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{{LSApp
  |name        = Biofuels
  |image       = 6584.jpg
  |type        = Sample Prep and Inject
  |id          = Biodiesel ASTM 6584
  |description = Determination of Free and Total Glycerin in B-100 Biodiesel Methyl Esters by Gas Chromatography
}}
{{logo}}
=== Overview ===
Glycerin content can indicate the quality of biodiesel. Glycerin can be in the form of free glycerin or bound glycerin in the form of glycerides. Total glycerin is the sum of these.  A high content of free and total glycerin can lead to buildup in fuel tanks, clogged fuel systems, injector fouling and valve deposits. Unrelated glycerides and free glycerin make the product behave more like soap rather than fuel. 

ASTM Method D6571 specifications serve as the benchmark which identifies the standards that pure biodiesel (B100) must meet before being used as a fuel or blended with petrodiesel. There are 14 different required tests according to ASTM D6751-03. The US National Biodiesel Board has adopted the ASTM biodiesel specification and analytical methodology.  ASTM recommends test method D6584 for the analysis of glycerin in biodiesel fuel by gas chromatography.

Gas chromatography can also serve as a tool for process troubleshooting during biodiesel production to ensure trouble-free operation of the fuel in diesel engines. Monitoring the level of free glycerin and any unrelated mono-, di-, and triglycerides will indicate the efficiency and progress of the chemical reaction during the process of making biodiesel.

ASTM Method D6584 provides for the quantitative determination of free and total glycerin in B-100 methyl esters by gas chromatography. The range of detection for free glycerin is 0.005 to 0.05 mass%, and total glycerin from 0.05 to 0.5 mass %. This method is not applicable to vegetable oil methyl esters obtained from lauric oils, such as coconut oil and palmkernel oil. ASTM Method D6584 deals with expensive and toxic reagents and requires very complex and time consuming procedures for preparing calibration standards and finished B100 biodiesel. Manual standards and sample preparation remains a tedious chore that can significantly contribute to errors and lost precision in the GC analysis. Automation can help with all of these. 

=== Significant Markets  ===
* Biodiesel Manufactures

* Biodiesel Blenders

* Biodiesel Distributors

* Biofuels CROs

* Fleet Managers

'''ASTM Method D684'''

'''9. Calibration and Standardization'''

'''9.2 Standard Solutions''' – Prepare the five standard solutions in ''Table 3'' by transferring the specified volumes by means of Microliter syringes to 10mL septa vials. Add to each of the five standard solutions 100uL of MSTFA. Close the vial and shake. Allow the vial to stand for 15 to 20 minutes at room temperature. Add approximately 8 mL n-Heptane to vial and shake.

{| border="1"
|+ '''TABLE 3 Standard Solutions'''
! Standard Solution Number !! 1 !!  2 !!  3 !!  4 !!  5 
|-
! uL of glycerin stock solution
| 10 || 30 || 50 || 70 || 100
|-
! uL of monoolein stock solution
| 20 || 50 || 100 || 150 || 200
|-
! uL of diolein stock solution
| 10 || 20 || 40 || 70 || 100
|-
! uL of triolein stock solution
| 10 || 20 || 40 || 70 || 100
|-
! uL of butanetriol stock solution
| 100 || 100 || 100 || 100 || 100
|-
! uL of tricaprin stock solution
| 100 || 100 || 100 || 100 || 100
|}

'''9.4 Standardization'''<br/>  
'''9.5''' Inject 1 uL of the reaction mixture into the cool-on-column injection port and start the analysis. 

'''10. Procedure'''<br/> 
'''10.1''' Weigh to the nearest 0.1 mg approximately 100 mg of sample directly into a 10 mL septa vial. Using Microliter syringes, add exactly 100 uL of each internal standard and MSTFA. Shake the vials, and allow to set for 15 to 20 minutes at room temperature. Add approximately 8 mL of n-Heptane to vial and shake. 

'''10.2''' Inject 1 uL of the reaction mixture into the cool on-column injection port and start the analysis.

=== LEAP's Approach ===

[[Image:6584.jpg|200px|thumb|left|System shown with Agilent 7890 and Twin PAL]]
               
The Lower PAL is the Prep PAL and runs on [http://www.leaptec.com/products/lc-related-instruments-and-accessories/ctc-hts-pal-and-ctc-htc-pal-software/cycle-composer-remote-control-software-106.php '''Cycle Composer Software''']. All of the sample prep is performed with this PAL. There is a 100ul syringe for the solvent transfers. There are (7) 2mL solvent locations. There is a DISPTool that is hooked up to a 5 mL dilutor syringe for the 8 mL Heptane addition. There is a fast wash station that Wash1 is filled with Toluene and Wash 2 is filled with Heptane. There is an agitator that is set at 35 deg C and 500RPM to do the mixing. 

The Upper PAL is the Inject PAL and runs under ChemStation Software control. This requires Agilent CTC Control Software supplied by Agilent. It is using a 5 ul syringe with a tapered needle to do 1 ul on column injections into the rear injection port. There is a fast wash station that Wash1 is filled with Toluene and Wash 2 is filled with Heptane. 

The expected Sample Prep Time is approximately 26 minutes<br/>
The expected GC Runtime is approximately 31.81 minutes<br/>
The expected GC Cool down time is approximately 7 minutes<br/>

<br/><br/>

=== Software Control ===
The Lower PAL is the Prep PAL and runs on Cycle Composer Software. 

The Upper PAL is the Inject PAL and runs under [http://www.leaptec.com/products/lc-related-instruments-and-accessories/ctc-hts-pal-and-ctc-htc-pal-software/cycle-composer-remote-control-software-106.php '''Cycle Composer Software''']control.


This process can be done on other GC's and data systems and does not require the Agilent approach.

Also, LEAP now has the ability use the new [http://www.leapwiki.com/mediawiki/index.php?title=Category:Chronos '''Chronos software'''] as it organizes parallel processes for sample preparation. This utilities the analysis system to a much greater extent, while observing the time margins of each individual sample preparation. There is a '''single sample list''' for the entire process and integrates well with ChemStation.

=== Screenshots ===
[[image:Photo_Icon.png|40px]]
<gallery>
  Image:5stndardsprep.png  | Cycle Composer 5 Standards Prep
  Image:6584SamplePrepISMSTFA.png | Cycle Composer Sample Prep
  Image:CCSTD prep sample list.png  | Cycle Composer Prep Standards
  Image:6584StandardsPrep.png | ChemStation Sequence Table
  Image:SequencetableA.png | ChemStation Sequence Table
  Image:1_ul_inj.png | ChemStation PAL Method for Injection
  Image:GCInjfor6584.png | ChemStation and Cycle for injection
</gallery>

=== Video ===

[[Image:Movie Icon.png|40px]]  [http://www.youtube.com/watch?v=T1K_zCkPkIE Dispense tool in action on youtube]
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===Useful links ===
[[Image:Www icon.png|40px]] [http://www.4cleanfuels.com/biofuels/BioDQuality8-07/FQ_workshop-PiedmontBioFuels.pdf An overview of all tests that must be run by Piedmont Biofuels]

[[Image:Www icon.png|40px]] [http://www.chem.agilent.com/cag/prod/GC/Biodiesel_QR.pdf A good general reference site by Agilent]

[[Image:Www icon.png|40px]] [http://biodiesel.engr.uconn.edu/home/Stuart.pdf UCONN.com   A good general reference site on Biodiesel ASTM Methods]

[[Image:Www icon.png|40px]] [http://www.biodiesel.org  A good general reference site on Biodiesel  ]

[[Image:Www icon.png|40px]] [http://www.biodieselmagazine.com/plant-list.jsp Biodiesel Plant Listing ]

[[Image:Www icon.png|40px]] [http://www.biodieselconference.org/2009/default.asp Biodiesel Conference 2009 ]

[[Image:Www icon.png|40px]] [http://www.biodieselconference.org/2010/default.asp Biodiesel Confernece 2010]

[[Image:Www icon.png|40px]] [http://www.nrel.gov/docs/fy07osti/41549.pdf NREL B100 ]

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LEAP provides automated workstation instrumentation solutions based on the LEAP CTC PAL X, Y, Z syringe only autosampler robot from LEAP Technologies. This extremely flexible, precise, and adaptable liquid handling robotic platform is available in a variety of lengths and options depending on the requirements of your sample preparation and injections for your UHPLC, LC or GC chromatography.LEAP offers full support and service for the PAL platform in addition to being able to write custom macros, cycles, and scheduling to your applications. Please contact LEAP Technologies on how we can help you get maximized throughput with flexible pipetting automation solutions.

=== Contact LEAP ===
{{contact|topic=the PAL and the application}}

[[Category: Biofuel]]
[[Category:Application_Solutions]]
[[Category:Cycle Composer]]
[[Category:Gas Chromatography]]
[[Category:Chronos]]