7/14/2014 Biodiesel Magazine - The Latest News and Data About Biodiesel Production

http://www.biodieselmagazine.com/articles/500/the-ethyl-biodiesel-alternative 1/3
BUSINESS POLICY FEEDSTOCK PRODUCTION DISTRIBUTION QUALITY USE Search Bi odi esel Magazi nesearch

North America Latin America Europe Asia-Pacific Africa & the Middle East
HOME MAGAZINE JOBS E-NEWSLETTER EVENTS BIODIESEL PLANTS SUBSCRIBE STORE DIRECTORY
NEW
FOLLOW US ON

The Ethyl Biodiesel Alternative
By Tom Novinson, Ph.D. | March 01, 2004
Small and medium sized biodiesel producers are growingly interested in exploring simpler,
more environment friendly ways to make biodiesel. Several factors make these alternative
production methods appealing: (1) producers can avoid the labor-intensive glycerol removal
process, (2) utilize ethanol instead of methanol and (3) sidestep the hazardous use of sodium
hydroxide or other strong alkali. Currently, methanol is preferred over ethanol only because it
is less sensitive to water in the alkali procedure. Imagine a process where one doesn't have to
worry about this (and where less toxic ethanol could be used).
Processes that allow biodiesel producers to simply mix alcohol and oil, pour the liquid over a
catalyst and collect the products as they drip into a receiver, are trouble-free, flexible and
growingly viable. Glycerol is still produced, but there is no need to wash the biodiesel esters
and neutralize the corrosive alkali.
Drawbacks of standard methods
Standard methods for producing biodiesel, a mixture of alkyl (methyl or ethyl) esters of fatty
acids, is to heat vegetable oils or mixed animal-vegetable oils with (a) a strong alkali and (b)
methanol or ethanol. Biodiesel forms during a process known as transesterifcation, which is
simply the exchange of the original alkyl group of the fat (oil) with the methyl group of the
methanol (or ethyl group of the ethanol). The diagram below displays transesterification.
RCOOR' (fat or oil) + NaOH (alkali) + MeOH (methanol) ? RCOOMe + glycerol (biodiesel ester)
The RCOOMe (mixture of several methyl esters) is the biodiesel (methyl ester of fatty acids
from the animal or vegetable oil).
The final biodiesel product still has to be washed with water, neutralized and "dried" or
"salted out" (to remove water) to be suitable for use as a biodiesel fuel or fuel additive.
The initial alkali reaction transesterification reaction requires the removal of glycerol, partway
through the reaction, which is a real time consumer and is labor intensive.
Methanol is convenient, because of its insensitivity to water, but it is a questionable
environmental choice. Methanol is highly toxic to humans. Even a few milliliters can cause
blindness and violent nausea, as historians can tell us. During the Prohibition, when ethanol
was not readily available, people drank "wood alcohol" (methanol) and went blind, or even
died. Vapors of methanol are irritating to the lungs and can damage the eyes, even in small
doses. Methanol is metabolized by the body to formaldehyde (which is also very toxic) and
then to formic acid (which is also toxic). Formic acid is found in the bodies of stinging ants.
Sodium hydroxide, also known as "lye," is very corrosive. It also dissolves slowly in methanol.
On a large scale, solid sodium hydroxide is exothermic (evolves heat) and can cause the
alcohol to heat or boil. Handling sodium hydroxide and methanol, can be dangerous to
workers-especially those without chemistry education and laboratory safety experience. A far
safer procedure is to avoid the sodium hydroxide altogether.
Another problem is the interference of glycerol (glycerine or propane-1, 2, 3-triol). The
glycerol has to be removed in order to drive the equilibrium of the reaction to the right, that
is, to get a good yield of the biodiesel methyl esters (instead of returning to the original oil
and alcohol).
Using a Simple, Greener Chemistry
For many producers-and future producers-the idea of using a process in which you could
simply mix alcohol and oil, pour it over a catalyst and collect the products as they drip into a
Join Our Mailing List
GO
ADVERTISEMENT
ADVERTISEMENT
More
7/14/2014 Biodiesel Magazine - The Latest News and Data About Biodiesel Production
http://www.biodieselmagazine.com/articles/500/the-ethyl-biodiesel-alternative 2/3
GOL to use farnesane biojet blend in
US-to-Brazil flights
Opinion: Building the Bioheat Bridge -
keys to playing offense
Aemetis biodiesel receives US EPA
approval, EU ISCC certification
Preview: the July/August issue of
Biodiesel Magazine
receiver (flask, jar or other collection vessel) is very attractive.
There's good news. These non-alkali methods have been developed by research chemists.
These processes are not only simple, but flexible as well.
First, a biodiesel producer could easily use ethanol in place of methanol, even if the ethanol
contains a little water. Ethanol is much less toxic than methanol, and you've probably tasted
it if you've ever consumed gin, vodka, rum or wine. Ethanol is metabolized in the body to
acetaldehyde, which quickly converts to acetic acid (which in dilute form is ordinary vinegar).
The author doesn't recommend that you start drinking, but at least you'll know that you and
your staff are less likely to go blind if you're exposed to a little alcohol vapor from the ethanol
(caution: nobody suggests drinking the ethanol at home).
Ethanol is readily available from fermentation of corn, of course. Now since we know that
there's plenty of vegetable oil (corn oil from the Midwest, palm kernel oil, cottonseed oil,
soybean oil, canola oil from Canada and avocado oil from California) and plenty of Midwestern
corn-produced ethanol, we can turn on the "green chemistry" machine and start making
biodiesel fuel with a minimum of environmental waste disposal problems and fewer worker
safety hazards. Let's call this "ethyl biodiesel," to distinguish from the "methyl biodiesel "
derived from methanol.
Catalysts: Enzymes or OrganometallicsWhat catalysts should we use if we're not using an
alkali, like sodium hydroxide? Well, for one thing, NaOH is not a catalyst but actually a co-
reactant, because you have to weigh out a certain amount. Catalysts can be used in small
amounts. They do not enter into the reaction. They can be used over and over again without
replacement.
These new catalysts for converting vegetable oil into ethyl biodiesel are not the same as the
platinum catalysts in your auto engine. Two types of catalysts can be used: (a) biochemical
enzymes or (b) "organometallics" (that is, inert catalysts based on organic and inorganic
chemistry).
You might know something about biochemically-derived enzymes, even if you are not a
scientist. Enzymes are used in converting (a) milk into cheese, and (b) hops into beer. They
are also used in modern enzyme based detergents.
Enzymes for making biodiesel esters include lipases and other "esterases." The enzymes can
be derived from several different sources, ranging from bacterial and yeast cells to pork tissue
(depending on your preferences).
The enzymatic process could simply be called the "trickle down theory." All you need to do is
to mix the reactants (oil and alcohol/EtOH) and pour them over the column containing the
enzyme. You can already buy the enzymes supported on an inexpensive material to prepare
your enzyme column.
The advantages? Well, there's (a) no heating (the reaction takes place at room temperature),
(b) no two-step reactions (the reaction goes to completion in one step), (c) no neutralization
for the caustic alkali (this is a neutral pH reaction), (d) no water washing (no acid to remove),
and (e) no drying to remove excess water. If you want the "pure" biodiesel esters-free from
the glycerol and anything else-you can remove the glycerol by gravity (just use a large glass,
gravity separator).
Organometallic catalysts are even better. They're commercially available and can also be
supported on inexpensive clay, diatomaceous earth, zeolites and other common materials.
You can also use the "trickle-down theory" and just pour the oil and alcohol over the column
and watch it "trickle down" the column into your waiting container. For many small producers,
especially in "environmentally aware" states, this method is much more suitable than using
the harsh, corrosive chemicals and worrying about the chemical waste.
Dr. Novinson works with chemists, chemical engineers, biologists and other scientists with
skills in environmental engineering, toxicology, government regulations, and analytical
chemistry.
Related Articles
7/14/2014 Biodiesel Magazine - The Latest News and Data About Biodiesel Production
http://www.biodieselmagazine.com/articles/500/the-ethyl-biodiesel-alternative 3/3
Home Subscribe Now Advertising Magazine Blog E-Newsletter Events About Us Contact Us
Biomass Magazine Ethanol Producer Magazine

ADVERTISEMENTS
Biodiesel innovator, NGSB supporter
Dallas Hanks dies at 51
Minn. biodiesel requirement jumps to
10 percent

0 Responses

Leave a Reply
Biodiesel Magazine encourages civil conversation and debate. However, comments containing
personal attacks, profanity, business solicitations or other advertising will be deleted.
Comments are closed

Copyright 2014 - BBI International - All rights reserved.