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EN 14103 - Thermo Scientific

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The world leader in serving science<br />

Recent Developments to<br />

Enhance Productivity in the GC<br />

Characterization of Pure<br />

Biodiesel (B100)<br />

Fausto Munari, Daniela Cavagnino,<br />

Andrea Cadoppi<br />

<strong>Thermo</strong> Fisher <strong>Scientific</strong> Inc., Italy


Biodiesel Production<br />

Oil (Triglicerydes)<br />

+ Methanol<br />

NaOH<br />

FAMEs<br />

+ Glycerine<br />

R<br />

CH 2<br />

--O-C=O<br />

|<br />

C H-O-C=O<br />

| R<br />

CH 2<br />

-O-C=O<br />

R<br />

3 CH 3 OH<br />

3<br />

R-C=O<br />

|<br />

OMe<br />

HO-CH 2<br />

|<br />

H-C -OH<br />

|<br />

HO-CH 2<br />

Raw Material Transesterification Main Product By-Product<br />

Agent<br />

2


Biodiesel Specification: GC-based Official Methods<br />

Definition of all quality criteria for commercial<br />

biodiesel based on physical and chemical properties<br />

needed for safe and satisfactory engine operation<br />

<strong>EN</strong> 14214<br />

catalyst<br />

ASTM D6751<br />

Total Glycerin < 0.25% m/m <strong>EN</strong>14105 < 0.24% m/m<br />

Oil Methanol BioDiesel Glycerin<br />

<strong>EN</strong>14105<br />

Free Glycerin < 0.02% m/m < 0.02% m/m D6584<br />

Mono-glycerides<br />

Di-glycerides<br />

Tri-glycerides<br />

Total Esters<br />

Linolenic acid<br />

methyl ester<br />

Methanol<br />

< 0.80% m/m<br />

< 0.2% m/m<br />

< 0.2% m/m<br />

> 96.5% m/m<br />

<strong>EN</strong>14105<br />

<strong>EN</strong>14105<br />

<strong>EN</strong>14105<br />

<strong>EN</strong><strong>14103</strong><br />

< 12.0 % m/m <strong>EN</strong><strong>14103</strong><br />

< 0.2% m/m<br />

<strong>EN</strong>14110<br />

D6584<br />

3


Official <strong>EN</strong> / ASTM Methods for Biodiesel analysis<br />

• <strong>EN</strong> 14105 / ASTM D6584 - Free and Total Glycerin analysis<br />

• GC: On-column/FID<br />

• Liquid AS<br />

catalyst<br />

• Non-polar column phase (High T)<br />

• <strong>EN</strong> <strong>14103</strong> - Total FAME and Linolenic acid methyl ester analysis<br />

Oil Methanol BioDiesel Glycerin<br />

• GC: PTV/FID<br />

• Liquid AS<br />

• Wax column phase<br />

• <strong>EN</strong> 14110 <strong>EN</strong> 14110 - Residual Methanol analysis<br />

• GC: SSL/FID<br />

• Headspace AS<br />

• Non-polar or polar column phase<br />

4


The world leader in serving science<br />

<strong>EN</strong> 14105 / ASTM D6584<br />

Free and Total Glycerin


<strong>EN</strong>14105 / D6584: Content of Free and Total Glycerin<br />

Purpose:<br />

<br />

Free and bonded glycerin reflect the quality of biodiesel<br />

<br />

Low levels of total glycerin ensure high conversion of the oil<br />

<br />

High levels of glycerin and glycerides can cause injector deposit,<br />

clogged fueling system and can affect cold weather operation<br />

6


<strong>EN</strong>14105 / D6584: Content of Free and Total Glycerin<br />

• The sample is derivatized with N-Methyl-N-Trimethylsylil-trifluoroacetamide<br />

(MSTFA) to convert the –OH groups into –<br />

OSi(Me) 3<br />

• Internal Standards and Reference materials:<br />

- Butan-Triol (IS1) for Glycerin<br />

- Tricaprin (IS2) for Mono, Di and Tri-Glycerides<br />

- Glycerin, Mono-Olein, Di-Olein, Tri-Olein<br />

• Analysis time about 30 min<br />

7


<strong>EN</strong>14105 / D6584: Content of Free and Total Glycerin<br />

The method requires:<br />

High oven temperature program<br />

A non-discriminative injector to get total recovery of compounds with<br />

a broad range of boiling points, and preserve sample integrity<br />

<strong>Thermo</strong> <strong>Scientific</strong> Solution<br />

• True cold On-column injector<br />

• TRACE TR-BIODIESEL(G) column (10 m, 0.32 mm i.d., 0.1 µm f.t.)<br />

• Low dead volume gas-purged metal connector<br />

8


<strong>Thermo</strong> <strong>Scientific</strong> True Cold On-Column Injector<br />

• Discrimination free (for definition)<br />

• Absolute sample integrity (the inlet is never<br />

heated!)<br />

• Absolutely free of any contamination or<br />

cross-contamination, when syringe<br />

cleaning is correctly performed<br />

• No septa for the injector, only valve and<br />

o-ring (no silicone contamination)<br />

• Fully automatic injection procedure<br />

performed by the TriPlus Autosampler<br />

9


<strong>Thermo</strong> <strong>Scientific</strong> High Temperature Column<br />

<br />

<strong>Thermo</strong> <strong>Scientific</strong> solution with TRACE TR-<br />

BIODIESEL (G) fused silica column can deliver<br />

proven enhanced mechanical robustness for this high<br />

oven temperature method, resulting in extended<br />

lifetime (no mechanical breakage, no loss of<br />

efficiency)<br />

Retention Gap is usually used<br />

Critical issue:<br />

The connection between the pre-column and the analytical column could<br />

be the weak point of the system at high oven temperatures.<br />

10


HT Connection – <strong>Thermo</strong> <strong>Scientific</strong> Solution<br />

High temperature purged connection for automatic OC injector<br />

Leak free even with large temperature variations<br />

Dead volumes are eliminated by purging inert gas<br />

No use of glass press-fits!<br />

11


Further Development: Integrated Retention Gap<br />

Direct On-column injection<br />

15 m, 0.25 mm ID tubing<br />

Narrow bore capillary 0.25 mm ID, 15 m<br />

(5 m integrated Retention Gap)<br />

Silicon phase, 0.25 µm film thickness<br />

5 m x 0.25 mm ID<br />

retention gap<br />

Biodiesel (G) phase<br />

12


Calibration Curves<br />

ASTM / <strong>EN</strong> requirement:<br />

R 2 > 0.99<br />

Glycerin<br />

Mono-glycerides<br />

Diglycerides<br />

Triglycerides<br />

R2 = 0.9993<br />

R2 = 0.999997<br />

R2 = 0.999994<br />

R2 = 0.99965<br />

13


<strong>EN</strong> 14105 / ASTM D6584: Example of Biodiesel Analysis<br />

14


<strong>EN</strong> 14105 / ASTM D6584: Example of Biodiesel Analysis<br />

15


<strong>EN</strong> 14105: Example of Repeatability<br />

Similar performance obtained by repeating the double<br />

runs in successive days<br />

16


No Carryover<br />

Blank analysis (solvent only) after a sequence of<br />

biodiesel samples<br />

Total absence of any carry-over effect: the heavy<br />

fraction has completely eluted from the column<br />

17


Summary for ASTM D6584/ <strong>EN</strong>14105<br />

Injection system<br />

• True Cold On-Column injector as recommended best injection system<br />

for glycerides<br />

Capillary Column and High T column connection<br />

• Excellent separation and column robustness for high T<br />

• No dead volumes and no leaks<br />

Excellent Performance<br />

• Linearity and repeatability exceed the minimum requirements of the official<br />

standards<br />

18


The world leader in serving science<br />

<strong>EN</strong> <strong>14103</strong><br />

Total FAME and Linolenic Acid<br />

Methyl Ester


<strong>EN</strong> <strong>14103</strong>: Total Esters and Linolenic methyl ester<br />

Purpose:<br />

<br />

<br />

<br />

<br />

The method allows to verify that the total esters content is > 96.5% m/m<br />

and the Linolenic acid methyl ester is < 12% m/m<br />

The method allows the characterization of FAMEs composition<br />

The cetane number of biodiesel depends on the distribution of fatty<br />

acids in the original oil<br />

An accurate characterization of FAMEs in biodiesel blends is essential<br />

for a more accurate calculation of the cetane index<br />

Method:<br />

<br />

<br />

Calculation of the percentage of FAMEs is achieved with Internal<br />

Standard calibration (Methyl Heptadecanoate)<br />

Analysis time about 12min<br />

20


<strong>EN</strong> <strong>14103</strong>: Total Esters and Linolenic methyl ester<br />

This method requires a detailed FAMEs GC analysis by using a polar<br />

stationary phase (Wax) type<br />

The method is suitable for FAMEs in the range between C14 and C24<br />

<strong>Thermo</strong> <strong>Scientific</strong> Solution<br />

• PTV with Backflush system<br />

• TRACE TM TR-BIODIESEL(F) column (30 m, 0.25 mm i.d., 0.25 µm f.t.)<br />

21


<strong>EN</strong> <strong>14103</strong>: Total Esters and Linolenic methyl ester<br />

Risk of column contamination by Tri-glycerides, affecting medium term<br />

column performance<br />

Oil<br />

Glycerin<br />

PTV backflush option prevents column<br />

contamination and delivers longer lifetime<br />

22


PTV Backflush<br />

When FAME are analyzed, the<br />

heavier fraction (Di, Tri-Glycerides<br />

and other heavy compounds) can<br />

be vented out of the injection<br />

system preventing Wax column<br />

contamination.<br />

Detector<br />

Analytical<br />

column<br />

Aux.<br />

connectio<br />

n<br />

Injector<br />

Precolumn<br />

T connection<br />

Oil<br />

Glycerin<br />

23


<strong>EN</strong> <strong>14103</strong>: Total Esters and Linolenic methyl ester<br />

Biodiesel sample with Methyl Heptadecanoate (IS)<br />

Backflush activated 3 min after injection<br />

24


<strong>EN</strong> <strong>14103</strong>: Total Esters and Linolenic methyl ester<br />

Repeatability test<br />

(*) The absolute difference between 2 independent single test results, obtained using the same method<br />

on identical test material in the same laboratory by the same operator using the same equipment with a<br />

short time interval (definition reported on <strong>EN</strong> <strong>14103</strong>).<br />

RSD% of Retention Times is approx. 0.05% (10 runs)<br />

The Backflush device preserves the column<br />

even after multiple injections<br />

25


The world leader in serving science<br />

<strong>EN</strong> 14110<br />

Residual Methanol


<strong>EN</strong> 14110: Content of Residual Methanol<br />

Purpose:<br />

<br />

<br />

<br />

The method allows to verify that the residual methanol is < 0.2% m/m<br />

Residual methanol is a safety issue since even small amounts reduce<br />

the flash point<br />

Residual methanol can affect also fuel pumps, seals and elastomer and<br />

can result in poor combustion properties<br />

Method:<br />

GC Headspace sampling technique is required after incubation at 80°C<br />

<br />

<br />

Calibration is achieved with external standard or internal standard<br />

(2-propanol)<br />

Analysis time about 5 min<br />

27


<strong>EN</strong> 14110: Content of Residual Methanol<br />

This method requires a suitable column (with polar or non-polar phase)<br />

capable of eluting methanol as a symmetric peak<br />

The method requires Headspace GC<br />

<strong>Thermo</strong> <strong>Scientific</strong> Solution<br />

• TRACE TR-BIODIESEL(M) column (30m, 0.32mm i.d., 3.0µm f.t.)<br />

• TriPlus Headspace autosampler<br />

28


<strong>EN</strong>14110 – Linearity and Repeatability<br />

29


The world leader in serving science<br />

Comprehensive GC Solution for<br />

Tremendous Productivity


GC Biodiesel Analysis: Summary<br />

• <strong>EN</strong> 14105 - Glycerin and Glycerides analysis<br />

GC: On-column/FID – Liquid AS<br />

Non-polar column phase (High T)<br />

catalyst<br />

• <strong>EN</strong> <strong>14103</strong> - Esters and linolenic acid - methyl ester<br />

analysis<br />

Oil Methanol BioDiesel Glycerin<br />

GC: PTV Backflush/FID – Liquid AS<br />

Wax column phase<br />

• <strong>EN</strong> 14110 - Methanol analysis<br />

GC: SSL/FID – Headspace AS<br />

Non-polar column phase<br />

NOTE: The Wax column and the non-polar high T column must be located in 2 different GC ovens<br />

31


Comprehensive Assembly for GC Biodiesel Methods<br />

1 Package, 3 Methods<br />

TriPlus Autosampler - Serving three injectors on two GCs<br />

Right GC:<br />

• OCI-FID High Oven T<br />

(<strong>EN</strong> 14105 / ASTM D6584 -<br />

Glycerin)<br />

Left GC:<br />

• SSL-FID, Headspace (<strong>EN</strong> 14110 - Methanol)<br />

• PTV-FID (<strong>EN</strong> <strong>14103</strong> - FAME)<br />

32


Conclusions<br />

Advanced GC Solutions for Biodiesel Analysis<br />

• True cold On-column injector for total sample integrity and<br />

recovery, delivering reliable determination of free and total glycerin<br />

• Leak-free column connection for high temperature chromatography<br />

• PTV Backflush device to preserve the system from contamination<br />

when tri-glycerides are not of interest<br />

• Accurate optimization of suitable column phases<br />

• 1 single assembly (2 GCs, 1 AS) for high productivity<br />

33


For More Information<br />

Visit www.thermo.com/gcbiodiesel<br />

34

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