EN 14103 - Thermo Scientific
EN 14103 - Thermo Scientific
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 />
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For More Information<br />
Visit www.thermo.com/gcbiodiesel<br />
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