Energy production from waste through Transesterification

So far we discussed some thermal and biochemical routes for the production of energy
from waste and biomass. Transesterification is the important chemical route for the waste to
energy conversion method.

Transesterification:
Definition:
In a transesterification reaction an alcohol molecule and an ester molecule react in either the
presence of an acid or base to form a new ester.
Reaction:
Transesterification is the process in which an alcohol(such as methanol) reacts with the
triglyceride oils (contained in plant oils,animal fats or recycled greases) to form fatty acid alkyl
esters(biodiesel) and glycerine.The reaction requires heat and a strong base catalyst such as
potassium hydroxide or sodium hydroxide.

Organic wastes for Transesterification:

All organic waste are not suitable for the transesterification process, part of the waste that
suitable are having some triglyceride. These are basically waste oil , cooking oil, recycled grease
and waste oil seeds.
 As different feed stocks, are available in waste those will not be processed in the same
process. If the waste is waste oil seeds then will go for oil extraction then bio-oil will be
produced and this bio-oil will be upgraded and thus biodiesel will be produced. This upgradation
process is basically transesterification process. If we have waste oil, cooking oil and recycled
grease will go for direct upgradation process there is no need for any bio-oil production.

Production of Bio-oil from waste oil seeds:

Methods for the production of bio-oil from oil seeds:
i)Conventional methods:
1.Expeller press method
2.Solvent Extraction method
ii)Advanced methods:
1.Ultrasonic assisted extraction method(UAE)
2.Supercritical fluid extraction method(SFE)

1.Expeller press method:

Oil pressing or expeller pressing means a mechanical method for extracting oil from
vegetables, nuts and seeds by physical pressure, without any chemical additive. Seeds are firstly
fed into the expeller press through the feeder opening, and then enter the pressing chamber,
where they will be pressed. 70% of the oil will be extracted; the oil residual in cake is around 15-
18%. The solid residue from pressing is used for solvent extraction process so that the remaining
oil can be extracted from it.

Advantages :
1. The expeller pressed oil is cleaner more pure oil, higher in natural colors and flavors.
2. Lower initial investment costs
3. Higher-value edible oil and cake meal
4. Less complex operation
5. Versatile to process many kinds of oil seeds
6. No solvent required.
Disadvantages:
1. Large biomass requirement
2. High power requirements, wear and tear on the equipment that requires
maintenance
3. Lower yield due to residual in the cake.

2.Solvent extraction method:

The solvent extraction method recovers almost all the oils and leaves behind only 0.5% to 0.7%
residual oil in the raw material. Solvent Extraction is basically a process of diffusion of a solvent
into oil-bearing cells of the raw material resulting in a solution of the oil in solvent. Various
solvents can be used for extraction. Normally for the solvent extraction soxhlet apparatus is used.
Advantages:
1.Solvent is recoverable
2.Efficient extraction.

Disadvantages:
1.Lengthy process(>24hrs)
2.Labour intensive
3.Large solvent requirement,expensive solvent recovery.

3.Ultrasonic assisted extraction(UAE):

The procedure involves use of ultrasound waves,which have frequencies higher than
20kHz,have great effect on extraction yield and kinetics.UAE involves ultrasonic effects of
acoustic cavitation.Under ultrasonic action solid and liquid particles are vibrated and accelerated
and because of that solute quickly diffuses out solid phase to solvent.
 Advantages:
1. It is an inexpensive, simple and efficient alternative to conventional extraction
technique.
2. Increase the extraction yield and fast kinetics.
3. Compared to novel extraction techniques this equipment is cheaper and its operation
is easier.
4. Less solvent requirement

Disadvantages:
1. Scale up is not easy
2. Power requirement is very high.

4.Supercritical fluid extraction(SFE):

Supercritical fluid extraction (SFE) is the process of separating one component (the
extractant) from another (the matrix) using supercritical fluids as the extracting solvent.
Extraction is usually from a solid matrix, but it can also be from liquids. Carbon dioxide (CO2)
is the most used supercritical fluid, sometimes modified by co-solvents such as ethanol or
methanol. Extraction conditions for supercritical CO2 are above the critical temperature of 31°C
and critical pressure of 74 bar.
Process:
The system must contain a pump for the CO2, a pressure cell to contain the sample, a means of
maintaining pressure in the system and a collecting vessel. The liquid is pumped to a heating
zone, where it is heated to supercritical conditions. It then passes into the extraction vessel,
where it rapidly diffuses into the solid matrix and dissolves the material to be extracted. The
dissolved material is swept from the extraction cell into a separator at lower pressure, and the
extracted material settles out. The CO2 can then be cooled, re-compressed and recycled, or
discharged to atmosphere.
Advantages:
1. Solvent is non-toxic and non-flammable.
2. Operation is simple
Disadvantages:
1. Extraction of polar analyses from biomass is difficult.
2. Limited interaction between supercritical CO2 and biomass.

Factors affecting bio oil extraction:

1.Type of solvent hexane, n-heptane
2.Biomass to solvent ratio
3.Temperature
4.Extraction method
5.Extraction time
6.Moisture content
7.particle size and shape

Bio-oil Upgradation:
Bio oil that produced that has to be converted or upgraded through the
transesterification. Other two sources we have discussed recycled grease and the waste
cooking oil and waste plant oil. So, these also are waste materials and lose their fuel
properties. So, upgradation improves the quality of this wastes.Fuel upgradation is
basically transesterification process. Transesterification improves the quality of this feed
stocks and impart fuel properties thus upgradation is to to get the bio diesel. The
components of the bio diesel is a mixture of fatty acid alkyl esters .As these are esters we
have sufficient oxygen in it so during combustion it burns completely unlike petrol,diesel.
Biodiesel:
 Biodiesel is a mixture of fatty acid alkyl esters.It is non hazardous, nontoxic and
biodegradable, and it reduces air pollutants such as particulataes, carbon
monoxide, hydrocarbons and air toxins.
 It burns more efficiently than petroleum diesel, and its higher lubricity can reduce
engine wear, prolonging its lifetime.
 It can be used as fuel for vehicles in its pure form, but it is usually used as a
petroleum diesel blend. The most common use of biodiesel is as B20( 20%
biodiesel, 80% diesel) and B2 (2% biodiesel, 98% diesel) or B1 (1% biodiesel,
99% diesel). Pure biodiesel requires special management in cold climates.
 The use of these blends requires no engine modifications.
 Due to slightly less energy density than petroleum diesel, the fuel economy tends
to fall 7% for every 10% biodiesel in a fuel blend. High viscosity and flash point
needs upgradation.

Important properties of Biodiesel:

1.Ash percentage:
Ash is the measure of the amount of metals contained in the fuel.Ash percentage
can be determined by approximate analysis.

2.Density:
Density is the weight per unit volume. Oils that are denser contain more energy.
The density of the biodiesel is slightly higher than that of the petrol diesel.

3.Cloudpoint:
The temperature at which an oil starts to solidify.While operating an oil at
temperatures below cloud point, heating will be necessary in order to avoid waxing of the
fuel.

4.Pour point:
 Pour point refers to the temperature at which the oil in solid form and starts to
melt or pour. Pour point will be lower than that of cloud point.

5.Cetane number:
It is a relative measure of the interval between the beginning of injection and
autoignition of the fuel.The higher the cetane number,the shorter the delay interval and
the greater its combustibility.
Cetane number of cetane (n-C16H34)=100;
1-methylnapthalene=0;
Isocetane=15
 Cetane number is measured by burning the fuel in a Cooperative Fuel
Research(CFR) engine,under standard test conditions. A hand-wheel is used to
increase the compression ratio(and therefore the peak pressure within the
cylinder) of the engine until the time between fuel injection and ignition is
2.407ms.
 The resulting cetane number is then calculated by determining which mixture of
cetane(hexadecane) and isocetane(2,2,4,4,6,8,8-heptamethylnonane)will result in
the same ignition delay.
6.Flash point:
Flash point is the minimum temperature at which the fuel will ignite on application of an
ignition source. Flash point varies inversely with the volatility of fuel. Minimum flash
point temperatures are required for proper safety and handling of fuel.
So, there are 2 methods for the measurement of flash point one is closed cup and another
is open cup method.
i)In open cup flash point varies with the height of the flame above the liquid
surface and at sufficient height, the measured flash point temperature coincides with the
fire point.
ii)In closed cup systems the cups are sealed with a lid through which the ignition
source can be introduced. Closed cup testers normally give lower values for the flash
point that open cup(typically 5-100C lower) and are a better approximation to the
temperature at which the vapour pressure reaches the lower flammable limit.

7.Heating value :
It is the amount of heating energy released by the combustion of a unit value of
fuels. It depends on C,H and O content in the fuel.

8.Iodine fuel:
The amount of iodine, measured in grams, absorbed by 100 ml of a given oil. The
degree of saturation is indicated by the iodine value of the oil.

9.Potassium Percentage: It is the percentage, by weight of potassium in the fuel.

 When bio diesel is produced as we have discussed that potassium hydroxide
which can be used as a catalyst. So, that can be available in the biodiesel and that
percentage has to be measured as it is coming from the biomass feed stocks. And also, it
can have some sulphur and sulphur can be measured.

10.Sulphur percentage: The percentage by weight of sulphur in the fuel.

There are number of methods for measurement of sulphur one is very primitive
one that is colorimetric method(barium sulphate precipitation), Wickbond combustion
method and X-ray fluorescence, ICP-MS method. These are the different methods
through which we can measure the sulphur content in bio diesel.

11.Viscosity:
 Viscosity refers to the thickenss of the oil,and is determined by measuring the
amount of the time taken for a given measure of oil to pass through an orifice of a
specified size.
When liquid flows through tubes, η=∏r4Pt ∕ 8VL (Poiseuille’s equation) Or
η=KPt →η α Kmt.
Thus, ratio of viscosity coefficient of a known and experimental sample ,
η ∕ ηr= mt/mrtr
where η is called the viscosity coefficient, t is the time of flow of liquid, V is the
volume of the liquid, P is the hydorstatic pressure, and L is the distance travelled
by the liquid during time t, r is radius of the tube , m is the mass of reference
liquid.
Viscosity can be measured using a viscometer. The different types of viscometer
are as follows:
 Ostwald visocometer
 Falling sphere viscometet
 Falling piston viscometer
 Oscillating piston viscometer
 Vibrational voscometers
 Rotational voscometers
 Bubble viscometer

General flowhseet for biodiesel production from various feedstocks:

Basically recycled grease are having high amount of free fatty acids in it along with
triglycerides. So, acid catalyzed transesterification must be there for the processing of this
recycled grease. Whereas, waste oil and cooking oil these are having very less free fatty
acids and the acid catalyzed state may be escaped. After transesterification reaction we
will be getting various products have that the glycerol and the fatty acid esters of alkyls.
So, those will be separated. So, one is glycerin and another is crude bio diesel. From
glycerine refining crude glycerine will be going to the alcohol recovery and refined
glycerine is recovered. Next crude bio diesel will further be refined. And we will get the
refined bio diesel will go for alcohol recovery and ultimately this is the flow sheet.

Production of methyl ester from plant oil and other feedstocks:

The complete process involves 5 steps:

1.Acid esterification
2.Transesterifcation
3.Methanol recovery
4.Biodiesel recovery
5.Glycerine recovery

Acid Esterifiction:

 Free fatty acids (FFAs) in biodiesel feedstocks react with alkali catalysts like
NaoH and KOH and from soaps, which reduce the oil properties of the biodiesel.
 Triglycerides + FFAs + Alcohol → Na∕K salt of FAs + Triglycerides.
 Low levels of FFAs (upto 4%) can be managed by using additional catalyst and
allowing soap formation. NaOH [%FFA](0.144) + 1%; KOH: [%FFA](0.197)∕
0.86 +1%;
Sodium methoxide:[%FFA](0.190) + 0.25%.
 Feedstock containing > 4 % FFAs (Animal fats and recycled greases) are first
filtered and then pre-processed to remove water and other contaminants such as
unwanted solids. The pretreated oil is then fed to the acid esterification process.
Most plant oils and some food-grade animal fats do not require AE, ( FFA<4%).
 The sulfuric acid, is dissolved in methanol and then mixed with the pretreated oil.
The mixture is heated and stirred , and the Fas are converted to biodiesel. Once
the reaction is complete , it is dewatered and fed to the transesterification process.

Alternative method to remove/ manage fatty acids (FFAs)

 Enzymatic methods – Very costly, not a popular choice.

 Glycerolysis – Glycerol is added to high FFA feedstock with catalyst (Zncl2) at
2000C, which converts FFAs to monoglycerides and diglycerides.
FFA + glycerol→ monoglyceride and diglycerides + water
 Waate is vented as it is formed. Required high temperature and slow process.
 Acid catalysis followed by base catalysts- Acid catalysis for conversion of
FFAs to methyl esters ,until FFA < 0.5 % followed by addition of methanol and
base catalyst to finish the reaction.
 Acid such as H2SO4 catalyzes both esterification and transesterification reactions.
Esterification of FFAs is fast (1 hour) but transesterification is slow ( 2days) at
600C.

Conversion of FFA
The conversion of FFAs can be determined from the following equation
η = (S0 – Si)/ S0
where S0 is initial acid value and Si is the acid value at some reaction time
Determination of acid value: Known amount of sample is added to some amount of neutralized
ethanol and is fully dissolved by heating. Phennolpthalein (0.5 ml) is used as an indicator. Thre
sample is then titrated with standard KOH solution;
The acid value is calculated as S= (56.1*V*c)/m
Where S is the acid value (mg KOH/g WCO); c is the concentration of the KOH used for
titration (mol/L); V is the volume of KOH employed for titration (mL); m is the mass of the
sample taken to be analyzed(g)
2.Transesterification:
 The plant oil, which contains less then 4% free fatty acids, is first filtered and then pre-
processed to remove water and other contaminants.
 The pretreated oil is then fed directly to the transesterification process along with any
products of the acid esterification process.
 The catalyst,potassium hydroxide, is dissolved in methanol and then mixed with the
pretreated oil.Heterogeneous catalyst can also be used.
 If an acid esterification process is used, then additional alkaline catalyst must be added to
neutralize any excess acid remaining from that step.
 Once the reaction is complete,the major co-products, biodieseln and glycerin are
separated into two layers.
Factors affecting transesterification process performance:
 Reaction temperature
 Reaction-time
 Alcohol to oil mole ratio
 Catalyst concentration
 Free fatty acids content
 Mixing
 Water content
 Types of alcohol
 Catalyst types

Methanol recovery
The methanol is usually removed immediately after the biodiesel and glycerine have been
separated, This is done to prevent the reaction from reversing itself. Recovered methanol is
cleaned and recycled back to the beginning of the process.
Biodiesel refining
 Once separated from the glycerine , the biodiesel goes through a series of cleaning up
or purification steps to remove excess alcohol, residual catalyst and soaps.
 These consist of mulitistage washings with clean water.
 The product biodiesel is then dried and sent to storage.
 It can be further refined through an additional distillation step to produce a colorless,
odorless, zero-sulfur, and premium quality biodiesel.

Glycerine recovery:
• The crude glycerin from the transesterification process may be recovered or used in a fuel
blend for steam production.
• The crude glycerin contains unreacted catalyst and soaps that must be neutralized with an
acid.
• The water and alcohol also removed to produce 50-80% crude glycerin.
• The remaining contaminants include unreacted fats and oils.
• In large biodiesel plants, the glycerin can further purified through a series of unit
operations to produce a product of 99% or higher purity.
• This purified product is suitable for use in the pharmaceutical and cosmetic industries.