Biofuels

Dr. Tatiana Ivanova

 Biofuels
1) Solid - Used mainly for heating purposes
– firewood
– straw bales
– forest chips, bark
– briquettes
– pellets…

2) Liquid - Used in engines….

– Alcohol type liquid biofuels (bioethanol, biomethanol)
– Oil type liquid biofuels (biodiesel)
– Biooil

3) Gaseous - Heating, electricity production, in transport

– Biogas or biomethan
– Wood gas, syngas
 1) Solid Biofuels
1) Physical/mechanical methods

2) Thermochemical methods
2) Liquid Biofuels: Alcohol type biofuels
2) Liquid Biofuels: Alcohol type biofuels

– Bioethanol is derived from sugar or starch yielding

plants (easier), or cellulose plants (which is more
difficult).
(Sugar cane, sugar beet, sweet sorghum, corn ….)
Ethanol is obtained by yeast fermentation.

– Biomethanol is derived from biomass (wood).

Methanol was historically produced by pyrolysis
(thermochemical decomposition without an access of
oxygen) of wood.
Nowdays is produced by gasification of organic materials
to synthesis gas (CO + H2) followed by conventional
methanol synthesis.
 Bioethanol (Ethanol fuel) C2H5OH
Alcohol produced from
starch and sugar
yielding plants, or
cellulose.

During ethanol fermentation, glucose and other sugars are converted

into ethanol and carbon dioxide.
The basic steps for large-scale production of ethanol are: microbial
(yeast) fermentation of sugars, distillation, dehydration.
Prior to fermentation, some crops require saccharification or hydrolysis of
carbohydrates such as cellulose and starch into sugars. Enzymes are
used to convert starch and cellulose into sugar.
Ethanol may also be produced industrially from ethene (ethylene) by
hydrolysis in the presence of catalysts and high temperature (petrolium
derived ethanol = synthetic ethanol – 5% of ethanol production).
Bioethanol production
 Bioethanol production
Microbial fermentation currently only works directly with sugars.
Fermentation is not 100% selective, and other side products such
acetic acid, glycols and many other products are formed to a
considerable extent and need to be removed during the purification of
the ethanol.
Fermentation takes place in aqueous solution and the resulting
solution after fermentation has an ethanol content of around 15%.
Ethanol is subsequently isolated and purified by a combination of
adsorption and distillation techniques. The purification is very
energy intensive.
 Bioethanol production
Distillation – most water is removed = hydrous ethanol (purity is
limited to 95-96 %). Can be used as fuel, but unlike anhydrous
ethanol, is not miscible with gasoline in all rations.

Dehydratation: 1) Azeotropic distillation (addition of benzene or

cyclohexane, distillation, condensation)
2) Extractive distillation (addition of ternary
component, distillation)
3) Use of molecular sieves – save energy,
adopted by majority of modern ethanol plants (ethanol vapour under
pressure passes through a bed of molecular sieves, pores are sized to
allow absorption of water while excluding ethanol, water removal)

http://www.youtube.com/watch?v=-7OoVfUgYX0
https://www.youtube.com/watch?v=4OT9ekEF9cg
 Sugars x Woody biomass
– Fermentation - Pretreatment
– Distillation ……………..
– Dehydratation
Termites are generally regarded
as nuisance to human society, but
they are in fact beneficial for the
nature since termites decompose
dead trees, and some 20 % of
plant biomass in the nature is
decomposed by termites. The
clarification of cellulose-
decomposition process in termite
guts will undoubtedly open the
way to establish a new
production technology for
bioethanol, since this new
technology can make it possible
to dispense with traditional
pretreatment of cellulose, and
hence it will be much more
energy-efficient and of low cost.
 Crop
Annual yield Greenhouse-
(Liters/hectare, gas savings Comments
US gal/acre) vs. petrol[a]

7300 L/ha, Low-input perennial grass. Ethanol production depends

Miscanthus 37%–73%
780 g/acre on development of cellulosic technology.

Low-input perennial grass. Ethanol production depends

on development of cellulosic technology. Breeding
3100–7600 L/ha,
Switchgrass 37%–73% efforts underway to increase yields. Higher biomass
330–810 g/acre production possible with mixed species of perennial
grasses.
Fast-growing tree. Ethanol production depends on
3700–6000 L/ha, development of cellulosic technology. Completion of
Poplar 400–640 g/acre
51%–100% genomic sequencing project will aid breeding efforts to
increase yields.
Long-season annual grass. Used as feedstock for most
bioethanol produced in Brazil. Newer processing
6800–8000 L/ha
Sugar cane 87%–96% plants residues not used for ethanol to generate
burn
727–870 g/acre
electricity. Only grows in tropical and subtropical
climates.
Low-input annual grass. Ethanol production possible
using existing technology. Grows in tropical and
2500–7000 L/ha,
Sweet sorghum No data temperate climates, but highest ethanol yield estimates
270–750 g/acre assume multiple crops per year (only possible in tropical
climates). Does not store well.
• Advantages: Bioethanol
– Low pollution
– Economical
in thous. Production Consumption Difference
• Disadvantages: tons
Brazil 23114 24335 -1221
– Biomass transport EU 4842 5947 -1105
– Car engine modification U.S. 53425 49584 3841

– Temperature use (difficult to start a cold engine in the winter, less

volatile than gasoline)
– Corrosive (contains contaminants, halide ions like chloride ions –
pitting corrosion and increase conductivity (electric, galvanic
corrosion); soluble contaminants clog fuel system over time)
– Hygroscopic - absorbs water vapor directly from the atmosphere
(separation of ethanol-gasoline blends, containers of ethanol fuels
must be kept tightly sealed; ethanol cannot be efficiently shipped
through modern pipelines, like liquid hydrocarbons, over long
distances).
Fuel ethanol production
 Biomethanol (Methanol fuel) CH3OH
• “Wood alcohol” is a alcohol produced from biomass.

Methanol was historically produced by pyrolysis

(thermochemical decomposition without an access of
oxygen) of wood.

Nowdays is produced by gasification of organic materials to

synthesis gas (CO + H2) followed by conventional methanol
synthesis

It melts at −97.8°C and boils at 67°C.

Blends with ethanol, gasoline…
 Biomethanol (Methanol fuel) CH3OH
• Advantages:
– Low pollution
Fuel supply options - renewable alternative to
petroleum-based hydrocarbons
– Fire safety (more difficult to ignite than gasoline & burns about
60% slower with cooler flame – great advantage over gasoline)
– High performance
– Economically attractive
 Biomethanol
• Disadvantages:
– Engine starting in cold weather more difficult
Corrosive (contains soluble and insoluble
contaminants) to some metals, including aluminum.
– Formation of acidic products during combustion
(wearing of valves, valve seats..)
100% methanol cannot be used in modern petroleum
cars without modification.
– Hydroscopic
• It is poisonous (10 ml can cause blindness and 60-100 ml can be
fatal); can be absorbed through skin and vapors through lungs.
Effective toxicity is not worse that those of benzene or gasoline,
methanol poisoning is far easier to treat successfully. Methanol
rapidly and non-toxically biodegrade – no long-term harm to
environment.
 Liquid Biofuels: Oil type biofuels

- Derived from oil yielding plants + animal fats

(Rape, sunflower, oil palm, soyabean, jatropha, algae or e.g.
Pongamia pinnata, etc.)

When these oils are heated, their viscosity is reduced and

they can be burned directly in modified diesel engines or
processed to produce biodiesel.
 Biodiesel - Fatty acid methyl esters (FAME)

• Biodiesel is a fuel made from natural, renewable sources,

such as new and used vegetable oils and animal fats, for
use in a diesel engine.

• Biodiesel has physical properties very similar to petroleum-

derived diesel fuel, but its emission properties are superior.
 Biodiesel production
• Biodiesel is obtained from vegetable oils/animal fats by
transesterification.

Transesterification is the process to produce diesel from

vegetable or animal oils. This process include a chemical
reaction. In the transesterification process, triglycerides are
converted into biodiesel (methyl-ester and ethyl-ester) with
the help of methanol.
- Catalysts are necessary for the transesterification process.
They help to split the triglycerides and to economically
produce biodiesel. In this case, the catalysts are
alcoholates, which are used as solutions in methanol. It is
crucial for the quality and yield of biodiesel that the catalyst
solutions are water-free.
- A by-product of the production of bio diesel is glycerin, which
can be used for pharmaceutical products, for example.
Biodiesel production
 Biodiesel production
Washing biodiesel with water is the oldest and most common
method of cleaning biodiesel - about 3% of raw unwashed biodiesel is
methanol. Methanol is a solvent, it captures soap and other impurities
and holds them dissolved in the biodiesel. Water soaks up that
methanol, releasing impurities to be washed away with water.

http://www.youtube.com/watch?v=xLa83KIaEyw
Rape Oil as fuel

• Rapeseed is an annual plant (Brassica napus) of the

mustard family, native to Europe.

• Rapeseed oil is used in the manufacture of biodiesel for

powering motor vehicles.

• Biodiesel may be used in pure form in newer engines without

engine damage, and is frequently combined with standard
diesel in ratios varying from 2% to 20% biodiesel.

• Some system to use rape oil as fuel is with a Elsbett Engine

(or Elko engine – invented by Ludwig Elsbett). It is a special
diesel engine which use clean rapeseed oil directly. A normal
diesel engine can be easy modified with a kit to run on
vegetable oil.
Vegetable oil engines are used in all types of machinery:

•Tractors, harvesters, and other agricultural machinery

•All types of forestry machinery
•Lorries, vans, pick-ups, etc.
•Industrial tractors, fork-lifters, and other industrial machinery
•Cement mixers, diggers, cranes, and other civil engineering
machinery
•Buses, taxis, and other public transport vehicles
•Private cars
•Boats, yachts, tugboats, and other transport and pleasure vessels
for sea or lakes or rivers
•Aircraft
•Mixers, mills, pumps, ventilators, and other stationary industrial
and agricultural machinery
•Electricity generating plant
•Combined electricity and heat generate plant
 Liquid Biofuels: Biooil
Produced by fast pyrolysis of lignocellulosic biomass:
- Carefully controlled pyrolysis temperature of around 500OC
- Short hot vapour residence time less than 10 seconds (2 sec.)
- Rapid cooling of vapours to produce biooil.
 Liquid Biofuels: Biooil
 70 % converted to bio-oil
 30 % - solid char + gas (can be use as fuel, char also for
higher-value uses: production of activated carbon, various
chemicals, charcoal..)
 If moisture level is higher (more than 20-25 %) water can
separate from biooil, incoming biomass feedstock should be
dried to 10 %.

Advantages:
- High oxygen content – help to improve combustion
characteristics, reduce the amount of CO2 emissions
- Low nitrogen content – reduce NOx emission
- Low sulfur content – reduce SOx emissions
 Biooil
Dark brown liquid with a smoky acrid smell.
Relatively high water content: typically 20 – 25 %.

Disadvantages:
• Lower calorific value than diesel fuel
High viscosity and acidity (can’t substitute diesel in internal-
combustion engines)
Moderately acidic: pH 2.5 – 3.0 (bio-oil storage tanks need to be
made of material that would not corrode, stainless steel, plastic,
fiberglass..).
• Is not as stable as petroleum fuel from viewpoint of storage
(lower char prolongs the stability)
• Does not naturally blend with conventional petroleum fuel
(possible to add solvents or to emulsify mixtures).
Liqued Biofuels
 World and EU demand
of liquid biofuels
World biofuels consumption EU biofuels consumption

in thous. of tons Source: Kingsman

World and EU demand
of liquid biofuels
 3) Gaseous biofuels - biogas
- Biogas - gases obtained from biowaste or biomass by
anaerobic digestion (fermentation)
Materials like vegetable biomass, manure or sewage,
municipal waste are used in fermentors (or special landfill)
and the resulting gas which contains mainly methan and
carbon dioxide is used in generators or motors.
 Biogas production
Process stages:
Four key biological and chemical stages of anaerobic digestion:
• Hydrolysis
• Acidogenesis
• Acetogenesis
• Methanogenesis

Temperature:
The two conventional operational temperature levels for anaerobic
digesters determine the species of methanogens in the digesters:
Mesophilic digestion takes place optimally around 30 to 38 °C, or at
ambient temperatures between 20 and 45 °C, where mesophiles are
the primary microorganism present.
Thermophilic digestion takes place optimally around 49 to 57 °C, or at
elevated temperatures up to 70 °C, where thermophiles are the primary
microorganisms present.
 Biogas production
Simple sketch of household biogas plant
 Biogas upgrading
Raw biogas produced from digestion it is not of high enough quality to be
used as fuel gas for machinery. The corrosive nature of H2S alone is
enough to destroy the internals of a plant.
Methane in biogas can be concentrated via a biogas upgrader to the
same standards as fossil natural gas, which itself has had to go
through a cleaning process, and becomes biomethane.
Gas must be very clean to reach pipeline quality and must be of the
correct composition for the distribution network to accept. Carbon
dioxide, water, hydrogen sulfide, and particulates must be removed.

There are four main methods of upgrading:

- water washing (most prevalent method),
- pressure swing adsorption,
- selexol adsorption,
- amine gas treating.
It takes roughly between 3% - 6% of the total energy output in gas to run
a biogas upgrading system.
Biogas http://www.youtube.com/watch?v=3UafRz3QeO8
 BENEFITS OF ANAEROBIC DIGESTION

THREE MAIN
CONDITIONS FOR
ANAEROBIC
DIGESTATION
IN AGRICULTURE

Disadvantages:
-Can be explosive when mixed one part biogas to 8-20 parts air (when the
tank is open for cleaning or repair work is being done open flames, sparks,
and smoking should be avoided. If light is needed a flashlight or sunlight
reflected off or a mirror should be used).
-Biogas leaks smell like rotten eggs (hydrogen sulfide) - frequent smell
checks must be performed on a biogas system.
Všechna zařízení s výrobou a využitím bioplynu
 u Městce Králové

Boiler for biomass

Pelleting line

Production of gas, electricity

and hot water
Cogeneration unit – production of heat and electricity
from biogas
 Use of biogas in transport

Tractor ZT 300 Biogas can be compressed, the

same way natural gas in
compressed to CNG, and used to
power motor vehicles.

IVECO

TEDOM L12G
 3) Gaseous biofuels – wood gas
- Wood gas, syngas (synthesis gas)
Wood gas is also known as producer gas which is produced by
thermal gasification of biomass in a gasifier or wood gas
generator within the air(oxygen)-limited environment to produce
CO and H2. These gases can then be burnt as a fuel with an
oxygen rich environment to produce CO2, water and heat.

In several gasifiers, the actual gasification process is preceded by

pyrolysis, where the biomass turns into char, releasing methane
(CH4) and bio-oil rich in polycyclic aromatic
hydrocarbons.

Wood gas is suggested as clean and efficient method to heat and

cook in developing countries, or even to produce electricity. Exhaust
gas emissions from an internal combustion engine is significantly lower
on wood gas than on petrol.
Thank you for your attention!!!