Professional Documents
Culture Documents
Production of Biofuels
Production of Biofuels
PRODUCTION OF BIOFUELS
TEAM:
BRANDON RODRIGUEZ
DANIEL ARCINIEGAS
JAIME CONTRERAS
GEOVANNI VERA
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]
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:
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]
2.1.2 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]
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]
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.
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 %
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]
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:
1.2.2 Heating and addition of water and enzymes for conversion into
fermentable sugar
Chemical reaction 2:
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.
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]
ASTM D 5798
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:
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]
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)
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]
Lowered viscosity
Complete removal of the glycerides
Lowered boiling point
Lowered flash point
Lowered pour point
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]
COMPOUND %
3.1.1 SOURCES
Biochemical processing
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]
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.
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.
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.
4.1 SOURCES
4.2.1.1 FLOCCULATION
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
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.
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.
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.
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.
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
[7] Bioethanol fact sheet, Bionett. Taken april 1, 2017. Avaliable at: http://www.sts-
technology.com/docs/Bioethanol-Fact-Sheet-Final.pdf
[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