Types of Biofuel

Biofuels, like fossil fuels, come in a number of forms and meet a number of different energy needs. The class of
biofuels is subdivided into two generations, each of which contains a number of different fuels that will be explored in
this article.

First Generation Biofuels

First generation biofuels are made from sugar, starch, or vegetable oil. They differ from second generation biofuels
in that their feedstock (the plant or algal material from which they are generated) is not sustainable/green or, if used
in large quantity, would have a large impact on the food supply. First generation biofuels are the original biofuels
and constitute the majority of biofuels currently in use.

Second Generation Biofuels

Second generation biofuels are greener in that they are made from sustainable feedstock. In this use, the term
sustainable is defined by the availability of the feedstock, the impact of its use on greenhouse gas emissions, its
impact on biodiversity, and its impact on land use (water, food supply, etc.). At this point, most second generation
fuels are underdevelopment and not widely available for use.

Biofuel Table
This table breaks biofuels down by generation and then explores their uses, energy densities, and greenhouse gas
impacts. Specific biofuels from the table are selected for further exploration on subsequent pages.

Fuel

Feedstock

Energy Density

Greenhouse
Gas

(megajoules/kilogr
am)
First Generation
By Type

By Type

30

1.91

34

N/A

36.6
37.8

2.37
2.85

48.1

3.4

By Type

By Type

39.5

2.7

Olive Oil

39

2.8

Fat

32

N/A

40
N/A

2.8
N/A

55

2.74 (does not

take into
account the
direct effect of
methane,
which is 23X
more effective
as a GHG than

Bioalcohol
Ethanol
Propanol
Butanol
Biodiesel

Green Diesel

Vegetable Oil
Castor Oil

Sunflower Oil
Bioethers

Biogas

Starches from
wheat, corn,
sugar cane,
molasses,
potatoes, other
fruits
Oils and fats
including
animal fats,
vegetable oils,
nut oils, hemp,
and algae
Made from
hydrocracking
oil and fat
feedstock
Unmodified or
slightly
modified

Dehydration of
alcohols

Methane made
from waste
crop material
through
anaerobic
digestion or
bacteria

Notes

CO2(kg/kg)

Chemically
identical to fossil
fuel diesel

These are
additives to other
fuels that increase
performance and
decrease
emissions,
particularly ozone
Same properties
as methane from
fossil fuels

Solid Biofuels
Wood
Dried plants
Bagasse

Everything
By Type
from wood and
sawdust to
16-21
garbage,
agricultural
10-16
waste, manure
10

CO2
By Type
1.9
1.8
1.3

Manure

10-15

Seeds

15
N/A
Second Generation

Cellulosic
ethanol

Algae - based
biofuels

Biohydrogen

Usually made
from wood,
grass, or
inedible parts
of plants
Multiple
different fuels
made from
algae
Made from
algae breaking
down water.

N/A

Can be used to
produce any of the
fuels above, as well
as jet fuel

See specific
fuels above

Hydrogen
compressed to 700
times atmospheric
pressure has energy
density of

Does not have

any
greenhouse
effect.

123
19.7

Methanol

Inedible plant
matter

Dimethylfuran

Made from
fructose found
in fruits and
some
vegetables

33.7

Fischer-Tropsch Waste from

paper and pulp
Biodiesel
manufacturing

37.8

This category
includes a very
wide variety of
materials. Manure
has low
CO2emissions,
but high nitrate
emissions.

1.37

2.85

More expensive,
but may yield 10100X more fuel
per unit area than
other biofuels
Used in place of
the hydrogen
produced from
fossil fuels

More toxic and

less energy dense
than ethanol
Energy density
close to that of
gasoline. Toxic to
respiratory tract
and nervous
system
Process is just an
elaborate
chemical reaction
that makes
hydrocarbon from
carbon monoxide
and hydrogen

Bioalcohols
The use of alcohol as a fuel is not a new concept. Henry Ford originally planned for his cars to run on ethanol, but the
value of alcohol for drinking made it more expensive for use as a fuel than the newly discovered petroleum. The first
four alcohols, (in order of carbon content) methanol, ethanol, propanol, and butanol, are of greatest interest for fuel
use as their chemical properties make them useful in internal combustion engines.

Fuel Economy and Octane

One of the problems with alcohols is that they have lower energy densities than gasoline. The chart below illustrates
the differences.
Fuel
Energy Density(megajoules/liter)
Average Octane (AKI rating/RON)
~33
85-96/90-105
Gasoline
~16
98.65/108.7
Methanol
~20
99.5/108.6
Ethanol
~24
108/118
Propanol
~30
97/103
Butanol
AKI - Anti-Knock Index: This octane rating is used in countries like Canada and the United States.
RON - Research Octane Number: This octane rating is used in Australia and most of Europe
The chart above also reveals average octane numbers for each fuel. Besides reducing knock, higher octane values
are indicative of a fuel that burns slowly. In general, the slower a fuel burns, the more efficient it is to extract energy
from it. Thus, a higher octane also reveals a more energy efficient fuel. The fact that alcohols have higher octane
values than gasoline helps to offset some of the difference in energy density. The net result is that the loss of fuel
economy (how far a car can travel on a volume of fuel) is not as drastic as it would be if the octane numbers were the
same.

Biological Production versus Refining

It is true that any of the alcohols above can be generated from fossil fuels. However, it is easier and more efficient to
derive these products from biomass or even carbon dioxide and water than to refine petroleum. It is also the case that
petroleum-derived alcohols tend to be less pure (ethanol is contaminated with methanol for instance) and often
cannot be purified through simple distillation.

Methanol
Methanol is closely related to methane. In fact, there is only one atom different between these two chemicals
(Oxygen shown in blue, carbon in black, hydrogen in red).

Methane

Methanol

Though these molecules are remarkably similar, their properties could not be more different. To begin, methane is a
gas at standard temperature and pressure. Methanol, on the other hand, is a liquid. Methane has an energy density
of 55 MJ/kg while methanol has an energy density of only 23 MJ/kg at best. Burning methane produces twice the
amount of carbon dioxide per kilogram as burning methanol does (2.74 kg CO2/kg methane versus 1.37 for
methanol).
How can two molecules that are so similar act so different? The answer is in the oxygen atom. This highly
electronegative atom (that means it like electrons) changes the structure of the bonds so much that the overall
reaction energy for the molecule is changed. Of course, losing energy is not the only consideration. Methane makes a
poor fuel because it is a gas, which makes it difficult to transport. On the other hand, methane isn't toxic, while
methanol will cause blindness or even death in small quantities. Perhaps there is a better alcohol that has the positive
properties of methane and methanol, with fewer of the negative properties.

Ethanol
Ethanol is standard drinking alcohol, so we know it isn't poisonous. Already we're off to a better start than methanol. It
also has a higher energy density than methanol and is still a liquid, which makes it an attractive alternative. Ethanol is
only one atom different than ethane. Like methane and methanol, the differences between these molecules are
drastic.

Ethane

Ethanol
Ethanol is a common additive to fuels in many countries. Globally, the average ethanol content in petrol is roughly
5.4%, though some countries supply 25% or even 100% ethanol for vehicle fuel. The world's largest producers of
ethanol are the United States and Brazil. In the U.S., petrol contains an average of 10% ethanol. In Brazil, petrol has
a minimum of 25% ethanol by law and as many as 17.3 million vehicles use 100% ethanol (called neat ethanol) as a
fuel.
Ethanol has some benefits as a fuel or as a fuel additive. First, because it has a higher octane number than ethane
and even many of the larger hydrocarbons, ethanol can be used to boost the octane of a fuel. Beyond that, it burns
cleaner than most hydrocarbon fuels and, if created from biomass rather than petroleum, contains little or no
contamination to damage vehicle parts or lead to smog.
The drawbacks to ethanol as a fuel, however, have prevented its widespread adoption. First of all, it takes about 1.5
times more ethanol than gasoline to get the same energy. That means you need a fuel tank 1.5 times larger if you
want to travel the same distance on ethanol that you do on gasoline. Another problem with ethanol is that it is
corrosive to the rubbers used in the gaskets and fuel delivery lines of older vehicles. A reformulation of rubber was
necessary to ensure that these components do not fail in modern cars, particularly those running on 100% ethanol.
Finally, ethanol absorbs water from the environment, which dilutes its concentration and makes it impossible to ship it
through pipelines.

So, ethanol isn't the optimal standalone fuel, but it does seem to make for a great fuel additive. In addition, some
inventive individuals have found ways to combine ethanol and gasoline combustion to improve fuel economy by up to
30%. At the Massachusetts Institute of Technology, the use of high compression engines that mix gasoline and
ethanol (each stored separately onboard) to combat knock during high engine loads has led to a car that is 30% more
fuel efficient than a standard gasoline engine and which avoids the high costs associated with diesel and hybrid
technology. Though ethanol may never be a standalone fuel, its potential as a fuel supplement appears high so long
as we remain a petroleum-based society.

Propanol
Propanol is the forgotten alcohol fuel, but for good reason. Propanol is the most difficult and expensive alcohol to
produce. Because its energy gains over ethanol are minimal, the large scale production and use of this fuel is hard to
justify.
Propanol is not without its uses, however. The major use, at least in the automotive segment, comes from the drying
properties of 2-propanol, which is better known as isopropyl alcohol or rubbing alcohol. It is known as a gas dryer, but
2-propanol actually keeps water in solution with gasoline, thereby preventing it from freezing in gas lines. You can
also buy isopropyl alcohol in spray cans to de-ice your windshield.

Butanol
Butanol is more similar to gasoline than ethanol or methanol. This similarity is a consequence of its longer
hydrocarbon chain, which means there is more carbon in relation to the single oxygen and thus the molecule is less
polar. The diagram below shows only one version of butanol. Because there are four carbons, there are four possible
structures to butanol.

Butane

n-Butanol

The similarity of butanol to gasoline means that it can be used in a standard vehicle without the need for
modifications. Also, because of its size, butanol has an energy density similar to that of gasoline. In fact, butanol is so
close to gasoline in energy content that its octane rating nearly makes up for the difference in energy density. In other
words, a liter of butanol will get your car about as far as a liter of gasoline, with the difference only being about 10%. It
is also true that butanol only produces about 2.03 kg of carbon dioxide per kilogram of butanol while gasoline
produces 3.3 kg of carbon dioxide per kilogram of gasoline.
With all of these advantages the natural question is why has butanol not replaced gasoline? The answer is three-fold.
First, butanol actually produces more carbon dioxide than what arises just from burning it. The reason for this
discrepancy is that producing the biomass, harvesting it, and processing it all requires energy which releases CO 2.
This input of energy needed just to produce butanol as raises questions about how efficient biofuels are, a topic
addressed in detail in another article. Right now there is a great deal of research into using algae to produce butanol.
Tulane University is leading the charge in this are as well as in the use of bacteria to produce butanol from cellulose.
The second reason that butanol has not replaced gasoline is that its health effects are not well understood. It is
thought to behave similar to ethanol in the human body, but further research into its effects, especially when burned
as a fuel, are required before it is considered safe.
Finally, butanol has not replaced gasoline because it is very difficult to produce. Until recently, butanol was not
considered a viable biofuels because it tended to kill the organisms that produce it before they were able to create it
in any great quantity. In order to prevent this, butanol has to be removed from solution as it is made. Until 2012, the
removal of butanol away from the organisms producing it was an energy intensive and expensive process. Research
out of the University of Illinois, however, may make the process simpler and allow for the efficient production of larger
quantities of butanol. It remains to be seen how effective this process is on larger scales, but it may pave the way for
butnaol to replace gasoline in the near future.

Understanding Carbon Dioxide and Carbon Fuels

In the sections above, mention is given to the amount of carbon dioxide that each alcohol produces and this is
compared to the carbon dioxide production of an equivalent amount of the fossil fuel that most closely resembles,
structurally, the alcohol. Comparing carbon dioxide in this way, however, can be misleading.
A better way to compare carbon dioxide production is in terms of energy produced per kilogram of carbon dioxide
expelled. This is a better example because even though a quantity of ethanol produces less carbon dioxide than the
same quantity of gasoline, it also produces less energy. The result is that it is necessary to burn more of the alcohol
to get the same amount of energy as the fossil fuel. The chart below contains a few examples that help to clarify the
point.
Fuel

Energy Density
Carbon Dioxide
Carbon Dioxide
Carbon Dioxide*
(MJ/kg)
production (kg/kg)
production (MJ/kg)
(kg/Equivalent)
~21
1.37
~15
~3.6
Methanol
~55
2.74
~20
N/A
Methane
~24.5
1.91
~13
~4.05
Ethanol
52
2.93
~18
N/A
Ethane
36
2.37
~15
~3.02
Butanol
~46
3.30
~14
N/A
Gasoline
* This measure compares an alcohol to its closest hydrocarbon equivalent. The value of carbon produced is arrived at
by determining how many kilograms of alcohol are needed to derive the same amount of energy as the hydrocarbon.
This number is multiplied by the CO2 production in kg/kg to determine how many kilograms carbon dioxide are
produced for when energy production is kept the same.
What the chart above tells us is that alcohols, no matter how they are produced, are not likely to be viable alternatives
to fossil fuels until they start to get larger. In other words, methanol and ethanol are not great fuel sources because
they produce more carbon dioxide than their equivalent hydrocarbons for the same amount of energy. Butanol,
however, begins to show a difference. Butanol produces LESS carbon dioxide than gasoline for the same amount of
energy. If humans can overcome the challenges of producing butanol in large quantity and avoid impact on the food
chain, then it may become a viable alternative to hydrocarbon fuels.

Long Chain Alcohols

The information in the chart above naturally brings about the question of why scientists don't just produce longer
chain alcohols (5 or more carbons) and use those as fuel. Part of the answer to that question is related to the food
supply as discussed in other articles. The other part relates to chemistry. Synthesizing long-chain alcohols is not
easy. In fact, five carbon alcohols (called pentanols or amyl alcohols) are the longest scientists have been able to
produce. Recently, however, a method of genetic engineering has revealed that bacteria may be the key to producing
long-chain alcohols, which hold even more benefit and have greater energy densities than butanol.
In the short term, alcohol fuels will not replace hydrocarbon fuels. They will, however, be important additives to fuels
for the foreseeable future. If science continues to progress and the problem of compromising the food chain can be
solved, then alcohol fuels may provide an excellent alternative to fossil fuels that allow us to better balance how much
carbon dioxide we put into the atmosphere with how much plants remove.

Aviation Biofuel
Fuels like methanol and ethanol are not practical for aviation because they have very low energy densities. Planes
would either be severely limited in their range or would not be able to take off thanks to the weight of the fuel they
would need to carry. Aviation fuel has an energy density of 42 to 50 MG/kg, which is roughly the same as gasoline. In
order for biofuels to compete with fossil fuels, they need to pack more punch.

Standard Aviation Fuel

To understand what an aviation biofuel needs to be, it is important to understand what makes current aviation fuels
practical. This chart lists the major properties that are required of a fuel that will be used in planes and helicopters.

Important Properties of
Aviation Fuels
High Quality
Does Not Freeze
Low Risk of Explosion
High Octane
Few Contaminants

The engines that are found in aircraft come in two types: turbines and piston engines. Each requires a different kind
of fuel and so the various aviation fuels will be discussed here briefly. The production of both of these fuels focuses
on providing high power outputs and stable performance under the demands of flight. Of critical importance is water.
Water in aviation fuel can freeze and cause lines to clog at higher altitudes. This is one of the reasons that alcohols,
which tend to attract water, are not useful as aviation fuels. Cold weather performance is the most important factor in
aviation fuel besides energy density.

Avgas
This is short for aviation gasoline and it is used in standard piston-engine aircraft (propellers). Its major difference
from gasoline is that it is less prone to explosion, has a higher octane, and won't freeze at the low temperatures of
higher altitudes. Avgas is generally being replaced by other aviation fuels. Avgas has an energy density of about 45
MG/kg.

Jet Fuel
Jet fuel is similar in many ways to kerosene and comes in two basic types: Jet A and Jet B (there are others, but we
don't consider them here). Jet A fuel is designed for use in turbine engines. It is designed to rest explosion by having
an autoignition temperature of 210 degrees Celsius. Jet A is subdivided into Jet A and Jet A-1. The major difference
between these fuels is freezing point. Jet A fuel freezes at -40 Celsius while Jet A-1 freezes at -47 Celsius. Jet A-1 is

used much more commonly than Jet A. The energy densities of these two fuels are nearly identical at about 43
MJ/kg.
Jet B fuel is lighter than Jet A, which means it is more prone to evaporation and thus more prone to explosion. Its
major use is for cold climates where its freezing point of -60 Celsius gives it a major advantage. Jet B has an energy
density of about 43 MJ/kg.

Uses of Aviation Biofuel

Despite the challenges, aviation biofuels have seen some use starting in 2008. The first flight, which was undertaken
by Virgin Atlantic, used a blend of 20% biofuels. This was followed by 50-50 blends through 2012. Then in October
2012, 100% biofuels was used by the National Research Council in Canada to power a Dassault Falcon 20.

Production of Aviation Biofuel

In all cases above the aviation biofuels were no different, chemically, from standard fossil fuels. It is the case that
direct alcohols cannot be used as aviation fuel because they freeze easily and have low energy densities. However,
alcohols can be converted to kerosene, which is the basis for all aviation fuels.
Production of kerosene from biomass can occur in several different ways. Research into the use of biological
organisms is ongoing and not yet viable. Current conversion processes take the form chemical cracking and
gasification, which are energy intensive and do not represent viable solutions to the large-scale production of
biofuels. At this point, aviation biofuel is more of a research curiosity than a practical consideration.

Biomass Feedstock
Where the biomass for producing aviation fuel comes from plays large part in how environmentally friendly these
fuels are. Both the type of plant used and the location in which it is grown are important.
Several studies have shown that using arid or former agricultural land to produce biofuels feedstock can reduce
greenhouse gas emissions. Plants like Jatropha or algae can be grown in these settings and are under investigation
for use as feedstock. A study from the Yale School of Forestry has shown, however, that using natural woodland to
grown these plants (that is cutting down existing forest to create land for growing plants) will INCREASE greenhouse
gas emissions over the use of fossil fuels.
To get an idea of just how much land would be needed to meet current demands for aviation fuel, let's consider the
following graph, which shows the land areas needed if a particular feedstock is to fully replace fossil fuels in aviation
and compares those to well-known land masses.

The graph above demonstrates something fantastic. Each year, 809,000 square kilometers of corn are planted, which
is a land area roughly twice as large as the U.S. state of Montana. If Jatropha were used exclusively to create
aviation fuel, 2.7 million square kilometers would be needed to meet current demand. Said another way, about 36%
of the land area of Australia would be need to grow enough of the plant Jatropha. It is easy to see that this could have
tremendous impact on land use and the food chain.
Note that algae require much less area than most other plants, which is why it is of interest to researchers. It is worth
nothing, however, that little is known about what kind of impact this would have on local and global ecosystems. A
great deal more needs to be learned about biofuel production before it becomes viable.

Biodiesel and Green Diesel

The terms biodiesel and green diesel are easy to confuse and often are. Both of these products are refined from
vegetable oil (and occasionally animal fat). What sets these two diesel fuels apart are the processes used to produce
them and the end product that results.
Biodiesel is produced by reacting triglycerides with alcohol to produce fatty acid esters as well as glycerol, which is a
byproduct. This chemical reaction is referred to as transesterification. It produces biodiesel, which is about 9% less
energy dense than petro diesel. Biodiesel requires that engines be modified so that damage to rings, fuel lines, and
other rubber components.
Green diesel is produced through a refining process, rather than through a chemical reaction. The result is that green
diesel is chemically identical to petro diesel, except that it does not contain sulfur. Green diesel is nothing more than
renewable diesel fuel. It is not necessarily green in the sense that it protects against global warming. It is "greener"
than standard diesel though because it reduces particulate emissions as well as odor. Green diesel will run in any
engine without modification.

Production of Biodiesel
The production of green diesel is, in many ways, no different from the production of petrol diesel. Both go through a
refining process to yield a fuel at the end. In other words, producing green or petrol diesel is more about separating
the components of interest from the rest of the material than about changing the fundamental properties of the
feedstock. Biodiesel, on the hand, is all about chemically altering the feedstock.
There are actually several processes for producing biodiesel that include batch processing, supercritical processing,
ultrasonic processing, and microprocessing. Though vastly different in application, each of these procedures has the
same outcome; the transesterification of triglycerides.
Triglycerides are a type of biological molecule common in plants and animals. They are made up of three atoms,
oxygen, carbon, and hydrogen. They look something like this.

The part in red is called glycerol and the three black chains are each fatty acids. So, a triglyceride molecule is made
up of one glycerol and three fatty acid molecules. The fatty acid chains are very similar to hydrocarbons, so scientists
use processes to break off the glycerol and release the fatty acids. This process is called transesterification and it
produces an ester (actually three, one for each fatty acid). An ester looks like this:

The red part is referred to as the "R group" and can be any length from one carbon up. Biodiesel also contains fatty
acid alcohols, which look like the following.

The process of transesterification also produces glycerol, a type of alcohol, as a byproduct. For every metric ton
(tone) of biodiesel that is produced, 100 kilograms of is produced. Glycerol looks like the following.

Biodiesel Properties and Cetane Rating

The esters in biodiesel are superior to petrol diesel in centane rating, which is similar to octane rating for gasoline.
The cetane rating is a measure of how well a fuel combusts under compression ignition. This is different from octane,
which measure combustion under spark combustion. What is the difference?
In spark combustion, an electric spark (from a spark plug), is used to ignite a fuel. This is similar to putting a flame to
a can of gasoline. Compression ignition works differently. In this process, a gas is compressed to well above
atmospheric pressure. Compressing a gas causes its temperature to increase because pressure and temperature are
related by one of the three gas laws as follows:

This law tells us that pressure is inversely related to temperature. In other words, if we raise the pressure, then we
also raise the temperature so that the equation P/T remains a constant. In diesel engines, the pressure is increased
to the point that temperature rises above the combustion point of the fuel, causing ignition. That is to say, no spark is
needed in a diesel engine. A standard petrol engine usually has a compression ratio of about 10:1. A diesel engine
will have a compression ratio that ranges from 14:1 to 18:1.
So, cetane rating tells us how well a fuel burns under the conditions found in a diesel engine and can basically be
thought of as a quality rating. The rating is based off of an alkane called cetane, which has the formula C 16H24. With
this fuel, the time between fuel being injected into the cylinder and ignition is 2.407 milliseconds, which gets a cetane
rating of 100. The longer ignition takes, the lower the cetane number will be.
Cetane number is not the only property of biodiesel that is of interest. Biodiesel is liquid, usually yellow to dark brown,
and has a high boiling point. Of most importance, biodiesel has no sulfur content.
Of note, diesel engines do not use lubricant. Instead, they rely on the fuel, which is more oil-like than gasoline, to
lubricate the pistons and reduce friction with the cylinder wall. Biodiesel is a better lubricant than low-sulfur diesel,
though not quite as good as standard diesel (which is being phased out due to pollution).

Gelling and Low Temperatures

One of the things that determines the temperature at which a molecule freezes is polarity. The more polar a molecule
is, the easier it is for it to form a repeating crystal structure and become solid. Biodiesel, because it contains oxygen,
is more polar than standard diesel and thus more prone to freezing. Though the fuel usually does not freeze solid, it
does develop small crystals. This is referred to as gelling.

Biodiesel will begin to gel at temperatures as high as 16 degrees Celsius depending on the feedstock used in its
production. The best feedstock in terms of gelling is canola oil, which produces biodiesel that gels at -10 degrees
Celsius. Petro diesel usually gels at -15 to -19 degrees Celsius.

Engine Impact
Like other biofuels, biodiesel cannot be used in standard diesel engines. The alcohol content and different structure
of biodiesel means that it can react with the rubbers used in standard engines and cause them to dry and crack. This
leads to leaks and engine failure. The solution is to use different rubbers, which is the case with newer diesel
engines.

Fuel Economy, Greenhouse Gases, and Acid Rain

Diesel engines are "lean burn" engines, which means they have more air in the combustion chamber than needed to
complete the reaction. This means they use less fuel to go the same distance than a gasoline engine. Biodiesel
usually offers about 9% less energy density than standard diesel, which reduces the distance traveled on a given
quantity of fuel. However, these engines are still more efficient than gasoline engines and provide better distance for
a given quantity of fuel.
By burning less fuel per distance, diesel engines also produce less greenhouse gas emissions. Even though a
burning the same quantity of diesel fuel will yield MORE CO2 than an equivalent amount of gasoline, the increased
fuel economy more than offsets this. A diesel engine will produce 10-20% less greenhouse gas than the same sized
gasoline engine. Overall, the EPA estimates that biofuels reduce greenhouse gas emissions by 57% compared to
diesel.
The down side to diesel is that it produces more nitrogen compounds, which means more acid rain. This is actually
made worse by using biodiesel because the inevitable contamination with biologic material means there is more
nitrogen present in biodiesel. Counterbalancing the production of acid rain from nitrogen compounds is the lack of
sulfur in biodiesel. This means there is less sulfuric acid produced by biodiesel.

Feedstock
As usual, feedstock and where it is grown can make or break biodiesel. Though most biodiesel is currently made from
waste vegetable oil or processed corn, there is research into algae, pongamia, Jatropha, Fungi, and used coffee
grounds. Algae presents the best situation as it would not result in land-use changes, would not replace or impact a
food crop, and is economical. What is even more appealing is that it may be possible to grow algae on ponds in
wastewater treatment facilities, making it possible to improve water quality while also producing fuel.

Bioethers
Ethers are a class of carbon compounds that contain an ether group, which looks as follows.

Either carbon in the basic ether above may be attached to other carbons as well. So, this image represents the most
basic ether. All that is needed to make an ether is an oxygen atom with a hydrocarbon chain on either side.

Uses
Ethers are currently used as substitutes for lead to improve engine performance. They also decrease oxygen wear
and toxic emissions, particularly ozone. The most commonly used fuel additive ethers are methyl-tertiary-butyl-ether
(MBTE) and ethyl-tertiary-butyl-ether (ETBE). You are likely to see these abbreviations on petrol pumps.

Bioether
Bioether is made from either wheat or sugar beet. It can also be produced from the waste glycerol that results from
the production of biodiesel. Bioether is likely to replace petro-ether as an additive to current fossil fuels. In the future,
it is unlikely to be a fuel in and of itself because it has a low energy density. In fact, its energy density is about half
that of standard diesel, which means you would need twice the volume of ether to go the same distance. Mostly
likely, it will become an additive to other biofuels to reduce emissions.

Energy Density (MJ/kg)

Cetane Number

Dimethyl Ether Diesel

28.8
42.7
55-60
40-55

Despite its drawbacks, there is some interest in using ether, particularly dimethyl ether, as a replacement for diesel
fuel. This is made possible by the fact that ether works well in compression ignition engines. The interest stems from
the reduced particulate emissions and reduced pollution of ether. In urban environments, where refueling frequently is
possible and pollution levels run high, the tradeoff of reduced emissions for more frequent refueling is an attractive
one. The only major problem to ether in these settings is that it must be compressed to be a liquid. At standard
temperatures and pressures, ether is a gas. To make it transportable, it must be compressed. Of course,
compression has benefits as well. If the gas can be compressed enough, then more can be carried and refueling
intervals will be longer. China is currently the leader in research regarding replacing diesel fuel with ether.

Biogas
Unlike the other biofuels mentioned so far, biogas is a gas and not a liquid. It is produced from the anaerobic (without
oxygen) breakdown of organic matter that can include anything ranging from manure to sewage to plant material and
even crops. It is given the generic name biogas because it is composed of several different chemicals.

The Chemicals in Biogas

The main chemical of interest in biogas is methane, which typically constitutes half of the mixture. The rest of the gas
includes carbon dioxide, water, oxygen, hydrogen, nitrogen, and often a small amount of hydrogen sulfide. The
presence of many of these other chemicals can be eliminated through refinement, processing, and through controlled
production procedures.

Production
Biogas is produced through the use of bacteria or other microorganisms that digest and degrade organic matter.
These bacteria work only in oxygen-free (anaerobic) environments and participate in fermentation reactions similar to
those used in the production of beer or wine.
Most biogas is produced from wastewater treatment facilities or from landfills. In these facilities, the process of
fermentation is carefully monitored to ensure that methane constitutes at least 50% of the gas produced. At times,
concentrations can reach as high as 75%. The methane is then refined and purified, often on site, before being used.
Often, the produced fuel is either used directly on site for energy generation or is pumped into a pipeline for
distribution. Biogas can also be compressed and transported by truck.

Environmental Impact
Other biofuels run into the question of land-use and how growing feedstock on virgin soil can actually lead to a
carbon debt that takes centuries to pay off. Biogas is different because it is often made directly from animal waste,
which has many environmental benefits.
First of all, manure and sewage have one major problem, which is that they contain high amounts of nitrogen. When
left to decompose in the presence of oxygen, this nitrogen is converted to nitrogen dioxide with is 310 times more
effective at trapping heat in the atmosphere than carbon dioxide. In fact, methane itself is 21 times more effective at
trapping heat than carbon dioxide. So, biogas helps in two ways. To start, by converting waste to methane in
anaerobic conditions, the production of nitrogen dioxide is avoided altogether. On top of the reduction in nitrogen
dioxide is the fact that methane is never released. Because it is burned as a fuel, it produces only carbon dioxide and
water (ideally), which means that the impact on global warming is greatly reduced by refining animal waste into
biogas.
In North America, using all available animal waste (including landfills and sewage) would produce electricity to meet
about 3% of energy needs. Thought of another way, one cow produces enough methane to power a 100 watt light
bulb for a day and there are roughly 100,000,000 cattle in the United States (which is only about 1/3 of the
280,000,000 in India).

Technological Investment
The largest investor in biogas technology is Germany with nearly 6,000 plants producing nearly 2.3 GW of electrical
power. This investment is part of Germany's push for energy independence and greener technology.
Behind Germany, the United States, the United Kingdom, India, and China are all major producers of biogas.
Coincidentally, the U.S., India, and China constitute three of the four largest cattle-owning nations in the world with
the fourth (second by ranking) being Brazil.

Syngas
Syngas is the short name for a gasification product known as synthesis gas. It s a mixture of hydrogen, carbon
monoxide, and carbon dioxide that used as an intermediate in processing synthetic petroleum and as a potential
intermediate in the conversion of certain biomass in fuel. To understand what syngas is, one must first understand
what gasification is.

Gasification
Gasification is a thermochemical process that converts organic carbon into carbon monoxide, hydrogen, and carbon
dioxide. The process is carried out at high temperatures (>700 C) in a controlled environment. Usually, a specific
mixture of oxygen or steam is injected into the reaction chamber. The key to this process in the combustion does not
occur.
The point of gasification to convert carbon compounds into syngas, which tends to burn more efficiently than the
original fuel because it burns at higher temperatures. Syngas can be burned directly or it can be used to produce
ethanol and hydrogen. It can also be processed into other synthetic fuels through a process known as the FischerTropsch process. Biomass can be converted to biofuel via gasification.
The gasification of biomass has historically resulted in low yields. Recently, the University of Minnesota developed a
metal catalyst, which reduces the reaction time for biomass by a factor of 100. It also allows the process to be carried
out autothermically, which means no exogenous heat need be applied. The catalyst therefore greatly improves the
efficiency of biomass gasification.

Uses of Syngas
The primary use of syngas is in the production of other fuels, namely methanol, and diesel fuel. In industrial setting
such as steel milling and petroleum refining, large amounts of waste gas are produced. Rather than vent these toxic
gases into the atmosphere, they are captured and used to produce syngas. Doing so not only benefits the
environment, but the products derived can be sold or used in cogeneration facilities, both of which can help to make
plants more profitable.
The production of diesel fuel relies on the Fischer-Tropsch process, which is a series of chemical reactions that
converts carbon monoxide and hydrogen into liquid hydrocarbon. In most cases, methane from landfills acts as the
feedstock for producing diesel fuel. This is technically considered biodiesel because it is not derived from fossil fuels.
A novel use of syngas is to directly power hydrogen fuel cells. Hydrogen is simply captured from the gas and refined
for use in fuel cells. Of course, this process tends to defeat the zero emissions aim of fuel cells and so is not widely
used outside of research settings.
Syngas can also be used for the production of:

Hydrogen
Nitrogen
Ammonia

Carbon Monoxide
Carbon Dioxide
Steam
Minerals and Solids
Sulfur

Whether the above products can be derived from synthesis gas depends upon the original feedstock. Though
synthesis gas need only contain hydrogen and carbon monoxide, it frequently contains other components as well.
Syngas can be burned directly in internal combustion engines, but, if it is to be used directly, is often burned in an
integrated gasification combined cycle where heat is captured for electricity, but waste heat for space or water
heating.

Syngas Fermentation
Microbial fermentation of syngas can be used to develop fuels and chemicals. Most notably, syngas fermentation can
produce:

Ethanol
Butanol
Acetic Acid
Butyric Acid
Methane

The benefit of fermentation is the it is simpler and takes place a lower temperatures than chemical conversion. Oddly
enough, biologic fermentation can also tolerate high levels of sulfur, making it ideal for use in steel factories and
power plants that burn coal. In general, the process is simpler because it does not require careful control of reaction
conditions or specific quantities of CO and hydrogen. The biggest disadvantage is that it is low throughput, which
means that it takes a long time.

Syngas Reactions
1. Stock + Air Low Energy Syngas Burned in IC engines or used to generate heat/power.
2. Stock + Steam Medium Energy Gas IC engines or used to heat/power generation.
3. Stock + Oxygen Medium Energy Gas Pipeline energy or chemicals like methanol, ammonia & gasoline.
4. Stock + Heat Char or Oil Oil used to produce pyrolysis oil
Ultimately, the stock provided is less important than the process it is subjected to so long as the stock has a high
carbon content. Thus, the reactions above work as well with biofuel stock as they do with fossil fuel stock. Biofuels
like Switchgrass and other lignocellulose feedstock are highly amenable to syngas production.

Biomass and Syngas

The basic biomass gasification reaction is as follows:
C6H12O6 + O2 + H2O CO + CO2 + H2 + other compounds
(other compounds result from contaminants like sulfur, nitrogen, etc.)
It is estimated that as much as 1.2 billion dry tones of biomass could be available for conversion to syngas by 2050.
This would result in about 21 quadrillion BTU/year of energy, which is well above the 16 quadrillion BTU/year used in
transport and roughly 21% of the total 98 billion BTU of energy used each year in the United States.
Now, biomass can be converted via biological mechanisms as well, so what are the advantages of using
thermochemical conversion via syngas to convert biomass? First, gasification is fast, taking minutes compared to
days or weeks for biochemical conversion. Second, gasification is able to extract more energy from the biomass and
this is its primary advantage. The reason it can extract more energy is that it can convert carbon stored in lignin (the
tough part of plants often found in stems and trunks) into usable products. At this point, gasification of biomass (other
than crops like corn and soybean) is more efficient than biochemical conversion. In particular, the gasification of
waste such as corn stalks, corn cobs, and other agricultural byproducts is highly efficient and ultimately can improve
the energy yield per acre of first generation biofuels.

Solid Biofuels
The term solid biofuel can be a bit misleading because many people associate biofuels with advanced refining and
chemical processes. In fact, a biofuels can be any renewable, biological material used as fuel. With that definition, it
becomes clear that things like wood, sawdust, leaves, and even dried animal dung all constitute biofuels. In fact, solid
biofuels are how humans have been heating themselves and their food since the dawn of...well...humans!

Production
There is no production necessary for a solid biofuels in most cases because it is often in a convenient form. On the
other hand, sawdust and wood chips are not so convenient and so they are often put through a process known as
densifying. All this means is that the biomass is compressed into a form that is easier to handle or is mixed with
some sort of bonding agent (tar for instance or tree sap) to hold it together for easier transport, storage, and use.
Pellets and bricks are common densified forms of solid biomass.

Environmental Impact
Studies have shown that solid biofuels create less environmental impact than doe solid fossil fuels like coal. The
United States Department of Energy has studied the impact of both biomass and fossil fuels on global warming over
the lifecycle of an electrical generating facility. When all aspects are taken into account, using biofuels rather than
coal, even when the carbon from burning the coal is sequestered, leads to a 148% reduction in the global warming
potential for the power plant.
On the reverse side of the environmental equation, raw biomass is known to emit a number of particulates as well as
polycyclic aromatic hydrocarbons (PAHs). Burning solid biomass directly contributes to reduction in air quality, often
to a greater degree than oil or other hydrocarbons. Burning animal waste creates more dioxin and chlorophenol
pollutants than burning wood does. This is particularly harmful when it is burned indoors without venting.
PAHs are well-known carcinogens having the potential to damage DNA and cause birth defects. Dioxins are
derivatives of PAHs and are known to be highly toxic to fish and wildlife. A dioxin level as low as 0.5
micrograms/kilogram (about 0.0000005% by mass) are lethal to some species. Chlorophenol is also an aromatic
compound. It is commonly used in pesticides, herbicides, and disinfectants. It is one of the primary components of
mothballs. Chlorophenol is less toxic than the above compounds, with lethal doses in the range of 600
milligrams/kilogram or about 50% by mass. Long-term exposure to relatively high levels can lead to damage to red
blood cells and to the immune system.

Wood
Wood constitutes the majority of biomass that is burned for fuel and comes in the forms firewood, charcoal, chips,
pellets, and sawdust. The use of wood as a fuel for cooking, heating, and other applications dates back to well before
humans when Neanderthals were the predominant species of hominid. In fact, the most troubling aspect of using
wood as a fuel is generating the spark to start the fire. Otherwise, wood is readily available, abundant, and can even
be collected from the ground if cutting tools are not available. Today, wood is even used in some electric generating
applications.

Wood is reasonably energy dense. Hardwoods have an energy density of around 14-15 MJ/kg if burned with 100%
efficiency. As with any fuel, however, the efficiency tends to be lower. Wood is actually more efficient than many
fuels, with about 70% of the energy content (10 MJ/kg) recoverable on average.
The downside to wood is pollution. Not only does it produce more carbon dioxide than fuels like methane, it also
produces other pollutants like soot, smoke, and PAHs. Research has lead to stoves that burn at extremely high
temperatures (over 600 degrees Celsius). Temperatures this high actually allow the smoke itself to burn, which
reduces emissions.

Animal Dung
More than 2 billion people across the planet burn dried animal dung for energy. Its benefits are that it is cheap, can
be found in areas were wood is scarce, is renewable, and contains a reasonable amount of energy. Cow dung, for
instance, is about 50% methane and 30% carbon dioxide by mass when converted into biogas. Of course, burning it
directly is a different matter and less energy can be extracted. Cow dung has an energy density of approximately 12
MJ/kg if burned with 100% efficiency.
Unfortunately, burning animal dung efficiently is even more difficult than burning wood efficiently. It also produces a
number of pollutants and is a major health hazard in countries where it is burned indoors with limited ventilation.
Animal dung tends to have much higher levels of dioxins and chlorophenols as explained above.

Municipal Waste
Otherwise known as rubbish, garbage, or refuse, this biofuel includes pretty much everything that humans discard on
a daily basis. In general, this waste is not directly burned, but rather is converted through a number of different
processes into useable, cleaner fuels.
Methane can be harvested from landfills through a process known as landfill gas capture. Waste can also be
gasified directly at high temperatures and with controlled concentrations of oxygen and steam to produce syngas.
Finally, waste can be put through a process known as pyrolysis. In this reaction, decomposition is enhanced though
the application of higher temperatures and anaerobic conditions. This is the process used to make char, which is
similar to charcoal. Finally, waste can be burned directly, which is generally not allowed in most developed nations as
it produces large amounts of pollutants and toxic gases.

Energy Crops
The last major category of solid biofuel includes crops grown explicitly for burning. Though some people include the
conversion of these crops to biofuels, they are no longer solid at that point and so are not included in this discussion.
Most crops grown for direct combustion are woody. In most cases, these crops are dried and converted to pellets for
easy transport. They are then burned either alone or in cogeneration plants where they are combined with other fuels.
Many home heating burners use pellets. Crops that are grown for conversion to liquid biofuel generally have high oil
content or produce lipid, which can be converted into various liquid fuels. Crops grown for direct combustion include
switchgrass and elephant grass, though both are also converted to ethanol in some settings

Advanced Biofuels
The term "advanced biofuel" is a bit misleading because any biofuel can be advanced as long as it is made from
sustainable feedstock. The definition of a sustainable feedstock is not well developed, but in general, a feedstock is
considered sustainable if it:

Is available in large enough quantity to meet a reasonable proportion of our energy demands;

Does not have an impact on biodiversity. In other words, it won't lead to an ecological problem like superpests and it is not so invasive so as to choke off native organisms;

Does not result in major land use changes. This, of course, goes back to the impact the fuel will have on
greenhouse gas emissions, but also evaluates its impact on food crops.

Has a limited impact on greenhouse gas emissions. This is a tough criteria as the impact a feedstock has
varies depending the land it is grown on, the fertilizers used, etc.;

As you can see, the criteria are rather loosely defined. They act more as conceptual, qualitative criteria than as
quantitative metrics for making definitive decisions about the value of a biofuel. The lines between an advanced and a
traditional biofuel are blurred in the sense that a fuel that has limited energy density, but can be grown on arid land
and have little impact on greenhouse gas emissions is going to be highly valued despite its poor performance in the
first criteria above.
When considering how "advanced" a feedstock is, one must consider water impacts, pesticide residue, fertilizer use
and runoff, biodiversity, invasiveness, energy content, impact on food supply, impact on the climate, ease of
production, and economic return just to name a few. Despite these vast considerations, a few feedstock sources have
risen to the forefront of the investigation into sustainable biofuel.

Lignocelluloses
Lignocelluloses is a derivative of plant biomass that contains cellulose and lignin. Cellulose is the main structural
component of plant walls and is often found in algae as well. It is a tough polysaccharide (sugar) that can be
hundreds to thousands of glucose (sugar) units long. Lignin is an extremely complex chemical that fills the spaces
between cellulose molecules and helps to stiffen the walls of plants.
Lignocelluloses can be broken down into ethanol because it contains carbon, hydrogen, and oxygen. However, doing
so is not so easily accomplished. Over the years, scientists have developed a number of ways of producing ethanol
from lignocelluloses, but the processes are not particularly economical. As of 2007, a gallon of ethanol produced from
cellulose cost roughly U.S. $7/gallon compared to the $1-$3/gallon for ethanol produced from corn.
The benefits of using cellulose for a feedstock derive primarily from the fact that it is usually the leftover, inedible part
of crop plants. In other words, we are already producing a large abundance of this feedstock and are simply throwing
it away. Estimates put the annual production at around 323 million tons (British tons) in the U.S. alone. This quantity,
combined with the use of marginal agricultural land for growing cellulose crops, is enough to substitute for all
petroleum imports (though not all petroleum used) in the United States.
In addition to waste agricultural products, paper and other cellulose components make up roughly 70% of all landfill
waste. When these decompose, they produce methane gas, which is 21 times more potent as a warming gas than
carbon dioxide. So, converting this material to ethanol may have a very positive net environmental impact.

Finally, lignocelluloses yield about 80% more energy than is consumed in growing the plant and converting it to
ethanol. This compares very favorably with corn, which yields only 26% more energy. The conversion rate is roughly
4-5 fold, meaning that energy invested in producing ethanol from lignocelluloses gives you 4-5 times more energy
than if it were invested into producing ethanol from corn. Estimates suggest that cellulosic ethanol could reduce
greenhouse gas emission over the long term by about 115%.

Jatropha
Jatropha is a type of flowering plant that, oddly enough, has never been fully domesticated. Despite this fact, the
plant has found use in a number of applications including land reclamation after oil contamination and as a decorative
addition to many gardens. What makes it interesting as a biofuel feedstock is that Jatropha is drought resistant, has
few pests, and produce seeds that contain 27 to 40% oil.
The oil from Jatropha can be refined into biodiesel and the leftover can be used as a solid biofuel or as a feedstock
for producing syngas. Because it is refined biodiesel and not chemically converted biodiesel, diesel from Jatropha
qualifies as "green diesel" and can be used in any standard diesel engine.
The major benefit of Jatropha is that it can grow in places where most other plants would die. This means it will not
threaten the world's food supply because it can be grown on land where food crops cannot survive. Unfortunately, the
plant does not produce many seeds (where the oil is found) in poor conditions and it turns out to need just as much
water and fertilizer as any other crop. Currently, research is being done into how Jatropha might be domesticated or
genetically altered to ensure that it produces oil even under harsh conditions.
The other problem with Jatropha may be the fact that it actually increases greenhouse gas emissions. Like any
biofuel, how and where Jatropha is planted impacts its overall greenhouse gas emissions. If it is planted on land that
contains other species, the potential carbon debt could take decades or even centuries to pay off. In recent years,
interest in Jatropha has dwindled as its need for more nutrient rich environments has undermined its initial appeal.

Camelina
Camelina is another type of flowering plant that produces seeds rich in oil. Like Jatropha, its seeds can contain up to
40% oil that is easily converted into biodiesel and even jet fuel. Camelina is a hardy plant and does well in waterscarce environments. However, like Jatropha it may face potential problems from the fact that it might actually
increase greenhouse gas emissions, does not produce as well in dry environments as in wet, and uses nearly twice
the land to produce the same quantity of biofuel as Jatropha. Camelina is of interest to the United States Air Force as
a potential replacement for up to 50% of their jet fuel with biofuel by 2016.

Algae
Algae produce lipid, which is oil that can be converted into a number of different fuels including biodiesel, ethanol,
methanol, butanol, jet fuel, and others. Unlike the refining processes above, the process of converting lipid to fuel
requires chemical reactions that produce esters and alcohols. Algae-derived biofuels cannot be used in standard
engines because they can erode and damage the seals, gaskets, and lines made of rubber. Specialized rubber is
needed if algae-based biofuels are to be used in an internal combustion engine.

One of the biggest benefits of algae compared to the feedstock above is its energy density. It can produce up to 300
times more oil per acre than any conventional crop and has a harvest cycle of 1-10 days, meaning it grows up to 30
times faster than other feedstock. Additionally, algae are highly suited to growth in extreme environments and grow
well in places with high salt and dry climates. In other words, algae have almost no impact on the food supply.
At this point, the energy that must be invested to grow enough algae to meet 5% of our energy demands is
unsustainable. In other words, more energy must be invested than is recovered in this process when it is carried out
on a large scale. On small scales, the situation is not the same and algae produce more energy than is invested into
them. So, the key to making algae a sustainable biofuel is to development methods of scaling up production while
maintaining the efficiency. At this point, producing 10 billion gallons of biofuel from algae would require 33 billion
gallons of water, 6 million metric tons of nitrogen, and up to 2 million metric tons of phosphorus. This is hugely
unsustainable.
The major initiative in the future of algal biofuels is genetic engineering of the algae to produce species that can
tolerate higher salt, less water, and fewer nutrients. One avenue of research, for instance, is to produce algae that
excrete oil so that the organisms need not be harvested and can be grown indefinitely. At this point, harvesting the
algae means that they are killed and that a new stock must be grown from a seed stock. This process is far more time
and resource intensive than if the lipid could be harvested without damaging the algae.
There is a good deal of research into the ability of various feedstocks to produce biofuels that can replace traditional
fossil fuels. The major problems arise from threats to the food supply, large energy investments that may not be
recovered, and the potential to worsen global warming. While some approaches are and will be easily adopted, such
as converting waste to energy, others are more problematic and will require more investment to determine if they can
be brought to fruition or should be abandoned.
With the complexities of biofuel production in mind, it is important that the lesson of Jatropha be carefully considered.
Farmers throughout Asian and Africa spent vast sums of money planting Jatropha because it was touted as the
"silver bullet" to end energy problems once and for all. Governments promised subsidies and huge investments were
made. Unfortunately, the science was not advanced enough to really draw the conclusions that were being drawn.
The result was that Jatropha turned out to require more nutrients and land than previously thought. Farmers who
planted the crop saw subsidies dry up and they were left holding the bag. Many lost their livelihoods and others lost
their farms altogether. The lesson is that the science must come first and it must be rigorous. As the adage goes, "If it
seems too good to be true, then it probably is." Science first, investment later.