UNAB

PORDUCTION & USE OF FUELS

PRODUCTION FO BIOFUELS
TEACHER:Luis Eduardo J. M.Sc.

AUTONOMOUS UNIVERSITY OF BUCARAMANGA

PRODUCTION OF BIOFUELS

PORDUCTION & USE OF FUELS

MSC. LUIS EDUARDO JAIMES R.

TEAM:
BRANDON RODRIGUEZ
DANIEL ARCINIEGAS
JAIME CONTRERAS
GEOVANNI VERA

BUCARAMANGA- SANTANDER April 3rd OF 2017

TABLE OF CONTENTS
1. INTRODUCTION ...................................................................................................................... 4
2. FIRST GENERATION BIOFUELS 1st................................................................................... 5
2.1 BIOETHANOL .................................................................................................................... 6
2.1.1 COMPOUND AND FEATURES OF GASOLINE AND ETHANOL ..................... 6
2.1.2 SOURCES................................................................................................................... 6
2.1.3 PRODUCTION OF BIOETHANOL (CONVERSION PROCESS) ...................... 7
2.1.3.1 ETHANOL PRODUCTION PROCESS FROM SUGARCANE .................. 9
2.1.3.2 ETHANOL PRODUCTION PROCESS FROM WHEAT ........................... 14
2.1.3.3 ETHANOL PRODUCTION PROCESS FROM LIGNOCELLULOSES ... 14
2.1.3.4 ETHANOL PRODUCTION PROCESS FROM CORN .............................. 15
2.1.4 STANDARD RULES .................................................................................................... 17
2.2 BIODIESEL....................................................................................................................... 18
2.2.1 SOURCES................................................................................................................. 18
2.2.2 BIODIESEL PRODUCTION PROCESSES ......................................................... 18
2.2.3 STANDARD RULES ................................................................................................ 22
2.3 BIOETHANOL VS BIODISEL ....................................................................................... 24
3 SECOND GENERATION BIOFUELS 2ND........................................................................... 25
3.1 LIGNOCELLULOSIC BIOMASS ................................................................................... 25
3.1.1 SOURCES................................................................................................................. 26
3.1.2 PRODUCTION OF BIODIESEL (CONVERSION PROCESS) .......................... 26
3.1.2.1 BIOCHEMICAL CONVERSION PROCESS ................................................ 28
3.1.2.2 THERMOCHEMICAL CONVERSION PROCESS...................................... 30
3.1.2.3 HYBRID CONVERSION PROCESS ............................................................ 31
3.1.3 SYNGAS VALORIZATION PROCESS ............................................................... 32
3.1.3.1 PROCESS FISCHER TROPSCH SYNTHESIS ........................................ 32
3.1.3.2 MOBIL PROCESS .......................................................................................... 33
3.1.4 BIO OIL VALORIZATION PROCESS ................................................................. 33
3.1.4.1 HYDROTHERMAL LIQUEFACTION ............................................................ 33
3.1.4.2 CATALYTIC FAST PYROLYSIS ................................................................... 33
4 THIRD GENERATION BIOFUELS 3rd ................................................................................ 35
4.1 SOURCES ........................................................................................................................ 36
4.2 BIOETHANOL AND BIODIESEL FROM MICROALGAE .......................................... 38
4.2.1 HARVESTING METHODS .................................................................................... 38
 4.2.1.1 FLOCCULATION ............................................................................................ 38
4.2.1.2 FLOTATION .................................................................................................... 38
4.2.1.3 CENTRIFUGATION ....................................................................................... 39
4.2.1.4 FILTRATION.................................................................................................... 39
4.2.2 EXTRACTION OF MICROALGAL LIPIDS ......................................................... 39
4.2.2.1 DRYING PROCESSES ................................................................................. 39
4.2.2.2 CELL DISRUPTION ....................................................................................... 39
4.2.3 METHODS FOR EXTRACTION OF LIPIDS ...................................................... 40
4.2.4 BIODIESEL PRODUCTION .................................................................................. 40
4.2.5 BIOETHANOL PRODUCTION ............................................................................. 40
4.3 STANDARDS RULES ..................................................................................................... 41
5. BIBLIOGRAPHY ..................................................................................................................... 41
 1. INTRODUCTION

Biofuels are fuels produced from biomass and organic matter that comes from a
biological process, which is usable as an energy source.

Primary biofuels such as fuelwood are used in an unprocessed form primarily for
heating, cooking or electricity production, secondary biofuels such as bioethanol
and biodiesel are produced by processing biomass and are able to be used in
vehicles and various industrial processes. [1]

The secondary biofuels according to the raw material and technology used in its
production may be classified into first, second and third generation. First
generation biofuels use food grade raw materials and process technologies such
as fermentation and transesterification; it is mainly these that have reached a
commercial production stage. Second generation biofuels are derived from raw
materials that have no food use, through the biochemical processes and through
thermochemical processes. Finally, third-generation biofuels use similar production
methods in specifically designed or adapted bioenergy crops with microalgaes;
these are still at an early stage of development and are a long way from being
produced on a commercial scale. The classification biofuels could be in Fig 1: [2]

Fig 1. Classification of Biofuels

 2. FIRST GENERATION BIOFUELS 1st

Corn, wheat, and sugar cane are the most commonly used first generation biofuel
feed stock. First Generation biofuels are produced directly from food crops by
abstracting the oils for use in biodiesel or producing bioethanol through
fermentation. Crops such as wheat and sugar are the most widely used feedstock
for bioethanol while oil seed rape has proved a very effective crop for use in
biodiesel. Some of the most popular types of first generation biofuels are:

 Biodiesel: This type of biofuel is mainly produced using a process called

transesterification. This fuel if very similar to the mineral diesel and is
chemically known as fatty acid methyl. This oil is produced after mixing the
biomass with methanol and sodium hydroxide. The chemical reaction
thereof produces biodiesel.
 Vegetable oil: The main fact that determines the usage of this oil is the
quality. The oil with good quality is generally used for cooking purpose.
Vegetable oil can even be used in most of the old diesel engines, but only in
warm atmosphere. In most of the countries, vegetable oil is mainly used for
the production of biodiesel.
 Biogas: Biogas is mainly produced after the anaerobic digestion of the
organic materials. Biogas can also be produced with the biodegradation of
waste materials which are fed into anaerobic digesters which yields biogas.
The residue or the by product can be easily used as manure or fertilizers for
agricultural use. The biogas produced is very rich in methane which can be
easily recovered through the use of mechanical biological treatment
systems.
 Bioalcohols: These are alcohols produced by the use if enzymes and
microorganisms through the process of fermentation of starches and sugar.
Ethanol is the most common type of bioalcohol whereas butanol and
propanol are some of the lesser known ones. Biobutanol is sometimes also
referred to as a direct replacement of gasoline because it can be directly
used in the various gasoline engines. Butanol is produced using the process
of ABE fermentation, and some of the experiments have also proved that
butanol is a more energy efficient fuel and can be directly used in the
various gasoline engines.
 Syngas: This is a gas that is produce after the combined process of
gasification, combustion and pyrolysis. Biofuel used in this process is
converted into carbon monoxide and then into energy by pyrolysis. During
the process, very little oxygen is supplied to keep combustion under control.
In the last step known as gasification the organic materials are converted
into gases like carbon monoxide and hydrogen. [3]
 2.1 BIOETHANOL BY FERMENTATION

Bioethanol (also known as ethyl or grain alcohol) is a clear, colourless liquid that
can be produced by the fermentation of virtually any source of sugar or starch, the
most common sources being sugar cane, corn, wheat and sugarbeet. Cellulosic
biomass (e.g. grasses, woody crops, and organic wastes) can also be used to
produce bioethanol through advanced processing techniques, most cars are
fuelled by sugar cane bioethanol either as pure alcohol or blended with petrol. High
percentage blends require engine modification/recalibration. Bioethanol can also
be used in ‘duel fuel’ diesel vehicles. show the table 2. [3]

2.1.1 COMPOUND AND FEATURES OF GASOLINE AND ETHANOL

Table 1. Chemical and Physical Characteristics of Ethanol and Hydrocarbons fuels

[5]

2.1.2 SOURCES

 Sugar cane and corn are the main feedstocks used for the production of
biodethanol due to the historical reliance of Brazil and the USA respectively
on these crops.
 In Europe, bioethanol is commercially produced using cereals wheat (50%)
and barley (20%), and sugarbeet (30%). Where a sugar-based feedstock is
used.
 The crop is first crushed and soaked to separate the sugar component.
Yeast is then added to the ‘mash’ to ferment the sugars so producing
alcohol and carbon dioxide.
  If the feedstock is sugar cane, the ‘bagasse’ (the woody fibres consisting of
cellulose and lignin that remains after the juice is extracted from the cane) is
usually combusted to provide process energy. [6]

2.1.3 PRODUCTION OF BIOETHANOL (CONVERSION PROCESS)

Figure 2. Bioethanol production process [6]

Sugar cane and corn are the main feedstocks used for the production of
biodethanol due to the historical reliance of Brazil and the USA respectively on
these crops. In Europe, bioethanol is commercially produced using cereals wheat
(50%) and barley (20%), and sugarbeet (30%).
Where a sugar-based feedstock is used, the crop is first crushed and soaked to
separate the sugar component. Yeast is then added to the ‘mash’ to ferment the
sugars so producing alcohol and carbon dioxide. The liquid fraction is then distilled
to produce ethanol to the required concentration. Where the ethanol is to be
blended with petrol, the remaining water is removed to produce ‘anhydrous
ethanol’. If the feedstock is sugar cane, the ‘bagasse’ (the woody fibres consisting
of cellulose and lignin that remains after the juice is extracted from the cane) is
usually combusted to provide process energy.
Where a cereal feedstock is used, the production process first starts by separating,
cleaning and milling the crop. Enzyme amylases are used to convert the starches
into fermentable sugars. From this point on, the process is similar to that for sugar
crops, although fossil fuels (usually natural gas) tend to be used for process heat.
The grain-to-ethanol process also yields several coproducts, such as protein-rich
animal feed (e.g. distillers dry grain soluble, or DDGS) and in some cases
sweetener, depending on the specific feedstock and process used. [6]

Bioethanol as a vehicle fuel

Bioethanol is well suited for use as a vehicle fuel – it is liquid at room temperature
and can be handled in a similar way to conventional fuels. Furthermore, the alcohol
has a high octane rating enabling high engine compression ratios that increases
engine efficiency and performance. The suitability of alcohol as vehicle fuel is
demonstrated by its use as a motor-racing fuel. Compared to petrol, the fuel has
low volumetric energy density that results in bioethanol vehicles requiring more fuel
per kilometre (by as much as 50%). Bioethanol can either be used in its pure or
‘hydrous’ form (4% water by volume) in dedicated vehicles, or as an ‘anhydrous’
bioethanol-petrol blend. To convert a conventional spark-ignition engine vehicle to
pure bioethanol operation requires the adjustment of the timing (and electronic
control systems where used) and the fitting of a larger fuel tank due to the fuel’s
low energy density. As alcohol fuels can degrade certain elastomers and
accelerate the corrosion of some metals, some components may also need to be
replaced. Used in pure form, bioethanol is difficult to vaporise at low temperatures
– E100 vehicles can be therefore difficult to start in cold weather. For this reason,
bioethanol is usually blended with a small amount of petrol to improve ignition (E85
is therefore a common high percentage blend). Low percentage bioethanol blends
(up to E10) can be used by most conventional petrol engines (and is covered by
most manufacturer’s warranties) and may even slightly improve their performance.
Indeed, given that bioethanol is increasingly used as an oxygenate additive (to
improve combustion) replacing MTBE (being phased out for health reasons), many
drivers will have already used bioethanol without being aware of the fact. The use
of E5-E10 avoids a barrier to the more widespread use of high percentage blends;
the need for a dedicated fuel infrastructure and distribution network. [7]

BIOETHANOL PRODUCTION PROCESSES

The basic steps for large scale production of ethanol are: fermentation of sugars,
distillation, dehydration and denaturing (optional). Prior to fermentation, some
crops require saccharification or hydrolysis of carbohydrates such as cellulose and
starch into sugars. Saccharification of cellulose is called cellulolysis (see cellulosic
ethanol). Enzymes are used to convert starch into sugar.

 Fermentation
Ethanol is produced by microbial fermentation of the sugar. Microbial
fermentation will currently only work directly with sugars. Two major
components of plants, starch and cellulose, are both made up of sugars,
and can in principle be converted to sugars for fermentation. Currently, only
the sugar (e.g. sugar cane) and starch (e.g. corn) portions can be
economically converted. However, there is much activity in the area of
cellulosic ethanol, where the cellulose part of a plant is broken down to
sugars and subsequently converted to ethanol.

 Distillation
For the ethanol to be usable as a fuel, water must be removed. Most of the
water is removed by distillation. The purity is limited to 95-96% due to the
formation of a low-boiling water-ethanol azeotrope. This may be used as
fuel alone but unlike anhydrous ethanol it is immiscible in Petrol meaning it
can not be mixed i.e. E85. The water fraction is typically removed in further
treatment in order to burn with in combination with petrol in petrol engines.
  Dehydration
Currently, the most widely used purification method is a physical absorption
process using a molecular sieve, for example, ZEOCHEM Z3-03 (a special
3A molecular sieve for EtOH dehydration). Another method, azeotropic
distillation, is achieved by adding the hydrocarbon benzene which also
denatures the ethanol (to render it undrinkable for duty purposes). A third
method involves use of calcium oxide as a desiccant.

2.1.3.1 ETHANOL PRODUCTION PROCESS FROM SUGARCANE

The first step of the ethanol production process takes place in the fields, where
sugarcane is harvested. The sugarcane plant is composed by roots, stalk, tops and
leaves. The stalks contain most of the sugars, thus being the fraction of interest in
industrial processing. Upon mechanical harvest, most of the leaves and tops,
which constitute the so-called “sugarcane trash”, are separated from the stalks and
left on the fields, increasing soil protection and inhibiting the growth of weed and
other plant species. Sugarcane received in the factory, comprised mainly by its
stalks, contains water, fibre, sugars, impurities and dirt (sand, simulated as silica).
The composition considered in this work is based on typical data obtained in the
industry and is given in the table 3. [7]

COMPOUND %

Table 2. Composition of the sugarcane received in the factory [7]

Ethanol production from sugarcane is comprised by the following steps: cleaning of

sugarcane and extraction of sugars; juice treatment, concentration and sterilization;
fermentation; distillation and dehydration. A detailed description of the simulation of
each of these steps is presented, and a block flow diagram is depicted in Fig. 3 [8]
Fig 3. Block Flow diagram of the conventional bioethanol production process from
sugarcane [8]

1.1 Cleaning of sugarcane, extraction of sugars and juice treatment

In order to remove part (70%) of the dirt dragged along with the sugarcane
from the fields, a dry–cleaning system is used. Sugar extraction is carried
out using mills, in which water at a rate of 28% of sugarcane flow is used to
enhance sugar recovery, in a process termed imbibition (Chen and Chou,
1993). Sugars recovery in the mills is considered equal to 96%. In the mills,
sugarcane juice and bagasse are obtained. Sugarcane juice, which contains
the sugars, is fed to the juice treatment operations, while sugarcane
bagasse (50% humidity) is burnt in boilers for generation of steam and
electrical energy. In this work bagasse surplus from the cogeneration
system is used as raw material for bioethanol production through the
hydrolysis process. Sugarcane juice contains impurities, such as minerals,
salts, acids, dirt and fibre, besides water and sugars. In order to be
efficiently used as a raw material for ethanol production through
fermentation, those impurities must be removed; thus, the juice is submitted
to physical and chemical treatments. Screens and hydrocyclones are used
in the physical treatment, where the majority of fibre and dirt particles are
removed. In a subsequent chemical treatment, phosphoric acid is added to
sugarcane juice, to increase juice phosphates content and enhance
impurities removal during settlement, followed by the first heating operation
in which juice temperature increases from 30 to 70 ◦C. Pre-heated juice
receives lime and is mixed with a recycle stream containing the filtrate
obtained at the cake filter, being then heated up again to 105 ◦C. Hot juice is
then flashed to remove air bubbles, and a flocculant polymer is added to the
de-aired juice, which is fed to the settler. In the settler impurities are
removed from the juice and two streams are obtained: mud, which contains
the impurities, and clarified juice. [8]

1.2 Juice concentration and sterilization

Clarified juice contains around 15 wt.% diluted solids, so it must be

concentrated before fermentation in order to achieve an adequate ethanol
content that allows reduction of energy consumption during product
purification steps. Concentration is carried out in a five-stage multiple effect
evaporator (MEE) up to 65 wt.% sucrose. Sucrose concentration in the juice
fed to the fermentation reactor is considered equal to 22 wt.%, thus only a
fraction of the clarified juice is concentrated on the MEE; concentrated juice
obtained on the MEE last effect is mixed with the remaining clarified juice.
Low pressure steam and concentrated juice are obtained on the last effect
of the MEE. Pressure and temperature on each effect of the MEE is shown
in Table 3. Juice is sterilized prior feeding the fermentation reactor, in order
to avoid contamination, which would decrease fermentation yields. During
sterilization juice is heated up to 130 ◦C during about 30min and then rapidly
cooled down to fermentation temperature. Show Table 4.[8]

PARAMETERS PRESSURE AND TEMPERATURE OF EVAPORATOR

Table 3. Pressure and Temperature on the MEE [8]

Fermentation

Yeast suspension containing about 28% yeast cells (v) is fed to the
fermentation reactor, along with sterilized juice. Yeast accounts for
approximately a quarter of the reactor capacity. During the fermentation
reactions, sucrose is hydrolyzed into fructose and glucose, which are
converted into ethanol and carbon dioxide:

C6H12O6 → 2C2H6O + 2CO2

Some by-products are formed as well, as a result of parallel fermentation

reactions, cells growth and impurities in the sugarcane juice, among other
 factors. In addition, around 4% of the glucose is not consumed by the yeast.
Conversion parameters for the by-products, based on industrial data of large
scale units, are given in Table 4. The fermentation temperature represents a
critical step in ethanol production, since higher temperatures affect yeast
behaviour, diminishing the ethanol content of the final wine, which increases
the consumption of energy during distillation as well as the volume of
vinasse per volume of ethanol produced. show the table 5.[8]

Table 5. Product formation based on glucose consumption in the fermentor

[8]

Bioethanol is a natural product and is manufactured by the fermentation of plants

containing sugar and starch.
The plant in Zeitz owned by crop. energies produces bioethanol from wheat,
maize, barley or triticale as well as from sugar syrups.
At this plant the production of bioethanol from starch-containing cereals takes
place in five steps:
1.2.1 Milling, the mechanical crushing of the cereal grains to release
the starch components. Exist two types of milling:
 Wet milling process: The corn kernel is soaked in warm water. The
proteins are broken down. Starch present in the corn is released
(thus, softening the kernel for the milling process). Microorganism,
fibre and starch products are produced. Finally in the distillation
process ethanol is produced
 Dry milling process: Clean and break down the corn kernel into fine
particles. The sugar solution is produced when the powder mixture
(corn germ/starch and fibre) is broken down into sucrose by dilute
acid or enzymes. Yeast is added to fermet the cooled mixture into
ethanol.

1.2.2 Heating and addition of water and enzymes for conversion into
fermentable sugar

1.2.3 Fermentation of the mash using yeast, whereby the sugar is

converted into bioethanol and CO 2. Hydrolysis process breaks
down the biomass cellulosic portion into sugar solutions which will
then be fermented into ethanol. Yeast is added and heated to the
solution. Invertase acts as a catalyst and convert the sucrose
sugars into glucose and fructose. (both C6H12O6). [6]
  Chemical reaction 1:

C12H22O11 + H2O → C6H12O6 + C6H12O6

The fructose and glucose sugars react with zymase to produce

ethanol and carbon dioxide

 Chemical reaction 2:

C6H12O6 → 2C2H5OH + 2CO2

Fermentation process requires 3 days to complete and is carried out

at a temperature between 250°C and 300°C

1.2.4 Distillation and rectification, i.e. concentration and cleaning the

ethanol produced by distillation. After the sugar fermentation
process, the ethanol still does contain a significant quantity of
water which have to be removed. In the distillation process, both
the water and ethanol mixture are boiled. Ethanol has a lower
boiling point than water, therefore, ethanol will be converted into
the vapour state first  condensed and separated from water. [6]

1.3.5 Drying (dehydration) of the bioethanol

Bioethanol can also be produced directly from sugar syrups. This dispenses with
steps 1 and 2, which serve to prepare the grain for fermentation. Show Figure 4.

Fig 4. Schematic diagram of production process of bioethanol (Zeitz Plant)[6]

 2.1.3.2 ETHANOL PRODUCTION PROCESS FROM WHEAT
(Fig 1) Flow chart showing bioethanol production from starchy raw materials.
The process of bioethanol production from wheat normally consists of five
major process steps:
1. Milling of the grain
2. Liquefication at high temperatures
3. Saccharification (enzymatic degradation of starch)
4. Fermentation with yeast
5. Distillation (rectification) of ethanol [6]

Fig 5. Flow chart. Bioethanol production process from wheat [6]

2.1.3.3 ETHANOL PRODUCTION PROCESS FROM

LIGNOCELLULOSES

The production of bioethanol from lignocelluloses follows more or less the same
principle and is composed of the following sub-steps: milling, thermophysical
pretreatment hydrolysis, fermentation, distillation and product
separation/processing (Fig. 6). [6]
 Fig 6. Flow chart bioethanol production process from lignocelluloses [6]

The cellulose in the lignocellulose is not accessible to enzymes. Therefore, lignin

and/or hemicelluloses have to be removed in order to make the enzymatic
degradation of the cellulose possible. Ideal pretreatment should lead to better
performance during bioethanol production from lignocelluloses. The pretreament
should cause the hydrolysis of hemicelluloses, high recovery of all carbohydrates,
and high digestibility of the cellulose in enzymatic hydrolysis. No sugars should
either be degraded or converted into inhibitory compounds. A high solid matter
content and high concentration of sugars should be possible. The process should
have low energy demands and require low capital and operational cost. The
pretreament methods can be classified roughly into three types: thermophysical
methods, acid-based methods and alkaline methods. Thermophysical methods like
steam pretreament, steam explosion or hydrothermolysis solubilise most of the
cellulose and hemicelluloses. There is only a low level of sugar conversion.
Cellulose and hemicelluloses have to be converted enzymatically into C6 sugars
(mainly glucose) and to C5 sugars (mainly xylose). Acid-based methods use
mineral acids like sulphuric acid and phosphoric acid. Hemicelluloses are degraded
to sugar monomers, cellulose has to be converted to glucose enzymatically.
Alkaline methods like ammonia fibre explosion leave some of the hydrocarbons in
the solid fraction. Hemicellulases acting both on solid and dissolved hemicelluloses
are required as well as the celluloytic enzymes. Lignocellulose containing
substrates are mainly composed of cellulose (40-50%), hemicellulose (25-35%)
and lignin (15-20%). Cellulose is a glucose polymer, hemicellulose is a
heteropolymer of mainly xylose and arabinose, and lignin is a complex poly-
aromatic compound. The different pretreatment methods are necessary to loosen
the close bonding between cellulose, hemicellulose and lignin. Wheat (Triticum
aestivum L.) straw is composed of 45% cellulose, 26% hemicellulose and 19%
lignin. Maize (Zea mays) straw is composed of 39% cellulose, 30% hemicellulose
and 17% lignin. The high percentage of hemicelluloses and the resulting pentoses,
e.g. xylose from the hydrolysis of the polymer, are a further challenge to a cost-
competitive bioethanol process with lignocelluloses as carbon source. Yeasts used
for the conversion of sugars into ethanol (mostly Saccharomyces spec.) usually
only convert glucose into ethanol. C5 sugars like xylose are only converted into
ethanol at. [6]

2.1.3.4 ETHANOL PRODUCTION PROCESS FROM CORN

The process of making corn into ethanol is a multistep process. The first step is
milling the corn. It can be done by dry milling or wet milling. Figures 3 and 4 show
the process steps for each wet and dry milling. For wet milling, the corn kernels are
broken down into starch, fiber, corn germ, and protein by heating in sulfurous acid
solution for 2 days. The starch is separated and can produce ethanol, corn syrup,
or food grade starch. As is noted in Figure 2, the wet milling process also produces
additional products including feed, corn oil, gluten meal and gluten feed. Dry milling
is a simpler process than wet milling, but it also produces fewer products. The main
products of dry milling are ethanol, CO2, and dried distiller grain with solubles
(DDGS). Let's go through each of the steps in the dry grind process. The five steps
are, Show Figure 7 and Show Figure 8.: [3]
1. Grinding
2. Cooking and liquefaction
3. Saccharification
4. Fermentation
5. Distillation

Fig 7. Wet milling process [3]

Fig 8. Dry grind ethanol process [3]

 2.1.4 STANDARD RULES

ASTM D 5798

Table 5. ASTM D 5798 STANDARD RULE

ASTM D 4806
 Table 6. ASTM D 4806 STANDARD RULE

2.2 BIODIESEL FROM STRAIGHT VEGETABLE OIL, ANIMAL OIL/FATS

Biodiesel is an alternative fuel similar to conventional or ‘fossil’ diesel. Biodiesel

can be produced from straight vegetable oil, animal oil/fats, tallow and waste
cooking oil. The process used to convert these oils to Biodiesel is called
transesterification. This process is described in more detail below. The largest
possible source of suitable oil comes from oil crops such as rapeseed, palm or
soybean. In the UK rapeseed represents the greatest potential for biodiesel
production. Most biodiesel produced at present is produced from waste vegetable
oil sourced from restaurants, chip shops, industrial food producers such as
Birdseye etc. Though oil straight from the agricultural industry represents the
greatest potential source it is not being produced commercially simply because the
raw oil is too expensive. After the cost of converting it to biodiesel has been added
on it is simply too expensive to compete with fossil diesel. Waste vegetable oil can
often be sourced for free or sourced already treated for a small price. (The waste
oil must be treated before conversion to biodiesel to remove impurities). The result
is Biodiesel produced from waste vegetable oil can compete with fossil diesel.
More about the cost of biodiesel and how factors such as duty play an important
role can be found here. [9]

2.2.1 SOURCES

As mentioned above biodiesel can be produced from straight vegetable oil, animal
oil/fats, tallow and waste oils. There are three basic routes to biodiesel production
from oils and fats:

 Base catalyzed transesterification of the oil.

 Direct acid catalyzed transesterification of the oil.
 Conversion of the oil to its fatty acids and then to biodiesel.

Almost all biodiesel is produced using base catalyzed transesterification as it is the

most economical process requiring only low temperatures and pressures and
producing a 98% conversion yield. For this reason, only this process will be
described in this report. Show Fig 9.

2.2.2 BIODIESEL PRODUCTION PROCESSES

 Fig 9. biodiesel production processes using base catalyzed transesterification

Mixing of alcohol and catalyst

The catalyst is typically sodium hydroxide (caustic soda) or potassium hydroxide
(potash). It is dissolved in the alcohol using a standard agitator or mixer. Reaction.
The alcohol/catalyst mix is then charged into a closed reaction vessel and the oil or
fat is added. The system from here on is totally closed to the atmosphere to
prevent the loss of alcohol. The reaction mix is kept just above the boiling point of
the alcohol (around 160 °F) to speed up the reaction and the reaction takes place.
Recommended reaction time varies from 1 to 8 hours, and some systems
recommend the reaction take place at room temperature. Excess alcohol is
normally used to ensure total conversion of the fat or oil to its esters. Care must be
taken to monitor the amount of water and free fatty acids in the incoming oil or fat.
If the free fatty acid level or water level is too high it may cause problems with soap
formation and the separation of the glycerin by-product downstream. [9]

Separation
Once the reaction is complete, two major products exist: glycerin and biodiesel.
Each has a substantial amount of the excess methanol that was used in the
reaction. The reacted mixture is sometimes neutralized at this step if needed. The
glycerin phase is much more dense than biodiesel phase and the two can be
gravity separated with glycerin simply drawn off the bottom of the settling vessel. In
some cases, a centrifuge is used to separate the two materials faster. [9]

Alcohol Removal
Once the glycerin and biodiesel phases have been separated, the excess alcohol
in each phase is removed with a flash evaporation process or by distillation. In
others systems, the alcohol is removed and the mixture neutralized before the
glycerin and esters have been separated. In either case, the alcohol is recovered
using distillation equipment and is re-used. Care must be taken to ensure no water
accumulates in the recovered alcohol stream. [9]

Glycerin Neutralization
The glycerin by-product contains unused catalyst and soaps that are neutralized
with an acid and sent to storage as crude glycerin. In some cases the salt formed
during this phase is recovered for use as fertilizer. In most cases the salt is left in
the glycerin. Water and alcohol are removed to produce 80-88% pure glycerin that
is ready to be sold as crude glycerin. In more sophisticated operations, the glycerin
is distilled to 99% or higher purity and sold into the cosmetic and pharmaceutical
markets. [9]

Methyl Ester Wash

Once separated from the glycerin, the biodiesel is sometimes purified by washing
gently with warm water to remove residual catalyst or soaps, dried, and sent to
storage. In some processes this step is unnecessary. This is normally the end of
the production process resulting in a clear amber-yellow liquid with a viscosity
similar to petrodiesel. In some systems the biodiesel is distilled in an additional
step to remove small amounts of color bodies to produce a colorless biodiesel. [9]

Product Quality
Prior to use as a commercial fuel, the finished biodiesel must be analyzed using
sophisticated analytical equipment to ensure it meets any required specifications.
The most important aspects of biodiesel production to ensure trouble free
operation in diesel engines are:

 Complete Reaction
 Removal of Glycerin
 Removal of Catalyst
 Removal of Alcohol
 Absence of Free Fatty Acids
 PRODUCTION OF BIODIESEL (CONVERSION PROCESS)

Fig 10.Biodiesel production line layout

The Transesterification process is the reaction of a triglyceride (fat/oil) with an

alcohol to form esters and glycerol. A triglyceride has a glycerine molecule as its
base with three long chain fatty acids attached. The characteristics of the fat are
determined by the nature of the fatty acids attached to the glycerine. The nature of
the fatty acids can in turn affect the characteristics of the biodiesel. During the
esterification process, the triglyceride is reacted with alcohol in the presence of a
catalyst, usually a strong alkaline like sodium hydroxide. The alcohol reacts with
the fatty acids to form the mono-alkyl ester, or biodiesel and crude glycerol. In most
production methanol or ethanol is the alcohol used (methanol produces methyl
esters, ethanol produces ethyl esters) and is base catalysed by either potassium or
sodium hydroxide. Potassium hydroxide has been found to be more suitable for the
ethyl ester biodiesel production, either base can be used for the methyl ester. A
common product of the transesterification process is Rape Methyl Ester (RME)
produced from raw rapeseed oil reacted with methanol. [9]

The Fig 11. below shows the chemical process for methyl ester biodiesel. The
reaction between the fat or oil and the alcohol is a reversible reaction and so the
alcohol must be added in excess to drive the reaction towards the right and ensure
complete conversion. [10]
 Fig 11. chemical process for methyl ester biodiesel

The products of the reaction are the biodiesel itself and glycerol. A successful
transesterification reaction is signified by the separation of the ester and glycerol
layers after the reaction time. The heavier, co-product, glycerol settles out and may
be sold as it is or it may be purified for use in other industries, e.g. the
pharmaceutical, cosmetics etc.
Straight vegetable oil (SVO) can be used directly as a fossil diesel substitute
however using this fuel can lead to some fairly serious engine problems. Due to its
relatively high viscosity SVO leads to poor atomisation of the fuel, incomplete
combustion, coking of the fuel injectors, ring carbonisation, and accumulation of
fuel in the lubricating oil. The best method for solving these problems is the
transesterification of the oil. [10]

The engine combustion benefits of the transesterification of the oil are:

 Lowered viscosity
 Complete removal of the glycerides
 Lowered boiling point
 Lowered flash point
 Lowered pour point

2.2.3 STANDARD RULES

SPECIFICATION FOR BIODIESEL (B100) – ASTM D 6751-07b

 Table 7.Standard Rule ASTM D 675-07b

Biodiesel specifications and test methods according to ASTM D6751 and EN

14214 are compared with those of petroleum diesel in Table 9. Both ASTM D6751
and EN 14214 establish specifications for key fuel properties for biodiesel—the
former for the biodiesel blend component, the latter for both blend stock and neat
biodiesel automotive fuel.
 Table 8. Standard Rule ASTM D6751 and EN 14214 international

2.3 BIOETHANOL VS BIODISEL

The two most widely used types of biofuels are ethanol and biodiesel. Ethanol is an
alcohol fuel derived from sugarcane, wheat, corn and biomass, thus including
wasted cooking oil. It can be blended with conventional petroleum diesel to
improve its octane level resulting in reduced greenhouse gas emissions.
Biodiesel is made from natural oils such as animal fats or vegetable oils, show the
table 1. [4]

Table 9. Bioethanol vs Biodisel [4]

3 SECOND GENERATION BIOFUELS 2ND

3.1 LIGNOCELLULOSIC BIOMASS

According to Directive 2009/28/EC, biomass is defined as “the biodegradable

fraction of products, wastes and residue from biological origin from agriculture
(including vegetable and animal substances), forestry and related industries
including fisheries and aquaculture, as well as the biodegradable fraction of
industrial and municipal waste". 2G biofuels are produced from lignocellulosic
biomass, a non-food resource, available in large quantities and in different forms.

Lignocellulose is made up of three polymers: cellulose, hemicellulose and lignin.

These three components combine to form a three-dimensional rigid, complex and
very resistant structure. The composition of the lignocellulosic biomass that can be
used in 2G biofuels production is shown in the table 10 below. [10]

COMPOUND %

Lignocellulosic biomass composition

 Table10. Advances in Valorization of Lignocellulosic Materials by Biotechnology:
an overview.
BioResources, 2013, 8, 3157-3176.

3.1.1 SOURCES

 Farm residue: cereal crop straw, stalks, sugar cane bagasse;

 Forestry residue (branches, twigs, damaged trucks left in the forest);
 Timber industry waste (sawdust, scraps) and paper waste (used paper,
black liquor);
 High yield crops: annual plants (triticale, alfalfa, etc.), short rotation
perennial crops (miscanthus, giant reed, poplar, willow, etc.);
 Household waste (organic fraction) and industrial waste (pallets, etc.).

3.1.2 PRODUCTION OF BIODIESEL (CONVERSION PROCESS)

show Fig 12.
 Fig 12. Production of biofuels from Lignocellulose

Lignocellulosic sugars biomass valorization process

The choice of lignocellulosic biomass valorization process depends on the

characteristics of the input biomass, its availability and the type of output fuel
required. Two main types of process are used to convert the lignocellulosic
biomass into biofuel: biochemical and thermochemical processes. A third, hybrid
process combines these two processes. Show Fig 13.
Fig 13. Main processes for conversion of lignocellulosic sugars biomass to Biofuel

3.1.2.1 BIOCHEMICAL CONVERSION PROCESS

The aim of the biochemical process is to hydrolyze the lignocellulosic biomass in

order to extract sugars which will then be fermented. The main product produced
by this type of process is known as “cellulosic” ethanol, made in three stages.
Show Fig 14.

Biochemical processing

Fig 14 SSF: simultaneous saccharification and fermentation

1.1.2 Pretreatment

Before being converted into fuel, the lignocellulosic biomass must be broken down
in a pretreatment stage, by thermal and/or chemical action. This is a key stage in
the technologies developed by industry. This stage may extract the lignin,
cellulose, and hemicellulose, or maybe could extract in pairs compounds, which is
non-fermentable and majoring the hydrolysis. In addition to lime treatment, which
appears to be the most economical, there are alternative solutions giving access to
the "sweet" part of the biomass, the only part that can be turned into ethanol: these
include cooking in the presence of dilute acid (chemical process) and steam
explosion (physico-chemical process). [10]

1.1.3 Cellulose Enzymatic Hydrolysis

An acid or micro-organisms (specific enzymes) act as a catalyst in this stage,

which consists of splitting the polysaccharides that make up the cellulose and
hemicellulose into simple, fermentable sugars (glucose, pentose, saccharide, etc.).
Enzyme fermentation is by far the most common method. The Danish company
Novozymes appears to be the best known enzyme supplier. IFPEN is also highly
committed in this respect with the Futurol project. Other players such as DSM and
Dupont Danisco license their enzymatic hydrolysis process. [10]

1.1.4 Ethanol fermentation and distillation

Ethanol fermentation/fermentation, also called alcoholic fermentation, is a

biological process which converts sugars such as glucose, fructose, and sucrose
into cellular energy, producing ethanol and carbon dioxide as a side-effect.
Because yeasts perform this conversion in the absence of oxygen, alcoholic
fermentation is considered an anaerobic process. It also takes place in some
species of fish (including goldfish and carp) where (along with lactic acid
fermentation) it provides energy when oxygen is scarce. [10]

The chemical equations below summarize the fermentation of sucrose

(C12H22O11) into ethanol (C2H5OH). Alcoholic fermentation converts one mole of
glucose into two moles of ethanol and two moles of carbon dioxide, producing two
moles of ATP in the process.

The overall chemical formula for alcoholic fermentation is:

 C6H12O6 → 2 C2H5OH + 2 CO2

Sucrose is a dimer of glucose and fructose molecules. In the first step of alcoholic
fermentation, the enzyme invertase cleaves the glycosidic linkage between the
glucose and fructose molecules.

 C12H22O11 + H2O + invertase → 2 C6H12O6

Next, each glucose molecule is broken down into two pyruvate molecules in a
process known as glycolysis. Glycolysis is summarized by the equation:

 C6H12O6 + 2 ADP + 2 Pi + 2 NAD+ → 2 CH3COCOO− + 2 ATP + 2 NADH

+ 2 H2O + 2 H+
The chemical formula of pyruvate is CH3COCOO−. Pi stands for the inorganic
phosphate.

Finally, pyruvate is converted to ethanol and CO2 in two steps, regenerating

oxidized NAD+ needed for glycolysis:

 CH3COCOO− + H+ → CH3CHO + CO2

catalyzed by pyruvate decarboxylase

 CH3CHO + NADH+H+ → C2H5OH + NAD+

This reaction is catalyzed by alcohol dehydrogenase (ADH1 in baker's yeast).

As shown by the reaction equation, glycolysis causes the reduction of two

molecules of NAD+ to NADH. Two ADP molecules are also converted to two ATP
and two water molecules via substrate-level phosphorylation. [10]

3.1.2.2 THERMOCHEMICAL CONVERSION PROCESS

Thermochemical processes (thermal treatment) break down the lignocellulosic

matrix and convert the solid and heterogeneous biomass into fuel, in the form of
either gas, Thermochemical processing uses heat and pressure to convert various
types of feedstocks into fuels and chemicals. Show Fig 15.

Fig 15. Themochemical Processing

  Fast pyrolysis followed by upgrading aimed at maximizing the liquid phase
obtained. In this process, the liquefaction stage takes place in the absence
of any hydrogen or catalyst (flash pyrolysis). The product obtained is
pyrolysis oil, or bio-oil, which can be used directly to produce electricity or
steam. This mixture cannot however be used as it is, in a conventional
combustion engine, and must therefore undergo an additional conversion or
upgrading phase (catalytic hydrotreatment ) to turn it into a compatible liquid
biofuel.
 Direct liquefaction of biomass whose end product, called biocrude, is more
stable than bio-oil and convertible to a diesel substitute. Research works
undertaken by the Dutch research centre TNO-MEP have led to
development of the Hydrothermal Upgrading process.
 Catalytic pyrolysis aims to combine flash pyrolysis and conversion in a one
and the same unit.
 The Biomass to Liquids or BtL process: this process uses gasification
(thermal treatment) to produce a synthesis gas (syngas) which, after
purification, is converted using synthesis processes, in particular Fischer-
Tropsch catalytic synthesis into liquid diesel or kerosene type products. The
end-products are very high quality (absence of sulphur, high cetane
number). Axens is already marketing the Fischer-Tropsch. Gasel technology
for BtL.

3.1.2.3 HYBRID CONVERSION PROCESS

The hybrid process combines thermochemical and biochemical methods. Obtained

via a biomass gasification stage, the synthetic gas is then fermented into mainly
alcohol. Hybrid processing is the biological utilization of thermochemically-
depolymerized biomass. This thermochemical treatment of biomass yields either
sugar- and organic-acid-rich bio-oil (i.e. "pyrolytic sugars") or CO- and H2-rich
syngas. This thermochemical treatment is a distinct alternative to enzymatic
breakdown or hydrolysis of biomass. These sugars, organic acids, and syngas are
attractive substrates for the fermentative production of biorenewable fuels and
chemicals. Show Fig 16.
 Fig 16.Hybrid Processing

3.1.3 SYNGAS VALORIZATION PROCESS

This is one of the most preferred routes because it utilizes almost all types of
biomass and do not require pretreatment of the biomass except minor adjustments
in its moisture level. The first step in the production of liquid transportation fuel is
the gasification at high temperature (1200 °C to 1600 °C) in the presence of limited
supply of oxygen. This leads to the conversion of carbonaceous biomass into
syngas which is primarily a mixture of carbon mono oxide and hydrogen. The
syngas can be converted into the transportation fuel leveraging from the
established technological pathways.
The two most developed routes to convert syngas into drop in fuel are given below.
Both of these come under the thermochemical route of drop in fuel production.

3.1.3.1 PROCESS FISCHER TROPSCH SYNTHESIS

The Fischer- Tropsch (or Fischer- Tropsch synthesis) is a collection of chemical

reactions that converts a mixture of carbon monoxide and hydrogen into liquid
hydrocarbons. The process, a key component of gas to liquids technology,
produces a synthetic lubrication oil and synthetic fuel, typically from coal, natural
gas or biomass-In general cobalt or iron based catalysts are used to catalyze the
reaction to convert syngas into drop in replacements of diesel. Show below Fig 17.

nC0 + 2nH2 → CnH2n + nH2O

nC0 + 2(n+1) H2 → CnH2n+2 + nH2O

 Fig 17. Reaction of Fisher –Tropsch synthesis

3.1.3.2 MOBIL PROCESS

in the first step syngas is converted into methanol which is converted into
dimethyl ether in the second step. Dimethyl ether in turn is converted into
hydrocarbons of different chain lengths. The presence of catalyst is required
in different steps.

3.1.4 BIO OIL VALORIZATION PROCESS

3.1.4.1 HYDROTHERMAL LIQUEFACTION

Hydrothermal liquefaction Water usually works as a medium in hydrothermal

liquefaction. It is kept at or below its critical temperature (374 °C). Under high
pressure of around 2500-3000 psi the heated biomass is cooked. The temperature
is subsequently brought down. The process results in the conversion of biomass
into bio oil.

3.1.4.2 CATALYTIC FAST PYROLYSIS

Catalytic fast pyrolysis in an air tight chamber dried biomass is heated at a

temperature around 500 °C in the presence of a catalyst. Its subsequent cooling
results in a kind of tar known as bio oil. Rich in oxygen it is different in chemical
composition from the bio oil generated by hydrothermal liquefaction of biomass.
The bio oil obtained by following either of the two procedures needs to undergo
hydro processing so as to become infrastructure compatible drop in fuel. Show Fig
18.
 Fig 18. Bio oil processing

There are several general chemical changes occurred during pyrolysis. Primary
pyrolysis reaction releases volatiles and at the same time forms char. On the next
step, condensation process can occurred in the cooler parts of the system to form
bio-oil. This process naturally followed by secondary reactions that produce tar.
Reforming, dehydration and polymerization can also occurred depend on the
reaction time and the heating rate. In the end, the volatile pyrolysis product can
have more than 120 components from unspecified low molecular product
contained phenolic OH-groups to cyclic and bicyclic products.

Process Biodiesel production from jatropha

Transesterification is the process of converting the oil produced from vegetables

into biodiesel. The process is less complex and it is quite easy. Transesterification
is a chemical based production of biodiesel from jatropha oil.
In this process a complex fatty acids like triglyceride molecule is taken and it is
neutralized. The glycerin is removed and an alcohol ester is created. This process
is completed when methanol is mixed with sodium hydroxide. This result in the
production of sodium methoxide which is then mixed with oil produced from the
jatropha seeds. When the mixture settles glycerin is left at the bottom and the
biodiesel (methyl esters) remains on the top. This methyl ester is washed and then
filtered.

4 THIRD GENERATION BIOFUELS 3rd

The Third Generation of biofuels is based on improvements in the production of
biomass. It takes advantage of specially engineered energy crops such as algae as
its energy source. The algae are cultured to act as a low-cost, high-energy and
entirely renewable feedstock. It is predicted that algae will have the potential to
produce more energy per acre than conventional crops. Algae can also be grown
using land and water unsuitable for food production, therefore reducing the strain
on already depleted water sources. A further benefit of algae based biofuels is that
the fuel can be manufactured into a wide range of fuels such as diesel, petrol and
jet fuel.
 COMPOUND %

Table 11 Compounds the algae expressed in dry matter.

4.1 SOURCES

Cultivation of Third Generation Biofuel

Another favorable property of algae is the diversity of ways in which it

can be cultivated. Algae can be grown in any of the following ways.

 Open ponds – These are the simplest systems in which algae is

grown in a pond in the open air. They are simple and have low capital
costs, but are less efficient than other systems. They are also of
concern because other organisms can contaminate the pond and
potentially damage or kill the algae
 Closed-loop systems – These are similar to open ponds, but they are not
exposed to the atmosphere and use a sterile source of carbon dioxide. Such
systems have potential because they may be able to be directly connected
to carbon dioxide sources (such as smokestacks) and thus use the gas
before it is every released into the atmosphere.
 Photobioreactors – These are the most advanced and thus most difficult
systems to implement, resulting in high capital costs. Their advantages in
terms of yield and control, however, are unparalleled. They are closed
systems.
PRODUCTION OF BIODIESEL AND BIOETHANOL

Fig 19. Production Biodiesel and bioethanol processing

MICROALGAE AND BIOFUELS PRODUCTION

Microalgae are microscopic photosynthetic organisms that are found in both

marine and fresh water environments. Their photosynthetic mechanism is similar to
land-based plants, due to a simple cellular structure, and the fact that they are
submerged in an aqueous environment, where they have efficient access to water,
CO2 and other nutrients, they are generally more efficient in converting solar
energy into biomass. The absence of non-photosynthetic supporting structures
(roots, stems, etc.) also favours the microalgae in aquaculture (John et al. 2010).
Microalgae appear to represent the only current renewable way to generate
biofuels (Chisti 2007; Schenk et al. 2008). Microalgae biofuels are also likely to
have a much lower impact on the environment and on the world’s food supply tan
conventional biofuel-producing crops. When Compared with plants biofuel,
microalgal biomass has a high caloric value, low viscosity and low density,
properties that make microalgae more suitable for biofuel than lignocellulosic
materials (Miao et al. 2004), as well as due their inherently high-lipid content, semi-
steadystate production, and suitability in a variety of climates (Clarens et al. 2010).
One unique aspect of algae as compared to other advanced feedstocks is the
spectrum of species available for amenability for biofuel production. Various
species may be selected to optimize the production of different biofuels. Algae offer
a diverse spectrum of valuable products and pollution solutions, such as food,
nutritional compounds, omega-3 fatty acids, animal feed, energy sources (including
jet fuel, aviation gas, biodiesel, gasoline, and bioethanol), organic fertilizers,
biodegradable plastics, recombinant proteins, pigments, medicines,
pharmaceuticals, and vaccines (Pulz 2004; Pienkos and Darzins 2009).
4.2 BIOETHANOL AND BIODIESEL FROM MICROALGAE

Fig 20. Bioethanol and biodiesel from microalgae processing

4.2.1 HARVESTING METHODS

Microalgal biomass harvesting can be achieved in several physical, chemical or

biological ways: flocculation, centrifugation, filtration, ultrafiltration, air-flotation,
autoflotation, etc. Generally, microalgae harvesting is a two stage process,
involving: (1) Bulk harvesting: aimed at separation of biomass from the bulk
suspension. The concentration factors for this operation are generally 100–800
times to reach 2– 7 % total solid matter. This will depend on the initial biomass
concentration and technologies employed, including flocculation, flotation or gravity
sedimentation; (2) Thickening: the aim is to concentrate the slurry through
techniques such as centrifugation, filtration and ultrasonic aggregation, hence, it is
generally a more energy intensive step than bulk harvesting.

4.2.1.1 FLOCCULATION

Flocculation can be used as an initial dewatering step in the bulk harvesting

process that will significantly enhance the ease of further processing. This stage is
intended to aggregate microalgal cells from the broth in order to increase the
effective ‘‘particle’’ size [49]. Since microalgae cells carry a negative charge that
prevents them from self-aggregation in suspension, addition of chemicals known
as flocculants neutralises or reduces the negative surface charge. These
chemicals coagulate the algae without affecting the composition and toxicity of the
product. Multivalent metal salts like ferric chloride (FeCl3), aluminium sulphate (Al2
(SO4)3) and ferric sulphate (Fe2 (SO4)3) are commonly used.

4.2.1.2 FLOTATION
Some strains naturally float at the surface of the water as the microalgal lipid
content increase. Although flotation has been mentioned as a potential harvesting
method, there is very limited evidence of its technical or economic viability.

4.2.1.3 CENTRIFUGATION

Centrifugation involves the application of centrifugal forces to separate microalgal

biomass from growth medium. Once separated, microalgae can be removed from
the culture by simply draining the excess medium. Centrifugal recovery is a rapid
method of recovering algal cells, especially for producing extended shelf-life
concentrates for aquaculture hatcheries and nurseries. However, high gravitational
and shear forces during the centrifugation process can damage cell structure.
Additionally, it is not cost effective due to high power consumption especially when
considering large volumes.

4.2.1.4 FILTRATION

Filtration is the method of harvesting that has proved to be the most competitive
compared to other harvesting options. There are many different forms of filtration,
such as dead end filtration, microfiltration, ultra filtration, pressure filtration, vacuum
filtration and tangential flow filtration (TFF). Generally, filtration involves running the
broth with algae through filters on which the algae accumulate and allow the
medium to pass through the filter. The broth continually run through the microfilters
until the filter contains a thick algae paste. Although filtration methods appear to be
an attractive dewatering option, they are associated with extensive running costs
and hidden pre-concentration requirements.

4.2.2 EXTRACTION OF MICROALGAL LIPIDS

The methods of lipid extraction are as follows:

4.2.2.1 DRYING PROCESSES

Biomass drying before further lipid extraction and/or thermochemical processing is

another step that needs to be taken into consideration. Sun drying is probably the
cheapest drying method that has been employed for the processing of microalgal
biomass. However, this method takes long drying time, requires large drying
surface, and risks the loss of some bioreactive products. More efficient but more
costly drying technologies having been investigated for drying microalgae include
drum drying, spray drying, fluidized bed drying, freeze drying and refractance
window dehydration technology.

4.2.2.2 CELL DISRUPTION

The majority of biodiesel today is produced from animal or plant oils through a
transesterification process following oil extraction with or without cell disruption [3].
Most cell disruption methods applicable to microalgae have been adapted from
applications on intracellular non-photosynthetic bioproducts. Cell disruption
methods that have been used successfully include high-pressure homogenisers,
autoclaving, and addition of hydrochloric acid, sodium hydroxide, or alkaline lysis.

4.2.3 METHODS FOR EXTRACTION OF LIPIDS

Numerous methods for extraction of lipids from microalgae have been applied; but
most common methods are expeller/oil press, liquid–liquid extraction (solvent
extraction), supercritical fluid extraction (SFE) and ultrasound techniques.
Expeller/oil pressing is a mechanical method for extracting oil from raw materials
such as nuts and seeds. Press uses high pressure to squeeze and break cells. In
order for this process to be effective, algae must first need to be dried. Although
this method can recover 75% of oil and no special skills is required, it was reported
less effective due to comparatively longer extraction time. Solvent extraction
proved to be successful in order to extract lipids from microalgae. In this approach,
organic solvents, such as benzene, cyclo-hexane, hexane, acetone, chloroform are
added to algae paste. Solvent destroy algal cell wall, and extract oil from aqueous
medium because of their higher solubility in organic solvents than water. Solvent
extract can then be subjected to distillation process to separate oil from solvent.
Latter can be reclaimed for further use. Hexane is reported to be the most efficient
solvent in extraction based on its highest extraction capability and low cost.

4.2.4 BIODIESEL PRODUCTION

After the extraction processes, the resulting microalgal oil can be converted into
biodiesel through a process called transesterification. The transesterification
reaction consists of transforming triglycerides into fatty acid alkyl esters, in the
presence of an alcohol, such as methanol or ethanol, and a catalyst, such as an
alkali or acid, with glycerol as a byproduct. For user acceptance, microalgal
biodiesel needs to comply with existing standards, such as ASTM Biodiesel
Standard D 6751 (United States) or Standard EN 14214 (European Union).
Microalgal oil contains a high degree of polyunsaturated fatty acids (with four or
more double bonds) when compared to vegetable oils, which makes it susceptible
to oxidation in storage and therefore reduces its acceptability for use in biodiesel.
However, the extent of unsaturation of microalgal oil and its content of fatty acids
with more than four double bonds can be reduced easily by partial catalytic
hydrogenation of the oil, the same technology that is commonly used in making
margarine from vegetable oils. Nevertheless, microalgal biodiesel has similar
physical and chemical properties to petroleum diesel, first generation biodiesel
from oil crops and compares favourably with the international standard EN14214.

4.2.5 BIOETHANOL PRODUCTION

The current interests in producing bioethanol are focusing on microalgae as a

feedstock for fermentation process. Microalgae provide carbohydrates (in the form
of glucose, starch and other polysaccharides) and proteins that can be used as
carbon sources for fermentation by bacteria, yeast or fungi. For instance, Chlorella
vulgaris has been considered as a potential raw material for bioethanol production
because it can accumulate high levels of starch. Chlorococum sp. was also used
as a substrate for bioethanol production under different fermentation conditions.
Results showed a maximum bioethanol concentration of 3.83 g l-1 obtained from
10 g l-1 of lipid-extracted microalgae debris. Production of bioethanol by using
microalgae can also be performed via self-fermentation. Previous studies reported
that dark fermentation in the marine green algae Chlorococcum littorale was able
to produce 450 µmol ethanol g-1 at 30 ºC.

4.3 STANDARDS RULES

Reference go to the Table 8. and Table 9. Standard rules ASTM D6751 and EN
14214.

5. BIBLIOGRAPHY

[1] UN Report; Sustainable Bioenergy: A Framework for Decision Makers; April 2007

[2] Review of EU Biofuels Directive; Public consultation exercise; April- July 2006

[3] Biofuels. The fuel of the future. Biofuel.org.uk. Taken april 1, 2017, available at
www.biofuel.org.uk/first-generation.html

[4] Bioethanol, Biodisel vs Bioethanol. Taken april 1, 2017. Avaliable at bioethanol-

np.blogspot.com.co/p/bioethanol-vs-biodisel.html

[5] Chemical and Physical Characteristics of Ethanol and Hydrocarbons fuel.

Taken april 1, 2017. Avaliable at ethanolrfa.3cdn.net

[6] Production processes, crop. Energies. Taken april 1, 2017. Avaliable at

http://www.cropenergies.com/en/Bioethanol/Produktionsverfahren/

[7] Bioethanol fact sheet, Bionett. Taken april 1, 2017. Avaliable at: http://www.sts-
technology.com/docs/Bioethanol-Fact-Sheet-Final.pdf

[8] Ethanol Production Process, ICMINC, available

fromhttp://www.icminc.com/innovation/ethanol/ethanol-production-process.html

[9] Second generation biofuels: a new milestone reached. Panorama 2015. Taken
march 29, 2017. Avaliable at http://www.enmc.pt/static-img/2015-08/2015-08-
12142856_f7664ca7-3a1a-4b25-9f46-2056eef44c33$$72f445d4-8e31-416a-bd01-
d7b980134d0f$$185b72d3-2445-4764-b130-f5d8dc08b080$$File$$pt$$1.pdf

[10] Chisti Y; Biodiesel from Microalgae; Biotechnology Advances 25 (2007) 294–

306 http://www.esru.strath.ac.uk/EandE/Web_sites/02-
03/biofuels/what_biodiesel.htm