GC-101. Testing of Biodiesel Using Gas Chromatography. by Bob Armantrout. Presented at: Local Biodiesel: A Biodiesel Coop Conference

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1 GC-101 Testing of Biodiesel Using Gas Chromatography by Bob Armantrout (Image Research Machines plc) Presented at: Local Biodiesel: A Biodiesel Coop Conference Strategies For Community-based Biodiesel Groups July 14 July 16, 2006

2 Triglycerides to Methyl Ester (Image Research Machines plc)

3 Why Glycerin is Bad in Biodiesel From: US Department of Energy Biodiesel Handling and Use Guidelines, Second Edition, March 2006 Free and total glycerin numbers measure the amount of unconverted or partially converted fats and by-product glycerin present in the fuel. Incomplete conversion of the fats and oils into biodiesel can lead to high total glycerin. Incomplete removal of glycerin can lead to high free glycerin and total glycerin. If these numbers are too high, storage tank, fuel system, and engine fouling can occur. Fuels that exceed these limits are highly likely to cause filter plugging and other problems.

4 How Glycerin is Removed from Biodiesel Converting the triglycerides, diglycerides, and monoglycerides to methyl esters to reduce the levels of bound glycerin. Washing the esters to remove glycerin.

5 ASTM Specification for Glycerin D e1 stipulates: Free Glycerin 0.020% mass or less Total Glycerin 0.240% mass or less The total glycerin method is used to determine the level of glycerin in the fuel and includes the free glycerin and the glycerin portion of any unreacted or partially reacted oil or fat. Low levels of total glycerin ensure that high conversion of the oil or fat into its mono-alkyl esters has taken place. High levels of mono-, di-, and triglycerides can cause injector deposits and may adversely affect cold weather operation and filter plugging. (ASTM e)

6 The Equipment Hewlett Packard - Model 5890A-II Gas Chromatograph Unit includes an autosampler, column, pc, software, and gas regulators AIR will provide delivery, installation, familiarization and a 6-month warranty AIR will provide service outside of warranty for a fee. Total quote price: $13, (Oct. 2005) Work will begin upon receipt of purchase commitment, leadtime is 1 to 2 weeks.

7 What the GC does Precisely measures the percent mass of free glycerin, mono, di and triglycerides in a sample of methyl esters.

8 How the GC works A Gas Chromatograph (GC) is a chemical analysis instrument for separating chemicals in a sample. It uses a thin capillary fiber known as the column, through which different chemicals pass at different rates depending on various chemical and physical properties. The function of the column is to separate different components, causing each one to exit the column at a different time. As the chemicals exit the end of the column, they are detected and identified electronically. (from Wikipedia)

9 How the GC works An FID is an ion detector which uses an air-hydrogen flame to produce ions. As components elute from the GC's column they pass through the flame and are burned, producing ions. The ions produce an electric current, which is the signal output of the detector. The greater the concentration of the component, the more ions are produced, and the greater the current. (from Wikipedia)

10 ASTM D6584 prescribes the method for GC setup, sample prep and chromatogram analysis. 4. Summary of Test Method 4.1 The sample is analyzed by gas chromatography, after silyating with N-methyl-N-trimethylsilyltrifluoracetamide (MSTFA). Calibration is achieved by the use of two internal standards and four reference materials. Mono-, di-, and triglycerides are determined by comparing to monoolein, diolein, and triolein standards respectively. Average conversion factors are applied to the mono-, di-, and triglycerides to calculate the bonded glycerin content of the sample. Copyright by ASTM Int'l

11 Maintenance and Repair Calibration Use Standards to calibrate GC for glycerol, monolein, diolein, butanetriol, tricaprin. Retention time (RT) changes indicate instrument status Decreasing RTs are are typically caused by column aging Increasing RTs typically caused by leaks in septa, connections, low gas pressures. Repair Septa replacement Column replacement Syringe replacement

12 Other Equipment and Supplies Additional Lab Ware required to use the GC: Analytical Balance - $1500 Pipetter 100 microliter (µl) $250 15ml vials for sample prep 2ml vials with septa top Compressed Gases Helium, Hydrogen, Compressed Air USP grade, tanks run about $50 to $70 each Chemical Standards, Carriers Calibration Standards monolein, diolein, triolein Butanetriol and Tricaprin - $150 each per 5ml Heptane used as a carrier for sample Hexane for syringe cleaning

13 Facility Considerations Sturdy Desk to set GC on Dedicated power circuit Small refrigerator for storage of standards Fire Cabinet for storage of reagents Proper storage of gas bottles

14 Equipment and Material Suppliers Analytical Instrument Recycle Telephone: Toll Free: (U.S.) Sigma-Aldrich/Supelco Telephone: (U.S.) 6390 Joyce Dr. Suite 200W Golden, CO 80403

15 Photo Essay of GC Testing Process

16 Sample Preparation (logbook & glassware) Weigh the Sample (analytical balance)

17 Lab refrigerator Add Internal Standards (micropipetter )- 100 microliters (µl) each of MSTFA, and internal standards 1 & 2 Add heptane 8 ml

18 Load sample to GC vial Place vial in GC autosampler

19 Load Sample Data into GC Software Start the Run

20 Analysis of Chromatograms

21 Approximate Relative Retention Times

22 Calculating Glycerin Levels

23 Chromatograms The Good

24 Chromatograms The Good

25 Chromatograms The Good

26 Chromatogram The Bad

27 Chromatogram The Ugly

28 Understanding your Processes Conversion recipe development

29 Understanding your Processes Tracking glycerin removal through washing

30 Verifying your testing process Lab cross checking is a good way to assure your lab equipment and procedures are providing valid results

31 Verifying your testing process

32 Third Party GC Testing Magellan will test biodiesel for Free & Total Glycerin for under $100 A 10 ml sample is required

33 Third Party GC Testing Intertek will test biodiesel for Free & Total Glycerin for $275 A 10 ml sample is required

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