Effects of Long-Term Storage on Biodiesel Quality For ... · PDF fileMarch 15, 2010 Revised: May 25, 2010 Portage la Prairie, Manitoba Project #21409R Final Report Effects of Long-Term

March 15, 2010 Revised: May 25, 2010

Portage la Prairie, Manitoba Project #21409R

Final Report

Effects of Long-Term Storage on Biodiesel Quality

For:

Natural Resources Canada

March 15, 2010 Revised: May 25, 2010 Portage la Prairie, MB

Project #21409R

Final Report

Effects of Long-Term Storage on Biodiesel Quality

Prepared For:

Natural Resources Canada 580 Booth, 18th floor, 18C6

Ottawa, ON K1A 0E4

Lorne Grieger, E.I.T. Project Manager Agricultural R&D

Harvey Chorney, P.Eng. Vice President Manitoba Operations

Acknowledgement PAMI wishes to acknowledge the funding support provided by Agriculture and Agri-Food Canada (AAFC) and Natural Resources Canada (NRCan).

Table of Contents Page

1. Introduction ............................................................................................................................ 1

2. Project Objective .................................................................................................................... 2

3. Executive Summary ............................................................................................................... 3

4. Project Description ................................................................................................................. 4

4.1 Biodiesel Demonstration in Manitoba ............................................................................. 4

4.2 Biodiesel from PAMI Project:Effect of Biodiesel Blend on Tractor Engine Performance 5

4.3 Analysis Test Protocol .................................................................................................... 6 4.3.1 BIODIESEL SAMPLES ....................................................................................... 6 4.3.2 ENGINE FUEL FILTERS ..................................................................................... 6

5. Results ................................................................................................................................... 7

5.1 Biodiesel samples ........................................................................................................... 7 5.1.1 BIODIESEL DEMONSTRATION IN MANITOBA ....................................................... 7 5.1.2 PAMI BIODIESEL STORED ON-SITE ............................................................... 10

5.2 Engine fuel filters .......................................................................................................... 15 5.2.1 CAT 465 COMBINE, SERIAL NO. 3HZ00515 .................................................. 15 5.2.2 CAT 465 COMBINE, SERIAL NO. 3HZ00516 .................................................. 16 5.2.3 CAT 480R COMBINE ................................................................................... 17

5.3 Long-term Storage Temperature Data ......................................................................... 18

6. Data Analysis and Discussion ............................................................................................. 20

6.1 Observations ................................................................................................................ 20 6.1.1 STORAGE CONDITIONS – COMBINES .............................................................. 20 6.1.2 SPECIFICATION FUEL TESTS – COMBINE SAMPLES .......................................... 21 6.1.3 ADDITIONAL TESTING – COMBINE SAMPLES .................................................... 22 6.1.4 GC/MS ANALYSIS – COMBINE FUEL FILTERS ................................................. 24 6.1.5 STORAGE CONDITIONS – PAMI DIESEL AND BIODIESEL STORAGE ................... 25 6.1.6 SPECIFICATION FUEL TESTS – PAMI DIESEL AND BIODIESEL ........................... 25 6.1.7 ADDITIONAL TESTING – PAMI DIESEL AND BIODIESEL SAMPLES ...................... 26

7. Project Photos ..................................................................................................................... 29

7.1 Fuel Filter and Fuel/Water Filter Photos ....................................................................... 29 7.1.1 CATERPILLAR LEXION 465 COMBINE .............................................................. 29 7.1.2 CATERPILLAR LEXION 480R COMBINE ........................................................... 32 7.1.3 MACDON 9300 WINDROWER ........................................................................ 35

7.2 Filter Analysis ............................................................................................................... 37

7.3 Photos from Filter Analysis ........................................................................................... 38 7.3.1 CAT 465 COMBINE, SERIAL NO. 3HZ00515 .................................................. 38 7.3.2 CAT 465 COMBINE, SERIAL NO. 3HZ00516 .................................................. 45 7.3.3 CAT 480R COMBINE ................................................................................... 52 7.3.4 MACDON 9300 WINDROWER ........................................................................ 57

7.4 Photos of Above Ground Storage Tanks ...................................................................... 60

Appendix I Results and Analysis…………………………..……………………………………….61

Appendix II Results and Analysis…………………………..……………………………………….62

Appendix III Results and Analysis…………………………..……………………………………….63

Appendix IV Results and Analysis…………………………..……………………………………….64

Appendix V Results and Analysis…………………………..……………………………………….65

Appendix VI Results and Analysis…………………………..……………………………………….66

1

1. Introduction

The Government of Canada has committed to implementing a renewable fuel regulation in diesel fuel and heating oil. Because of Canada’s unique environment and driving conditions, the federal government would like to address outstanding performance questions raised during industry consultations, prior to implementation of new regulation. One of the questions remaining includes the impact of storage on the performance of biodiesel fuel. The intent of this project is to determine the effects of long-term storage on biodiesel blends. This is especially important in agricultural applications, where fuel may remain dormant in storage tanks or equipment for 8 to 10 months, due to the seasonal usage of equipment. This report does not necessarily reflect the views or positions of the federal government.

2

2. Project Objective

One of the concerns regarding the use of biodiesel is the impact of long-term storage on the quality of the fuel. In the Canadian agricultural sector, the seasonality of fuel use is of particular interest to the end-user, since the fuel typically remains in equipment and storage tanks over several seasons. For example, a combine is typically used only during the harvest season, and is then stored through the remaining 8-10 months of the year, before being put back into service. During this time, the fuel remains dormant in the fuel tank and is subjected to seasonal extremes in temperature.

The Prairie Agricultural Machinery Institute (PAMI) has recently performed a demonstration project involving farmers in Manitoba using biodiesel, and a research project involving tractor performance with different blends of biodiesel. In both of these projects, biodiesel fuel was stored in either equipment fuel tanks or above-ground storage tanks, for extended periods of time. The objective of this project is to gather information regarding the effects of long-term storage on biodiesel quality by sampling the fuel used during these previous projects.

3

3. Executive Summary

The Prairie Agricultural Machinery Institute (PAMI) has been contracted by the Minister of Natural Resources, acting through the Office of Energy Efficiency (NRCan), to investigate the impacts of long-term storage on biodiesel quality. This research will add to the body of knowledge concerning the impact of long-term storage on the quality and usability of biodiesel under typical operating conditions in the agricultural sector. In 2008, PAMI participated in a biodiesel demonstration project that included the cooperation of ten farmers who agreed to use biodiesel in their harvest equipment. Upon completion of this project, the biodiesel was left in the fuel tanks of the combines. Approximately nine months later, in August 2009, PAMI collected biodiesel samples for analysis of the remaining fuel in three of these combines. Fuel filters were also removed for analysis, to determine the composition of residual compounds on the filters. In addition, PAMI also collected diesel, B5, B10, and B20 canola-based biodiesel blend samples that have been stored for approximately two years in outdoor above-ground storage tanks, without the use of any additives. Modified full specification testing was performed on each fuel sample by Manitoba Hydro laboratories, following CAN/CGSB-3.520 (for biodiesel blends B5 and less) or ASTM D7467 (for biodiesel blends B6 to B20). All biodiesel samples met the specifications for the applicable standard. The fuel samples were also subjected to the following tests: Oxidative stability (EN 15751); acid number (ASTM D664); sediment/total insoluble analysis (ASTM D4625); water and sediment (ASTM D2709); and filter blocking tendency (ASTM D2068). Where these results are required as part of the specification testing, the samples met the specification criteria. The filter testing was completed using Gas Chromatography / Mass Spectroscopy techniques by Manitoba Hydro laboratories. Monoglycerides, sterols and Tocopherol were identified as being present on many of the filter elements. The results of this testing demonstrate that long-term storage of biodiesel blends up to concentrations of B20, for periods of up to two years, does not adversely affect the quality of the biodiesel to the point where it fails specification testing. Further study on additional quality attributes of biodiesel that may not currently be a part of the standard specification, and further study on the performance of biodiesel stored for long periods of time under real world conditions, would add to the findings of this research project.

4

4. Project Description

The project has been divided into two different sections as described below.

4.1 Biodiesel Demonstration in Manitoba Since 2007, PAMI has been working with ten cooperating farmers to demonstrate the use of biodiesel in a typical agricultural setting. B100 biodiesel was provided to the farmers for use in their agricultural equipment. Two demonstrations were performed, one in 2007 using a canola-based biodiesel; and again in 2008 with soy-based biodiesel. Samples for this project were taken from the soy-based biodiesel remaining in the equipment fuel tanks from the demonstration in fall, 2008. For the 2008 biodiesel demonstration, farmers prepared a biodiesel blend by splash-blending a soy-based B100 biodiesel with diesel fuel on site. At each farm, a 1000L biodiesel tote was installed next to the main fuel tanks. A pump and a volume meter were used to dispense a known volume of B100 into the equipment fuel tanks for blending. The B100 supplied to the farmers met ASTM 6751 standards, as specified by the certificate of analysis supplied with the biodiesel at the time of purchase. A copy of the certificate of analysis is provided in Appendix I. However, the base diesel was not tested before it was blended with the biodiesel. The equipment fuel tanks were not cleaned before the biodiesel was added in the fall 2008.

At the commencement of this research project in 2009, several of the cooperating farmers were identified as having harvest equipment that had been stored with biodiesel in the tanks since the end of the biodiesel demonstration. These pieces of equipment had not been run since the 2008 harvest season. Fuel samples were collected from four such pieces of equipment in August 2009, which is identified in the Table 1, below. Table 1. Equipment Sampled from Biodiesel Demonstration.

Location Equipment Type

Make Model Serial Number

Sample ID

Beausejour Combine Caterpillar Lexion 465 3HZ00515 515* Beausejour Combine Caterpillar Lexion 465 3HZ00516 516 Beausejour Combine Caterpillar Lexion 480R COL00480P86600889 480R Arborg Swather MacDon 9300 124703 SW**

*The initial fuel sample for Sample 515 was taken after a combine start-up performed by the farmer the previous day as part of his harvest preparation. **The initial fuel filters sampled for the MacDon swather were new filters installed by the farmer in the summer of 2009.

5

Agricultural equipment is typically stored with the fuel filters that were in use at the end of the season, and then changed before use the next year. In this case, the fuel and filters from several pieces of harvesting equipment were sampled. If no fuel filter plugging issues were experienced during the harvest season, the same fuel filters would be used throughout the season, and then changed before use in the following year.

Initially, the fuel/water separator was removed from the equipment for analysis. A fuel sample was taken at the inlet to the fuel/water separator, which is located at the tank outlet near the bottom of the tank prior to starting the equipment. After the initial fuel sample was taken, the fuel filter(s) were removed for analysis. New filters were installed and the engines were run at high idle for a minimum of ½ hour before a second fuel sample was taken and filters collected for analysis. Samples to analyze included fuel samples and filters collected before starting, and then again after running for ½ hour.

4.2 Biodiesel from PAMI Project: Effect of Biodiesel Blend on Tractor Engine Performance PAMI has stored B5, B10, B20 and B50 blends of biodiesel in on-site storage tanks for the past two years. The B100 used to make the biodiesel blends was canola-based and met ASTM 6751 specifications. A copy of the certificate of analysis for the biodiesel used in the PAMI research project is provided in Appendix II. The biodiesel was then splash-blended in new above-ground storage tanks with the base diesel. These biodiesel blends were not treated with additives. Since the original blend, they have been moved to different storage tanks using a transfer tank with an unknown history.

Fuel samples were collected from each of the following storage tanks for analysis: diesel fuel, B5, B10 and B20 in order to identify effects that storage had on fuel quality. The biodiesel blends had been in storage for 22 months before being sampled for this project.

6

4.3 Analysis Test Protocol

4.3.1 Biodiesel samples A fuel test schedule was identified to focus on contamination and fuel degradation. The test methods in Table 2 have been identified as essential for analysis of the biodiesel samples collected from both the farm biodiesel demonstration and the tractor engine performance test.

Table 2. Test Methods for Biodiesel Samples.

Item Individual Test Test Method1 Full Specification Test CGSB 3.520 or ASTM D7467 2 Oxidative stability EN 15571 (replacement for 14112) 3 Acid Number ASTM D664 4 Sediment/Total Insoluble’s ASTM D4625 (at time zero only) 5 Filter Blocking Tendency ASTM D2068* 6 Total Water using Karl Fischer ASTM 6304

*The test method following Procedure B of ASTM D2068 (using Whatman Puradisc 13mm diameter GF/A glass microfibre syringe filters, Part No. 6820-1316 or 6806-1316) was used.

4.3.2 Engine fuel filters Deposits on fuel filter elements and fuel/water separator elements were tested as follows:

• Varian 450 Gas Chromatograph (GC) with a 30 meter X 0.25 mm ID X 250um film of 5%cyano/95% polydimethylsiloxane (PDMS) (DB-5 equivalent)

• Varian 320 Mass Spectrometer. The MS will be operated in Full Scan mode scanning from 50 to 500 atomic mass units

Notes of sub-sampling were taken to help ascertain the condition of the filters. Chemical reference materials such as Sitosterol, Stigmasterol, Cholesterol, Cholestanol, Monolinolein, Monolinolenin, Monopalmitin, Monolaurin, and Monostearin were purchased in order to focus on specific monoglycerides and sterols. Other compounds found (ie. Tocopherol) were also investigated. B100 of varying sources was also analyzed to help identify potential compounds specific to biodiesel that may be of interest. All extracts were run at varying levels of dilution using the split mode capabilities of the GC, as there were significant interferences from the diesel in the filters. In order to assist in identifying unknown materials, the NIST 2005 mass spectral library (contains ~ 100,000 spectra) was used. Results were semi-quantitative due to the nature of open-scan gas-chromatography-mass spectrometry (GC/MS).

7

5. Results

5.1 Biodiesel samples

5.1.1 Biodiesel Demonstration in Manitoba The biodiesel blend for samples taken from harvest equipment stored since the 2008 harvest season was determined according to ASTM D7371. All blends are less than B5, as shown by the results in Table 3 below. The results obtained from the MacDon swather show that the fuel was, in fact, not a biodiesel blend. As a result, all testing on samples SW-1 and SW-2 were suspended, and no results will be reported for these samples. Table 3. Percentage Biodiesel Blend Results Summary

Item Equipment Type Sample No.

Sample Time Biodiesel% v/v

1 CAT 465 Combine 515-1 Before running engine 1.7 515-2 After running engine for ½ hr 1.7

2 CAT 465 Combine 516-1 Before running engine 2.8 516-2 After running engine for ½ hr 2.7

3 CAT 480R Combine 480R-1 Before running engine 4.2 480R-2 After running engine for ½ hr 4.3

4 MacDon Swather SW-1 Before running engine <0.1 SW-2 After running engine for ½ hr <0.1

Because all blends are less than B5, the results of these test samples are compared to CAN/CGSB-3.520 Automotive Low-Sulphur Diesel Fuel Containing Low Levels of Biodiesel Esters (B1-B5) in Table 4, on the following page. Table 5, on page 11, is a summary of the remaining samples identified as essential for analysis: oxidative stability, acid number, sediment/total insolubles, filter blocking tendency, and total water using Karl Fischer. The full certificate of analysis reports from Manitoba Hydro are found in Appendix III.

8

Table 4 below summarizes the results of biodiesel analysis for specifications following of CAN/CGSB 3.520. These fuel samples were collected from the Caterpillar 465 combine serial number 3HZ00515, Caterpillar 465 combine serial number 3HZ00516, and Caterpillar 480R combine. Samples ending with a -1 were collected before the engine was run, and samples ending with a -2 were collected after the filters were replaced and the engine was run for ½ hour.

Table 4. Results of equipment biodiesel analysis as per CAN/CGSB-3.520

Test Name Test Method

Units Limits from CAN/CGSB-3.520-2005

Caterpillar 480R Combine

Caterpillar 465 Combine Serial no. 3HZ00515


Sample 480R-1

Sample 480R-2

Sample 515-1

Sample 515-2

Sample 516-1

Sample 516-2

Biodiesel Blend Determination

ASTM D7371

% B1-B5 4.2 4.3 1.7 1.7 2.8 2.7

Cloud Point ASTM D2500

°C N/A -27.5 -28.9 -29.3 -28.4 -29.9 -21.4

Flash Point ASTM D93

°C Minimum 40 43 44 48 48 54 54

Kinematic Viscosity @40C

ASTM D445

mm2/s 1.70-4.10 2.30 2.30 2.39 2.40 2.25 2.20

Distillation Temperature, 90% recovery

ASTM D86

°C 360.0 314.6 315.0 320.8 321.9 311.0 311.3

Water & Sediment by Centrifuge

ASTM D2709

% Maximum 0.05 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005

Total Acid Number ASTM D664

mg KOH/g Maximum 0.10 0.01 0.01 <0.01 <0.01 0.01 0.01

Sulphur ASTM D5453

μg/g (ppm)Maximum 500 mg/kg

6.7 6.4 9.2 7.9 10.5 10.6

Copper Corrosion @ 100C

ASTM D130

N/A Maximum No.1 1a 1a 1a 1a 1a 1a

Carbon Residue ASTM D4530

% Maximum 0.16 0.005 0.006 0.012 <0.004 <0.004 <0.004

Ash ASTM D482

% Maximum 0.010 <0.002 <0.002 <0.002 0.002 0.002 0.002

Cetane Number ASTM D6890

N/A Minimum 40.0 43.11 42.21 42.51 42.81 42.73 42.31

Lubricity by HFRR – Minor axis

ASTM D6079

mm

Maximum wear scar 460μm at 60C

0.230 0.210 0.280 0.260 0.240 0.220

Lubricity by HFRR – Major axis

mm 0.360 0.290 0.340 0.340 0.300 0.300

Lubricity by HFRR – Wear Scar diameter

μm 290 250 310 300 270 260

9

Table 5 below summarizes the results of biodiesel analysis for additional tests as specified in the project outline. These fuel samples were collected from the Caterpillar 465 combine serial number 3HZ00515, Caterpillar 465 combine serial number 3HZ00516, and Caterpillar 480R combine. Samples ending with a -1 were collected before the engine was run, and samples ending with a -2 were collected after the filters were replaced and the engine was run for ½ hour. Table 5. Results of equipment biodiesel analysis – additional testing. Test Name Test

Method Units Caterpillar 480R

Combine Caterpillar 465

Combine Serial no. 3HZ00515


Sample 480R-1

Sample 480R-2

Sample 515-1

Sample 515-2

Sample 516-1

Sample 516-2

Filer Blocking Tendency, Procedure B

ASTM D2068

units 1.2 1.3 1.0 1.0 1.0 1.1

Oxidative Stability EN

15751 hours 7.6 7.7 6.1 6.2 4.4 4.4

Specific Gravity ASTM D1298

units 0.8483 0.8481 0.8483 0.8479 0.8474 0.8476

Water & Sediment

ASTM D4625

mg/100mL 0.40 0.60 0.28 0.32 0.38 0.25

Filterable insolubles (reported in remarks section)

mg 1.1 1.1 0.2 0.3 1.4 0.8

Adherent insolubles (reported in remarks section)

mg 0.5 1.3 0.9 1.0 0.1 0.2

Water (Oven and Coulometric KF Titration)

ASTM D6304

μg/g (ppm) 34 28 27 23 45 34

10

5.1.2 PAMI Biodiesel Stored On-site The full certificate of analysis reports from Manitoba Hydro are found in Appendix IV. The biodiesel blend for samples taken from the PAMI biodiesel stored on-site since March 2008 was determined according to ASTM D7371. The results are provided in Table 6 below. Table 6. Percentage Biodiesel Blend Results Summary for PAMI biodiesel Blend/Sample Number Biodiesel

% v/v PAMI B5 5.3% PAMI B10 10.1% PAMI B20 20.2% PAMI Diesel <0.1%

The PAMI biodiesel results for B10 and B20 will be compared to ASTM D7467 Standard Specification for Diesel Fuel Oil, Biodiesel Blend (B6 to B20) in Table 7 on page 13. The PAMI biodiesel results for the B% blend will be compared to CAN/CGSB-3.520 Automotive Low-Sulphur Diesel Fuel Containing Low Levels of Biodiesel Esters (B1-B5) in Table 8 on page 14. The results for PAMI diesel will be compared to CAN/CGSB-3.517 Automotive (On-Road Diesel Fuel) and ASTM D975 Standard Specification for Diesel Fuel Oils in Table 9 on page 15. Additional test results for all samples are found in Table 10 on page 16.

11

Table 7 below summarizes the results of the B10 and B20 biodiesel analysis for the fuel samples collected from the fuel stored since 2007 on-site at PAMI. This biodiesel is compared to the specifications of ASTM D7467. Table 7. Fuel analysis results for the PAMI B10 and B20 biodiesel.

Test Name Test Method Units Limits from ASTM D7467

Sample: PAMI B10

Sample:PAMI B20

Total Acid Number ASTM D664 mg KOH/g Max 0.3 0.05 0.10

Kinematic Viscosity @ 40°C

ASTM D445 mm2/s 1.9-4.1 2.45 2.58

Flash Point ASTM D93 °C Min 52 68 70

Cloud Point ASTM D2500 °C N/A -29.7 -23.7

Sulphur ASTM D5453 μg/g (ppm) Max 15 4.9 4.9


ASTM D86 °C Max 343 322.2 331.5

Carbon Residue ASTM D4530 % Max 0.35 <0.004 0.005

Cetane Number ASTM D6890 N/A Min 40 41.64 43.92

Ash ASTM D482 % Max 0.01 <0.002 <0.002


ASTM D2709 % Max 0.05 <0.005 <0.005

Copper Corrosion @ 100C

ASTM D130 N/A No.3 1a 1a


ASTM D7371 % 6-20 10.1 20.2

Oxidative Stability EN 15751 hours Min 6 12.3 6.2

Lubricity by HFRR ASTM D6079 Wear scar

diameter (μg) Max 520 μg 310 230

12

Table 8 below summarizes the results of the B5 biodiesel analysis for the fuel samples collected from the fuel stored since 2007 on-site at PAMI. This biodiesel is compared to the specifications of CAN/CGSB-3.520. Table 8. Fuel analysis results for the PAMI B5 biodiesel.

Test Name Test Method Units Limits from CAN/CGSB-3.520-2005

PAMI B5 Biodiesel sample

Biodiesel Blend determination ASTM D7371 % B1-B5 5.3

Cloud Point ASTM D2500 °C N/A -34.4

Flash Point ASTM D93 °C Minimum 40 68

Kinematic Viscosity @40C ASTM D445 mm2/s 1.70-4.10 2.39


ASTM D86 °C Maximum 360.0 314.9

Water & Sediment by Centrifuge ASTM D2709 % Maximum 0.05 <0.005

Total Acid Number ASTM D664 mg KOH/g Maximum 0.10 0.02

Sulphur ASTM D5453 μg/g (ppm) Maximum 500 mg/kg 5.4

Copper Corrosion @ 100C ASTM D130 N/A Maximum No.1 1a

Carbon Residue ASTM D4530 % Maximum 0.16 <0.004

Ash ASTM D482 % Maximum 0.010 <0.002

Cetane Number ASTM D6890 N/A Minimum 40.0 41.50


ASTM D6079

mm


0.410

Lubricity by HFRR – Major axis mm 0.440


μm 420

13

Table 9 below summarizes the results of biodiesel analysis for additional tests as specified in the project outline. These fuel samples were collected from PAMI on-site storage tanks, including regular diesel fuel, a B5 blend, a B10 blend, and a B20 blend. Table 9. Results of equipment biodiesel analysis – additional testing

Test Name Test Method

Units Sample:PAMI Diesel

Sample:PAMI B5

Sample: PAMI B10

Sample:PAMI B20

Filer Blocking Tendency, Procedure B

ASTM D2068

N/A 1.0 1.0 1.0 1.0

Oxidative Stability EN 15751 hours 12.4 15.2 12.3 6.2

Specific Gravity ASTM D1298

N/A 0.8556 0.8573 0.8591 0.8606

Water & Sediment

ASTM D4625

mg/100mL 0.05 0.10 0.18 0.20

Filterable insolubles (reported in remarks section)

mg 0.2 0.2 0.2 0.1

Adherent insolubles (reported in remarks section)

mg 0 0.2 0.5 0.7

Water (Oven and Coulometric KF Titration)

ASTM D6304

μg/g (ppm) 4 5 8 9

14

Table 10 below summarizes the results of the diesel fuel analysis for the fuel samples collected from the fuel stored since 2007 on-site at PAMI. This is compared to the specifications of CAN/CGSB-3.517 and ASTM D975. Table 10. Fuel analysis results for the PAMI diesel.

Test Name Test Method Units Limits from CAN/CGSB-

3.517-2007 PAMI Diesel

Biodiesel Blend determination

ASTM D7371 % N/A <0.1

Cloud Point ASTM D2500 °C N/A -41.5

Flash Point ASTM D93 °C Minimum 40 64

Kinematic Viscosity @40C ASTM D445 mm2/s 1.70-4.10 2.30


ASTM D86 °C Maximum 360.0 305.2


ASTM D2709 % Maximum 0.05 <0.005

Total Acid Number ASTM D664 mg KOH/g Maximum 0.10 <0.01

Sulphur ASTM D5453 μg/g (ppm) Maximum 500 mg/kg 5.6

Copper Corrosion @ 100C ASTM D130 N/A Maximum No.1 1b

Carbon Residue ASTM D4530 % Maximum 0.2 <0.004

Ash ASTM D482 % Maximum 0.010 <0.002

Cetane Number ASTM D6890 N/A Minimum 40.0 39.8


ASTM D6079

mm


0.270

Lubricity by HFRR – Major axis

mm 0.410


μm 340

15

5.2 Engine fuel filters In addition to the biodiesel samples collected from the equipment involved in the on-farm biodiesel demonstration, a total of sixteen fuel filters were collected for analysis. Gas chromatography-mass spectrometry (GC/MS) was used to analyze the compounds on the filter elements, in order to understand the effect biodiesel blends had on fuel filters when equipment is stored over seasons. The results are summarized in Tables 11 thru 13 on the following pages, with compounds not detected in the samples listed as ND. Full GC/MS results from Manitoba Hydro are provided in Appendix VI.

5.2.1 CAT 465 Combine, Serial No. 3HZ00515 Table 11 below summarizes the results of the GC/MS analysis for the fuel/water separators and the engine fuel filters from the CAT 465 combine, serial number 3HZ00515. The original filters were removed for testing and new filters installed prior to the ½ hour engine run. The new filters were then removed for testing.

Table 11. Summary of Analysis of Fuel Separators from the CAT 465 Combine. Compound Name* Fuel/water

Separator Primary (left)

Fuel Filter Secondary (right)

Fuel Filter

Results Before ½ Hour Run (Total μg)

Results After ½

Hour Run (Total μg)

Results Before ½ Hour Run(Total μg)

Results After ½



Results After ½

Hour Run(Total μg)

beta-Sitosterol TMS 330 208 ND ND 53 ND

Cholesterol TMS ND ND ND ND ND ND

Monoolein TMS 463 ND ND ND ND ND

Monopalmitin TMS 115 ND ND ND ND ND

Monostearin TMS 185 ND 56 ND 110 ND

Stigmasterol TMS 166 151 ND ND ND ND

Tocopherol TMS 710 498 167 160 89 166

*For compounds listed, TMS: trimethyl-silyl

16

5.2.2 CAT 465 Combine, Serial No. 3HZ00516 Table 12 below summarizes the results of the GC/MS analysis for the fuel/water separators and the engine fuel filters from the CAT 465 combine, serial number 3HZ00516. The original filters were removed for testing and new filters installed prior to the ½ hour engine run. The new filters were then removed for testing.

Table 12. Summary of Analysis of Fuel Separators from the CAT 465 Combine Compound Name* Fuel/water separators Primary (left) fuel Filter Secondary (right) fuel

Filter


Results After ½



Results After ½



Results After ½

Hour Run(Total μg)

beta-Sitosterol TMS 305 327 ND 83 ND 91

Cholesterol TMS 161 172 ND 52 ND 60

Monoolein TMS 3,951 1,404 899 873 834 1,534

Monopalmitin TMS 534 ND 134 136 131 159

Monostearin TMS 291 115 80 75 72 96

Stigmasterol TMS 185 151 ND ND ND ND

Tocopherol TMS 485 508 97 105 99 140


17

5.2.3 CAT 480R Combine

Table 13, below summarizes the results of the GC/MS analysis for the fuel/water separators and the engine fuel filters from the CAT 480R combine. The original filters were removed for testing and new filters installed prior to the ½ hour engine run. The new filters were then removed for testing.

Table 13. Summary of Analysis of Fuel Filters from the CAT 480R Combine Compound Name* Fuel/water Separator Primary Fuel Filter


Results After ½



Results After ½


beta-Sitosterol TMS 618 754 182 85

Cholesterol TMS 296 275 64 ND

Monoolein TMS 5,233 2,739 1,144 536

Monopalmitin TMS 804 ND 192 85

Monostearin TMS 804 194 217 61

Stigmasterol TMS 345 374 98 ND

Tocopherol TMS 3,183 1,935 1,263 1,120


18

5.3 Long-term Storage Temperature Data The seasonal variations in temperature are a naturally occurring challenge to the long-term storage of biodiesel blends. The temperature data presented in Graph 1 below is for Winnipeg, MB, representing the Environment Canada monitoring station located nearest to Beausejour, MB, where all three Cat combines are located. The temperature data presented in Graph 2 is for the PAMI on-site storage tanks, which are located in Portage la Prairie, MB. Winnipeg is approximately one hour from the both Beausejour and Portage la Prairie, MB and represents the nearest Environment Canada monitoring station with historical data. Graph 1: Temperature Data for Biodiesel Stored in Equipment as Part of the On-Farm Biodiesel Demonstration: October 2008 – August 2009.

Based on Environment Canada Data.

19

Graph 2: Temperature Data for Biodiesel Stored in Above-Ground Storage Tanks as part of PAMI Research Project: January 2008 – January 2010.

Based on Environment Canada Data.

20

6. Data Analysis and Discussion

6.1 Observations

6.1.1 Storage Conditions – Combines Before discussing the results of the combine fuel samples, it is worthwhile to include additional details on the storage conditions of the three Caterpillar combines. The storage conditions were not specified as part of the testing, but they are noted here for information. All three Caterpillar combines used in the biodiesel demonstration project are owned by the same farmer, located near Beausejour, MB. The Caterpillar 465 combine, serial no. 3HZ00515, had 2222 hours on it at the time of fuel sampling. On the digital cab display, the fuel gauge showed four bars, which is below ¼ full. The Caterpillar 465 combine, serial no. 3HZ00516, had 2357 hours on it at the time of fuel sampling. On the digital cab display, the fuel gauge showed only one bar remaining, and the display also read “Fuel tank content <10%.” The Caterpillar 480R combine had 1375 hours on it at the time of fuel sampling. The digital cab display showed that the combine had been stored with ¾ tank of fuel. The combines were all stored in a non-insulated, covered storage shed. In this environment, the combines will still experience ambient outdoor temperatures, including the daily variations in temperature as well as the seasonal variations in temperature. The covered shed will protect the machines from experiencing extreme daily temperature swings that may occur due to exposure to direct sunlight or strong wind chills. Two different models of Caterpillar combines were used in testing. Caterpillar combine model 465 has a 3126 engine. This engine consumes fuel at a rate of 55.2L/hr at full load, and the maximum allowable fuel return flow is approximately 113L/hr. This means that during the ½ hour run at high idle, the new fuel filters could have filtered as much as 84.1L of biodiesel. Because the engine was running at high idle but not under full load, it is expected that the actual filtered volume is less.

21

The Caterpillar model 480R has a C-12 engine. This engine consumes fuel at a rate of 71.4L/hr at full load, and the maximum allowable fuel return flow is approximately 402.7L/hr. This means that during the ½ hour run at high idle, the new fuel filters could have filtered as much as 237L of biodiesel. Because the engine was running at high idle but not under full load, it is expected that the actual filtered volume is less.

6.1.2 Specification Fuel Tests – Combine samples All six fuel samples taken from the three combines met the biodiesel specifications for CAN/CGSB 3.520. All six fuel samples taken from the three combines also met the specifications for ASTM D975 Standard Specification for Diesel Fuel Oils, when taking into consideration the following notes. Point 7.3.2 of this specification states that “Diesel fuel oil containing up to 5 vol% biodiesel shall meet the requirements for the appropriate grade No.1 or No.2-D fuel, as listed in Table 1.” In the case of these samples, the cloud point of all samples was below -12C, indicating that the fuel was a blend of No.1 and No.2. This means that the acceptance criteria for the minimum flash point is 38C, the minimum required viscosity at 40C is 1.7mm2/s, and the minimum 90% recovered temperature is waived (see footnote E to table 1 in ASTM D975). The cloud point value of sample 516-2 appears to be an outlier in the data. While all other sample results ranged between -27.5C and -29.9C, this sample had a cloud point value of -21.4C. Because of this, samples 516-1 and 516-2 were re-tested for cloud point. The result for 516-2 was -21.6C, confirming the original result. The certificate of analysis report from Manitoba Hydro for the retest results are found in Appendix V. Sample 516-1 retest came back with a result of -19.9C, 10C higher than the original sample. This limited data shows that the cloud point did not change significantly from the original sample to the sample taken after the ½ hour run.

22

6.1.3 Additional Testing – Combine samples Five additional tests were performed on the combine samples: Oxidative stability, acid number, sediment/total insolubles analysis, filter blocking tendency, and total water determined by Coulometric Karl Fischer titration. These tests have been identified as possible indicators of biodiesel contamination or degradation.

6.1.3.1 Filter Blocking Tendency Filter blocking tendency is a method of evaluating the cleanliness of fuels, including biodiesel. ASTM D2068 states under point 5.6 that filter blocking tendency values may range anywhere from 1 to greater than 100. A fuel with a filter blocking tendency of 1 has very good filterability. The filter blocking tendency for the combine samples ranged from 1.0 – 1.6. There were no significant differences observed when comparing sample 1 and sample 2 for any combine. Based on these results and the comments from ASTM D2068, it can be concluded that the fuel found in the combines had good filterability.

6.1.3.2 Oxidative Stability Oxidative stability is a specification requirement for biodiesel blends B6 and greater, as well as B100 biodiesel blend stock. The minimum required oxidative stability for blends B6 and greater is six hours (ASTM D7467). The oxidative stability requirement for B100 biodiesel blend stock is 3 hours (ASTM D6751). Oxidative stability is not a specification requirement for biodiesel blends B5 and less. Taking this into consideration, an oxidative stability minimum of six hours will be used as a point of reference for discussion purposes. The oxidative stability results for the combine samples ranged from 7.7 hours to 4.4 hours. Samples 480R-1 and 480R-2 reported the highest oxidative stability at 7.6 hours and 7.7 hours. Combine 480R was also the machine stored with ¾ tank of fuel. Samples 515-1 and 515-2 were slightly lower, but were still above six hours, at 6.1 hours and 6.2 hours. These results are from the Caterpillar 465 combine, stored with less than ¼ tank of fuel. Samples 516-1 and 516-2 had oxidative stability results of less than six hours, each reporting 4.4 hours. These results correspond with the Caterpillar 465 combine stored with less than 10% fuel remaining in the tank, the least amount of fuel.

23

In CAN/CGSB-3.520-2005, appendix C, section 12 states “reports from Europe indicate that simple organic acids, such as formic and acetic acid, which can be formed by oxidative degradation of biodiesel esters, are more corrosive than long-chain fatty acids which can be left in biodiesel esters from the manufacturing process.” Based on this statement, a possible link may be expected between increasing oxidative degradation as indicated by a decreasing oxidative stability value, and an increasing total acid number. However, in this data set, no correlation can be drawn between the oxidative stability and the total acid number. Total acid for samples 480R-1, 480R-2, 516-1, and 516-2 were all 0.01mg KOH/g, well below the limit of 0.10 mg KOH/g. Total acid for 515-1 and 515-2 were reported as <0.01 mg KOH/g, again well below the acceptable limit specified in CAN/CGSB-3.520. A possible cause of the lower oxidative stability values is the fact that this combine was stored with less than 10% fuel remaining in the tank. The cloud point for samples 516-1 and 516-2 were noticeably higher than the other four fuel samples. However, other tests that also indicate fuel degradation such as water and sediment, copper corrosion, and lubricity, did not show any out of specification or out of trend results. This leads to the question of best practices for the long-term storage of equipment. Typically, equipment is not stored with near-empty fuel tanks. Recommended practice for fuel storage conditions for diesel fuel according to X3.7.1 of ASTM D975 and biodiesel blends (B6 – B20) according to X2.7.1 of ASTM D7467 state “Fixed roof tanks should be kept full to limit oxygen supply and tank breathing.” Similarly, consideration should also be given to the level of fuel being stored in equipment fuel tanks.

6.1.3.3 Sediment/Total Insolubles (ASTM D4625) and Water (D6304) Filter plugging can be caused by sediment and water in diesel fuel. The current standards for diesel, as well as low-level biodiesel blends, specify ASTM D2709 Water & Sediment by Centrifuge as the approved test method. ASTM D4625 “Test Method for Middle Distillate Fuel Storage Stability at 43C” also has a test method for the determination of water and sediment. In addition to ASTM D2709, ASTM D6304 and ASTM D4625 (water and sediment determination method at time zero) were both used to test the biodiesel samples for sediment, total insolubles, and water for this project. For water by ASTM D6304, the results ranged from 23-45 ppm. One observation that can be made, with respect to these results, is that the water sample of each sample 1 (samples taken before the combines were run) show higher water content than each sample 2 (samples taken after the combines had been run for ½ hour).

24

Water and sediment by ASTM D4625 ranged from 0.28 – 0.60 mg/100mL. There are no discernible trends in the data set to make any conclusions about the quality of the biodiesel found in the combines based on water and sediment.

6.1.4 GC/MS Analysis – Combine Fuel Filters It is difficult to fully assess the level of contaminant present in the individual fuel filters tested through the GC-MS process. The process is semi-quantative in nature and, although compounds are present in the filters, it is not necessarily an indication of plugging.

GC-MS was selected as the tool of choice to identify substances present on the filter elements due to its ability to definitively determine compounds. Because GC-MS was used for the compound determination and blended biodiesel was the fuel being studied, a procedure other than ASTM D6584 was required. ASTM D6584 is the standard test method of free and total glycerine determination in B-100 biodiesel methyl esters by gas chromatography. Although the ASTM D6584 was not applicable for this testing, an equivalent column to that specified in ASTM D6584 was used for this testing.

The focus of the GC-MS analysis of the substances on the filter elements was to detect the presence of monoglycerides and sterol glucosides. A build-up of these compounds may pose the risk of reducing the filter performance and eventual filter plugging. The presence of these compounds on the filter is expected with biodiesel, but it is unknown at what levels they will begin to have a negative effect on the filter performance and fuel flow. It is expected that these characteristics will vary from machine to machine. Testing of the fuel from the combines for filter blocking tendency showed that the fuel had good filterability.

The analysis performed identified the presence of monoglycerides (Monoolein, Monopalmitin and Monstearin) and sterols (beta-Sitosterol and Sigmasterol) in several of the filters, although a definitive pattern was not detected. For the three combines, almost all samples in the fuel/water separator had higher levels of all compounds than the fuel filters downstream. In addition to the presence of the monoglycerides and sterols, Tocopherol was present in all filter samples.

25

6.1.5 Storage Conditions – PAMI Diesel and Biodiesel Storage The PAMI diesel and biodiesel blends used in the 2008 research project were stored in new outdoor, above-ground storage tanks. These tanks are white, and each one has a capacity of 4100L. The tanks were located alongside the PAMI building under a grey tarp enclosure (as shown in Figure 57-59 of Section 7) until May 2008, when they were relocated to the south side of the building. As part of the relocation process, the content of a tank was pumped into a transfer tank of unknown history, the storage tank was relocated, and the fuel was pumped back into the storage tank from the transfer tank. The grey tarp enclosure was not moved with the tanks. The tank storing the B5 biodiesel blend had approximately 1000L remaining in the tank at the time of sampling. The tank storing the B10 blend had approximately 2000L remaining in the tank at the time of sampling. The tank storing the B20 biodiesel blend had approximately 1000L remaining in it at the time of sampling. The PAMI diesel was stored in a grey storage tank with approximately 1200L capacity after the initial research project. There was approximately 500L remaining in the tank at the time of sampling.

6.1.6 Specification Fuel Tests – PAMI Diesel and Biodiesel The PAMI B5 biodiesel met the specifications for CAN/CGSB-3.520 and ASTM D975. The PAMI B10 and B20 met the specifications for ASTM D7467. The PAMI diesel met the specifications for CAN/CGSB-3.517, with the exception of cetane number. The minimum acceptable cetane value for CAN/CGSB-3.517 is 40.0. The measured cetane number for the PAMI diesel was 39.82. However, this value does meet the criteria for ASTM D975, which requires a minimum cetane value of 40 for diesel fuel. This ASTM also states under appendix X1.4 that “Increase in cetane number over values actually required does not materially improve engine performance. Accordingly, the cetane number specified should be as low as possible to assure maximum fuel availability.” What is most critical for this study is that all PAMI biodiesel blends made with this diesel met the specification for cetane number.

26

The oxidative stability of the PAMI B20 biodiesel was found to be approximately half of the value of the other PAMI samples: the PAMI B20 blend oxidative stability was 6.2 hours, the PAMI diesel was 12.4 hours, the PAMI B5 biodiesel was 15.2 hours, and the PAMI B10 biodiesel was 12.3 hours. This is discussed in section 6.1.7.2 below.

6.1.7 Additional Testing – PAMI Diesel and Biodiesel Samples Five additional tests were performed on the PAMI diesel and biodiesel samples: oxidative stability, acid number, sediment/total insolubles analysis, filter blocking tendency, and total water determined by Coulometric Karl Fischer titration. These tests have been identified as possible indicators of biodiesel contamination or degradation.

6.1.7.1 Filter Blocking Tendency As stated in section 6.1.3.1, filter blocking tendency is a measure of evaluating the cleanliness of fuels. Values may range anywhere from 1 to greater than 10. A fuel with a filter blocking tendency of 1 has very good filterability. All PAMI diesel and biodiesel samples reported a filter blocking tendency value of 1.0, indicating that after two years of storage in ambient temperatures ranging from above +30C to below -30C, the fuel has retained good filterability characteristics. This finding may hold significance when evaluated in conjunction with the test results from ASTM D4625 (Water and Sediment) and ASTM D6304 (Determination of Water in Petroleum Products, Lubricating Oils, and Additives by Coulometric Karl Fischer Titration). Although there is a definite upward trend in the water and sediment results, the adherent insolubles, and the water by ASTM D6304, the filter blocking tendency remains unchanged. These characteristics of biodiesel are known to cause filtration issues, but according to these results, a clear the relationship between filter blocking tendency and any one or a matrix of these fuel characteristics was not identified. Future research may reveal the basis for this relationship.

6.1.7.2 Oxidative Stability Oxidative stability is a specification requirement for biodiesel blends B6 and greater, as well as B100 biodiesel blend stock. The minimum required oxidative stability for blends B6 and greater is six hours (ASTM D7467). The oxidative stability requirement for B100 biodiesel blend stock is 3 hours (ASTM D6751).

27

All PAMI diesel and biodiesel samples met the acceptance criteria for oxidative stability. However, the result of 6.2 hours for the B20 blend appears to be an outlier. To determine if there is a relationship between the blend ratio and a “normal” or “expected” oxidative stability value, the results from the combine samples can be used for comparison. All combine samples were less than a B5 blend. These samples ranged in value from 7.7-4.4 hours for oxidative stability. The PAMI B5 blend, which had been stored for a longer period of time than the combine biodiesel, had an oxidative stability value of 15.2 hours, which is more than double the combine samples values. From this limited data set, there does not appear to be a relationship between oxidative stability and blend concentration. Oxidative stability has been directly linked with total acid number (CAN/CGSB-3.520-2005, Appendix C, sec.12). Comparing these two values for the PAMI diesel and biodiesel does reveal some correlation, as shown in Table 14 below. Table 14. Summary of Oxidative Stability and Total Acid Number Fuel Oxidative Stability Total Acid Number

PAMI diesel 12.4 hours <0.01mg KOH/g

PAMI B5 15.2 hours 0.02 mg KOH/g



As a general observation, the oxidative stability decreases as the total acid number increases. However, this observation was not made in the combine biodiesel samples. They all reported total acid values of 0.01 mg KOH/g or less, and yet they also had lower oxidative stability values than the PAMI biodiesels with higher total acid numbers. This study did not attempt to control the biodiesel storage conditions, such as the condition of the storage tanks, the percent fill volume of the tanks, or the condition of other auxiliary devices that may have come in contact with the biodiesel (such as transfer pumps). Without this control, it is not possible to draw any firm conclusions as to the cause of the lower oxidative stability for the B20 biodiesel blend. While the oxidative stability is lower than the other samples, it still meets the required specification. Further research under controlled field conditions could be used to investigate variables affecting oxidative stability.

28

6.1.7.3 Sediment/Total Insolubles (ASTM D4625) and Water (D6304)

As stated in 6.1.3.3 above, filter plugging can be caused by sediment and water in diesel fuel. For this project, ASTM D6304 and ASTM D4625 (water and sediment determination method at time zero) were both used to test the biodiesel samples for sediment, total insolubles, and water. The results using both test methods show an increasing trend in water and sediment, adherent insolubles, and water determined by Coulometric Karl Fischer titration as the biodiesel blend concentration increased. This is a logical result; given the statement that biodiesel has a greater affinity for water. It can be expected that the higher the biodiesel blend concentration, the higher the water content. The adherent insoluble results are also logical, as the samples range from straight diesel with 0.0mg of insoluble adherents to a B20 biodiesel blend with the highest amount of adherent insolubles of 0.7mg.

29

7. Project Photos

7.1 Fuel Filter and Fuel/Water Filter Photos

7.1.1 Caterpillar Lexion 465 Combine

Figure 1. Caterpillar Lexion 465 Combine.

Figure 2. Configuration of fuel tank.

Fuel Tank

Fuel/Water Separator Location

Engine Compartment Location

30

Figure 3. Location of fuel/water separator.

Figure 4. Photo of underside of fuel/water separator head where fuel samples were taken.


Fuel/Water Separator Filter Head Where Fuel Samples Were Taken From

31

Figure 5. Location of engine fuel filters.

Left Fuel Filter Designated with an “L” During Sampling

Right Fuel Filter Designated with an “R” During Sampling (Filter immediately before injector pump)

32

7.1.2 Caterpillar Lexion 480R Combine

Figure 6. Caterpillar Lexion 480R Combine.

Figure 7. Configuration of fuel tank on 480R combine.

Engine Compartment Location


Fuel Tank Location

Fuel Tank

33

Figure 8. Location of fuel/water separator.

Figure 9. Photo of underside of fuel/water separator head where fuel samples were taken.


34

Figure 10. Location of Engine Fuel Filters.

Location of Engine Fuel Filter

35

7.1.3 MacDon 9300 Windrower

Figure 11. MacDon 9300 Windrower.

Figure 12. Location of engine compartment and fuel tank.

Engine Compartment

Fuel Tank

36

Figure 13. Location of fuel filters and fuel sample location.

Engine Fuel Filter

Fuel/Water Separator

Engine Fuel Supply Line Where Fuel Samples Were Collected

37

7.2 Filter Analysis The fuel filters and fuel/water separators were opened up to expose the filter element using a filter housing cutter as shown below.

Figure 14. Fuel filter housing cutter used during project.

38

7.3 Photos from Filter Analysis Photos taken during the filter analysis portion of the project are provided below and on the following pates. Photos of the contents at the bottom of the fuel/water separators are provided for the three CAT combines. No photos are available for the MacDon windrower since the fuel/water separator elements did not have clear bowl attached like the CAT fuel/water separators.

7.3.1 CAT 465 Combine, Serial No. 3HZ00515 7.3.1.1 Fuel/Water Separator, Sample No15-1

Figure 15. Contents of sediment bowl before filter analysis.

39

Figure 16. Filter element before analysis.

Figure 17. Remaining filter sample extract after GC/MS analysis.

40

7.3.1.2 Left Fuel Filter, Sample No. 515-1L



41

7.3.1.3 Right Fuel Filter, Sample No. 515-1R



42

7.3.1.4 Fuel/Water Separator, Sample No. 515-2



43

Figure 24. Remaining filter sample extract after GC/MS analysis. 7.3.1.5 Left Fuel Filter, Sample No. 515-2L


44

Figure 26. Remaining filter sample extract after GC/MS analysis. 7.3.1.6 Right Fuel Filter, Sample No. 515-2R


45


7.3.2 CAT 465 Combine, Serial No. 3HZ00516 7.3.2.1 Fuel/Water Separator, Sample No. 516-1


46



47

7.3.2.2 Left Fuel Filter, Sample No. 516-1L



48

7.3.2.3 Right Fuel Filter, Sample No. 516-1R



49

7.3.2.4 Fuel/Water Separator, Sample No. 516-2



50

Figure 38. Remaining filter sample extract after GC/MS analysis. 7.3.2.5 Left Fuel Filter, Sample No. 516-2L


51

Figure 40. Remaining filter sample extract after GC/MS analysis. 7.3.2.6 Right Fuel Filter, Sample No. 516-2R


52


7.3.3 CAT 480R Combine 7.3.3.1 Fuel/Water Separator, Sample No. 480R-1


53



54

7.3.3.2 Fuel Filter, Sample No. 480R-1



55

7.3.3.3 Fuel/Water Separator, Sample No. 480R -2



56

Figure 50. Remaining filter sample extract after GC/MS analysis. 7.3.3.4 Fuel Filter, Sample No. 480R -2


57


7.3.4 MacDon 9300 Windrower 7.3.4.1 Fuel/Water Separator, Sample No. SW-2


58

Figure 54. Remaining filter sample extract after GC/MS analysis. 7.3.4.2 Fuel Filter, Sample No. SW-2


59


60

7.4 Photos of Above Ground Storage Tanks The following photos were are of the above ground storage tanks used to store the biodiesel and diesel fuel during the PAMI Project “Effect of Biodiesel Blend on Tractor Engine Performance”. The fuel storage tanks were located outside of the building in and enclosed in a heated shelter during testing. The fuel tanks were emptied into another fuel tank before being moved and refilled. Photos of the original tank location during the research project and subsequent storage location are below.

Figures 57 and 58. Original tank location during the PAMI research project on the east side of PAMI’s building.

Figure 59. Subsequent location of aboveground storage tanks on the south side of PAMI’s

building.

61

Appendix I

Results and Analysis:

Certificate of Analysis for B100 Biodiesel Used in 2008 On-Farm Biodiesel Demonstration

62

Appendix II


Certificate of Analysis for B100 Biodiesel Used in PAMI Research Project

Alberta Research Council ~ Fuels & Lubricants

Certified by the Standards Council of Canada as an Accredited TestingOrganization complying with the requirements of ISO/IEC 17025 for

Report of AnalysisThis report may only be reproduced in its entirety

specific tests registered with the Council

Page 1 of 2

Report GO-2007-5429

250 Karl Clark Road, Edmonton, Alberta, Canada T6N 1E4

Client: Milligan Bio Tech

Attention: Zenneth FayeBox 822 , Foam Lake, Saskatchewan, S0A 1AO

Laboratory Sample Number: GO-2007-5429Product: B100 Biodiesel

Specification: ASTM D6751-07b B100 Grade S15Date Received: 13-Dec-2007

Analysis Method Minimum Maximum Results Notes

Sample ReferenceMBTI-CF-DEC-s007-01

Fuel Filter Blocking Potential of Biodiesel (B100) Blend Stock by Cold Soak Laboratory Filtration

ASTM DXXXX 1

309.0360Filtration Time, seconds300Volume Filtered, mL

Flash Point, °C ASTM D93, Procedure A 159.093Alcohol Control ASTM D93, Procedure A

159.0130Flash Point, °CWater and Sediment, Volume % ASTM D2709 0.0000.050Kinematic Viscosity, mm2/s(cSt) ASTM D445

4.4051.9 6.0Clear, at 40 °CAsh, Sulfated, Mass % ASTM D874 0.0020.020Total Sulfur by Ultraviolet Fluorescence, mg/kg ASTM D5453 7.215Copper Corrosion ASTM D130 1aNo. 3Cetane Number ASTM D613 53.347Cloud Point, °C ASTM D5773 -1.4Carbon Residue, Mass % ASTM D4530 0.001 20.050Acid Number, mg KOH/g ASTM D664 0.490.50Test Method for Determination of Free and Total Glycerine in B-100 Biodiesel Methyl Ester by Gas Chromatography

ASTM D6584

0.0040.020Free Glycerin, mass %0.1060.240Total Glycerin, mass %0.353Monoglycerides, mass%0.055Diglycerides, mass %0.024Triglycerides, mass %

Inductively Coupled Argon Plasma EN 14107 modified 355.0Group I Metals (Na + K), mg/kg15.0Group II Metals (Ca + Mg), mg/kg210.0Phosphorus Content, mg/kg

Oxidation Stability, 110°C, hours EN 14112 10.73.0Water, mg/kg ASTM D6304,

Procedure A510 4500

Density, kg/m³, @ 15 °C ASTM D4052 883.6

Alberta Research Council ~ Fuels & Lubricants

Certified by the Standards Council of Canada as an Accredited TestingOrganization complying with the requirements of ISO/IEC 17025 for

Report of AnalysisThis report may only be reproduced in its entirety

specific tests registered with the Council

Page 2 of 2

Report GO-2007-5429

250 Karl Clark Road, Edmonton, Alberta, Canada T6N 1E4

Client: Milligan Bio Tech

Attention: Zenneth FayeBox 822 , Foam Lake, Saskatchewan, S0A 1AO

Laboratory Sample Number: GO-2007-5429Product: B100 Biodiesel

Specification: ASTM D6751-07b B100 Grade S15Date Received: 13-Dec-2007

Analysis Method Minimum Maximum Results Notes

Sample ReferenceMBTI-CF-DEC-s007-01

Distillation of Petroleum Products at Reduced Pressure, Atmospheric Equivalent Temperature (AET), % Recovered, °C

ASTM D1160

346.1IBP348.35%348.710%349.020%349.830%350.040%350.350%350.760%351.270%352.080%353.736090%358.095%425.9FBP

A ballot is currently being worked on to make the Cold Soak Filtration test an ASTM method. Since the Cold Soak Filtration method is not yet a standard ASTM method, ASTM has decided to include the Cold Soak Filtration method as an Annex in D 6751.

ASTM D6751 states that B100 intended for blending into diesel fuel shall give a maximum cold soak filtration limit of 360 seconds, and B100 that is expected to give satisfactory vehicle performance at fuel temperatures at or below -12°C (+10.4°F) shall comply with a maximum cold soak filtration limit of 200 seconds.ASTM D6751 Standard Specification for Biodiesel Fuel (B100) Blend Stock for Distillate Fuels states that for the carbon residue (ASTM D4530) a 100% sample is used to replace the 10% residual sample, with the calculation executed as if it were the 10% residual.The method was modified to include calcium, potassium, magnesium and sodium. A Conostan S21+K multielement standard was used in place of the single element standard described in the method.This test is under consideration but not yet adopted by ASTM. The data is provided for information purposes only. An industry accepted limit is listed in the table.

1

2

3

4

Notes and Remarks

The results obtained on your sample comply with the detailed requirements of ASTM Standard Specification for Biodiesel Fuel (B100) Blend Stock for Distillate Fuels (ASTM D6751-07b), Grade S15.

Signature:

Business Unit ManagerPhone: (780) 450-5108 Fax: (780) 988-9053

Date:

63

Appendix III


Certificate of Analysis from Manitoba Hydro for Biodiesel Samples Collected from On-Farm Biodiesel Demonstration Equipment

Certificate of Analysis Report

Grieger, Lorne

390 River Road Portage La Prairie R1N 3C5 [email protected]

PAMI - Blended Biodiesel for D7467 (Modified)

Report To: Phone: 204-239-5445 x229 Fax:

A2009-004575

Additional Information: ARC Inv #57042 pd 10/02/03

BiodieselMaterial:

480R-1 Fuel Sample Location:Sample Description:

A2009-004575-001

L. Grieger 2010/02/10Sample Date: Sampled By: Required by:

DefaultProfile:

Test Results

Acid Number by Buffer Endpoint Auto Titration

Result Units

Run No. Team

Analysis DateTest Name

4,669 S-Oil/Fuel

AnalystUncertainty

Total Acid Number 0.01 mg KOH/g 2010/01/14 IS

Ash

Result Units

Run No. Team


5,053 S-Oil/Fuel

AnalystUncertainty

Ash <0.002 % 2010/02/10 IS


Result Units

Run No. Team


4,544 S-Oil/Fuel

AnalystUncertainty

Biodiesel Blend Determination 4.2 % 2010/01/06 SP

Carbon Residue

Result Units

Run No. Team


4,541 S-Oil/Fuel

AnalystUncertainty

Carbon Residue 0.005 % 2010/01/14 JS

Cetane Number

Result Units

Run No. Team


4,533 S-Oil/Fuel

AnalystUncertainty

Cetane Number 43.11 2010/01/08 SP

Cloud Point - Automated

Result Units

Run No. Team


4,193 S-Oil/Fuel

AnalystUncertainty

Cloud Point -27.5 °C 2010/02/08 KS

Copper Corrosion by Copper Strip Tarnish Test

Result Units

Run No. Team


4,624 S-Oil/Fuel

AnalystUncertainty

Copper Corrosion @ 100C 1a N/A 2010/01/18 IS

Distillation Temperature - D86

Result Units

Run No. Team


4,535 S-Distillation

AnalystUncertainty

Initial boiling point 176.5 °C 2010/01/06 SP

Distillation temp - 10 C 203.9 °C 2010/01/06 SP






Page 1 of 152010/03/26Date Printed: A2009-004575

Brandon Laboratory Selkirk Laboratory Waverley Laboratory

3305 Victoria Ave E. 9567 Henderson Hwy 1840 Chevrier Blvd

Brandon, MB, R7A 7J8 East Selkirk, R1A 2B3 Winnipeg, MB, R3T 1Y6

(204) 578-3138 (204) 785-7142 (204) 360-4381

1Version: Folder Number:Print Time: 9:08:19AM






Filter blocking tendency (D2068)

Result Units

Run No. Team


4,502 Subcontract

AnalystUncertainty

Filter blocking tendency (D2068) 1.2 units 2010/03/26 ARC

Volume of fuel pumped No reading mL 2010/02/06 ARC

Pressure at end of test No reading kPa 2010/02/06 ARC

Sample temperature No reading °C 2010/02/06 ARC

Flash Point by Pensky-Martens Closed Cup

Result Units

Run No. Team


4,981 S-Oil/Fuel

AnalystUncertainty

Flash Point 43 °C 2010/02/08 KS

Lubricity by HFRR

Result Units

Run No. Team


4,782 S-Oil/Fuel

AnalystUncertainty

Minor axis 0.230 mm 2010/02/11 JS

Major axis 0.360 mm 2010/02/11 JS

Wear scar diameter 290 µm 2010/02/11 JS

Manual Kinematic Viscosity

Result Units

Run No. Team


4,623 S-Oil/Fuel

AnalystUncertainty

Kinematic Viscosity @ 40°C 2.30 mm²/s 2010/01/13 IS

Oxidative Stability (EN 15751)

Result Units

Run No. Team


4,502 Subcontract

AnalystUncertainty

Oxidative Stability (EN 15751) 7.6 hours 2010/02/06 ARC

Physical Properties by Automated Viscometer

Result Units

Run No. Team


5,011 S-Oil/Fuel

AnalystUncertainty

Specific Gravity 0.8483 units 2010/02/09 IS

Sulphur by UV Fluorescence

Result Units

Run No. Team


4,540 S-Oil/Fuel

AnalystUncertainty

Sulphur 6.7 µg/g (ppm) 2010/01/13 JS

Water and Sediment (D4625)

Result Units

Run No. Team


4,502 Subcontract

AnalystUncertainty

Water and Sediment (D4625) 0.40 mg/100mL 2010/02/06 ARC

Remarks: Filterable insolubles = 1.1 mg

Adherent insolubles = 0.5 mg

Total insolubles = 0.40 mg/100mL

Water and Sediment by Centrifuge

Result Units

Run No. Team


4,654 S-Oil/Fuel

AnalystUncertainty

Water & Sediment <0.005 % 2010/01/13 IS

Water by Oven and Coulometric KF Titration

Result Units

Run No. Team


4,506 S-Oil/Fuel

AnalystUncertainty

Water 34 µg/g (ppm) 2010/01/11 IS





(204) 578-3138 (204) 785-7142 (204) 360-4381



BiodieselMaterial:

480R-2 Fuel Sample Location:Sample Description:

A2009-004575-002


DefaultProfile:

Test Results


Result Units

Run No. Team


4,669 S-Oil/Fuel

AnalystUncertainty


Ash

Result Units

Run No. Team


5,053 S-Oil/Fuel

AnalystUncertainty

Ash <0.002 % 2010/02/10 IS


Result Units

Run No. Team


4,544 S-Oil/Fuel

AnalystUncertainty


Carbon Residue

Result Units

Run No. Team


4,541 S-Oil/Fuel

AnalystUncertainty


Cetane Number

Result Units

Run No. Team


4,533 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,193 S-Oil/Fuel

AnalystUncertainty

Cloud Point -28.9 °C 2010/02/08 KS


Result Units

Run No. Team


4,624 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team



AnalystUncertainty













Result Units

Run No. Team


4,502 Subcontract

AnalystUncertainty





(204) 578-3138 (204) 785-7142 (204) 360-4381








Result Units

Run No. Team


4,981 S-Oil/Fuel

AnalystUncertainty


Lubricity by HFRR

Result Units

Run No. Team


4,782 S-Oil/Fuel

AnalystUncertainty

Minor axis 0.210 mm 2010/02/11 JS

Major axis 0.290 mm 2010/02/11 JS



Result Units

Run No. Team


4,623 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,502 Subcontract

AnalystUncertainty



Result Units

Run No. Team


5,011 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,540 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,502 Subcontract

AnalystUncertainty






Result Units

Run No. Team


4,654 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,506 S-Oil/Fuel

AnalystUncertainty

Water 28 µg/g (ppm) 2010/01/11 IS

BiodieselMaterial:

515-1 Fuel Sample Location:Sample Description:

A2009-004575-003


DefaultProfile:





(204) 578-3138 (204) 785-7142 (204) 360-4381



Test Results


Result Units

Run No. Team


4,669 S-Oil/Fuel

AnalystUncertainty

Total Acid Number <.01 mg KOH/g 2010/01/14 IS

Ash

Result Units

Run No. Team


5,053 S-Oil/Fuel

AnalystUncertainty

Ash <0.002 % 2010/02/10 IS


Result Units

Run No. Team


4,544 S-Oil/Fuel

AnalystUncertainty


Carbon Residue

Result Units

Run No. Team


4,541 S-Oil/Fuel

AnalystUncertainty


Cetane Number

Result Units

Run No. Team


4,533 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,193 S-Oil/Fuel

AnalystUncertainty

Cloud Point -29.3 °C 2010/02/08 KS


Result Units

Run No. Team


4,624 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team



AnalystUncertainty













Result Units

Run No. Team


4,502 Subcontract

AnalystUncertainty






Result Units

Run No. Team


4,981 S-Oil/Fuel

AnalystUncertainty






(204) 578-3138 (204) 785-7142 (204) 360-4381



Lubricity by HFRR

Result Units

Run No. Team


4,782 S-Oil/Fuel

AnalystUncertainty

Minor axis 0.280 mm 2010/02/11 JS

Major axis 0.340 mm 2010/02/11 JS



Result Units

Run No. Team


4,623 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,502 Subcontract

AnalystUncertainty



Result Units

Run No. Team


5,011 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,540 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,502 Subcontract

AnalystUncertainty






Result Units

Run No. Team


4,654 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,506 S-Oil/Fuel

AnalystUncertainty

Water 27 µg/g (ppm) 2010/01/11 IS

BiodieselMaterial:


A2009-004575-004


DefaultProfile:

Test Results


Result Units

Run No. Team


4,669 S-Oil/Fuel

AnalystUncertainty


Ash

Result Units

Run No. Team


5,053 S-Oil/Fuel

AnalystUncertainty

Ash 0.002 % 2010/02/10 IS





(204) 578-3138 (204) 785-7142 (204) 360-4381




Result Units

Run No. Team


4,544 S-Oil/Fuel

AnalystUncertainty


Carbon Residue

Result Units

Run No. Team


4,541 S-Oil/Fuel

AnalystUncertainty

Carbon Residue <0.004 % 2010/01/14 JS

Cetane Number

Result Units

Run No. Team


4,533 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,193 S-Oil/Fuel

AnalystUncertainty

Cloud Point -28.4 °C 2010/02/08 KS


Result Units

Run No. Team


4,624 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team



AnalystUncertainty













Result Units

Run No. Team


4,502 Subcontract

AnalystUncertainty






Result Units

Run No. Team


4,981 S-Oil/Fuel

AnalystUncertainty


Lubricity by HFRR

Result Units

Run No. Team


4,782 S-Oil/Fuel

AnalystUncertainty

Minor axis 0.260 mm 2010/02/11 JS

Major axis 0.340 mm 2010/02/11 JS



Result Units

Run No. Team


4,623 S-Oil/Fuel

AnalystUncertainty





(204) 578-3138 (204) 785-7142 (204) 360-4381





Result Units

Run No. Team


4,502 Subcontract

AnalystUncertainty



Result Units

Run No. Team


5,011 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,540 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,502 Subcontract

AnalystUncertainty






Result Units

Run No. Team


4,654 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,506 S-Oil/Fuel

AnalystUncertainty

Water 23 µg/g (ppm) 2010/01/11 IS

BiodieselMaterial:


A2009-004575-005


DefaultProfile:

Test Results


Result Units

Run No. Team


4,669 S-Oil/Fuel

AnalystUncertainty


Ash

Result Units

Run No. Team


5,053 S-Oil/Fuel

AnalystUncertainty

Ash 0.002 % 2010/02/10 IS


Result Units

Run No. Team


4,544 S-Oil/Fuel

AnalystUncertainty


Carbon Residue

Result Units

Run No. Team


4,541 S-Oil/Fuel

AnalystUncertainty


Cetane Number

Result Units

Run No. Team


4,533 S-Oil/Fuel

AnalystUncertainty





(204) 578-3138 (204) 785-7142 (204) 360-4381





Result Units

Run No. Team


4,193 S-Oil/Fuel

AnalystUncertainty

Cloud Point -29.9 °C 2010/02/08 KS


Result Units

Run No. Team


4,624 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team



AnalystUncertainty













Result Units

Run No. Team


4,502 Subcontract

AnalystUncertainty






Result Units

Run No. Team


4,981 S-Oil/Fuel

AnalystUncertainty


Lubricity by HFRR

Result Units

Run No. Team


4,782 S-Oil/Fuel

AnalystUncertainty

Minor axis 0.240 mm 2010/02/11 JS

Major axis 0.300 mm 2010/02/11 JS



Result Units

Run No. Team


4,623 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,502 Subcontract

AnalystUncertainty



Result Units

Run No. Team


5,011 S-Oil/Fuel

AnalystUncertainty






(204) 578-3138 (204) 785-7142 (204) 360-4381




Result Units

Run No. Team


4,540 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,502 Subcontract

AnalystUncertainty






Result Units

Run No. Team


4,654 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,506 S-Oil/Fuel

AnalystUncertainty

Water 45 µg/g (ppm) 2010/01/11 IS

BiodieselMaterial:


A2009-004575-006


DefaultProfile:

Test Results


Result Units

Run No. Team


4,669 S-Oil/Fuel

AnalystUncertainty


Ash

Result Units

Run No. Team


5,053 S-Oil/Fuel

AnalystUncertainty

Ash 0.002 % 2010/02/10 IS


Result Units

Run No. Team


4,544 S-Oil/Fuel

AnalystUncertainty


Carbon Residue

Result Units

Run No. Team


4,541 S-Oil/Fuel

AnalystUncertainty


Cetane Number

Result Units

Run No. Team


4,533 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,193 S-Oil/Fuel

AnalystUncertainty

Cloud Point -21.4 °C 2010/02/08 KS


Result Units

Run No. Team


4,624 S-Oil/Fuel

AnalystUncertainty






(204) 578-3138 (204) 785-7142 (204) 360-4381




Result Units

Run No. Team



AnalystUncertainty













Result Units

Run No. Team


4,502 Subcontract

AnalystUncertainty






Result Units

Run No. Team


4,981 S-Oil/Fuel

AnalystUncertainty


Lubricity by HFRR

Result Units

Run No. Team


4,782 S-Oil/Fuel

AnalystUncertainty

Minor axis 0.220 mm 2010/02/11 JS

Major axis 0.300 mm 2010/02/11 JS



Result Units

Run No. Team


4,623 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,502 Subcontract

AnalystUncertainty



Result Units

Run No. Team


5,011 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,540 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,502 Subcontract

AnalystUncertainty









(204) 578-3138 (204) 785-7142 (204) 360-4381




Result Units

Run No. Team


4,654 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,506 S-Oil/Fuel

AnalystUncertainty

Water 34 µg/g (ppm) 2010/01/11 IS

BiodieselMaterial:

SW-1 Fuel Sample Location:Sample Description:

A2009-004575-007


DefaultProfile:

Test Results


Result Units

Run No. Team


4,544 S-Oil/Fuel

AnalystUncertainty

Biodiesel Blend Determination <0.1 % 2010/01/06 SP

BiodieselMaterial:

SW-2 Fuel Sample Location:Sample Description:

A2009-004575-008


DefaultProfile:

Test Results


Result Units

Run No. Team


4,544 S-Oil/Fuel

AnalystUncertainty


BiodieselMaterial:

SW-1 PURGE Sample Location:Sample Description:

A2009-004575-009


DefaultProfile:

DISCARDRemarks:





(204) 578-3138 (204) 785-7142 (204) 360-4381



BiodieselMaterial:

SW-2 PURGE Sample Location:Sample Description:

A2009-004575-010


DefaultProfile:

DISCARDRemarks:

BiodieselMaterial:

SW-1 Sample Location:Sample Description:

A2009-004575-011


DefaultProfile:

BiodieselMaterial:

SW-2 Sample Location:Sample Description:

A2009-004575-012


DefaultProfile:

Acid Number by Buffer Endpoint & Auto TitrationMETHOD:

1Version:

Principle: A sample is dissolved in a mixture of toluene and propanol containing a small amount of water and titrated

potentiometrically with alcoholic potassium hydroxide using a combination electrode. End points are taken at meter

readings corresponding to those found for aqueous acidic and basic buffer solutions.

This method covers the procedure for the determination of acidic constituents in petroleum products and lubricants soluble or nearly soluble in mixtures of toluene and propanol. It is applicable to acids whose dissociation constant in water are larger than 10¯9. This method may be used to indicate relative changes that occur in oil during use under oxidizing conditions.Scope:

A platinum electrode my be used to increase the electrode stability.Interferences:

The minimum mass of oil required is 20 grams.Sample Requirements:

ASTM D664Reference:

AshMETHOD:

1Version:

Principle: Sample is allowed to burn until only ash and carbon remain. The residue is reduced to ash and weeighed to constant

weight.

Determination of ash in the range 0.001-0.180 mass %, from distillate and residual fuels, gas turbine fuels, crude and lubricating oils, waxes and other Petroleum Products (PP) in which any ash-forming materials pesent are undesirable impurities or contaminants •The test method is limited to PP which are free from added ash-forming additives including P compounds.Scope:

Approximately 100 g of sample is required for this analysis.Sample Requirements:

ASTM D D482- 03Reference:

Carbon ResidueMETHOD:

1Version:

Cetane NumberMETHOD:

1Version:

Cloud Point by Constant Cooling Rate & Phase AnalyzerMETHOD:

1Version:





(204) 578-3138 (204) 785-7142 (204) 360-4381



Principle: A specimen is cooled by a Peltier device at a constant rate of 1.5 ± 0.1°C/min while continuously being illuminated by

a light source. The specimen is continuously monitored by an array of optical detectors for the first appearance of a

cloud of wax crystals. The detectors are sufficient in number to ensure that any solid phase hydrocarbon crystals that

may form are detected. The temperature at which the appearance of a cloud of wax crystals is first detected in the

specimen is recorded to 0.1°C

This test method describes the determination of the cloud point of petroleum products and biodiesel fuels that are transparent in layers 40 mm in thickness by an automatic instrument using a constant cooling rate. This test method covers the range of temperatures from -60 to +49°C with temperature resolution of 0.1°C.Scope:

Moisture in the sample may affect the cloud point determination.Sample Requirements:

ASTM D5773Reference:

Copper Strip Corrosion by Copper Strip Tarnish TestMETHOD:

1Version:

Principle: A polished copper strip is immersed in a specific volume of the sample being tested and heated under conditions of

temperature and time that are specific to the class of material being tested. At the end of the heating period, the

copper strip is removed, washed and the color and tarnish level assessed against the ASTM Copper Strip Corrosion

Standard.

This test method covers the determination of the corrosiveness to copper of automotive gasoline, cleaners (Stoddard) solvent, kerosine, diesel fuel, distillate fuel oil, lubricating oil, and/or other hydrocarbons having a vapor pressure no greater than 124 kPa (18 psi) at 37.8°C.Scope:

Contact of the copper strip with water before, during or after completion of the test run will cause staining, making it

difficult to evaluate the strips.

Interferences:

A minimum of 30 mL of sample is required.Sample Requirements:

ASTM D130Reference:

Determination of Kinematic Viscosity @ 40°CMETHOD:

1Version:

Principle: The time is measured for a fixed volume of liquid to flow under gravity through the capillary of a calibrated viscometer

at 40°C. The kinematic viscosity is the product of the measured flow time and the calibration constant of the

viscometer.

This method was validated for biodiesel and biodiesel blends, but is applicable to all fluids.Scope:

Particulate matter may plug the capillary tube.Interferences:

Aproximately 15 mL is required for a single test.Sample Requirements:

ASTM D445Reference:

Distillation-D86METHOD:

1Version:

Principle: A sample is slowly distilled until at least 95% of the starting material has distilled.

This method is suitable for all materials with a distillation range of 50 to 400 CScope:


D86Reference:

Flash Point by Pensky-Martens Closed CupMETHOD:

1Version:

Principle: Biodiesel is heated in a closed cup. An ignition source is introduced. If the air mixture above the sample ignites and

extinguishs immediately, a flash has been observed

Suitable to FAME & FAEE biodiesel, diesel/biodiesel blends, diesel fuel.Scope:

Volatile non-flammable compounds such as halogenated hydrocarbons and water.Interferences:

Minimum 320mL may be required. Submitted in a non-gas permeable contained with no more than 65% headspace

and no less than 95% headspace.

Sample Requirements:

ASTM D93Reference:

Lubricity - D679METHOD:

1Version:

Principle: A metal ball is 'rubbed' against a metal disc using the a biodiesel blend as the lubricant. A wear scar is created on the

ball and is measured.

Suitable to diesel/biodiesel blends, diesel fuel, and can be use on FAME & FAEE biodiesel.Scope:

rticulate matter contamination will cause lower lubricity results.Interferences:

Approximately 10 mL collected in an amber borosillicate glass jar that has been triple rinsed with the sample.Sample Requirements:


Physical Properties by Automated ViscometerMETHOD:

1Version:

Sulphur in oilMETHOD:

1Version:





(204) 578-3138 (204) 785-7142 (204) 360-4381



Principle: Biodiesel is combusted in the presences of oxygen and argon to produce SO4. The SO4 is exposed to UV which

excites the molecules. A photo detector analyzes the energy emitted as the molecules return to a normal state.

Suitable to FAME & FAEE biodiesel, diesel/biodiesel blends, diesel fuel, and other hydrocarbons.Scope:

NoneInterferences:

Approximately 4 mL.Sample Requirements:


Water & Sediment by CentrifugeMETHOD:

1Version:

Principle: A 100 ml sample is cetrifuges at 800 (rcf) for 10 min at 21 - 32°C in a tube readable to 0.005 mL and measurable to

0.01 mL

Test method covers the determination of the volume of free water and sediment in Middle Distillate Fuels with Visc at 40°C in the range of 1.0-4.1 mm2/s and Densitys 770-900 Kg/m3Scope:

Approx. 100 mL of sample is required.Sample Requirements:

ASTM D 2709-96Reference:

Water by Oven and Coulometric KF TitrationMETHOD:

1Version:

Report Authorized by: 2010/03/10Mark Dalmaijer

Winnipeg MB R3T 1Y6 [email protected]

Technical Supervisor Reliability & Performance Department

Release Date:

1840 Chevrier Blvd

Phone:

Phone: 204-239-5445 [email protected], Lorne YCopies to:

Phone: [email protected] Dalmaijer Y

Note: 1. < means the analyte cannot be reliably determined to be present at or below the reporting detection limit.

2. The results in this report apply to the samples submitted. Report not be reproduced except in whole unless written

permission is obtained from the laboratory.

3. Samples are destroyed 90 days after the report is issued unless requested in writing to be held.

4. In order to improve our management system, testing activities and customer service, please respond to this email with any comments that you

may have.





(204) 578-3138 (204) 785-7142 (204) 360-4381


64

Appendix IV


Certificate of Analysis from Manitoba Hydro for Biodiesel Samples Collected from PAMI Research Project


Grieger, Lorne




A2009-004576 PO/WO #: 2009-116V2

Additional Information: ARC Inv #56992 pd 10/02/03

BiodieselMaterial:

PAMI Diesel Sample Location:Sample Description:

A2009-004576-001

2010/01/07 L. Grieger 2010/02/18Sample Date: Sampled By: Required by:

DefaultProfile:

Test Results


Result Units

Run No. Team


4,669 S-Oil/Fuel

AnalystUncertainty


Ash

Result Units

Run No. Team


5,054 S-Oil/Fuel

AnalystUncertainty

Ash <0.002 % 2010/02/11 IS


Result Units

Run No. Team


4,544 S-Oil/Fuel

AnalystUncertainty


Carbon Residue

Result Units

Run No. Team


4,541 S-Oil/Fuel

AnalystUncertainty


Cetane Number

Result Units

Run No. Team


4,533 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,193 S-Oil/Fuel

AnalystUncertainty

Cloud Point -41.5 °C 2010/02/08 KS


Result Units

Run No. Team


4,624 S-Oil/Fuel

AnalystUncertainty

Copper Corrosion @ 100C 1b N/A 2010/01/18 IS


Result Units

Run No. Team



AnalystUncertainty












(204) 578-3138 (204) 785-7142 (204) 360-4381








Result Units

Run No. Team


4,502 Subcontract

AnalystUncertainty






Result Units

Run No. Team


4,981 S-Oil/Fuel

AnalystUncertainty


Lubricity by HFRR

Result Units

Run No. Team


4,782 S-Oil/Fuel

AnalystUncertainty

Minor axis 0.270 mm 2010/02/11 JS

Major axis 0.410 mm 2010/02/11 JS



Result Units

Run No. Team


4,623 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,502 Subcontract

AnalystUncertainty



Result Units

Run No. Team


5,011 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,628 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,502 Subcontract

AnalystUncertainty



Adherent insolubles = 0 mg



Result Units

Run No. Team


4,654 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,506 S-Oil/Fuel

AnalystUncertainty

Water 4 µg/g (ppm) 2010/01/11 IS





(204) 578-3138 (204) 785-7142 (204) 360-4381



BiodieselMaterial:

PAMI B5 Sample Location:Sample Description:

A2009-004576-002


DefaultProfile:

Test Results


Result Units

Run No. Team


4,669 S-Oil/Fuel

AnalystUncertainty


Ash

Result Units

Run No. Team


5,054 S-Oil/Fuel

AnalystUncertainty

Ash <0.002 % 2010/02/11 IS


Result Units

Run No. Team


4,544 S-Oil/Fuel

AnalystUncertainty


Carbon Residue

Result Units

Run No. Team


4,541 S-Oil/Fuel

AnalystUncertainty


Cetane Number

Result Units

Run No. Team


4,533 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,193 S-Oil/Fuel

AnalystUncertainty

Cloud Point -34.4 °C 2010/02/08 KS


Result Units

Run No. Team


4,624 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team



AnalystUncertainty













Result Units

Run No. Team


4,502 Subcontract

AnalystUncertainty





(204) 578-3138 (204) 785-7142 (204) 360-4381








Result Units

Run No. Team


4,981 S-Oil/Fuel

AnalystUncertainty


Lubricity by HFRR

Result Units

Run No. Team


4,782 S-Oil/Fuel

AnalystUncertainty

Minor axis 0.410 mm 2010/02/11 JS

Major axis 0.440 mm 2010/02/11 JS



Result Units

Run No. Team


4,623 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,502 Subcontract

AnalystUncertainty



Result Units

Run No. Team


5,011 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,628 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,502 Subcontract

AnalystUncertainty






Result Units

Run No. Team


4,654 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,506 S-Oil/Fuel

AnalystUncertainty


BiodieselMaterial:


A2009-004576-003


DefaultProfile:





(204) 578-3138 (204) 785-7142 (204) 360-4381



Test Results


Result Units

Run No. Team


4,669 S-Oil/Fuel

AnalystUncertainty


Ash

Result Units

Run No. Team


5,054 S-Oil/Fuel

AnalystUncertainty

Ash <0.002 % 2010/02/11 IS


Result Units

Run No. Team


4,544 S-Oil/Fuel

AnalystUncertainty


Carbon Residue

Result Units

Run No. Team


4,541 S-Oil/Fuel

AnalystUncertainty


Cetane Number

Result Units

Run No. Team


4,533 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,193 S-Oil/Fuel

AnalystUncertainty

Cloud Point -29.7 °C 2010/02/08 KS


Result Units

Run No. Team


4,624 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team



AnalystUncertainty













Result Units

Run No. Team


4,502 Subcontract

AnalystUncertainty






Result Units

Run No. Team


4,981 S-Oil/Fuel

AnalystUncertainty






(204) 578-3138 (204) 785-7142 (204) 360-4381



Lubricity by HFRR

Result Units

Run No. Team


4,782 S-Oil/Fuel

AnalystUncertainty

Minor axis 0.290 mm 2010/02/11 JS

Major axis 0.330 mm 2010/02/11 JS



Result Units

Run No. Team


4,623 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,502 Subcontract

AnalystUncertainty



Result Units

Run No. Team


5,011 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,628 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,502 Subcontract

AnalystUncertainty






Result Units

Run No. Team


4,654 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,506 S-Oil/Fuel

AnalystUncertainty


BiodieselMaterial:


A2009-004576-004


DefaultProfile:

Test Results


Result Units

Run No. Team


4,669 S-Oil/Fuel

AnalystUncertainty


Ash

Result Units

Run No. Team


5,054 S-Oil/Fuel

AnalystUncertainty

Ash <0.002 % 2010/02/11 IS





(204) 578-3138 (204) 785-7142 (204) 360-4381




Result Units

Run No. Team


4,544 S-Oil/Fuel

AnalystUncertainty


Carbon Residue

Result Units

Run No. Team


4,541 S-Oil/Fuel

AnalystUncertainty


Cetane Number

Result Units

Run No. Team


4,533 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,193 S-Oil/Fuel

AnalystUncertainty

Cloud Point -23.7 °C 2010/02/08 KS


Result Units

Run No. Team


4,624 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team



AnalystUncertainty













Result Units

Run No. Team


4,502 Subcontract

AnalystUncertainty






Result Units

Run No. Team


4,981 S-Oil/Fuel

AnalystUncertainty


Lubricity by HFRR

Result Units

Run No. Team


4,782 S-Oil/Fuel

AnalystUncertainty

Minor axis 0.190 mm 2010/02/11 JS

Major axis 0.270 mm 2010/02/11 JS



Result Units

Run No. Team


4,623 S-Oil/Fuel

AnalystUncertainty





(204) 578-3138 (204) 785-7142 (204) 360-4381





Result Units

Run No. Team


4,502 Subcontract

AnalystUncertainty



Result Units

Run No. Team


5,011 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,628 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,502 Subcontract

AnalystUncertainty






Result Units

Run No. Team


4,654 S-Oil/Fuel

AnalystUncertainty



Result Units

Run No. Team


4,506 S-Oil/Fuel

AnalystUncertainty


Acid Number by Buffer Endpoint & Auto TitrationMETHOD:

1Version:

Principle: A sample is dissolved in a mixture of toluene and propanol containing a small amount of water and titrated

potentiometrically with alcoholic potassium hydroxide using a combination electrode. End points are taken at meter

readings corresponding to those found for aqueous acidic and basic buffer solutions.

This method covers the procedure for the determination of acidic constituents in petroleum products and lubricants soluble or nearly soluble in mixtures of toluene and propanol. It is applicable to acids whose dissociation constant in water are larger than 10¯9. This method may be used to indicate relative changes that occur in oil during use under oxidizing conditions.Scope:

A platinum electrode my be used to increase the electrode stability.Interferences:

The minimum mass of oil required is 20 grams.Sample Requirements:

ASTM D664Reference:

AshMETHOD:

1Version:

Principle: Sample is allowed to burn until only ash and carbon remain. The residue is reduced to ash and weeighed to constant

weight.

Determination of ash in the range 0.001-0.180 mass %, from distillate and residual fuels, gas turbine fuels, crude and lubricating oils, waxes and other Petroleum Products (PP) in which any ash-forming materials pesent are undesirable impurities or contaminants •The test method is limited to PP which are free from added ash-forming additives including P compounds.Scope:

Approximately 100 g of sample is required for this analysis.Sample Requirements:

ASTM D D482- 03Reference:

Biodiesel blend determination by FTIRMETHOD:

1Version:

Carbon ResidueMETHOD:

1Version:

Cetane NumberMETHOD:

1Version:


1Version:





(204) 578-3138 (204) 785-7142 (204) 360-4381











Copper Strip Corrosion by Copper Strip Tarnish TestMETHOD:

1Version:

Principle: A polished copper strip is immersed in a specific volume of the sample being tested and heated under conditions of

temperature and time that are specific to the class of material being tested. At the end of the heating period, the

copper strip is removed, washed and the color and tarnish level assessed against the ASTM Copper Strip Corrosion

Standard.

This test method covers the determination of the corrosiveness to copper of automotive gasoline, cleaners (Stoddard) solvent, kerosine, diesel fuel, distillate fuel oil, lubricating oil, and/or other hydrocarbons having a vapor pressure no greater than 124 kPa (18 psi) at 37.8°C.Scope:

Contact of the copper strip with water before, during or after completion of the test run will cause staining, making it

difficult to evaluate the strips.

Interferences:


ASTM D130Reference:

Determination of Kinematic Viscosity @ 40°CMETHOD:

1Version:

Principle: The time is measured for a fixed volume of liquid to flow under gravity through the capillary of a calibrated viscometer

at 40°C. The kinematic viscosity is the product of the measured flow time and the calibration constant of the

viscometer.

This method was validated for biodiesel and biodiesel blends, but is applicable to all fluids.Scope:

Particulate matter may plug the capillary tube.Interferences:

Aproximately 15 mL is required for a single test.Sample Requirements:

ASTM D445Reference:

Distillation-D86METHOD:

1Version:

Principle: A sample is slowly distilled until at least 95% of the starting material has distilled.

This method is suitable for all materials with a distillation range of 50 to 400 CScope:


D86Reference:

Flash Point by Pensky-Martens Closed CupMETHOD:

1Version:

Principle: Biodiesel is heated in a closed cup. An ignition source is introduced. If the air mixture above the sample ignites and

extinguishs immediately, a flash has been observed

Suitable to FAME & FAEE biodiesel, diesel/biodiesel blends, diesel fuel.Scope:

Volatile non-flammable compounds such as halogenated hydrocarbons and water.Interferences:

Minimum 320mL may be required. Submitted in a non-gas permeable contained with no more than 65% headspace

and no less than 95% headspace.

Sample Requirements:

ASTM D93Reference:


1Version:







Physical Properties by Automated ViscometerMETHOD:

1Version:

Sulphur in oilMETHOD:

1Version:





(204) 578-3138 (204) 785-7142 (204) 360-4381



Principle: Biodiesel is combusted in the presences of oxygen and argon to produce SO4. The SO4 is exposed to UV which

excites the molecules. A photo detector analyzes the energy emitted as the molecules return to a normal state.

Suitable to FAME & FAEE biodiesel, diesel/biodiesel blends, diesel fuel, and other hydrocarbons.Scope:

NoneInterferences:

Approximately 4 mL.Sample Requirements:


Water & Sediment by CentrifugeMETHOD:

1Version:

Principle: A 100 ml sample is cetrifuges at 800 (rcf) for 10 min at 21 - 32°C in a tube readable to 0.005 mL and measurable to

0.01 mL

Test method covers the determination of the volume of free water and sediment in Middle Distillate Fuels with Visc at 40°C in the range of 1.0-4.1 mm2/s and Densitys 770-900 Kg/m3Scope:

Approx. 100 mL of sample is required.Sample Requirements:

ASTM D 2709-96Reference:

Water by Oven and Coulometric KF TitrationMETHOD:

1Version:




Release Date:

1840 Chevrier Blvd

Phone:







may have.





(204) 578-3138 (204) 785-7142 (204) 360-4381


65

Appendix V


Certificate of Analysis from Manitoba Hydro for Retested Samples


Grieger, Lorne




A2010-000806

Additional Information: Refer to folders A2009-004575 & A2009-004576

BiodieselMaterial:

516-1 Sample Location:Sample Description:

A2010-000806-001

L. Greieger 2010/04/01Sample Date: Sampled By: Required by:

DefaultProfile:

Test Results


Result Units

Run No. Team


5,452 S-Oil/Fuel

AnalystUncertainty

Cloud Point -19.9 °C 2010/02/22 KS

BiodieselMaterial:

516-2 Sample Location:Sample Description:

A2010-000806-002


DefaultProfile:

Test Results


Result Units

Run No. Team


5,452 S-Oil/Fuel

AnalystUncertainty

Cloud Point -21.6 °C 2010/02/22 KS

BiodieselMaterial:


A2010-000806-003


DefaultProfile:

Test Results

Lubricity by HFRR

Result Units

Run No. Team


5,392 S-Oil/Fuel

AnalystUncertainty

Minor axis 0.250 mm 2010/03/08 JS

Major axis 0.360 mm 2010/03/08 JS






(204) 578-3138 (204) 785-7142 (204) 360-4381

1Version: Folder Number:Print Time: 1:48:04PM



1Version:










1Version:










Release Date:

1840 Chevrier Blvd

Phone:







may have.





(204) 578-3138 (204) 785-7142 (204) 360-4381


66

Appendix VI


Gas Chromatography/Mass Spectrometry Results


Grieger, Lorne


PAMI -


A2009-004574

Due to the complexity of report GC/MS characterization results, the report was sent separately by email.Report Evaluation:

OtherMaterial:

480R-1 Fuel filter Sample Location:Sample Description:

A2009-004574-001


DefaultProfile:

Test Results

GC/MS Characterization

Result Units

Run No. Team


4,501 S-GCMS-1

AnalystUncertainty

GC/MS Characterization See non-LIMS report N/A 2010/01/19 MD

OtherMaterial:

480R-2 Fuel filter Sample Location:Sample Description:

A2009-004574-002


DefaultProfile:

Test Results


Result Units

Run No. Team


4,501 S-GCMS-1

AnalystUncertainty


OtherMaterial:

515-1L Fuel filter Sample Location:Sample Description:

A2009-004574-003


DefaultProfile:

Test Results


Result Units

Run No. Team


4,501 S-GCMS-1

AnalystUncertainty






(204) 578-3138 (204) 785-7142 (204) 360-4381



OtherMaterial:

515-1R Fuel filter Sample Location:Sample Description:

A2009-004574-004


DefaultProfile:

Test Results


Result Units

Run No. Team


4,501 S-GCMS-1

AnalystUncertainty


OtherMaterial:


A2009-004574-005


DefaultProfile:

Test Results


Result Units

Run No. Team


4,501 S-GCMS-1

AnalystUncertainty


OtherMaterial:


A2009-004574-006


DefaultProfile:

Test Results


Result Units

Run No. Team


4,501 S-GCMS-1

AnalystUncertainty


OtherMaterial:


A2009-004574-007


DefaultProfile:





(204) 578-3138 (204) 785-7142 (204) 360-4381



Test Results


Result Units

Run No. Team


4,501 S-GCMS-1

AnalystUncertainty


OtherMaterial:


A2009-004574-008


DefaultProfile:

Test Results


Result Units

Run No. Team


4,501 S-GCMS-1

AnalystUncertainty


OtherMaterial:


A2009-004574-009


DefaultProfile:

Test Results


Result Units

Run No. Team


4,501 S-GCMS-1

AnalystUncertainty


OtherMaterial:


A2009-004574-010


DefaultProfile:

Test Results


Result Units

Run No. Team


4,501 S-GCMS-1

AnalystUncertainty






(204) 578-3138 (204) 785-7142 (204) 360-4381



OtherMaterial:

SW-2 Fuel filter Sample Location:Sample Description:

A2009-004574-011


DefaultProfile:

Test Results


Result Units

Run No. Team


4,501 S-GCMS-1

AnalystUncertainty


OtherMaterial:

480R-1 Fuel/water separator filter Sample Location:Sample Description:

A2009-004574-012


DefaultProfile:

Test Results


Result Units

Run No. Team


4,501 S-GCMS-1

AnalystUncertainty


OtherMaterial:

480R-2 Fuel/water separator filter Sample Location:Sample Description:

A2009-004574-013


DefaultProfile:

Test Results


Result Units

Run No. Team


4,501 S-GCMS-1

AnalystUncertainty


OtherMaterial:

515-1 Fuel/water separator filter Sample Location:Sample Description:

A2009-004574-014


DefaultProfile:





(204) 578-3138 (204) 785-7142 (204) 360-4381



Test Results


Result Units

Run No. Team


4,501 S-GCMS-1

AnalystUncertainty


OtherMaterial:


A2009-004574-015


DefaultProfile:

Test Results


Result Units

Run No. Team


4,501 S-GCMS-1

AnalystUncertainty


OtherMaterial:


A2009-004574-016


DefaultProfile:

Test Results


Result Units

Run No. Team


4,501 S-GCMS-1

AnalystUncertainty


OtherMaterial:


A2009-004574-017


DefaultProfile:

Test Results


Result Units

Run No. Team


4,501 S-GCMS-1

AnalystUncertainty






(204) 578-3138 (204) 785-7142 (204) 360-4381



OtherMaterial:

SW-2 Fuel/water separator filter Sample Location:Sample Description:

A2009-004574-018


DefaultProfile:

Test Results


Result Units

Run No. Team


4,501 S-GCMS-1

AnalystUncertainty


No methodMETHOD:

1Version:

No method document associated with this testing.Scope:




Release Date:

1840 Chevrier Blvd

Phone:







may have.





(204) 578-3138 (204) 785-7142 (204) 360-4381


Folder A2009-004574 Attachment Experiment description All fuel filters were sampled by cutting the lower section and lifting the housing from its base. The filters varied in size for each unit therefore the percentage of paper filter subsampled differed for each sample. Most fuel filters had liquid fuel in the housing; this fuel was drained as much as practical. Once the paper filter was subsample, the filter was opened as much as possible, visually inspected and then a solvent mixture of dichloromethane and n-hexane was used to wash organic residues from the filter. The solvent mixture was left overnight in a fumehood to allow the solvent to evaporate and the mixture was reconstituted in toluene. The sample extracts were shaken and sonicated to bring as much of the organic residues into solution. A small aliquot of each sample was transferred to an autosampler vial and 25 μL of N-Methyl-N-trifluoroacetamide (MSTFA) was added to derivatize compounds such as phenols, sterols and acids to trimethyl-silyl derivatives to facilitate improved response and chromatography. The fuel filter sample extracts were analyzed on an instrument configured as follows:

CTC Analytics CombiPal liquid autosampler equipped with a 10 μL microsyringe. Varian 450 Gas Chromatograph (GC) with a 30 meter X 0.25 mm ID X 250um film of

5%cyano/95%PDMS (DB-5 equivalent). The injector was operated in hot splitless mode and the column was ramped from 90°C to 310°C over a period of 30 minutes to resolve potential compounds of interest using helium as a carrier gas.

Varian 320 Mass Spectrometer. The quadrupole Mass Spectrometer (MS) was operated in Full Scan mode scanning from 50 to 600 atomic mass units. It was operated in 70mV Electron Impact ionization mode to facilitate NIST library searching.

Purchased chemical reference materials Sitosterol, Stigmasterol, Cholesterol, Cholestanol, Monolinolein, Monolinolenin, Monopalmitin, Monolaurin, and Monostearin were used to confirm the presence of some expected compounds. Standards of sterol glucosides were not purchased; at the outset of this project a source of reference material had not been found. In order to assist in identifying unknown materials, a NIST 2005 mass spectral library containing about 100,000 spectra was used to scan spectra of unknown compounds. We analyzed B100 of varying sources to help identify potential compounds specific to biodiesel that may be of interest. Results - Fuel Filter Subsampling A visual inspection of each filter did not reveal any particulates of a crystalline nature however there were particles that, over time, settled from the solvent rinsings. Once constituted in toluene, many of the sample extracts contained particulates that settled to the bottom of the vial; although toluene is a good choice of solvent for injecting into a gas chromatograph, not all organics will constitute in toluene. Although other choices of solvent may have led to the identification of other compounds there is no one perfect blend of solvents that would have dissolved all compounds that may have been of interest. Results - Fuel Filter Sample Extract Analysis by GC/MS Despite best efforts to decant all liquid fuel from the fuel filters, the fuel filters contained varying levels of residual fuel that is seen clearly in all chromatograms (see appendix 1). The very high level of diesel fuel masked the presence of the compounds of interest in some cases. All samples had a diesel pattern and varying levels of fatty acid methyl ester (FAME) peaks dependant on the blend level, as expected. As shown in Table 1, samples had varying levels of identified monoglycerides, sterols and Tocopherol.

Although the blend levels may have been consistent, the significant variability in the levels of identified compounds from sample to sample is likely related to the level of residual fuel remaining in the filter. According to Dunn1, these compounds are expected in plant-based biodiesel. Tocopherol, an inhibited phenol, is an antioxidant and therefore beneficial to the stability of biodiesel2. As initially requested, the testing was to focus on the identification of sterol glucosides however none were identified. Although according to Dunn2, soy-based biodiesel contains among the highest levels of sterol glucosides, the low blend level (2-5% biodiesel/petroleum diesel) may have contributed to the inability to identify sterol glucosides. Tang et al report that soy-based biodiesel may contain sterol glucosides at levels of 25 to 272 ppm3; incorporating the dilution effect one may expect that sterol glucosides exist at very low ppm levels in blended fuels. The ability to detect these compounds is a function of the volume of fuel filtered. Additionally, pyridine has been used as a solvent for dissolving sterol glucosides so perhaps may have better dissolved remaining particulates. The level of C18 FAME was very high and no testing was done to resolve and identify the specific FAMEs. Other FAMES were also present (~C10 to ~C20) in all samples but aside from identifying them as FAMES, the compounds were neither quantified nor reported as they are expected in B100 biofuel although this remains an analytical option. It is important to note that all results found in Table one are semi-quantitative due to the nature of open-scan GC/MS and method of calibration used for quantitation.

Table 1: GC/MS Analysis: Compound Identification Sample ID Compound Name Results

(Total ug) Sample ID Compound Name Results

(Total ug)

A2009-004574-1 beta-Sitosterol TMS 182 A2009-004574-11 beta-Sitosterol TMS 1,177 A2009-004574-1 Cholesterol TMS 64 A2009-004574-11 Monolien TMS 8,578 A2009-004574-1 Monolien TMS 1,144 A2009-004574-11 Monopalmitin TMS 326 A2009-004574-1 Monopalmitin TMS 192 A2009-004574-11 Monostearin TMS 159 A2009-004574-1 Monostearin TMS 217 A2009-004574-11 Tocopherol TMS 28,763 A2009-004574-1 Stigmasterol TMS 98 A2009-004574-12 beta-Sitosterol TMS 618 A2009-004574-1 Tocopherol TMS 1,263 A2009-004574-12 Cholesterol TMS 296 A2009-004574-2 beta-Sitosterol TMS 85 A2009-004574-12 Monolien TMS 5,233 A2009-004574-2 Monolien TMS 536 A2009-004574-12 Monopalmitin TMS 804 A2009-004574-2 Monopalmitin TMS 85 A2009-004574-12 Monostearin TMS 804 A2009-004574-2 Monostearin TMS 61 A2009-004574-12 Stigmasterol TMS 345 A2009-004574-2 Tocopherol TMS 1,120 A2009-004574-12 Tocopherol TMS 3,183 A2009-004574-3 Monostearin TMS 56 A2009-004574-13 beta-Sitosterol TMS 754 A2009-004574-3 Tocopherol TMS 167 A2009-004574-13 Cholesterol TMS 275 A2009-004574-4 beta-Sitosterol TMS 53 A2009-004574-13 Monolien TMS 2,739 A2009-004574-4 Monostearin TMS 110 A2009-004574-13 Monostearin TMS 194 A2009-004574-4 Tocopherol TMS 89 A2009-004574-13 Stigmasterol TMS 374 A2009-004574-5 Tocopherol TMS 160 A2009-004574-13 Tocopherol TMS 1,935 A2009-004574-6 Tocopherol TMS 166 A2009-004574-14 beta-Sitosterol TMS 330 A2009-004574-7 Monolien TMS 899 A2009-004574-14 Monolien TMS 463 A2009-004574-7 Monopalmitin TMS 134 A2009-004574-14 Monopalmitin TMS 115 A2009-004574-7 Monostearin TMS 80 A2009-004574-14 Monostearin TMS 185 A2009-004574-7 Tocopherol TMS 97 A2009-004574-14 Stigmasterol TMS 166 A2009-004574-8 Monolien TMS 834 A2009-004574-14 Tocopherol TMS 710 A2009-004574-8 Monopalmitin TMS 131 A2009-004574-15 beta-Sitosterol TMS 208 A2009-004574-8 Monostearin TMS 72 A2009-004574-15 Stigmasterol TMS 151 A2009-004574-8 Tocopherol TMS 99 A2009-004574-15 Tocopherol TMS 498 A2009-004574-9 beta-Sitosterol TMS 83 A2009-004574-16 beta-Sitosterol TMS 305 A2009-004574-9 Cholesterol TMS 52 A2009-004574-16 Cholesterol TMS 161 A2009-004574-9 Monolien TMS 873 A2009-004574-16 Monolien TMS 3,951 A2009-004574-9 Monopalmitin TMS 136 A2009-004574-16 Monopalmitin TMS 534 A2009-004574-9 Monostearin TMS 75 A2009-004574-16 Monostearin TMS 291 A2009-004574-9 Tocopherol TMS 105 A2009-004574-16 Stigmasterol TMS 185 A2009-004574-10 beta-Sitosterol TMS 91 A2009-004574-16 Tocopherol TMS 485 A2009-004574-10 Cholesterol TMS 60 A2009-004574-17 beta-Sitosterol TMS 327 A2009-004574-10 Monolien TMS 1,534 A2009-004574-17 Cholesterol TMS 172 A2009-004574-10 Monopalmitin TMS 159 A2009-004574-17 Monolien TMS 1,404 A2009-004574-10 Monostearin TMS 96 A2009-004574-17 Monostearin TMS 115 A2009-004574-10 Tocopherol TMS 140 A2009-004574-17 Stigmasterol TMS 151

A2009-004574-17 Tocopherol TMS 508 * TMS: trimethyl-silyl

References

1. R.O. Dunn, “Effects of minor constituents on cold flow properties and performance of biodiesel” Progress in Energy and Combustion Science, 35 (2009) 484

2. R.O. Dunn, “Effects of minor constituents on cold flow properties and performance of biodiesel”,

484

3. Haiying Tang et all, “Fuel properties and precipate formation at low temperature in soy-, cottonseed- and poultry fat-based biodiesel blends” Fuel, 87 (2008) 3014

APPENDIX 1: BI00 (Biodiesel chromatograms)

Print Date: 31 Dec 2009 11 :55:33

Chromatogram Plots ,

a2009-4131-001 unde.xms TIC Filtered

50 ~, oDli:5u... - 6A/5t ,,;~ 40

30

20

10

a2009-4458·001 unde.xms TIC Filtered

arc b224 unde.xms TIC Filtered

A2009-4559-001 unde.xms TIC Filtered

~olJi~~

APPENDIX 2: Sample chromatograms

Print Date: 02 Jan 201012:01:50

Chromatogram Plots

a2009-004574·1 der.xms Ions: 250.0:1000.0 Filtered

• a .... ...... ., ~ .,."...._ ,

V""., - ........ .

a2009-004574·2 der.xms Ions: 250.0:1000.0 Filtered

•• ' ...... or !'"' ''1''-- ~

...

a2009·004574-3 der.xms Ions: 250.0:1000.0 Filtered

- ... r... . . ...,.. If !"'"" .p.

minules

Print Date: 02 Jan 2010 11 :57:03 . ~ ". ..~., ... '" .~ .........

Chromatogram Plots

a2009-004574-1 der.xms Ions: 250.0:1000.0 Filtered

•.... ,.... - ..... ,..- .

..,..., - .. .. ..

12

1 .5 2 .0 2 .5

~ ....,.


•.... 'y-..,. _............ ....


... , ,",... '" - ..... .-.

2 .0 2 .5 minutes

t-'nnt uate: U2 Jan 201012:02:16

Chromatogram Plots


~ ........ ......... ~'~~-

..... 'it -.!Of) .,...

- ..... "" ........ If ~~ ...-



- .... ;.,..... ~......

~

...

~

minu es

Print Date: 02 Jan 201011:57:39

Chromatogram Plots .. .,.

1 .5 2 .0 2 .5

a2009-004574-4 der.xms Ions; 250.0;1000.0 Filtered

r..,

. . . . . , ... '"


..... .,


2 .0 2 .5 minutes

- ...... _..

- ....._.. ,

~ ''''!"-- ..

~ .~. ....... ., - ......

Print Date: 02 Jan 201012:02:47

..." - ......Chromatogram Plots

'

a2009-004574-7 der,xms Ions: 250,0:1000,0 Filtered

.... '"


a2009-004574-9 der.xms tons: 250,0:1000,0 Filtered

Print Date: 02 Jan 201011 :58:12

Chromatogram Plots .. ~.,

a2009-004574-7 der.xms Ions: 250.0:1000.0 Filtered.' ., -...._" ,

,. ."

'... ., -. ""'''~ ...

•• ""f

a2009-004574-8 der.xms Ions: 250.0:1000.0 FiHered - ............... ....

... , , .... ., ~ .-;.,."... .....

a2009-004574-9 der.xms Ions: 250.0:1000.0 FiHered . . ~ ., .,""'"

... .,

1 .5 2 .0 2 .5 2.0 . • ... 2 .4'millltes - .-.- _

Print Date: 02 Jan 2010 12:03:16

Chromatogram Plots

.---~------------------------------------------------------~~------~~----'~.~'~'~'~'~'~~~~~~~.~-a2009-004574-10 der.xms Ions: 250.0:1000.0 Filtered

50.0:600.0>

V'~'" - '0" ,,

. ,. ~ ... '.... .. .,...' .....- ~

92009-004574-11 der.xms Ions: 250.0:1000.0 Filtered 50.0:600.0>

- •• t,... ...... 'tf !""" ~....- '"

- •• •. - ...... '" !'" ,""- ..

92009-004574-12 der.xms Ions: 250.0:1000.0 Filtered 50.0:600.0>

• •••.• ...... '" !"" ,""- ..

minJes

Print Date: 02 Jan 2010 11 :59:11

Chromatogram Plots .~ .... , .... ., ~.~.......

MCou a2009-004574-10 der .xms Ions: 250.0:1000.0 Filtered

w' 'V ... ,fJlo. ,'w

. ., ...... .,~

~.~.,., .... ., a2009-004574-11 der.xms Ions: 250.0:1000.0 Filtered

..... ,......,. -...,.~-...


• ~ •• ,......., ~' • ..... _. '01

1 .5 2 .0 2 .5 2 .0 2.5 . t immuesi

I"'nnt uate: 02 Jan 201012:03:49

Chromatogram Plots . • .... 'P" !'" •.,..

82009-004574-13 der.xms Ions: 250,0:1000,0 Filtered

•• "Ii ."'f>' ..

rwq

~ ........ '.....

82009-004574-14 der.xms Ions: 250.0:1000.0 Filtered

_ .........

!""" ...

,

..

- ." .......... ., !I'"'~""-"

- ........ •. .,..,

82009-004574-15 der.xms Ions: 250.0:1000.0 Filtered

!!"'" ••,.. ...

minues

....nnt uate: U2 Jan 2010 11 :59:42

Chromatogram Plots .... '" ~' .....

1 .5 2.0 2 .5

...........


. .. .. . .... ~~

• • ". • "r If ~ ..~ ......- '"


. ..... ...... If ~~ .1!"...... ..

" .".-. . r " ' -~ .""!"''''..... ~


••• I • or" .. ~ ."!"'--..... ~

2 .0 2 .5 minutes

Print Date: 02 Jan 201012:04:19

Chromatogram Plots

MCount 60 50.0:600.0>

MCount 50.0:600.0>

•

a2009-004574-16 der.xms Ions: 250.0:1000.0 Filtered ".... !'" .,...


~ ... W' ........." """ .......... "

a2009-004574-1B der.xms Ions: 250.0:1000.0 Filtered

- •••• ....... '~' ''1''-

minu

Print Dale: 02 Jan 201012:00:18

Chromatogram Plots

12

1 .5 2 .0 2 .5


- ............ "

a2009-o04574-17 der.xms Ions: 250.0:1000.0 Filtered

- ..."...'..."

•' • ~ . ... '..."


- ..... , ..... "

- ....'... '...."

2 .0 2 .5 minutes

~~ ~.....

~...~- ..

!"'"'" .~- ....

~ .. ~- "II!

~~ .~- ...

Prairie Agricultural Machinery Institute

HEAD OFFICE: P.O. Box 1900, Humboldt, Saskatchewan, Canada S0K 2A0 Telephone: (306) 682-2555

TEST STATIONS: P.O. Box 1060, Portage la Prairie, Manitoba, Canada R1N 3C5 Telephone: (204) 239-5445 P.O. Box 1150, Humboldt, Saskatchewan, Canada S0K 2A0 Telephone: (306) 682-5033 For further information with regards to this report contact:

Portage Test Station

For further information on other evaluations, facilities, or services contact:

Head Office

Note: This report may not be reproduced in whole or in part without prior approval of the Prairie Agricultural Machinery Institute. The involvement of PAMI does not imply endorsement of the product. No references may be made by the Client to imply endorsement.

Effects of Long-Term Storage on Biodiesel Quality For ... · PDF fileMarch 15, 2010 Revised: May 25, 2010 Portage la Prairie, Manitoba Project #21409R Final Report Effects of Long-Term

Documents