LCMR Work Program

Evaluate Biodiesel Made from Waste Fats and Oils Final Report June 2002

Prepared by:

Rose Patzer Max Norris Agricultural Utilization Research Institute

Executive Summary There is an increasing interest in the United States to produce alternative or renewable fuels, thereby reducing the dependency on imported petroleum products. Renewable fuels, such as biodiesel, can play a role toward that goal. In addition, as production and usage in the United States continues to increase, favorable impacts such as new jobs, environmental benefits, and new markets for agricultural products may be observed. Soybean oil is the primary agricultural feedstock used in biodiesel production across the United States. This vegetable oil is abundantly available and is easily converted to a renewable fuel known as biodiesel or soy methyl esters. The process requires 7.4 pounds of vegetable oils or animal fats to produce a gallon of biodiesel. Material costs rise above one dollar per gallon when the five year average market price of soybean oil (fifteen cents per pound) is factored into the production cost for biodiesel. Thus, the higher price at the fuel pumps for this renewable fuel versus petroleum diesel instills a hurdle in the market place for distributors and consumers. One of the means to address the higher priced hurdle is to research and develop methods to reduce the cost of biodiesel. This project is directed toward those efforts. Neat animal fats and vegetable oils can be converted to biodiesel, but they carry with them the higher material cost into production. A reduced cost option is to produce biodiesel from waste fats and oils. However difficulties are encountered including poorer cold temperature properties and lesser yields when synthesizing biodiesel from these lower cost feedstocks. The work reported in this paper includes producing biodiesel from soybean oil and a variety of waste greases utilizing methanol in the process. When investigating traditional methods, the difficulties in the reaction processes range from tight emulsions, poor yields, to “no reactions”. Due to project time constraints and the difficulties listed above, the project moves toward purchasing waste grease (WGME) and soy methyl esters (SME). Since the properties of SME are generally more favorable than WGME, the esters are blended and thoroughly evaluated. The results of the analysis assist the collaborators decision in developing a new reduced cost biodiesel fuel that will undergo engine testing under the direction of the University of Minnesota.

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Objectives The identified objective that AURI participated in for this project include the following: 1. Produce methyl esters from soybean oil and a variety of waste greases. 2. Produce methyl esters from a blend of soybean oil and waste grease. 3. Determine a material balance sheet of the produced blended methyl esters. 4. Forward the developed process to a commercial methyl ester processor for production of 1,000 gallons of biodiesel fuel. The biodiesel fuel will be intended for engine testing conducted by the University of Minnesota’s Center for Diesel Research.

Accomplishments SME and WGME were produced at the bench top level via three published methods. Some of the reaction attempts failed. Others were successful. Most of the inconsistencies lied in the esterification of waste greases. Therefore, a new method was developed that increased the consistencies and yield of waste grease methyl esters. Commercially available SME and WGME were purchased. The waste grease esters were blended with two separate soy methyl esters in ten percent increments. The blended samples were analyzed and reviewed to find the most favorable characteristics including fuel properties and least cost analysis. The esters were also blended in twenty-five percent increments. These were analyzed with emphasis lying on the cold temperature properties. Staff members from AURI and the University of Minnesota’s Center for Diesel Research reviewed the collected data and determined the blend that would best suit the requirements for this project. Approximately 110 gallons of the targeted blend was ordered and shipped to the University of Minnesota’s Center for Diesel Research to undergo engine testing.

Recommendations The results of the work presented in this report together with the information reported from the other project collaborators can favorably impact the biodiesel industry. It is understood that the petroleum diesel fuel industry blends fuels with additives to accommodate colder climates and weather conditions. SME together with cold temperature property enhancers can be used in the same manner when WGME are used as fuels. In regard to fuel costs, waste grease methyl esters can be produced industrially at a lesser cost than soy methyl esters. Therefore, blending the methyl esters becomes a favorable option in the production of “winterized” biodiesel, and higher percentages of WGME can be used in the summer months to further reduce the cost of these alternative fuels.

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TABLE OF CONTENTS Executive Summary ....................................................................................................................... i Objectives ...................................................................................................................................... ii Accomplishments .......................................................................................................................... ii Recommendations.......................................................................................................................... ii I. ........Introduction ……………………………………………………………………………… 1 II. Results and Discussion ……………………………………………………………. 2 - 13 IIA. Feedstock Collection and Clean-Up ……………………………………………………. 2 IIB. Small Scale Biodiesel Production ………………………………………………………. 3 First Method: Processing, Characterization and Performance of Eight Fuels form Lipids, Peterson, et al. ……………………………………………….………….. 4 Second Method: Biodiesel Production Based on Waste Cooking Oil: Promotion of the Establishment of an Industry in Ireland, Rice et al. …………………..... 5 Third Method: Process for Production of Esters for Use as a Diesel Fuel Substitute Using a Non-alkaline Catalyst, Basu, et al. …………………………….. 5 Fourth Method: Two-Step Reaction for Waste Grease Biodiesel Synthesis, Unpublished Information, Patzer et al. …………………………………. 6 IIC. Commercially Produced Methyl Esters ………………………………………………… 8 III. Conclusion …...………………………………………………………………………... 14 IV. ......Acknowledgements …………………………………………………………………….. 14

LIST OF TABLES TABLE 1. Fatty Acid Composition of Waste Grease .................................................................... 3 TABLE 2. Methyl Ester Analysis .............................................................................................6 – 7 TABLE 3. Analytical Properties of Waste Grease Methyl Esters ..................................................8 TABLE 4. Fatty Acid Composition of Fatty Acid Methyl Esters ................................................. 9 TABLE 5. Analyses of Purchased Methyl Esters .........................................................................10 TABLE 6. Cold Temperature and Sulfur Properties of Biodiesel and Diesel Fuel ......................11 TABLE 7. Cold Temperature Properties of Samples Blended with the Schaeffer Additive..................................................................11 TABLE 8. Cold Temperature Properties of B20 Samples Blended with the Schaeffer Additive .................................................................12 TABLE 9. Cold Temperature Properties of B20 Samples Blended with Twice the Recommended Schaeffer Additive .....................................................12 TABLE 10. Cold Temperature Properties of Blended B20 Samples Without Additive.............................................................12 TABLE 11. Biodiesel Price Per Gallon (Delivered) .....................................................................13 TABLE 12. Blended Biodiesel Price Per Gallon (Delivered) ...................................................... 13

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I. Introduction AURI’s initial experimental design consisted of four phases: 1. Produce methyl esters from a variety of waste greases. 2. Produce a methyl ester from a blend of soybean oil and waste grease. 3. Determine a material balance sheet of the produced blended methyl ester. 4. Forward the developed process to a commercial methyl ester processor for production of 1,000 gallons of biodiesel fuel for engine testing at the CDR. AURI obtained and partially cleaned up a variety of waste greases from various Marshall, Minnesota area restaurants. Active work with these starting materials included various attempts in producing methyl esters and minimally analyzing their properties (kinnematic viscosity, specific gravity, and free fatty acid content). As expected, many difficulties were encountered in the production of waste grease methyl esters using traditional methods. It was understood that industry’s preference in any production avoids the use of solvents, heat/pressure combinations, and distillation. Loose and tight emulsions, poor yield of esters, and “no reactions” were the primary difficulties encountered in the esterification process using industry’s preferences as guidelines. Therefore, extensive research and development was necessary to obtain esterification of these waste greases. Due to the encountered difficulties, AURI moved toward evaluating and purchasing industrially produced waste grease (WGME) and soybean methyl esters (SME). The investigated esters included soy esters produced from West Central Co-Operative, Ralston, IA (extruded oil), Ag Environmental Products, Lenexa KS (chemically processed oil), and waste grease esters from Griffin Industries, Inc. Cold Spring, KY (recycled grease). The WGME was blended in combinations at ten percent increments with both SMEs. The samples were subjected to thorough analyses with regard to the National Biodiesel Board (NBB) specifications for biodiesel. The esters were also blended in twenty-five percent increments. These samples were evaluated with extensive emphasis in regard to their cold temperature properties. The additive package produced by Schaeffer Manufacturing Company was included in these mixtures to evaluate the promoted benefits of that product. Additional cold temperature analyses was accomplished on B20 blends containing the biodiesel samples and #1 and #2 diesel. Staff members from AURI and the University of Minnesota’s Center for Diesel Research reviewed the collected data and determined the blend that would best suit the requirements for this project. Approximately 110 gallons of the targeted blend was ordered and shipped to the University of Minnesota’s Center for Diesel Research to undergo engine testing. 1

II. Results and Discussion IIA. Feedstock Collection and Clean-Up The collected waste vegetable oils from some of the Marshall, Minnesota restaurants and food service establishments included corn, soybean, and canola feedstocks. Information gathered from the participating establishments, showed that the cooking temperature of the oils varied from 350-400°F. The oils were kept at these temperatures from ten to twenty hours per day and were replaced two to three times per week. To avoid negatively impacting the production costs, the clean-up process of the waste greases was minimized as much as possible. The clean-up included heating the oil to approximately 225°F until moisture levels dropped below 0.5%. After the water was removed, the oil was filtered through a screen to remove large particles and debris. The waste greases were covered and stored individually at room temperature. In addition, an unknown volume from each feedstock plus other readily available fats and oils was blended in a storage container and labeled “mixed greases.” The dried oils were evaluated for moisture, free fatty acid content, and fatty acid composition. The results of the moisture testing showed that the levels in all of the samples were below 0.10%. The free fatty acid (FFA) content in the samples from the fryer pits did not deviate from expectations and ranged from 1.5 – 5.4 percent (as oleic). Other fats and oils that were investigated in this project included acidulated soap stock (46.9% FFAoleic), tallow (1.42% FFAoleic), yellow grease (7.25% FFAoleic), and animal/vegetable blended grease (6.87% FFAoleic). The combined “mixed greases” contained 16.9% FFAoleic. The fatty acid composition (FAC) of the waste greases was listed in the Table 1. Exact FAC specifications were not available for the yellow grease but the supplying company stated that the fatty acid composition was very similar to the animal/vegetable blend. Therefore, the FAC for yellow grease has been intentionally omitted from the table.

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Table 1. Fatty Acid Composition of Waste Greases Soy 1

Canola 1 Tallow 2 Corn 1 Partially An./Veg. Acid. Soap 1 Hydrog. Soy Blend 3 Stock 4 C8:0 0.2 0.0 0.0 0.0 0.0 0.0 0.0 C12:0 0.5 0.0 0.0 0.0 0.1 0.0 0.0 C14:0 0.5 0.2 0.2 0.4 3.2 1.0 0.1 C14:1 0.1 0.0 0.0 0.0 0.0 0.3 0.0 C15:0 0.0 0.0 0.0 0.0 0.0 0.2 0.0 C16:0 12.7 11.4 6.6 8.5 25.5 17.3 13.3 C16:1 0.5 0.3 0.4 0.0 0.0 2.8 0.0 C17:0 0.0 0.1 0.1 0.3 0.0 0.5 0.0 C17:1 0.1 0.0 0.1 0.2 0.0 0.0 0.0 C18:0 0.0 7.1 4.1 6.4 21.6 9.9 4.8 C18:1 63.3 43.1 63.0 61.7 38.7 42.6 20.1 C18:2 19.7 34.4 18.2 17.5 2.2 22.1 52.4 C18:3 0.3 0.0 3.4 1.2 0.0 2.2 8.6 C19:1 0.0 0.1 0.0 0.7 0.0 0.0 0.0 C20:0 0.4 0.7 0.1 1.1 0.1 0.0 0.3 C20:1 0.2 0.2 1.0 0.9 0.0 0.4 0.0 C22:0 0.4 0.4 0.0 0.0 0.0 0.0 0.4 C24:0 0.1 0.1 0.0 0.0 0.0 0.0 0.0 Other 1.0 0.9 1.8 0.1 8.6 0.7 1. In-House Analyses of Collected Waste Grease: AOCS Ce 2-66 2. Guaranteed Specifications: Tri-State Grease and Tallow Company, Inc., New Ulm, MN 3/18/99 3. Guaranteed Specifications: Van Hovens Company, Inc., South Saint Paul, MN, 9/12/97 4. Guaranteed Specifications: Cenex harvest States Cooperatives, Mankato, MN 11/30/98

The two waste grease soy samples greatly deviated from the normal fatty acid composition of soybean oil in the C18:1Oleic and C18:2Linoleic fatty acids. According to Bailey’s Industrial Oil and Fat Products (Fifth Edition, 196), general specifications for soybean oil were approximately 23% for oleic acid and 55% for linoleic acid. It appeared as though the data listed in the table was reversed. However, it was noted that heat can break double bonds, and the data was allowed to stand. Furthermore, the data was reaffirmed by the data listed in Table 5. The data listed under the Griffin WGME (recycled restaurant grease ester) depicted this scenario as well.

IIB. Small-Scale Biodiesel Production Biodiesel fuel was produced from reacting animal fat or vegetable oil together with an alcohol and a catalyst. The three components were mixed and vigorously stirred for 1 to 3 hours. Occasionally, it was necessary to add heat to the reaction process, but this was generally not necessary if one used clean, fresh vegetable oil. After the reaction time was completed, the mixture was transferred to a tall, thin vessel or a separatory funnel. The solution was allowed to separate into one to three layers for a minimum of one hour and up to twenty-four hours. The top layer was the biodiesel (methyl ester), and the middle and/or bottom layer(s) contains un-reacted methanol, salts, glycerine, 3

and impurities. When the top layer appeared clear, it was decanted carefully into a clean vessel. The bottom layer(s) was discarded according to hazardous waste regulations. Methanol was recovered from the middle layer and the remaining un-reacted material was discarded with the bottom layer. The biodiesel solution was washed carefully with water or with a salted water solution. Washing was accomplished by adding the water to the ester with little or no agitation to the container. The methyl ester was allowed to settle and separate after each addition of water. Some observations that indicated washing was completed included a clear water layer, or the same amount of water was removed as was added in the solution, or the water layer reached approximately pH 7. When all three criteria for the above observations were met, the reaction process was considered complete. Occasionally, it was necessary to remove water from the ester. This was accomplished easily by slowly heating the methyl ester to 212°F (while stirring) until all traces of bubbles and/or foaming were gone. The ester was filtered over anhydrous sodium sulfate and stored in glass or metal containers. The feedstocks were individually and collectively subjected to four different experimental methods. Each of the first three methods was obtained from readily published information. The first, second and fourth methods follow the general procedure written above. The third method deviated from the usual and customary procedures by utilizing a high pressure, high temperature reactor equipped with a stirring apparatus. The methods are outlined below. Terms/Abbreviations MeOH – Methanol KOH – Potassium Hydroxide KCl – Potassium Chloride

BaAce – Barium Acetate CaAce – Calcium Acetate NaOH – Sodium Hydroxide

First Method University of Idaho, C.L. Peterson et al. Processing, Characterization & Performance of Eight Fuels from Lipids By weight: MeOH = Oil X 0.225 KOH = Oil/100

Reaction Time: 2 hours (stirring, no heat) Separation/washing up to one week Some washes include tannic acid/water mix

% Yield on fresh oil: 91 – 92% % Yield on waste grease: “no reactions”

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Second Method B. Rice, et al. Bio-diesel Production Based on Waste Cooking Oil: Promotion of the Establishment of an Industry in Ireland. Ireland Method 1: 120 g oil 1.8 g KOH in 33.5 ml MeOH

Reaction Time: 1 hour (stirring, no heat) Separation/washing up to one week Some washes include KCl/water mix

% Yield on fresh oil: 90 – 92% % Yield on waste grease: “no reactions” Ireland Method 2: 120 g oil 2.5 g KOH in 24 ml MeOH

Reaction Time: 1 hour (stirring, no heat) Separation/KCl & water washes ≅ one wk.

% Yield on fresh oil: 83 – 90% % Yield on waste grease: “no reactions” Third Method Basu, et al. Process for productin of Esters for Use as a Diesel Fuel Substitute Using a Non-alkaline Catalyst. United States Patent Number 5,525,126. Basu Method 1 - By weight: 176 g oil 66 g MeOH 0.22 g BaAce 0.66 g CaAce

High pressure/high temp. reactor Reaction time: 2-3 hours Pet. Ether as solvent system

% Yield on fresh oil: 87 – 94% % Yield on waste grease: 59 – 83% Basu Method 2 – Same system as above, except Sodium Bicarb. washes, tannic acid washes, and water were substituted for pet ether. % Yield on fresh oil: cloudy appearing esters not evaluated % Yield on waste grease: cloudy appearing esters not evaluated

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Fourth Method Unpublished Information. R. Patzer, et al. Two-Step method for Biodiesel Synthesis By weight: 4% H2SO4/MeOH = Oil X 0.33 Time: 1.5 hours (stirring, 90oC) KOH = (Oil X .03) dissolved in MeOH (Oil X 0.3) Time: 3.5 hours (stirring, 90oC) Separation/salted washings – 1-2 weeks % Yields, waste grease: 40-85% Difficulties: poor yield, soaps, pH high on esters The following table was an extensive list of the different esterification attempts made on various feedstocks. The table listed the analysis necessary for preliminary qualification of the esters. The many failed esterification attempts were not listed, but rather were referred to as “no reactions” in the outline listed above. In the table, methods were identified in the “Sample ID” column with “ID-” matching the First Method (Idaho), “IR-” related to the Second Method (Ireland methods), “R-“ stood for the Third Method (Reactor), and “2S-“ regarded the Fourth Method (AURI 2-Step). Table 2. Waste Grease Methyl Ester Analyses Sample ID

Feedstock

ID-22900 Soy (fresh) ID-301002 Soy (fresh) IR-302001 Soy (fresh) IR-302002 Soy (Fresh) IR-306001 Soy (fresh) IR-306002 Soy (fresh) IR-306003 Soy (fresh) ID-307001 Soy (fresh) 2S-321001 Corn(waste) R-403001 Corn(waste) R-405001 Corn(waste) R-407001 Soy (waste) 2S-407002 Soy (waste) R-408001 Soy (waste) R-411001 Canola (wg) R-411002 Canola (wg) R-412001 Canola (wg) 2S-413001 Canola (wg) R-413002 Canola (wg) 2S-418001 Canola (wg) R-418002 Canola (wg) IR-302001 Soy (fresh) IR-302002 Soy (fresh) R-420001 Soy (waste) R-425001 Canola (waste) Continued on the next page

K.V.

(%) FFA

(cSt at 40°C)

4.27 4.31 4.34 4.39 4.15 4.51 4.11 4.31 39.95 6.22 5.13 5.40 Cloudy 5.655 5.66 Too Thick 5.72 Too Thick 6.29 Too Thick 5.43 4.39 4.39 5.37 5.81

0.12 0.08 0.12 0.08 0.08 0.09 0.08 0.08 0.18 0.50 0.36 0.239 0.480 0.60 0.20 0.36 0.16 1.825 0.275 0.48 0.20 0.12 0.08 0.20 0.44

(at 25°C)

Cloud/ Pour Pt.

0.88 0.88 0.88 0.88 0.88 0.88 0.88 0.88 0.91 0.88 0.88 0.88 ----0.88 0.88 Too Thick 0.88 Too Thick 0.88 Too Thick 0.88 0.88 0.88 0.88 0.88

-3/-0.1 -3.0/0.0 -3.0/-0.1 -3.0/-0.1 -2.9/-0.1 -3.1/-0.2 -3.1/-0.2 -3.0/-0.1 1.8/3.4 -1.3/2.1 -1.0/2.0 -2.6/0.0 -----2.6/1.4 -1.0/2.9 -----1.3/3.1 -----1.5/3.0 -----0.5/3.0 -3.0/-0.1 -3.0/-0.1 -2.2/0.0 -1.2/3.0

S.G.

(°C)

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Table 2. Waste Grease Methyl Ester Analyses cont’d. Sample ID 2S-505001 2S-508001 2S-509001 2S-512001 2S-516001 2S-519001 2S-522001 2S-602001 2S-605001 2S-606001 2S-608001 2S-609001 2S-614001 2S-615001 2S-619001 2S-621001 2S-629001 2S-705001 2S-724001 2S-726001 2S-717001 2S-719001 2S-720001 2S-905001 2S-911001

Feedstock

K.V.

(%) FFA

(cSt at 40°C)

Soy (waste) Soy (waste) Soy (waste) Canola (wg) Canola (wg) Soy (waste) Corn (waste) Canola (wg) Soy (waste) Soy (waste) Soy (waste) Soy (waste) Corn (waste) Soy (waste) Soy (waste) Soy (waste) Soy (waste) Soy (waste) Acid. Soap Stock Tallow Animal/Vegetable

Mixed Greases Mixed Greases Acid. Soap Stock Mixed Greases

6.27 5.62 5.20 5.33 5.25 4.75 5.19 5.14 5.05 5.05 5.04 5.43 5.06 4.41 5.06 5.13 5.25 5.20 5.12 5.79 5.54 5.78 5.62 5.51 5.85

0.16 0.16 0.12 0.16 0.16 0.20 0.12 0.24 0.16 0.16 0.16 0.16 0.16 0.08 0.16 0.16 0.20 0.20 0.90 0.16 0.20 0.16 0.20 1.17 0.24

S.G.

(at 25°C)

0.88 0.88 0.88 0.88 0.88 0.88 0.88 0.88 0.88 0.87 0.88 0.87 0.88 0.88 0.88 0.88 0.88 0.88 0.88 0.88 0.88 0.88 0.88 0.88 0.88

Cloud/ Pour Pt. (°C)

0.9/3.1 0.9/3.1 -1.1/2.8 -1.0/1.2 -1.1/1.0 0.5/3.4 -1.4/2.0 -1.1/1.5 -1.9/1.0 -2.2/-0.1 -2.1/0.0 -2.4/-0.3 -2.0/1.0 -1.2/3.3 -2.1/0.4 0.9/3.0 0.8/2.9 1.0/3.0 0.7/2.8 1.2/3.6 2.0/3.8 2.6/4.9 2.8/5.4 0.8/3.0 2.8/5.0

The two-step procedure that was defined in the fourth method most consistently produced methyl esters when waste greases were involved in the reaction. Ester yields ranged from approximately forty to eighty-five percent, and the lower yields resulted from incomplete reactions. One of the Idaho (ID-) esters and thirteen of the two-step (2S-) esters were sent out for additional analyses. Investigations included cold filter plugging point, water and sediment, free and total glycerine, and sulfur testing. These analyses were completed to further qualify (or disqualify) the methyl esters produced from waste greases. The data was listed in Table 3.

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Table 3. Analyses of Waste Grease Methyl Esters Sample ID

Feedstock

Water & Free Glyc. Sed. (%) (%)

Total Glyc. (%)

Sulfur

ASTM 6371

ASTM D2709

C. Plank

ASTM D2622

By Customer

NBB Specs: ID-301002 2S-602001 2S-615001 2S-614001 2S-629001 2S-621001 2S-522001 2S-605001 2S-512002 2S-911001 2S-719001 2S-726001 2S-905001 2S-717001

CFPP (oC)

Fresh Soy Canola Soy Corn Soy Soy Corn P.H. Soy Canola Mixed Mixed Tallow A.S.S. An./Veg. Blend

-4 -2 0 -9 1 7 -9 6 -4 -2 -6 12 -5 -3

C. Plank

0.050 max 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

0.020 max 0.006 0.001 0.001 0.000 0.004 0.001 0.005 0.000 0.037 0.009 0.003 0.008 0.001 0.000

(mass %)

0.240 max 0.05 max 0.165 0.165 0.139 0.226 0.151 0.069 0.237 0.118 0.189 0.097 0.598 0.061 1.507 0.089

0.000045 0.000068 0.000149 0.000237 0.000137 0.000172 0.000170 0.000262 0.000205 0.000420 0.000363 0.000264 0.001084 0.000766

The foremost anticipated data points from these tests were the glycerine content. Glycerine was a byproduct from breaking the fatty acids off of the glyceride “backbone” during methyl ester synthesis of fats and oils. It is common knowledge that glycerine has enough solubility in biodiesel to potentially cause engine problems when the glycerine levels in the fuel exceed the limits established by the National Biodiesel Board. In the reaction process, glycerine was removed by washing the ester with water. However, “out-of-spec” total glycerine levels in samples 2S-719001 and 2S-905001 suggested that there was remaining “bound glycerine” or glycerides (mono-, di-, tri-, and phospho-) which could not be removed in the water wash step. Through professional communications, it was determined possible that the second step of the reaction process did not allow for complete removal of the glycerides in the reaction. In lieu of this and due to time constraints, the direction of the project turned toward purchasing industrially produced soy and recycled grease esters. IIB. Commercially Produced Methyl Esters A list of seven biodiesel producers recognized by the National Biodiesel Board as producers of quality biodiesel fuels was reviewed. From this list, the process for choosing the suppliers 8

was based on location. Producers located closest to the state of Minnesota were considered because delivery costs incurred through shipment could render the price-per-gallon too costly. Therefore, the decision was made to purchase soy methyl esters from Ag Environmental Products (AEP), Lenexa, Kansas, and from West Central Cooperative (WCC), Ralston, Iowa. The decision to analyze two soy-based biodiesel fuels stemmed from the fact that AEP produced esters from chemically processed soybean oil and WCC produced biodiesel from expelled soybean oil. It was determined that analytical evaluations of both types of soy methyl esters would prove valuable to the scope of the project as well as to future related projects. Secondly, the only waste (or recycled) grease methyl ester producer at the time of this evaluating process was Griffin Industries located in Cold Spring, Kentucky. Consequently, the determination of which WGME would be used in the investigation was already decided for our group. The fatty acid compositions of the fuels were listed in Table 4. Table 4. FAC of Purchased Methyl Esters Fatty Ralston A.E.P. Griffin Acid SME SME WGME C14:0 C14:1 C15:0 C16:0 C16:1 C17:0 C17:1 C18:0 C18:1 C18:2 C18:3 C19:1 C20:0 C20:1 C21:0 C22:0 C24:0 Total %:

0 0 0 10.4 0 0 0 4.6 22.3 53.4 8.2 0 0.4 0.2 0 0.4 0.1 100

0 0 0 10.4 0 0 0 4.6 23.7 52.9 6.9 0 0.7 0.2 0 0.4 0.2 100

0.7 0.2 0.1 15.2 1.3 0.3 0.3 9.9 42.6 26.5 1.2 0.3 0.6 0.2 0.2 0.3 0.1 100

The recycled grease methyl ester was blended in combinations at 10% increments with both soy biodiesel fuels. Thorough testing was completed on the blended samples with special emphasis placed on their cold temperature properties. Complete analyses of these blended esters can be found in Table 5.

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Table 5. Analyses of Purchased Methyl Esters Sample ID

% Cloud Soy Pt. o ( C)

Pour Pt. (oC)

CFPP H2O & (oC) Sed. (%)

ASTM D5773

ASTM D5949

IP 309

By By By Customer Customer Customer

NBB Specs:

Total Glyc. (%)

(cSt @ 40oC)

K.V.

Acid # Carbon Res. (%)

Sulfur

Cetane

Copper Sulfated Strip Ash Corrosion (mass %) ASTM D130

(mass %)

ASTM D2709

C. Plank

ASTM D445

ASTM D664

ASTM D524

ASTM D2622

ASTM D613

ASTM D874

0.050 max

0.240 max

1.9-6.5

0.80 max

0.050 max

0.05 max

40 min.

No. 3b max

0.020 max

0S100W-A

0

6

4

2

0.00

0.0820

4.62

0.56

0.030

0.0019

50.90

1A

0.0040

10S90W-A 20S80W-A 30S70W-A 40S60W-A 50S50W-A 60S40W-A 70S30W-A 80S20W-A 90S10W-A 100S0W-A

10 20 30 40 50 60 70 80 90 100

5 5 5 4 3 2 2 2 1 0

4 4 4 2 2 0 0 0 -2 -2

2 1 1 0 0 -1 -3 -3 -4 -6

0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

0.0928 0.1036 0.1144 0.1252 0.1360 0.1468 0.1576 0.1684 0.1792 0.1900

4.72 5.00 4.44 4.55 4.49 4.40 4.31 4.29 4.11 4.08

0.48 0.48 0.42 0.40 0.40 0.32 0.32 0.32 0.24 0.16

0.029 0.028 0.027 0.026 0.025 0.024 0.023 0.022 0.021 0.020

0.0018 0.0017 0.0016 0.0015 0.0014 0.0013 0.0012 0.0011 0.0010 0.0009

50.73 50.56 50.39 50.22 50.05 49.88 49.71 49.54 49.37 49.20

1A 1A 1A 1A 1A 1A 1A 1A 1A 1A

0.0036 0.0032 0.0028 0.0024 0.0020 0.0016 0.0012 0.0008 0.0004 0.0000

10S90W-R 20S80W-R 30S70W-R 40S60W-R 50S50W-R 60S40W-R 70S30W-R 80S20W-R 90S10W-R 100S0W-R

10 6 20 5 30 4 40 4 50 3 60 3 70 2 80 1 90 0 100 0 A = A.E.P.

0.0897 4.82 0.48 0.030 0.0974 4.58 0.40 0.030 0.1051 4.50 0.40 0.030 0.1128 4.31 0.40 0.030 0.1205 4.35 0.32 0.030 0.1282 4.36 0.32 0.030 0.1359 4.37 0.32 0.030 0.1436 4.58 0.32 0.030 0.1513 4.41 0.24 0.030 0.1590 4.40 0.24 0.030 W = Waste Grease (Griffin)

0.0017 0.0015 0.0013 0.0011 0.0010 0.0008 0.0006 0.0004 0.0002 0.0000

50.80 50.70 50.60 50.50 50.40 50.30 50.20 50.10 50.00 49.90

1A 1A 1A 1A 1A 1A 1A 1A 1A 1A

0.0041 0.0042 0.0043 0.0044 0.0045 0.0046 0.0047 0.0048 0.0049 0.0050

S = Soy

4 4 2 2 0 2 0 0 -2 -2

2 0.00 2 0.00 0 0.00 0 0.00 -1 0.00 -2 0.00 -2 0.00 -3 0.00 -4 0.00 -4 0.00 R = Ralston

Many discussions between staff from AURI and the University of Minnesota occurred regarding the information in Table 5. The initial data of interest focused on the sulfur content in the neat fuels. Although each of the biodiesel fuels fell within specifications, concerns were stated due to the 2007 projected sulfur limitations (15 ppm maximum) set forth by the EPA. Because of Griffins WGME sulfur content at 19 ppm, the decision was made to stay below the EPAs 2007 sulfur limitations. This assisted the group’s decision to investigate 50/50 blends of the waste grease ester with both of the soy esters. Further analyses progressed toward soy and waste grease ester blends using twenty-five percent increments. These samples were also blended with petroleum diesel into B20 blends. Attempts were made at obtaining data from #1, #2 and 50/50 blends of petroleum diesel mixed with the biodiesel fuels. Cold temperature properties and sulfur contents were shown in Table 6. 10

Table 6. Cold Temperature and Sulfur Properties of Biodiesel and Diesel Fuel Sample

A.E.P. Soy Ester Griffin Waste Grease Ester Griffin W.G.E. RR 75% AEP / 25% Griffin 50% AEP / 50% Griffin 25% AEP / 75% Griffin Ralston Soy Ester Ralston Soy Ester RR 75% Ralston / 25% Griffin 50% Ralston / 50% Griffin 25% Ralston / 75% Griffin #1 Diesel #2 Diesel 50% #1 / 50% #2 Diesel Old Schaeffers Additive RR = Re-Run

Cloud Pt. (oC)

Pour Pt. (oC)

CFPP (oC)

Sulfur (Mass %)

ASTM D5773

ASTM D5949

IP 309

ASTM ASTM D5453 D2622 0.000114 0.0009 0.002072 0.0019 0.001582 0.0019 0.000604 0.0012 0.001093 0.0014 0.001583 0.0017 0.000046 0.0000 0.000046 0.0000 0.000430 0.0005 0.000814 0.0010 0.001198 0.0014 -----0.0371 -----0.0333 -----0.0341 -----0.0324

0 6 6 1.5 3 4.5 0 -1 1.5 3 4.5 -13 -15 -14 -----------

-2 4 4 -0.5 1 2.5 -2 -4 -0.5 1 2.5 -26 -26 -26 ------

-6 5 5 -3.25 -0.5 2.25 -4 -4 -1.75 0.5 2.75 -14 -16 -14 ------

Sulfur (Mass %)

= not analyzed

Two sulfur methods were run on the biodiesel samples for verification purposes. The original biodiesel specifications established by the National Biodiesel Board included the method, ASTM 2622 for sulfur analysis. As advances and technologies advanced over the years in the biodiesel arena, the movement has been toward adopting the ASTM 5453 method for sulfur testing in biodiesel fuels. The ASTM 2622 method has been determined to yield falsely high sulfur levels in because of the oxygen content in pure biodiesel fuels. With few exceptions, the data in Table 6 depicted that scenario. Further steps were made with blending the different fuels with a cold temperature additive package produced by Schaeffer Manufacturing Company. These results were listed in Tables 7 through 10. Table 7. Cold Temp. Properties of Samples Blended with Recommended Schaeffer Additive Sample AEP Griffin Ralston #1 Diesel #2 Diesel 50/50 #1 & #2 Diesel

Cloud Point Pour Point (oC) (oC) 0 5 -2 -14 -18 -16

-3 6 -3 -30 -39 -36

CFPP (oC)

-3 0 -3 -21 -27 -24 11

Table 8. Cold Temperature Properties of B20 Samples Blended with Recommended Schaeffer Additive 20% Biodiesel*

Cloud Point Pour Point (oC) (oC)

CFPP (oC)

75/25 AEP Griffin -12 -27 50/50 AEP/Griffin -10 -24 25/75 AEP Griffin -10 -24 75/25 Ralston/Griffin -12 -27 50/50 Ralston/Griffin -10 -24 25/75 Ralston/Griffin -12 -24 * 80% diesel fuel is 50% #1 diesel blended with 50% #2 diesel.

-16 -15 -13 -15 -15 -13

Table 9. Cold Temperature Properties of B20 Samples Blended with Twice the Recommended Schaeffer Additive 20% Biodiesel*

Cloud Point Pour Point (oC) (oC)

CFPP (oC)

50/50 AEP/Griffin -10 -24 50/50 AEP/Griffin RR -10 -34 50/50 Ralston/Griffin -10 -24 50/50 Ralston/Griffin RR -10 -34 * 80% diesel fuel is 50% #1 diesel blended with 50% #2 diesel. RR = Re-Run

-23 -14 -17 -13

Table 10. Cold Temperature Properties of B20 Samples Without Additive 20% Biodiesel*

Cloud Point Pour Point (oC) (oC)

CFPP (oC)

50/50 AEP/Griffin -12 -18 50/50 Ralston/Griffin -12 -20 * 80% diesel fuel is 50% #1 diesel blended with 50% #2 diesel.

-13 -17

Concurrent efforts were directed toward the least cost analyses of the biodiesel fuels. In June 2000, freight on board (F.O.B.) and delivered (to Minneapolis, MN) prices were sought to establish the effects of transportation on the cost of the fuel. Table 11 showed the delivered price per gallon of fuel in 1000, 2500, and 6200 gallon quantities, and Table 12 depicted data for the blended fuels that consisted of the waste grease esters mixed with each of the soy oil esters. F.O.B. prices for the same month were listed below: Griffin Industries $1.60 gallon (F.O.B.) West Central Co-Op $2.49 gallon (F.O.B.) A.E.P. $2.00 gallon (F.O.B.) 12

Table 11. Biodiesel Price Per Gallon (Delivered). Griffin A.E.P. Ralston 1000 gal. 2500 gal. 6200 gal.

$2.95 $2.15 $1.85

$2.64 $2.24 $2.08

$3.11 $2.74 $2.59

Table 12. Blended Biodiesel Price Per Gallon (Delivered). 1000 Gallons 2500 Gallons 6200 Gallons % Ralston A.E.P. Ralston A.E.P. Ralston A.E.P. Soy/WG 0/100 $2.95 $2.95 $2.15 $2.15 $1.85 $1.85 10/90 $2.97 $2.92 $2.21 $2.16 $1.92 $1.87 20/80 $2.98 $2.89 $2.27 $2.17 $2.00 $1.90 30/70 $3.00 $2.86 $2.33 $2.18 $2.07 $1.92 40/60 $3.01 $2.83 $2.39 $2.19 $2.15 $1.94 50/50 $3.03 $2.80 $2.45 $2.20 $2.22 $1.97 60/40 $3.05 $2.76 $2.50 $2.20 $2.29 $1.99 70/30 $3.06 $2.73 $2.56 $2.21 $2.37 $2.01 80/20 $3.08 $2.70 $2.62 $2.22 $2.44 $2.03 90/10 $3.09 $2.67 $2.68 $2.23 $2.52 $2.06 100/0 $3.11 $2.64 $2.74 $2.24 $2.59 $2.08 One of the objectives in this project was to minimize the cost of biodiesel. Because the waste grease methyl esters were lower in price versus the SMEs, a blend to maximize the volume of WGME in the fuel was sought. However, in this least-cost-consideration, it was also necessary to minimize the negative effects that the WGME would contribute to the cold temperature properties. Although each of the three evaluated biodiesel fuels were within specifications established by the NBB, it was concluded that it was necessary to blend an ester that remained at or below 15 ppm for sulfur. The decision to purchase methyl esters was finalized after collaborative review of all of the data listed in Tables 5 – 12. The recommendation that resulted from this review was 50% WGME from Griffin Industries, Inc. blended with 50% SME for Ag Environmental Products, LLC. This decision was supported because even though the soy methyl esters were characteristically similar (with the exception of the sulfur content), AEP’s biodiesel was $0.51 per gallon cheaper than Ralston’s at the 6200 gallon delivered price. It was determined that a 50-50 blend of esters from Griffin and AEP yielded the minimum cost with a 14 ppm sulfur content. This scenario resulted in approximately a fourteen percent cost-reduction than if we used only soy methyl esters in the B20 blend. 13

IV. Conclusion Evidence from this report suggested that the cost of biodiesel can be reduced. An obvious attempt not previously mentioned would be to build a biodiesel production plant in Minnesota thereby reducing the costs associated with transportation. Another option is to consider purchasing waste grease esters in bulk quantities that were well below the cost of soy methyl esters. The WGME can be blended with petroleum diesel that would more than likely run efficiently in a diesel engine in the warmer months. However, the option that potentially offers greater over-all success of the cost-reduction process was determined to be a blend of waste or recycled grease methyl esters with soy methyl esters. Analyses suggested that soy methyl esters would perform better in colder climates than the waste grease methyl esters. Blending the WGME with the SME could minimize the negative effects of cold temperature properties that appeared to characterize the waste grease esters. Many different blended ratios of the two esters could offer varying degrees of engine testing success. Nevertheless, the “best-fit” blend for this project was determined by analyses to be 50% waste grease methyl esters purchased from Griffin Industries, Inc. with 50% soy methyl esters purchased from Ag Environmental Products, LLC. One fifty-five gallon drum of each ester was ordered and delivered to the University of Minnesota’s Center for Diesel Research to undergo engine testing.

Acknowledgements Agricultural Utilization Research Institute would like to acknowledge and thank the Legislative Commission for Minnesota Resources for their support in this collaborative project. A.U.R.I. would also like to recognize the following people and groups that have contributed to this segment of the project: Rachel Masyukos laboratory skills and effort in the project, the Marshall area eating establishments that provided information and contributed their fryer-pit grease, Mr. Ken Bickel and Mr. Kelly Strebig from the University of Minnesota Center for Diesel Research, Mr. Mike Youngerberg from the Minnesota Soybean Growers Association, and Mr. Steve Howell from the National Biodiesel Board.

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