BioDiesel | Uses for Supercritical Fluids

Supercritical Alcohol Reaction for Biodiesel Synthesis without Catalysts

This new technology utilizes supercritical alcohol to allow the normally immiscible oil and alcohol to form a single phase solution. At supercritical alcohol conditions, the solubility parameter of an alcohol is reduced and leads to formation of a homogeneous phase between the alcohol and oil.


Supercritical alcohol reaction allows for the use of inexpensive feedstock such as waste oils and fats which contain high proportions of these impurities.

                             Triglycerides + 3 Methanol =3 FAME+ Glycerol


In addition to the supercritical alcohol reaction, there are many other supercritical methods for carrying out the transesterification reaction.


Two-step SCFs Process for Non-Catalytic Biodiesel Synthesis using Subcritical H2O

An alternative non-catalytic process in supercritical fluids for the synthesis of biodiesel fuel consists in a two steps process. In this method, triglycerides are firstly hydrolyzed to free fatty acids, and in a second step are esterified to the corresponding esters. The reduction of the dielectric constant of water with increasing temperature promotes the miscibility between water and the oil, favoring a hydrolysis process. This allows acid and base catalysed reactions to be performed in high temperature pressurized water with no catalyst. Hence, subcritical H2O is used as both the solvent and the catalyst for the hydrolysis step at 270 °C, 7 MPa at a volumetric water/triglyceride ratio of 1:1.  After hydrolysis, two layers are formed, the upper portion containing fatty acids and the lower portion water with glycerol. In a second step, FAMEs are produced in supercritical methanol at 270 °C and 7 MPa.


                            Step 1          Triglycerides + H2O = 3 Fatty Acids + Glycerol

                          Step 2           Fatty acids +Methanol = FAMEs +Water


Glycerol Free Supercritical Reactions


Supercritical Methyl Acetate

In order to prevent the production of glycerol as a by-product, methyl acetate instead of methanol is used under supercritical conditions. The supercritical methyl acetate method converts triglycerides into fatty acid methyl esters (FAMEs) and triacetin, instead of glycerol without catalyst.  Triacetin, a valuable fuel additive is formed simultaneously which leads to simplified downstream processes compared to conventional catalytic reactions while the mixture of FAME and triacetin can be utilized as biodiesel, rather than FAMEs only.


Triglycerides + 3 Methyl Acetate = 3 FAMEs +Triacetin


Supercritical Dimethyl Carbonate

Biodiesel can be produced from triglycerides and dimethyl carbonate in a non-catalytic process by using supercritical dimethyl carbonate. Triglycerides as well as fatty acids are converted to fatty acid methyl esters (FAMEs). With this methodology another valuable compound, glycerol carbonate, is obtained as a secondary product, instead of the undesirable glycerol, and a weak acid, such as citramalic acid, as the main by-product.


 Triglycerides +3 DMC = 3 FAMEs + Glycerol carbonate + Citramalic acid



Biodiesel is a fuel that is typically made by chemically reacting lipids (triglycerides) with an alcohol producing fatty acid esters. The most common alcohol used in the reaction is methanol which produces fatty acid methyl esters.  Conventionally, the transesterification reaction of triglycerides is conducted using homogeneous basic catalysts such as sodium hydroxide and potassium hydroxide or acid catalysts including sulfuric acid and phosphoric acid.

These catalytic reactions have many problems that make them unattractive. Generally, alcohol and vegetable oil do not form a single phase solution. The poor contact between these two reactants causes reactions to proceed slowly, and therefore require intense mixing.  Also, the recovery of glycerol is difficult due to contamination with methanol and catalyst.  Moreover, the alkaline or acidic waste water generated from the separation requires additional disposal costs. All together, these problems are the result of using catalyst in the reaction, but without catalyst, the reaction rate is too slow to effectively produce biodiesel. Therefore, alternative technologies which do not require a catalytic process are the subject of intensive research.

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