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The four primary driving forces behind biofuels are the world's increasing thirst for petroleum (80 Mbarrels/day), the diminishing supply of fossil fuels, global warming and the intention to reduce the dependence on fuel imports. Additionally, most biofuels are produced by straightforward manufacturing processes, are readily biodegradable and nontoxic, have low emission profiles and can be used as is or blended with conventional fuels. Biodiesel is produced by transesterifying the triglycerides in the parent oil or fat with an alcohol, usually methanol, in the presence of a catalyst (base, acid or enzyme) to yield fatty acid methyl esters (FAME) and free glycerol as co-product. Since reaction rates under acid or enzyme catalysis are relatively slow, most producers use the rapid alkali-catalyzed transesterification.
As mentioned above, molecular glycerol in the biofuel is called free glycerol. Generally, a high free glycerol content points to incomplete separation of the ester and glycerol phase.
Free glycerol in B2 blend Sample vessel: separating funnel Sample prep.: extraction - weigh 5 g sample - add 45 g distilled water - seal and shake for 5 minutes - allow phase separation - withdraw aqueous phase - place in autosampler Column: Eluent: Flow: Loop: Metrosep Carb 1 250 100 mmol/L NaOH 1.0 mL/min 10 L
Petroleum diesel fuel sample B0 Sample prep.: as mentioned above Column: Eluent: Flow: Loop: Metrosep Carb 1 250 100 mmol/L NaOH 1.0 mL/min 10 L
Total glycerol
Incomplete reaction leads to the formation of residual glycerol intermediates such as mono-, di- and triacylglycerides (bonded glycerols). In contrast, complete conversion results in the formation of highly water-soluble glycerol (free glycerol). The latter is separated from the final product at the end of the production process. However, traces of glycerol are frequently found in the ester phase. Both free and bonded glycerols (= total glycerol) lead to severe operational problems such as injector deposits or filter clogging. Accordingly, the US ASTM D 6751 and the European EN 14214 specify a maximum total glycerol content of 2400 ppm (0.24%) and 2500 ppm (0.25%), respectively. The maximum free glycerol content is limited to 200 ppm (0.02 %) in both standards, which stipulate gas chromatographic (GC) analysis involving time- and reagent-consuming derivatizations. In addition, GC methods still encounter coelution problems with biodiesel samples produced from or containing lauric oils, such as coconut and palm kernel oil. This paper demonstrates sensitive analysis of the free and total glycerol content via simple and innovative ion chromatography followed by pulsed amperometric detection. Total glycerol is the sum of free and bound glycerol. The latter is the sum of residual mono-, di- and triglycerides and is due to incomplete esterification reactions.
Total glycerol in B2 blend Sample vessel: sealed reflux vessel Sample prep.: saponification/extraction - weigh 2 g sample - add 5 mL 1.0 mol/L KOH - heat to 95 C and stir under reflux for 30 minutes - cool to room temperature - rinse 3 times with 510 mL H2O - adjust volume to 50 mL - place in autosampler Column: Eluent: Flow: Loop: Metrosep Carb 1 250 100 mmol/L NaOH 1.0 mL/min 10 L
Sample prep.: glycerolfree: extraction glyceroltotal: saponification/extraction Column: Eluent: Flow: Loop: Metrosep Carb 1 250 100 mmol/L NaOH 1.0 mL/min 10 L
The excellent MDL of 0.7 ppm (7105%) for free and total glycerol determination exceeds by far the MDL required by the ASTM D 6751 or EN 14214 standard (both 200 ppm, 0.02%).
Summary
The free and total content of detrimental glycerol in vegetable oil methyl esters (biodiesel) is of paramount importance for the quality of biodiesel and is therefore limited by the US ASTM D 6751 and the European EN 14214 standards. Both regulations currently stipulate gas chromatographic (GC) analysis of free and total glycerol. However, the GC method, apart from being expensive, requires tedious derivatizations and fails for glycerol determinations in coconut or palm kernel oil methyl esters. In contrast, the presented ion chromatographic method is applicable to all types of vegetable oil methyl esters. Prior to chromatographic separation, free glycerol and bound glycerol are isolated by a straightforward extraction and saponificationextraction technique, respectively. Integrated pulsed amperometric detection following chromatographic separation achieves an outstanding method detection limit (MDL) of 0.7 ppm for free and total glycerol and thus easily exceeds ASTM and EN performance specifications. Spike recovery rates for free and total glycerol are within 93104% and 87100%, respectively.
Total glycerol Recovery [%] 103.71 98.11 102.39 93.62 Measured1 [10 %] 1.086 2.975 6.103 12.413
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System setup