Renewable Resources

Literature Sources
• Journals
Patil P.D., Gude V.G., Reddy, K.H., Muppaneni, T., Deng, S. Journal of
Environmental Protection, 2012, 3, 107-113
Salvi B. L, Panwar N. L. Renewable and Sustainable Energy Review, 2012, 16, 3680-
3689.
Hossain A.B.M.S., Boyce, A.N. Balgarian Journal of Agricultural Science , 2009, 15,
312-317.

• Book
Graziani, Mauro. ‘Renewable resources and renewable energy : a global
challenge’, 2007

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 Fossil Energy
• The world’s energy needs are met through
non-renewable resources such as petroleum,
naturals gas and coal.

Figure 1. 86% of the worlds energy consumption is derived from

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fossil resources 3
 Fossil Energy
• Fossil resources are derived from decomposed
organic material occurring underground.
• There are increasing concerns of :
 Depletion of fossil fuel reserves
 High concentration of Green House Gases (GHGs)
 Global warming (CO2 concentration)
 Renewability and Sustainability
 Environmentally unfriendly
 Increasing the fuels demands

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 Green House Effect
Solar Energy reflected by
atmosphere, GREEN HOUSE
GAS and earth’s surface

Solar Energy passes

through atmosphere

Green House Gases (CH4, CO2, H2O, N2O)

Reflected infrared radiation (in the form

of heat) is reabsorbed by GHG and
reflected in all direction (earth get
warmer)

Solar Energy absorbed by earth’s surface and converted to infrared radiation

(longer wavelength, in the from of heat)

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 Biomass
• is a term used to describe any material of
recent biological origin, including agricultural
and forestry residues, wood, organic parts of
municipal sludge wastes, agricultural crops,
and even animal manure.
• Biomass could be converted into value added
products such as fuel, natural gas and
chemicals.
• Biomass is a carbon neutral and sustainable
energy source.

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 Why Biomass?
• Its renewable and sustainable energy sources.
• Reduces the production of green house gases
and so-called greenhouse effect (minimise
global warming).
• Cheap and easily available.
• Reduce reliance on other countries to import
crude oil (unstable oil prices).
• Helps to reduce pollution (recycling).

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• challenges
 Land
 High moisture make collection and
transportation expensive.
 Extensive use compete with food.

Three main process technologies to convert

biomass to energy.

1. Thermo-chemical conversion.
2. biological conversion.
3. Chemical conversion.

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 Thermo-chemical conversion
• The objective is to convert biomass to fuels,
chemicals and other materials that are cost
competitive with conventional commodities.
1. Gasification
• Biomass is converted into syngas (CO and H2),
ash and char at high temperatures in the
presence of an oxidizing agent (O2, H2O H2)

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 Gasification
• These gasses can be converted to methanol
using Cu/ZnO (methanol synthesis reaction)
• Equations:

Fischer-Tropsch Synthesis
• Method used to convert syngas to alkanes
(including methane, gasoline range, diesel
range) in the presence of Fe or Co catalyst.
• Equations:

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 Pyrolysis
• Biomass or organic material is thermally
decomposed at TºC ranging from 350-800ºC
in the absence of oxygen.
• Large biomass molecules are cracked into
smaller molecules such as methanol, acetic
acid, bio oil and solid char.
Pyrolysis bio-oil
• Liquid from pyrolysis consisting of > 300
organic compounds with different
functional groups, including carbonyls,
carboxyl and phenolics.

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 Pyrolysis Products

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 Advantages
• Can be converted to different value added
chemicals.
• Carbon neutral.
• Renewable resource.

Disadvantages
• Stability: pyrolysis bio-oil become more
vicious due to chemical and physical changes
on storage.
• High content of oxygen make boi-oil heating
value low compared to petroleum derived fuel.
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 Biological Conversion
• Fermentation: ethanol is produced from
sugars and starch using enzymes and
yeast.
Equation:

• Syngas can also be converted to ethanol via

fermentation.
• Attractive way to produce ethanol for
transportation.
Equations:

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 • Biochemical Conversion: Microorganisms
(bacteria) break down plants material into
gases, liquid biofuel and solids. Fermentation.

Enzymes Glucose

Lactic Acid Ethanol H2, CO2, CH4

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• Chemical conversion: Chemicals processes
converts animal lipids and oils into biofuel.
Trasestarification. Waste
animal fat
and
vegetable
oil

Alcohol Trasesta
and rification Biodiesel
Catalyst

Glycerol
Soap Alcohol
Catalyst
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 Biofuel
• Fuel that is derived from biological materials.
• Most common are methane, bioethanol,
biodiesel and bio-hydrogen.

• Biodiesel is the most recently researched and

attractive biofuel.

• Because it is a potential substitutes for

petro-diesel.
• It is environmentally friendly, economically
feasible, sustainable and could be produced
cheaply and easily.
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 Biodiesel
• Is defined as methyl or ethyl esters of long chain
fatty acids which are derived from triglyceride
molecules present in vegetable oil and animal fat
by the process called trasestarification reaction.

Glycerine portion Triglyceride molecule

O
H2C O

O
HC O

Ester linkage O
H2C O

Fatty acid portion

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 Pure Vegetable Oil
• The use of straight vegetable oil is not suitable for
use in diesel engine because of it high viscosity (28-
40 mm2/s), low vapour pressure and low volatility.

• This is because Vegetable oil consist of large

triglyceride molecules which are more vicious
making it difficult to flow to the engine.

• Which leads to operational problems due to

poor vaporisation and atomisation.
• Carbon deposit due to incomplete combustion.

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 Transesterification Reaction
• Transesterification changes both physical and
chemical properties of vegetable oil into diesel
like properties making it suitable for use in
diesel engines.

• Transesterification reduces the viscosity of the

oil to the range (4-5mm2/s) comparable to that
of petro-diesel.

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 Trasestarification Reaction
• During this process, triglycerides are reacted
with methanol or ethanol in the presence of
strong base to produce Fatty Acid Methyl
Esters (FAME) or Fatty Acid Ethyl Esters (FAEE).
O
O
H2C O
R MeOH H2C OH Me O
NaOH
O
(Catalyst) O
HC O
R' + MeOH HC OH + Me O
O
H2C O MeOH O
R'' H2C OH
Me O

Glycerol
FAME (Biodiesel)

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 Mechanism of Transesterification

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 Pure Vegetable Oil
• Production of biodiesel from pure vegetable
oil (PVO) has disadvantages such as.
 High cost
• The price of vegetable oil will increase as
the demand increases (starvation).
• The feedstock prices will be high, biodiesel
price will also be high.
 There is insufficient land for plantation

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 Pure Vegetable Oil
O
H2C O

O
HC O
Triglycerides
O
H2C O

Transesterification of pure oil requires:

• Methanol = 20% (v/v) of vegetable oil
•Catalyst (NaOH) =3.5 g /L of pure vegetable oil

Q? : Calculate the amount of a catalyst and methanol required to make

biodiesel from 100 g of pure vegetable oil.
density of VEGETABLE OIL = 0.90 g/mL
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 Calculations

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 Waste Vegetable Oil
 Advantages
• Obtained freely from restaurants
• No need for extra land for plantation
• Reduce pollution (oil disposal minimised)
• Encourage recycling.
Problems with WVO!!
Waste cooking oil contain Free Fatty Acids!!
O
H2C OH HO

O
HC OH + HO FFA
O
H2C O

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Water react with triglycerides cleaving the ester bond
Producing Free Fatty Acids (FFA)
O
H2C O

O
2H2O + HC O

O
H2C O

HEAT

O
H2C OH HO

O
HC OH + HO FFA
Ester linkage
O
H2C O
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 Waste Vegetable Oil
FFA must be < 1% (g/g) for transesterification
reaction.
• FFA react with catalyst to form soap
(saponification).
• FFA consume the catalyst, leading to incomplete
transesterification reaction.
• Reduce the yield of biodiesel, formation of
by-product (soap)
O O
NaOH
H O
OH R ONa + 2

Soap formation
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 Waste Vegetable Oil
• Two methods to solve these problems
1. Determine FFA content in WVO (Titration)

Methanol = 20% (v/v) of cooking oil

Catalyst = 3.5g + grams required to nuetralise FFA

Mr (oleic acid) = 282.47 g mol-1 , density of WVO = 0.92 g/mL

Q1? : An average volume of 0.1 M NaOH required to neutralize FFA in 1mL

WVO was found to be 1.75 mL. Calculate the % FFA in 100 g waste
vegetable oil assuming only oleic acid molecule are present.
Q2? : Calculate the amount of the catalyst required to convert 100 g of
this oil to biodiesel. 31
 Calculations

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 Esterification reaction.
• IF FFA must be > 1% (g/g) (grams FFA/grams of Oil)
2. Perform a pre-treatment to neutralize FFA
• By converting FFA into methyl esters through
acid catalysed Esterification reaction.
O O
MeOH
R OMe + H2 O
OH +
H

• FFAs are neutralised, then transesterification

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 Mechanism of Esterification.

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 WVO (55°C)

NaOH + MeOH

Trasestarification

Standing/Separation

Upper layer Lower

(biodiesel) Layer(glycerol)

Wash with H2O Evaporate MeOH

Filter, Dry Dry
Biodiesel Soap
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 Advantages of Biodiesel
• Higher cetane number and high flash point
meaning better and safer performance
• Higher lubricity, which prolongs engine life span

• Presence of oxygen (10%) improves combustion,

reduce CO and carbon deposit

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 Quality of Biodiesel
• American Society for Testing and Material
(ASTM).
Property Petro-diesel Biodiesel
Standard ASTM D975 ASTM D6751
Kinematic viscosity 1.9-4.1 1.9-6.0
(mm2/s) 40 °C
Density (g/mL) 0.867 0.860-0.894
Cloud point (°C) -1 -3 to 15
Pour point (°C) -4.4 -5 to 10
Glycerol content - <0.25%(g/g)

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 Determination of Glycerol
O O
- 2x
+ 2IO 4 + + 2IO-3 + H2O
OH OH OH
H H H OH

2 moles of periodic acid are reacted with glycerol to give 2 formaldehydes,

formic acid, 2 moles of iodate and water.

If a known excess amount of periodate is added to unknown amount of

glycerol, we can determine the amount of glycerol in the sample by analyzing
excess periodate on completion of a reaction.

IO4- + 3I- + 2H+ I3- + IO3- + H2O

I3- + 2S2O32- S4O62- + 3I-

Overall IO4- + 2S2O32- + 2H+ S4O62- + H2O

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 Determination of Glycerol

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