GREEN PROCESS FOR BIODIESEL:

A CASE STUDY

Ramkrishna Sen

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Indian energy scenario

Alternative sources of energy

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Alternative energy sources

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 Biomass to bioenergy

Biodiesel Uses of petroleum diesel

• Major transportation fuel
Bioethanol • Agriculture
• Extracting agent

Biohydrogen
Limitations of Diesel
Biomethane Finite amount, getting exhausted rapidly
Emission of greenhouse gases

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 Biodiesel
Mono alkyl esters of long chain fatty acids

Advantages
Any lipid can be used as feedstock — sustainable
Bio-diesel is biodegradable, renewable and emissions of GHG is much low
Higher Cetane number (> 51 as against 48 for diesel)— less ignition delay
Requires no engine modifications
Higher flash point (>100 as against 38 for diesel) — safer use of biodiesel

(Atabani et al., 2012)

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 Transesterification

Edible oil
(soybean,
Food Vs. Fuel
sunflower,
palm)
R&D level, cultivation, harvesting
Microbial Semi/Non- and extraction
and edible oil
micro- Triglyceride (CSO, castor,
algal lipid Jatropha,
Karanja)
Logistics and sustainability

Waste
cooking (Karmakar et al., 2010)
oil,
animal
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fats
Transesterification

•Low MW
Methanol
•Easy availability
Ethanol
Propanol •Low price
Butanol

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 Transesterification

Chemical catalyst Bio catalyst

(Alkali or Acid ) (Enzymes)

Alcohol Immobilized
lipase

Fats or oils
(any % FFA)

Biodiesel
Separator

Reactor Glycerol

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(Ghaly et al., 2010)
 Enzyme catalyzed transesterification reaction
E-MG E-Ac + G
E

MG + E-Ac

E-DG Al

E + TG E-TG DG + E-Ac E-Ac-Al AlEst (BD) + E

W Al
Al

E + FFA
E-Al
(Inactive)

Fig: Overall reaction mechanism for biodiesel (BD) production. E—enzyme, TG—
triglyceride, DG—diglyceride, MG—monoglyceride, Al—alcohol, W—water, E-Ac—enzyme
acylated, FFA—free fatty acid, G—glycerol, AlEst—alkyl ester
(Al-Zuhair et al., 2007)
 Comparison between chemical and enzyme catalyzed
transesterification reaction
Parameters Chemical catalyst Enzyme catalyst
Reaction rate Relatively high Relatively low
Catalyst cost Relatively less Relatively high
Temperature 60–70 °C 37–40 °C
Energy input High Low
Soap formation Yes No
High FFA substrate Difficult to process Easy to process
Glycerol quality Low High
Reusability of catalyst Not possible Possible by immobilization
Downstream processing More Less
Environmental problems Hazardous, requires waste No waste water treatment
water treatment
(Gog et al., 2012)
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Humps & Bumps
High throughput techniques for FAME quantification

Properties of feedstocks

Inhibitory effect of methanol on enzyme

Enzyme cost

Biodiesel productivity and purification

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 Research Challenges
Development of an easy, accurate and high throughput analytical method to
calculate percentage conversion

Use of a sustainable non-edible feedstock with a FA composition that leads to

biodiesel product of desired fuel properties on transesterification

Development of a reactor system capable of eliminating the inhibitory effect of

methanol with less reaction time

Cheaper immobilized enzyme system as an alternative to expensive Novozyme

435 and multi enzyme complex

A perfectly continuous process ensuring greater enzyme stability and hence,

higher biodiesel productivity than the reported ones with simultaneous
product purification

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 (Chattopadhyay et al., 2011a)

Percentage conversion (FAME content)

Table: Comparing percentage conversions of same sample analyzed through HPTLC scanning

Number of % conversion Mean SD

spots (%)
1 38.81
2 38.30
3 39.04 38.83 0.33
4 39.16
5 38.85

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 (Chattopadhyay et al., 2011a)

Comparative estimation between GC and HPTLC method for

FAME quantification
Methods

GC HPTLC

Number of sample analyzed 1 19

Time required (min) 25 25 to 30

FFA detection Not detected Detected

Remarks • Less accurate • More accurate

• Not high throughput • High throughput

HPTLC based analytical method for calculating percentage conversion of oil into
methyl ester was found to be better alternative than conventional GC method

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 Factor for lower conversion
 Enzyme purity and activity

 Oil to methanol molar ratio

 Mode of methanol addition

 Solubility of methanol in oil

 Various critical parameters influencing FAME production

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 Biodiesel Product purification – Why?
 To remove glycerol from biodiesel product

 To remove partially converted oil components (MG, DG, FFA, TG)

 To meet the standard biodiesel fuel specifications

 To ensure the efficiency of diesel engine with biodiesel-diesel blends

 To reduce the pollution level in terms of emission

(Behcet, 2011)

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Objective 5

Purification strategies

 Membrane separation (Leung et al., 2010)

 Alkali washing (Chongkhong et al., 2009)

 Water washing (Atadashi et al., 2011)

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Biodiesel from Jatropha Oil: Process Layout

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Instruments to measure fuel properties
Specific gravity Kinematic viscosity

Specific gravity bottle Cannon fenske viscometer

Flash point Calorific Value

Pensky Marten close cup apparatus Bomb calorimeter 19

 Fuel properties
νoil/BD and νwater = kinematic viscosity of
t
Kinematic viscosity (ν oil/BD ) = ν water × oil/BD the oil (or biodiesel) and water
respectively at 40 °C
t water
toil/BD and twater = time required by oil (or
BD) and water respectively to move
between two marked points

56.1× N × V N= normality of the ethanolic KOH

Acid value (AV) =
m V= volume need to titrate
m= mass of sample

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Calorific Value (CV) = CV = Calorific value of the sample, MJ.kg-1
M S {WC × ΔT − (CVt × L t + CVW × L W )} Wc = Heat capacity of the calorimeter,
ΔT = Rise in temperature, °C
Ms = Mass of fuel sample, g
CVt = Calorific value of cotton thread,
Lt = Length of the thread consumed
CVw = Calorific value of nichrome wire,
Lw = Length of wire consumed
(ASTM D6751)

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Results: Objective 5

Fuel properties
Our experiment Qi et al., 2010
ASTM
Properties standards Blend with Blend with
Biodiesel Virgin Petroleum
for B100 diesel diesel
B100 CSO diesel
B10 (10:90) B 20 (20:80)
Specific gravity
@ 15 °C (kg.m-3) 860–900 867 ± 2 814 ± 4 821 ± 4 920 812

Acid value
(mg KOH.g-1) < 0.5 0.45 ± 0.05 0.3 ± 0.1 0.37 ± 0.04 0.7 —

Kinematic
viscosity @ 40 °C 1.9–6.0 8.5 ± 1.7 4.3 ± 0.6 4.6 ± 0.2 42 3.94
(cSt)

>120 140 ± 5 62 ± 2 60 ± 5 >250 55

Flash point (°C)

Calorific value
>37.5 38.3 41.6 40.2 39.3 42.5
(MJ.kg-1)

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 Cetane (C16H34) number and index

Cetane index Cetane number

• Cetane index is a value that is • Cetane number is the actual
calculated based on the density measured ignition quality of
and distillation characteristics of
diesel fuel
the fuel
• Includes the effect of
• The index indicates the ignition
quality of the basic fuel, before any additives
chemicals are added to it • Indicates the ignition delay
• The index doesn't change when
you add a cetane booster to it

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 Example 1
• Determine the amount of vegetable oil, catalyst and
methanol required to produce 35 x106 lb/yr (5 million
gallons per year) of biodiesel.

– Molecular Weight of FAMEs = 292.2

– Molecular Weight of Methanol = 32.1
– Molecular weight of Glycerol = 92.1
– Molecular weight of soybean oil = 885
• 35 x 106 lb of FAMEs x (1 lb mol/292.2 lb)
= 120 x 103 lb mol of FAMEs

Amount of VO = 40 x 103 lb mol = 35.06 x 106 lb

Assuming methanol/oil molar ratio = 6:1

Amount of Methanol = 6 x 40 x 103 lb mol
= 240 x 103 lb mol = 7.68 x 106 lb
Amount of Glycerol = 40 x 103 lb mol = 3.68 x 106 lb
Weight of Catalyst = 0.01 x 35.06 x 106 lb
= 350.6 x 103 lb
Impact Factor: 5.6

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Impact factor: 2.648

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Thank you

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