which it is produced) coupled with an ester linkage with a short chain alcohol (usually methanol or ethanol) provides for naturally high cetane, good lubricity, biodegradability, and lower emissions [1]. Combustion of biodiesel in a diesel engine results in lower emissions of unburned hydrocarbons, carbon monoxide, and particulate matter (i.e., black smoke) when used in unregulated engines and compared to conventional petrodiesel [1]. For some applications biodiesel also provides reductions in nitric oxide (NOx) due to its oxygen content (i.e., 20 % NOx reduction with B20 for home heating oil), while in other applications the use of biodiesel can be NOx

MNL1-EB/May 2010

neutral or have a slightly higher NOx (i.e., 10 % NOx increase for B100 in on-road diesel engines) depending on the amount of biodiesel, the duty cycle and the engine technology [1]. Beginning in 2010, new diesel engines will be fitted with catalytic technology to reduce NOx from both biodiesel and diesel fueled engines by over 90 %, so any detriment of biodiesel on NOx will not be an issue with post2010 diesel engines. The 2008 volatility in the cost of a barrel of crude oil, with a high of over $140/bbl, and increased concern over global warming has caused the interest in biomass-based fuels, and biodiesel in particular, to skyrocket. Federal legislation in the United States provides for a $1.00 per gallon tax incentive for B100, and there are some state incentives and some state usage requirements. The state of Minnesota requires 5 % biodiesel in most of the diesel fuel used in the state, and the states of Washington and Oregon also require biodiesel to be blended into diesel. Additionally, the U.S. Congress, as part of the Energy Independence and Security Act of 2007, passed the second version of a national Renewable Fuel Standard (RFS2), which requires over 1 billion gallons of biomass-based diesel be used in the U.S. diesel fuel pool by 2012. These state and anticipated federal mandate volumes, specific to biodiesel, have caused a dramatic increase in the building of production capacity and overall product volumes for biodiesel (see Figs. 1 and 2). ASTMs support and achievements in integrating biodiesel as a blend stock into diesel have been an integral part of the development of the biodiesel industry. A key part of the recent legislation supporting biodiesel was that an ASTM standard be issued and in use in commerce. This requirement for an ASTM Standard Specification for biodiesel is embedded in the tax incentive and RFS2 language as a condition of the legislation and participation in the tax incentive programs. Biodiesel so far introduced to the market has, for the most part, been made with the oils and fats that were readily available in the commercial marketplace in the United States, none of which were originally tailored or designed for fuel use. In the United States, the primary oils and fats for biodiesel are soybean oil, animal fats or tallow (beef, pork, poultry), and used restaurant frying oils (referred to as yellow grease, which comes in a variety of quality levels). All of these oils and fats are produced as minor by-products of growing food or animal feed or, in the case of used cooking oil, as a second-use product. Soybeans are grown primarily as a high protein animal feed because they are 80 % high protein meal and only 20 % oil. Beef, hogs, and chickens are grown for meat for human consumption and yield only

MARC-IV Consulting, Inc., Kearney, MO.

53
Copyright 2010 by ASTM International www.astm.org

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Fig. 1Estimated US biodiesel production by fiscal year (Oct. 1Sept. 30). (Published with permission from www.biodiesel.org.)

around 10 % fat. These existing oils and fats can be used to produce a product meeting the ASTM specifications for biodiesel. The chemical structure of these existing oils and fats, however, can result in fuel with some deficiencies compared to conventional petrodiesel. Examples of this are long-term stability and cold flow properties. These deficiencies can be overcome by choice of feedstock and process technology or blending with petrodiesel. In some cases, these deficiencies can also be ameliorated or corrected by the selective and judicious use of additives (e.g., using an antioxidant additive for storage improvement). The increase in interest in biodiesel, and long-term mandates for a minimum of 1 billion gallons per year of biodiesel use, is providing the economic incentives for further development and improvement of oilseed crops for biodiesel purposes (i.e., breeding and genetics to provide oils with lower polyunsaturates and lower saturates for improved stability, shorter chain lengths for improved cold flow properties) as well as a plethora of new production technologies (solid catalysts, use of resins for filtering and drying, further processing and separation to produce a jet fuellike product) and relatively new or novel oil sources such as jatropha, algae, enzymatic production of triglycerides from cellulose, use of microorganisms for direct production of methyl esters from sugar, and even production of biodiesel from the municipal sludge. Some of these so-called second- or thirdgeneration biodiesel routes can provide a biodiesel that has superior cold flow properties and stability even compared to petrodiesel, while keeping the already beneficial biodegradability, high cetane, improved lubricity and emissions reductions associated with current first-generation biodiesel produced from the traditional oils and fats by transesterification to the methyl and ethyl esters. Over time, it is expected that biodiesel processing and the finished product will improve and its usage rate will ultimately be driven by

economics and market forces but also requirements to meet mandates on carbon dioxide (CO2) to ameliorate climate change. The need to meet sustainability goals will also likely play a role in the future of biodiesel.

ASTM BIODIESEL TASK FORCE HISTORY

In 1993, a Task Force was formed within ASTM Committee D02 on Petroleum Products and Lubricants to begin development of an industry consensus standard for biodiesel. The first step undertaken by the Task Force was the determination of the philosophy to be used for the standard. Various options were considered, from adding a section to the existing ASTM petrodiesel standard (D975), to development of a standard for a blend with petrodiesel, to a stand-alone standard. The following was agreed on by the Biodiesel Task Force and subsequently by the membership of ASTM. 1. Develop a stand-alone specification for pure biodiesel. It was assumed the biodiesel would most likely be produced by a different commercial entity than the petrodiesel refinery and then blended at terminals with petrodiesel. For such third-party blending, a trading standard for the pure biodiesel would be needed. 2. If biodiesel meets its B100 specification, it can be blended with petrodiesel in any percentage. This is similar to status of No. 1 (kerosene type) diesel product being blended into No. 2 grade fuels as long as they meet the respective specifications within ASTM D975. 3. Base the development of the standard for the end product on performance tests needed for a fit for purpose fuel in existing diesel engines, not on the source or processing used to make the biodiesel. This is similar to how the petrodiesel specifications were developed. Use physical and chemical tests as deemed essential in defining the product, or where it makes sense to use such tests in place of a performance test.

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Fig. 2Commercial biodiesel production plants in the United States as of September 29, 2008. (Published with permission from www.biodiesel.org.)

Begin with the existing D975 petrodiesel specification as the baseline for a fit for purpose fuel for use in conventional diesel engines. 5. For the biodiesel blend stock specification, eliminate items not applicable to biodiesel such as the distillation curve, cetane index, and aromatics content. 6. Extend the biodiesel specification to address biodieselspecific quality properties not in D975 and required for acceptable performance, such as acid value, total and free glycerin, and phosphorous content. 7. Extend the biodiesel specification to new characteristics being considered for D975, and as D975 is updated add characteristics such as lubricity and conductivity. This philosophy formed the basis used as the biodiesel standards progressed through the ASTM development and balloting process and led to the formal issuance of ASTM D6751, Standard Specification for Biodiesel Fuel Blend Stock (B100) for Middle Distillate Fuels, and incorporation of up to 5 volume percent biodiesel into ASTM D975, Standard Specification for Diesel Fuel Oils, ASTM D396, Standard Specification for Fuel Oils, and ASTM D7467, Standard Specification for Diesel Fuel Oil, Biodiesel Blend (B6 to B20). Many references to biofuels and to biodiesel fuels can be found in the technical literature, but the definitions are not always clear. In literature outside ASTM, the term biodiesel has been associated with fuel-like materials such as pure vegetable oils, mixtures of vegetable oils and petrodiesel, partially esterified natural oils, and mixtures of esters with petrodiesel. In the extreme, a case has been made for coal slurry being a biodiesel on the grounds that it is derived from long-decayed biomass. There has been significant negative experience with the use of

4.

unprocessed or raw vegetable oils in existing diesel engines in the past [2]. After discussions with the engine and vehicle manufacturers regarding their negative experience with a variety of these materials in the past, and the generally positive experience with the methyl esters of vegetable oils in the United States and Europe, it was apparent that once the philosophy for the development of the standard was agreed on, a written description narrowing the scope of what could be called biodiesel was the next essential step. The ASTM Biodiesel Task Force therefore adopted the following description of biodiesel: biodiesel, nfuel comprised of mono-alkyl esters of long chain fatty acids derived from vegetable oils or animal fats, designated B100. Discussion-biodiesel, as defined above, is registered with the U.S. Environmental Protection Agency (EPA) as a fuel and a fuel additive under Section 211(b) of the Clean Air Act. There is, however, other usage of the term biodiesel in the marketplace. Due to its EPA registration and the widespread commercial use of the term biodiesel in the U.S. marketplace, the term biodiesel will be maintained for this specification. DiscussionBiodiesel is typically produced by a reaction of a vegetable oil or animal fat with an alcohol such as methanol or ethanol in the presence of a catalyst to yield mono-alkyl esters and glycerin, which is removed. The finished biodiesel derives approximately 10 % of its mass from the reacted alcohol. The alcohol used in the reaction may or may not come from renewable resources. The first key point in this definition is that biodiesel is a mono-alkyl ester. Conventionally, biodiesel is produced through a transesterification reaction of a natural oil triglyceride

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TABLE 1Typical Biodiesel Reaction

Catalyst 100 pounds Triglyceride (Soybean oil) 10 pounds Alcohol (Methanol) = 10 pounds Glycerin 100 pounds Mono-alkyl esters (Biodiesel)

(animal fat or vegetable oil) with a short chain alcohol (typically methanol) in the presence of a catalyst (usually sodium or potassium hydroxide). The reaction occurs stepwise, with one fatty acid chain being removed from the glycerin backbone first (forming one mono-alkyl ester and a diglyceride), the second fatty acid removed next (forming two molecules of mono-alkyl esters and a monoglyceride), and last, reaction of the third fatty acid. The resulting products are three monoalkyl esters (biodiesel) and glycerin. Glycerin is removed as a co-product and can be upgraded to a valuable pharmaceutical grade. The reaction is depicted in Table 1. The mono-alkyl ester definition, therefore, eliminates pure vegetable oils as well as monoglycerides and diglycerides from consideration as biodiesel. During the 1970s and 1980s, research was conducted with pure vegetable oils and partially esterified oils in their neat (or pure) form as well as with blends of petrodiesel. The use of these pure or partially esterified oils caused a variety of engine and injector problems and should not be confused with biodiesel meeting todays ASTM specification for B100 blend stock, ASTM D6751. The second key point is that biodiesel is produced from a vegetable oil or animal fat. This eliminates some of the confusion over other materials referenced as biodiesel in the past. Another key point is biodiesels intended use in compression ignition (diesel) engines. Biodiesel is not suitable for use in gasoline enginesit is strictly intended for use in diesel engines. The ASTM Biodiesel Task Force determined that the critical items in the determination of biodiesel quality are as follows: 1. Complete reaction to the mono-alkyl esters 2. The removal of free glycerin 3. The removal of residual processing catalyst 4. The removal of reactant alcohol 5. The absence of free fatty acids The B100 standard was developed to address each of these quality assurance needs. While the initial proposal for the biodiesel specification at ASTM was focused on B100 as a stand-alone fuel, experience of the fuel in use with blends above B20 was insufficient to provide the technical data needed to secure approval from the ASTM members for B100 as a stand-alone fuel. Based on this, efforts after 1994 were focused on defining the properties for pure biodiesel needed to provide a fit for purpose fuel for use in existing diesel engines at a B20 or lower level blend. The biodiesel industry was extremely small in the United States during the 19931998 period, and efforts focused on securing the technical data on the use of biodiesel, primarily in bus fleets, as well as emissions and health effects information needed for EPA registration as a legal fuel or fuel additive in the United States. Over $50 million in research and development investments occurred to secure this information, with the majority of that funding coming from American soybean farmers through the soybean check-off program. One-half of 1 % of the purchase price of a bushel

of soybeans is provided by each soybean farmer into the soybean check-off fund each year. Representatives are elected from the farmers inputting into the check-off program, and they invest the funds in research, marketing, new uses, and promotion of soybeans as a means to increase the profitability of soybean farming. Soybeans are 80 % high protein meal, primarily used as feed for hogs (pigs) and poultry, and 20 % oil. Because the demand for meal was increasing faster than the demand for oil, large excess supplies of soybean oil were a consistent problem for the soybean industry over the years. Farmers viewed this excess supply of oil as an increasing threat to profitability in the future, because demand for meal would likely increase even more as countries like China and India gradually include more meat, especially hogs and poultry, in their diet, which today is mostly grain based. As interest in cleaner burning fuels increased in the late 1990s, biodiesel volumes began to grow and there was increasing interest in finalizing ASTM specifications for biodiesel. A provisional specification, ASTM PS121, for B100 as a blend stock was approved by ASTM in 1999. The primary reason for the provisional specification was to secure a formal ASTM test method for the GC method for measurement of the total and free glycerinone of the most critical specifications for biodieselbecause it was necessary to include the test method in a mandatory appendix for PS121. After securing an ASTM test method for total and free glycerin, ASTM D6584, the first full specification was developed and approved in 2001 and released for use in 2002 as ASTM D6751, Standard Specification for Biodiesel Fuel Blend Stock (B100) for Middle Distillate Fuels. The philosophy used to approve D6751 as a blend stock was the same as that used for the blending of kerosene-type fuel, No. 1 grade, into a No. 2 grade of fuel within the conventional specification, ASTM D975. If the parent fuels meet their respective specifications, then the two can be blended in any percentage and used in conventional diesel engines. These same conditions hold true for biodiesel; if biodiesel meets ASTM D6751 and conventional diesel meets ASTM D975, the two can be blended and used in conventional engines. Users should note there may be OEM warranty and usage recommendations, which usually include an upper limit of biodiesel content in the finished fuel (i.e., B5 or B20) with either no restrictions or some minor service modifications such as limits on oil drain intervals. The most important aspect of successful use of B20 and lower blends over the past 5 years has been to ensure B100 meets D6751 prior to blending. While this philosophy of meeting a base stock specification for blending has served the U.S. market well, there has been substantial effort since 2003 to develop and formally approve specifications for the finished blends of biodiesel and conventional diesel fuel. In addition, several improvements and changes to D6751 were also undertaken, some as a result of changes needed to secure approval of the finished blended biodiesel specifications.

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BIODIESEL STANDARDS
ASTM D6751-09 is the most recent version of the ASTM specifications for pure biodiesel, B100, as a blend component with middle distillate fuels. The specification contains two grades of biodiesel, S15 and S500, although almost all of the biodiesel in use in the United States is of the S15 variety. Natural vegetable oil feedstocks have virtually no sulfur (usually less than 1 or 2 ppm), but some animal fats or yellow greasebased biodiesel may have sulfur slightly higher than 15 ppm due to the presence of hair or hide materials from the animal fat rendering process or the frying of foods high in sulfur like onion rings. D6751 has been officially approved by ASTM only for use in blends up to B20, as noted in the requirements section of the standard states:

2A considerable amount of experience exists in the U.S. with a 20 % blend of biodiesel, primarily produced from soybean oil, with 80 % diesel fuel (B20). Experience with biodiesel produced from animal fat and other oils is similar. Experience with B20 and lower blends in other applications is not as prevalent. Although biodiesel (B100) can be used, blends of over 20 % biodiesel with diesel fuel (B20) should be evaluated on a case by case basis until further experience is available. NOTE 3The user should consult the equipment manufacturer or owners manual regarding the suitability of using biodiesel or biodiesel blends in a particular engine or application.
NOTE

Table 2 is taken from ASTM D6751-09.

TABLE 2Detailed Requirements for Biodiesel (B100) (All Sulfur Levels)

Property Calcium and Magnesium, combined Flash point (closed cup) Alcohol control One of the following must be met: 1. Methanol content 2. Flash point Water and sediment Kinematic viscosity, 40C Sulfated ash Sulfur
C

Test MethodA EN 14538 D93

Grade S15 Limits 5 max 93 min

Grade S500 Limits 5 max 93 min

Units ppm (mg/g) C

EN 14110 D93 D2709 D445 D874 D5453 D130 D613 D2500

0.2 max 130 min 0.050 max 1.96.0B 0.020 max 0.0015 max (15) No. 3 max 47 min Report
D

0.2 max 130 min 0.050 max 1.96.0B 0.020 max 0.05 max (500) No. 3 max 47 min ReportD 0.050 max 0.50 max 360 max
F

mass percent C volume percent mm2/s mass percent mass percent (ppm)

Copper strip corrosion Cetane number Cloud point Carbon residue Acid number Cold soak filterability Free glycerin Total glycerin Phosphorus content Distillation temperature, atmospheric equivalent temperature, 90 % recovered Sodium and potassium, combined Oxidation stability
A B C

C mass percent mg KOH/g seconds mass percent mass percent mass percent C ppm (mg/g) hours

D4530 D664 Annex A1 D6584 D6584 D4951 D1160 EN 14538 EN 14112

0.050 max 0.50 max 360 max

F

0.020 max 0.240 max 0.001 max 360 max 5 max 3 min

0.020 max 0.240 max 0.001 max 360 max 5 max 3 min

The test methods indicated are the approved referee methods. Other acceptable methods are indicated in 5.1. See X1.3.1. The 6.0 mm2/s upper viscosity limit is higher than petroleum-based diesel fuel and should be taken into consideration when blending. Other sulfur limits can apply in selected areas in the United States and in other countries. D The cloud point of biodiesel is generally higher than petroleum-based diesel fuel and should be taken into consideration when blending. E Carbon residue shall be run on the 100 % sample (see 5.1.11). F B100 intended for blending into diesel fuel that is expected to give satisfactory vehicle performance at fuel temperatures at or below 12C shall comply with a cold soak filterability limit of 200 s maximum.

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The key issues with regard to biodiesel quality identified by the ASTM Biodiesel Task Force are controlled by parameters in the specification in the following way: 1. Conversion of the fat or oil to mono-alkyl esters is ensured through measurement of the total glycerin (D6584), which includes all bound glycerin (i.e., mono-, di-, and triglycerides) as well as the unbound free glycerin. 2. Removal of the unbound glycerin is ensured through measurement of the free glycerin (D6584). 3. Removal of the catalyst used in the production of biodiesel is ensured through the measurement of the sulfated ash (D874), and is further controlled by limiting the levels of combined sodium and potassium (EN 14538). 4. Removal of the alcohol (usually methanol) is ensured through direct measurement of methanol by either GC (EN14110) or by use of a high flash point value (D93), or by use of a high flash point value if alcohols other than methanol are used. 5. The absence of fatty acids is ensured through measurement of the acid number (D664). There are several key distinctions between petrodiesel and biodiesel that are evidenced in the biodiesel standard and the testing methods employed. Perhaps the most important is that the cetane number, ASTM D613, commonly referred to as the cetane engine test, must be used. You cannot use the Calculated Cetane Index method for biodiesel. The Calculated Cetane Index (CCI), ASTM D4737, is based on historical data for the distillation curve of petroleum diesel and is not applicable to biodiesel. If a Calculated Cetane Index is performed for either biodiesel or a biodiesel blend, the result will be artificially lower than the cetane number derived from the cetane engine test. If one only desires a go/no-go answer for a minimum cetane value, it is possible to use the Calculated Cetane Index on biodiesel or a biodiesel blend for that purpose because the real cetane value will be higher. The lack of applicability of the cetane index is primarily due to the lack of a distillation curve for biodiesel. Where petrodiesel is comprised of hundreds of compounds boiling at differing temperatures (determined by the petroleum refining process), biodiesel contains only a few compoundsprimarily C16 to 18 carbon chain length alkyl esters (determined by the feedstock) along with minor variations in carbon double bonds, but these compounds all boil at approximately the same temperature. Most biodiesel processes today produce what petroleum refiners would call a whole cut product, where virtually all of the feedstock is made into one biodiesel product without further separation or distillation of the individual fatty acid esters that make up biodiesel. Biodiesel, therefore, exhibits more of a tight series of boiling points over a short temperature range than a distillation curve. The fats and oils commonly used today have a very similar fatty acid profile, as seen in Table 3, giving biodiesel a very tight boiling range regardless of the feedstock. The molecular weight and composition of biodiesel also account for its high flash point, which gives an additional safety margin in enclosed areas such as underground mines. There are some additional important differences in the testing methods necessary for measurement of biodiesel: The carbon residue must be run on the 100 % sample, not the 10 % residue after distillation as done with petrodiesel. It is difficult to leave only 10 % of the sample upon distillation because biodiesel all boils at about the same temperature.

TABLE 3Oil Types and Length of Fatty Acid Chains in U.S. Fats and Oils A
No. of Carbons in Fatty Acid Chain Oil type Corn Tallow Peanut Used frying oilB Rapeseed Pork Soybean
A B

<14

16

18

>20

12 5

88 32 12 64 81 1 1 1 7

19 5

76 94 70 87

27 13

Source: Procter and Gamble. Source: Fats and Proteins Research Foundation.

The ash content is changed from oxidative ash (ASTM D482) to sulfated ash (ASTM D874) to ensure more accurate measurement of sodium or potassium, which could be present as residual catalyst from the transesterification reaction in the manufacture of the biodiesel B100. The flash point is substantially higher (93C minimum) than that for ASTM D975 (52C minimum for No. 2, and 38C minimum for No. 1). All properly processed biodiesel from available fats and oils already meets the higher flash point value, and 93C (200F) minimum was chosen to coincide with the value that places B100 in a nonhazardous shipping classification in the United States. A vacuum distillation (ASTM D1160) with a T-90 maximum of 360C is used to ensure the absence of contaminants that would otherwise go undetected, such as used motor oil. The cetane number is set substantially higher (47 minimum) than that in D975 (40 minimum). Properly processed biodiesel in the United States will naturally meet this higher cetane and the 47 value was selected based on that being the minimum cetane number for premium diesel fuel as determined by the National Conference on Weights and Measures (NCWM) in the United States. Combined sodium and potassium, as well as combined calcium and magnesium, are both controlled to 5 ppm where there are no such controls in ASTM D975. Phosphorous is controlled to 10 ppm, whereas there is no such control for ASTM D975. Phosphorous is a natural element found in all plant matter and is a concern in fuels where it can react adversely with exhaust catalysts causing some deactivation of the catalyst, referred to as poisoning of the catalyst. Stability is controlled to 3 hours minimum, where there are no such controls in ASTM D975. The 3-hour minimum was selected to coincide with acceptable ASTM D4625 long-term storage results for B20 blends representing approximately 6 months or longer under normal storage conditions [3]. Certain applications may require a higher level of stability, which can be attained through selection of various processing or feedstock options or by using an antioxidant additive.

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A cold soak filterability parameter was recently included to control minor compounds at the B100 level, which are not detected or controlled by other means within the spec and which may cause some biodiesel blends to exhibit filter clogging at temperatures above the cloud point of the blend. There are no such controls in ASTM D975. ASTM D6751 has undergone several improvements since its passage in 2001 and it will continue to undergo improvements over time, especially improvements in analytical methods and techniques.

BIODIESEL BLEND SPECIFICATIONS

Immediately after the passage of ASTM D6751 in 2001 as a blend stock, the ASTM Biodiesel Task Force began efforts to secure standards for finished blends of biodiesel with diesel fuel. Passage of D6751 and the common operating practice of ensuring the B100 met D6751 prior to blending and having biodiesel or petrodiesel blends treated similar to the way No. 1 and No. 2 diesel fuels are treated (if the parent fuels meet their specifications, they can be blended and used in diesel engines with no need to test or measure the blend) allowed the industry to grow while deliberations on finished specifications were conducted. However, large biodiesel blend purchasers and users such as the Defense Energy Support Center and the military, and fuel enforcement entities like NCWM representatives, and engine companies desired a set of properties that could be measured for the finished blends. Having one specification for the finished blends would facilitate the purchasing of biodiesel blends (only need to specify or monitor one specification versus two specifications for the components of a blend), it would facilitate engine testing (because the engine sees the finished blend not the components individually), and it would facilitate fuel quality enforcement because regulators may not have access to samples of the blend components. As Subcommittee E began the deliberations on the blended fuel specifications in the 20012003 time frame, there were several new fuels under consideration that claimed to be usable in existing diesel engines with little or no modification. Biodiesel blend, ethanol-diesel blends, and water-emulsified diesel blends all had active task forces or working groups within Subcommittee E. The idea of a Fill and Go concept as a means to incorporate all these nonconventional fuels into ASTM D975 came into being during this time period as a mechanism by which all these new fuels could potentially be incorporated into ASTM D975. There were several key aspects that gained momentum at the June 2003 ASTM meeting: A new category that all new Fill and Go fuels will fall under should be developed. While used in the same engine and vehicle as D975 fuel, Fill and Go fuels may need new methods, different limits, or different parameters than currently exist in D975. B20 and lower should be part of D975. D975 is embedded into a variety of state and federal laws, regulations, safety codes, tax codes, etc. and it would be very beneficial to have B20 covered by D975 rather than adding a new ASTM specification everywhere D975 is already codified. Specs should cover all blends B20 and lower (i.e., B2, B5, B11, B20). Finished properties should be set based on satisfactory engine performance.

Existing D975 properties covered B5 and lower, if B100 meets D6751. Additional properties are needed for B6 to B20. It was originally proposed to incorporate B20 and lower blends into the specification for conventional petroleumbased diesel fuel, ASTM D975. After some deliberation, in June 2005, Subcommittee E settled on the following general guidelines for incorporation of biodiesel, and other new blending components, in order to be balloted into D975: Identify an ASTM specification the blend component must meet. Specify upper limit of component allowed. Set the test method for determining the level of the component in the finished D975 blend. Use existing test methods and limits for D975. Expanding limits or test method is NOT acceptable, unless it is also acceptable to change the limit for the D975 fuel(s). With this much agreed, it was decided the blended fuel specification should be set in such a fashion so that if the biodiesel and diesel fuel both met their parent specifications the blended fuel would also always meet its specification [3]. This will prevent the need for reanalysis after blending, except to confirm proper blending and to monitor for contamination or changes in the fuel over time. Based on this, ballots moved forward to incorporate B5 and lower blends of biodiesel into the conventional on/off road diesel spec, ASTM D975, and the conventional heating oil specification, ASTM D396. Blends between 6 and 20 % biodiesel would be balloted under a new specification, as in the end it was determined that two additional parameters were needed for a B6 to B20 blend specification that are not needed for petrodiesel. These were acid number and stability. It was also agreed to increase the T90 distillation temperature of the B6 to B20 blend by 5C in order to keep the principle of the blend always meeting specification if two in-spec parent fuels were used, because B100 has a slightly higher T90 than petrodiesel. A higher T90 for petrodiesel is viewed by some as problematic, as it can increase particulate emissions and therefore affect long-term durability of engine components and exhaust emissions, but because biodiesel reduces particulates the higher T90 for blends was acceptable to the engine communityprovided the diesel fuel was qualified to its T90 prior to blending. Wording explaining this is embedded it the B6 to B20 specification D7467. In June 2008, ASTMs Committee D02 on Petroleum Products and Lubricants passed the incorporation of B5 into both the D396 Fuel Oil specification and the D975 Diesel Fuel specification. No changes in Table 1 for either the test methods or the specifications were involvedthe finished blend of biodiesel blend stock and petrodiesel, and biodiesel blend stock and heating oil, just needs to meet the same respective properties in Table 1 that conventional diesel fuel and heating oil meets. The wording below is contained in the Section 7 Requirements of ASTM D975-09 and similar wording is contained in ASTM D396-08: 7.3 Fuels Blended with BiodieselThe detailed requirements for fuels blended with biodiesel shall be as follows: 7.3.1 Biodiesel for BlendingIf biodiesel is a component of any diesel fuel, the biodiesel shall meet the requirements of Specification D6751.

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7.3.2 Diesel fuel oil containing up to 5 vol% biodiesel shall meet the requirements for the appropriate grade No. 1-D or No. 2-D fuel, as listed in Table 1. 7.3.3 Test Method EN 14078 shall be used for determination of the vol% biodiesel in a biodiesel blend. 7.3.4 Diesel fuels containing more than 5 vol% biodiesel component are not included in this specification. 7.3.5 Biodiesel blends with No. 4-D fuel are not covered by this specification. One of the key aspects of the blended fuel specifications is the necessity that the biodiesel meet its specification, ASTM D6751, prior to blending. Several requirements were added to ASTM D6751 as part of the ballot negotiating process in order to help ensure that if biodiesel meets the ASTM D6751 specification, then no other requirements for the blend were needed beyond those already in ASTM D975. The acid number was lowered, new specifications for combined calcium and magnesium and combined sodium and potassium were added (for adequate exhaust diesel particulate filter life on new engines on sale after model year 2007), a stability specification was added to the B100, and most recently a new cold soak filtration test was added. The last change, the addition of the cold soak filtration, was somewhat unexpected as very few problems in the field had been seen with biodiesel meeting all the other parameters already in ASTM D6751. However, a small amount of B100 was found to contain trace amounts of saturated monoglycerides, soaps, and sterol glucosides that are not specifically controlled by the other parameters in the specification. The presence of these minor compounds, and potentially other as yet not identified compounds, in certain levels may cause the cloud point of the blended fuel to no longer be predictive of filter clogging and operability in cold winter conditions. The presence of allowable amounts of water can exacerbate the phenomenon. These minor compounds (saturated monoglycerides, soaps, and sterol glucosides) are found in natural oils and fats and can remain in biodiesel B100 product as trace contaminants. But they are not found in crude oils and therefore are not picked up by any of the tests in D975. Before ASTM members would allow up to 5 % biodiesel in the fungible diesel fuel pool, a performance test was required to be developed (the new cold soak filterability test) to address this issue at the B100 level so that no additional testing would be needed for the finished blend other than those tests already in D975. The B6 to B20 specification presented new challenges, particularly how to handle the differences between the No. 1 and No. 2 grades of fuels. Because both No. 1 and No. 2 are used interchangeably in todays diesel engines, in the end it was decided the new B6 to B20 specification (ASTM D746708) would be stripped of the No. 1/No. 2 designation and create grades only based on sulfur level. ASTM D7467 was largely based on the D975 performance requirements, with the widest value of the parameters between the No. 1 and No. 2 grades of D975 used for each D975 parameter with the exception of the T90, which is allowed to be 5C higher for B6 to B20. An acid number of 0.3 mg KOH/g maximum was added as an additional and convenient control for stability, and a stability parameter of 6 hours minimum was added. Table 1 from D7467 and the footnotes are given in Table 4.

IMPORTANCE OF GENERAL FUEL CHARACTERISTICS

Biodiesel or biodiesel blends described in this chapter (up to B5 in ASTM D975 and B6 to B20 covered by ASTM D7467) are used in the same equipment as conventional diesel fuels, often without modification or restrictions. Therefore, the same general fuel characteristics and considerations for engines and equipment with conventional diesel fuels also applies to the use of biodiesel and biodiesel blends. The reader is referenced to those sections in this manual for more information and this will not be repeated here. We will instead focus the next information on the considerations that vary from those of conventional petrodiesel.

Sulfated Ash
Ash-forming materials may be present in biodiesel in three forms: (1) abrasive solids, (2) soluble metallic soaps, and (3) unremoved catalysts. Abrasive solids and unremoved catalysts can contribute to injector, fuel pump, piston and ring wear, and engine deposits. Soluble metallic soaps have little effect on wear but may contribute to filter plugging and engine deposits. The ash-forming materials may also contribute to exhaust catalyst plugging and additional deposition in diesel particulate filters (sometimes referred to as particulate traps).

Sulfur
B100 is essentially sulfur free, although some animal fatbased biodiesel has been found with up to 100 ppm sulfur (a result of hides and hair from the animal fatrendering process) and some yellow greasebased biodiesel has been found with similar levels (a result of frying foods high in sulfur like onion rings). Test Method ASTM D5453 should be used with biodiesel. Use of other test methods may provide falsely high results when analyzing B100 with extremely low sulfur levels (less than 5 ppm). Biodiesel sulfur analysis from RR: D02-1480, Biodiesel Fuel Cetane Number Testing Program, JanuaryApril, 1999, using Test Method D2622 yielded falsely high results due to the presence of the oxygen in the biodiesel. Sulfur results using Test Method D2622 were more accurate with B20 than with B100 due to the lower oxygen content of B20. Potential future improvements to Test Method D2622 may provide more accurate values.

Cetane Number
Cetane number is a measure of the ignition quality of the fuel and influences startability, white smoke, and combustion roughness. The cetane number requirements depend on engine design, size, nature of speed and load variations, and starting and atmospheric conditions. The calculated cetane index, Test Method D976 or D4737, may not be used to approximate the cetane number with biodiesel or its blends as it will result in falsely low values. There is, as yet, no substantiating data to support the calculation of cetane index with biodiesel or biodiesel blends.

Carbon Residue
Carbon residue gives a measure of the carbon depositing tendencies of a fuel. While not directly correlating with engine deposits, this property is considered an approximation. Although biodiesel is in the petroleum diesel boiling range, most biodiesels boil at approximately the same temperature and it is difficult to leave a 10 % residual upon distillation. Thus, a 100 % sample is used to replace the 10 % residual sample.

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TABLE 4Detailed Requirements for B6 to B20 Biodiesel Blends

Property Test Method B6 to B20 S15 Acid umber, mg KOH/g, max Viscosity, mm /s at 40C
2

Grade B6 to B20 S500A 0.3

C

B6 to B20 S5000B 0.3

D664 D445 D93 D2500, D4539, D6371 D5453 D2622 D129 D86 D524 D613F D976-80H D1319-03H D482 D2709 D130 D7371 EN 14112 D6079

0.3 1.94.1 52D

E

1.94.1 52D
E

1.94.1C 52D
E

Flash point, C, min Cloud point, C, max or LTFT/CFPP, C, max Sulfur content (mg/g) mass percent, max mass percent, max Distillation temperature, C, 90 % vol recovered, max Ramsbottom carbon residue on 10 % bottoms, mass percent, max Cetane number, min One of the following must be met: (1) Cetane index, min. (2) Aromaticity, % vol, max Ash content, mass percent, max Water and sediment, volume percent, max Copper corrosion, 3 h at 50C, max Biodiesel content, % (V/V) Oxidation stability, hours, min Lubricity, HFRR at 60C, micron (mm), max

15 ... ... 343 0.35 40G 40 35 0.01 0.05 No. 3 6. - 20. 6 520I

... 0.05 ... 343 0.35 40G 40 35 0.01 0.05 No. 3 6. - 20. 6 520I

... ... 0.50 343 0.35 40G 40 ... 0.01 0.05 No. 3 6. - 20. 6 520I

A Under United States of America regulations, if Grades B6-20 S500 are sold for tax exempt purposes then, at, or beyond terminal storage tanks, they are required by 26 CFR Part 48 to contain the dye Solvent Red 164 at a concentration spectrally equivalent to 3.9 lb per thousand barrels of the solid dye standard Solvent Red 164, or the tax must be collected. B Under United States of America regulations, Grades B6-20 S5000 are required by 40 CFR part 80 to contain a sufficient amount of the dye Solvent Red 164 so its presence is visually apparent. At or beyond terminal storage tanks, they are required by 26 CFR Part 48 to contain the dye Solvent Red 164 at a concentration spectrally equivalent to 3.9 lb per thousand barrels of the solid dye standard Solvent Red 26. C If Grade No. 1-D or blends of Grade No. 1-D and Grade No. 2-D diesel fuel are used, the minimum viscosity shall be 1.3 mm2/s. D If Grade No. 1-D or blends of Grade No. 1-D and Grade No. 2-D diesel fuel are used, or a cloud point of less than 12C is specified, the minimum flash point shall be 38C. E It is unrealistic to specify low temperature properties that will ensure satisfactory operation at all ambient conditions. In general, cloud point (or wax appearance point) Low Temperature Flow Test, and Cold Filter Plugging Point Test may be useful to estimate vehicle low temperature operability limits but their use with B6 to B20 has not been validated. However, satisfactory operation below the cloud point (or wax appearance point) may be achieved depending on equipment design, operating conditions, and the use of flow-improver additives as described in X3.1.2. Appropriate low temperature operability properties should be agreed upon between the fuel supplier and purchaser for the intended use and expected ambient temperatures. Test Methods D4539 and D6371 may be especially useful to estimate vehicle low temperature operability limits when flow improvers are used but their use with B6 to B20 from a full range of biodiesel feedstock sources has not been validated. Due to fuel delivery system, engine design, and test method differences, low temperature operability tests may not provide the same degree of protection in various vehicle operating classes. Tenth percentile minimum air temperatures for U.S. locations are provided in Appendix X3 as a means of estimating expected regional temperatures. The tenth percentile minimum air temperatures may be used to estimate expected regional target temperatures for use with Test Methods D2500, D4539, and D6371. Refer to X3.1.3 for further general guidance on test application. F Calculated cetane index approximation, Test Method D4737, is not applicable to biodiesel blends. G Low ambient temperatures, as well as engine operation at high altitudes, may require the use of fuels with higher cetane ratings. If the diesel fuel is qualified under Table 1 of Specification D975 for cetane, it is not necessary to measure the cetane number of the blend. This is because the cetane number of the individual blend components will be at least 40, so the resulting blend will also be at least 40 cetane number. H These test methods are specified in 40 CFR Part 80. I If the diesel fuel is qualified under Table 1 of Specification D975 for lubricity, it is not necessary to measure the lubricity of the blend. This is because the lubricity of the individual blend components will be less than 520 micron (mm) so the resulting blend will also be less than 520 (mm).

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Acid Number
The acid number is used to determine the level of free fatty acids or processing acids that may be present in biodiesel. Biodiesel with a high acid number has been shown to increase fueling system deposits and may increase the likelihood for corrosion. The acid number measures a different phenomenon for biodiesel than petroleum based diesel fuel. The acid number for biodiesel measures free fatty acids or degradation byproducts not found in petroleum-based diesel fuel. Increased fuel temperatures in some new fuel designs due to fuel recycling from common rail injector systems, may accelerate fuel degradation, which could result in high acid values and increased filter plugging potential.

Lubricity
In certain fuel injection equipment in compression ignition engines, such as rotary/distributor fuel pumps and injectors, the fuel functions as a lubricant. Blending biodiesel fuel with petroleum-based compression-ignition fuel typically improves fuel lubricity. No specification is needed for biodiesel lubricity as values are lower than a 300 m Wear Scar Diameter (WSD) using HFRR with B100.

Alcohol Control
Alcohol control is to limit the level of unreacted alcohol remaining in the finished fuel. This can be measured directly by the volume percent alcohol or indirectly through a high flash point value. The flash point specification, when used for alcohol control for biodiesel, is intended to be 100C minimum, which has been correlated to 0.2 volume percent alcohol. Typical values are over 160C. Due to high variability with Test Method D93 as the flash point approaches 100C, the flash point specification has been set at 130C minimum to ensure an actual value of 100C minimum. Improvements and alternatives to Test Method D93 are being investigated. Once complete, the specification of 100C minimum may be reevaluated for alcohol control.

Free Glycerin
The free glycerin method is used to determine the level of glycerin in the fuel. High levels of free glycerin can cause injector deposits, as well as clogged fueling systems, and result in a build up of free glycerin in the bottom of storage tanks and fueling systems.

Total Glycerin
The total glycerin method is used to determine the level of glycerin in the fuel and includes the free glycerin and the glycerin portion of any unreacted or partially reacted oil or fat. Low levels of total glycerin ensure that high conversion of the oil or fat into its mono-alkyl esters has taken place. High levels of monoglycerides, diglycerides, and triglycerides can cause injector deposits and may adversely affect cold weather operation and filter plugging.

Calcium and Magnesium

Calcium and magnesium may be present in biodiesel as abrasive solids or soluble metallic soaps. Abrasive solids can contribute to injector, fuel pump, piston, and ring wear, as well as to engine deposits. Soluble metallic soaps have little effect on wear, but they may contribute to filter plugging and engine deposits. High levels of calcium and magnesium compounds may also collect in the exhaust catalyst and in the diesel particulate filter (DPF). These compounds are not typically removed from the diesel particulate filter during passive or active regeneration, and may result in ash accumulation on the catalyst or in the DPF, producing increased back pressure and the potential for reduced time between service intervals.

Phosphorus Content
Phosphorus, a natural element in all plants that is also found in vegetable oils, can affect the conversion rates in diesel exhaust catalytic converters used to control emissions. Accordingly, the phosphorous level should be kept low. Catalytic converters are increasingly being used globally on diesel-powered equipment as emissions standards are tightened. Biodiesel produced from U.S. sources has been shown to have low phosphorus content (below 1 ppm) and the specification value of 10 ppm maximum is not problematic. Biodiesel from other sources may or may not contain higher levels of phosphorus, and this specification was added to ensure that all biodiesel, regardless of the source, has low phosphorus content.

Sodium and Potassium

Sodium and potassium may be present in biodiesel as abrasive solids or soluble metallic soaps. Abrasive solids can contribute to injector, fuel pump, piston and ring wear, and also to engine deposits. Soluble metallic soaps have little effect on wear, but they may contribute to filter plugging and engine deposits. High levels of sodium or potassium compounds may also collect in the exhaust catalysts and in the DPF. These compounds are not typically removed from the diesel particulate filter during passive or active regeneration and may result in ash accumulation on the catalyst or in the DPF producing increased back pressure and the potential for reduced time between service intervals.

Reduced Pressure Distillation

Biodiesel exhibits a series of close boiling points rather than a distillation curve. The fatty acids chains in the raw oils and fats from which biodiesel is produced are mainly comprised of straight chain hydrocarbons with 16 to 18 carbons that have similar boiling temperatures. The atmospheric boiling point of biodiesel generally ranges from 330 to 357C, thus the specification value of 360C is not problematic. This specification was incorporated as an added precaution to ensure the fuel has not been adulterated with high boiling contaminants.

Oxidation Stability Density

The density of biodiesel meeting the specifications in Table 1 (Table 1 in D396 and D975) falls between 0.86 and 0.90, with typical values falling between 0.88 and 0.89. Because biodiesel density falls between 0.86 and 0.90, a separate specification is not needed. The density of raw oils and fats can be similar to biodiesel and the use of density as an expedient check of fuel quality may not be as useful for biodiesel as it is for petroleum-based diesel fuel. Products of oxidation in biodiesel can take the form of various acids or polymers, which, if in high enough concentration, can cause fuel system deposits and lead to filter clogging and fuel system malfunctions. Additives designed to terminate reactions leading to the formation of peroxides that precede the formation of polymers and gums can significantly improve the oxidation stability performance of biodiesel.

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ASTM Test Methods

Number D93 D130 D189 D445 Title Test Methods for Flash Point by PenskyMartens Closed Cup Tester Test Method for Corrosiveness to Copper from Petroleum Products by Copper Strip Test Test Method for Conradson Carbon Residue of Petroleum Products

Number D4057 D4177 D4294

Title Practice for Manual Sampling of Petroleum and Petroleum Products Practice for Automatic Sampling of Petroleum and Petroleum Products Test Method for Sulfur in Petroleum and Petroleum Products by Energy Dispersive X-Ray Fluorescence Spectrometry Test Method for Determination of Carbon Residue (Micro Method) Test Method for Calculated Cetane Index by Four Variable Equation Guide for Generation and Dissipation of Static Electricity in Petroleum Fuel Systems Test Method for Determination of Additive Elements in Lubricating Oils by Inductively Coupled Plasma Atomic Emission Spectrometry Test Method for Particulate Contamination in Aviation Fuels by Laboratory Filtration Test Method for Determination of Total Sulfur in Light Hydrocarbons, Spark Ignition Engine Fuel, Diesel Engine Fuel, and Engine Oil by Ultraviolet Fluorescence Test Method for Cloud Point of Petroleum Products (Constant Cooling Rate Method) Test Method for Particulate Contamination in Middle Distillate Fuels by Laboratory Filtration Practice for Determination of Precision and Bias Data for Use in Test Methods for Petroleum Products and Lubricants Test Method for Flash Point by Continuously Closed Cup (CCCFP) Tester Guide for Microbial Contamination in Fuels and Fuel Systems Test Method for Determination of Free and Total Glycerin in B-100 Biodiesel Methyl Esters by Gas Chromatography Test Method for Determination of Ignition Delay and Derived Cetane Number (DCN) of Diesel Fuel Oils by Combustion in a Constant Volume Chamber Test Method for Sulfur in Gasoline and Diesel Fuel by Monochromatic Wavelength Dispersive X-Ray Fluorescence Spectrometry Government Standard: Registration of Fuels and Fuel Additives Section 211(b) Clean Air ActA Other Documents: Trace Metals in Oils by Wet Ashing and ICP-OES

D4530 Test Method for Kinematic Viscosity of Transparent and Opaque Liquids (and Calculation of Dynamic Viscosity) Test Method for Ramsbottom Carbon Residue of Petroleum Products Test Method for Cetane Number of Diesel Fuel Oil D4951 D664 D874 D974 D975 D976 D1160 D1266 D1796 Test Method for Acid Number of Petroleum Products by Potentiometric Titration Test Method for Sulfated Ash from Lubricating Oils and Additives Test Method for Acid and Base Number by Color-Indicator Titration Specification for Diesel Fuel Oils Test Method for Calculated Cetane Index of Distillate Fuels Test Method for Distillation of Petroleum Products at Reduced Pressure Test Method for Sulfur in Petroleum Products (Lamp Method) Test Method for Water and Sediment in Fuel Oils by the Centrifuge Method (Laboratory Procedure) Test Method for Oxidation Stability of Distillate Fuel Oil (Accelerated Method) Test Method for Cloud Point of Petroleum Products Test Method for Sulfur in Petroleum Products by Wavelength Dispersive X-Ray Fluorescence Spectrometry Test Method for Water and Sediment in Middle Distillate Fuels by Centrifuge Specification for Gas Turbine Fuel Oils Test Method for Wax Appearance Point of Distillate Fuels Test Method for Trace Quantities of Sulfur in Light Liquid Petroleum Hydrocarbons by Oxidative Microcoulometry Test Method for Acidity in Aviation Turbine Fuel Test Methods for Flash Point by Small Scale Closed Cup Tester D7039 D6300 D4737 D4865

D524 D613

D5452 D5453

D5773 D6217

D2274 D2500 D2622

D6450 D6469 D6584

D2709 D2880 D3117 D3120

D6890

2.2 40 CFR Part 79 2.3 UOP 389

D3242 D3828

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SIGNIFICANCE OF TESTS FOR PETROLEUM PRODUCTS

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Number UOP 39191 EN 14112

Title Trace Metals in Petroleum Products or Organics by AAS Fat and Oil DerivativesFatty Acid Methyl Esters (FAME)Determination of Oxidation Stability (Accelerated Oxidation Test) Fat and Oil DerivativesFatty Acid Methyl Esters (FAME)Determination of Methanol Content

Number EN 14538

Title Fat and Oil DerivativesFatty Acid Methyl Esters (FAME)Determination of Ca, K, Mg and Na Content by Optical Emission Spectral Analysis with Inductively Coupled Plasma (ICP OES)

EN 14110

A Available from U.S. Government Printing Office Superintendent of Documents, 732 N. Capitol St., NW, Mail Stop: SDE, Washington, DC 20401.

References
[1] Hoekman, S. K., Gertler, A., Broch, A., and Robbins, C., Investigation of Biodistillates as Potential Blendstocks for Transportation Fuels, CRC Project No. AVFL-17 Final Report, June 2009. [2] Engine Manufacturers Association, Alliance of Automobile Manufacturers, Use of Raw Vegetable Oil or Animal Fats in Diesel Engines, March 2006.

[3] McCormick, R. L., Alleman, T. L., Waynick, J. A., Westbrook, S. R., and Porter, S., Stability of Biodiesel and Biodiesel Blends: Interim Report, prepared under Task No. FC06.9400, NREL/ TP-540-39721, April 2006.