Various scenarios are discussed with biomass as source of energy and chemicals

1. Biomass
The future source of energy and chemicals
Janardhan.H.L
Material science Division
PPISR, Bidlur,Devanhalli
Bengaluru - 562110

2. Present sources of Energy
Global Scenario:
Petroleum
33%
Coal
24%
Natural gas
19%
Nuclear power
5%
Hydropower
6%
Biomass
13%

3. Time for energy concern
Peak oil is defined as the point in time when the rate of global petroleum extraction is
reached maximum, after which the rate of production enters terminal decline.

4. Time for energy concern
 India ranks among the top 10 largest oilconsuming countries.
 Oil accounts for about 30% of India's total energy
consumption.
 Presently, India imports about 70% of its total oil
consumption and makes no exports.
 This naturally would create a supply deficit, as
domestic oil production is unlikely to keep pace with
demand.
 India's rough production is only 0.8 million barrels
per day.

5. Traditional Idea Modern Approach
Energy and Chemicals from Biomass

6. Fuelwood Demand in India in 1996
Consumption of
Fuelwood
Million Tons
1. Household
(a) Forested Rural
(b) Non Forested
Rural
(c) Urban Areas
Sub Total
78
74
10
162
2. Cottage Industry
3. Rituals
4. Hotels etc.
Total
25
4
10
201

7. Bio-Digester as fuel source
Plant, kitchen, animal and human waste is used as feed and
methanogenic bacteria converts organic molecule into
methane

8. Fuel from Agricultural products
Enzymatic breakdown of sugars present in sugarcane,
maize, sugar-beet, etc; to get Ethanol,
Mild acid hydrolysis of agricultural waste, including wood,
followed by enzymatic breakdown to get Methanol/Ethanol.
Transesterification of oils and fats to produce biodiesel
Gasification of biomass to produce syngas, used in the
manufacture of liquid by Fischer-Tropsh synthesis

9. Better option?
The daily input of dung and urine from a single
cow produces 1–2 kilowatt-hours of electricity
or 8–9 kilowatt-hours of heat, from biogas plant.
Dilute acid hydrolysis of wood followed by
fermentation produces 11% of ethanol, and
generates 40.2 kg of waste per kg of ethanol,
If the starting material of the biodiesel is edible
oil/fodder it may compete with the agricultural
land for food/fodder.

10. Big challenge!
70.6% of crude oil as
fuel generates US$
385 billion a year, but
3.4% 0f crude oil
consumed
for
petrochemicals
and
specialties
generate
roughly same amount
of money

11. Role of biomass conversion in CO2 cycle

12. Composition of wood based biomass
 Cellulose
40%
 Hemicellulose 25%
 Lignin 30%
 Oil,fats,proteins and other
substances 5%

13. Second generation biofuels
Bagasse
First generation biofuels
Steam splitting
Heat
power
Burn
Juice
Lignin
Extraction
and trans
ester’n
Cellulose
Hemi
cellulose
Hydrolysis , pt-catayst (e.g: PtUSY)
Glucose
Thermal cracking
250-600°C, base
cat.
Low mol wt
feedstocks
(phenols)
Hydro
processing
Alkyl
benzenes
(Biofuel)
Bio-Oil
Gasification
Syngas
Bioethanol
Water Pt
catalyst
separation
Phenolic
fraction
Hydrogen
Flow-chart of
Biomass conversion
Methanol
FischerTropsch
products
Biodiesel
+
+
Glycerol
Carbohydrate
fraction
Catalytic
steam
reform
Phenolic
resins
Fermentation
Complete gasification
800-1000°C ( 2 bar)
Catalyst
500 °C
MTO
MTG
MTP
Glycerol
Biological
gasification
Hydrogen

14. Generations of Bio-Fuels
 At present the production of first generation bio
ethanol
mainly
utilizes
plants
rich
in
carbohydrates.
 First generation biodiesel produced by transesterification of vegetable oils, or animal fats.
 Second generation biofuels are still under
development, and the focus lies on the utilization
of wood-based biomass.

15. Bio-Refinery
 Lignocellulosic biomass is converted through a
number of different processes into a mixture of
products, including biofuels, valuable chemicals,
heat and electricity.
 Lignocellulosic biorefinary attempts to parallel the
working of crude-oil refinery.
 An abundant raw material, consisting mainly
lignin, cellulose, and hemicellulose, enters
biorefinery.

16. Bio-Refining process
Wood is converted into bio oil by fast pyrolysis,
subsequently it is refined or/and gasification of bio
mass, followed by catalytic upgrading of the
products
or/and
separation
of
sugars
with
subsequent catalytic upgrading of the products.

17. Characteristics of bio-oil
 High water and oxygen content
 Corrosive
 Lower stability
 Immiscibility with crude-oil-based fuels
 High acidity
 High viscosity
 Low calorific value

18. Bio-Refining process
Highly oxygenated raw material is functionalized or
controllably defunctionalized as the energy liberated by
the compound decreases with the increase in the O/C
molar ratio, as compared with its analogue.
Methanol on combustion yields 727kJ/mol
Methane on combustion yields 891kJ/mol
Ethanol on combustion yields 1367kJ/mol
Ethane on combustion yields 1560kJ/mol

19. Bio-Refining process using
solid Acid/Base
Pyrolysis of cellulose and hemicellulose results in many
simultaneous reactions such as hydrolysis, oxidation,
depolymerization, dehydration and decarboxylation.

Pyrolysis of lignin between 250 and 600°C yields valuable
low molecular weight feedstocks.

Application of shape selective cracking catalysts would
allow the process to be run at low temperatures and
improved product distribution.


20. Bio-Refining process using
solid Acid/Base
Micro or Mesoporous hybrid materials doped with noble and
transition metals, and base catalysts are used to selective
decarboxylation, to produce high quality bio oil with less amount
oxygen and water.
Ex: AlMCM-41, MSU, ZSM-5,etc.

21. Catalyst testing for biorefining

The catalyst is
placed in the reactor
and the biomass is
placed in the piston
cylinder. The reactor
and piston cylinder
are connected.
Experiment is started
when the temperature
reaches 500°C,
biomass enters the
reactor and the
reaction starts.
Fixed-bed unit for the catalytic
conversion of wood based biomass

22. Catalyst activity comparision

AlMCM-41 is a
promising catalyst in
biorefining

23. Continued…

MSU type molecular sieve
is next to MCM type, but
lower organic phase in biooil and higher coke and
char yields compared to
Al-MCM-41
and
non
catalytic pyrolysis.
Non-catalytic MSU-S/H
Non-catalytic MSU-S/H
MSU-S/W
MSU-S/W
Al-MCM-41
Al-MCM-41

24. Chemicals from Biomass
Acid hydrolysis and cracking
Hemicellulose + water at
170°C, 5MpaN2 for 3hrs
Dhepe et.al, DOI: 10.1039/c004128a

25. Cellulose hydrolysis by solid acids
A. Onda,et.al. Green Chem., 2008, 10, 1033
Hydrolysis of cellulose over various solid acid catalysts at 423 K. Reaction conditions: milled
cellulose 45 mg, catalyst 50 mg, distilled water 5.0 mL, 24 h.

26. Energy and chemicals from bagasse
Bagasse waste production in sugar plant

27. What cane variety for bio-energy ?
Current variety
Sugar
Bagasse for electricity & ethanol
High quality
High quality
More Sugar
More bagasse for electricity & ethanol
High fibre
Less Sugar
Much more bagasse for electricity & ethanol
Energy cane
Small amount of sugar for ethanol
Much more bagasse for electricity & ethanol
Fibre 10 – 12 %
-
Fibre 17 - 22 %
Fibre 17 - 22 %
Fibre 20 - 30 %
Fibre > 30 %

28. Ethanol and Bioplastic from Bagasse
3 Steps
1. Lignin removal from bagasse
2. Convert hemicellulose and cellulose into simple sugars
3. Convert simple sugars into ethanol and bioplastic
Lignin
19.6
Ash
6.3
Hemicellulose
28.4
Cellulose
40.6
Sugar
3.1

29. Bio-diesel

First generation Bio-diesel is manufactured by the tansesterification of the oils / Fat
NaOH
Triglyceride

Methanol
Bio-Diesel
(Methyl Ester)
Glycerol
Recent development is catalytic cracking of non edible
oils to get mixture of hydrocarbons that are present in
various fractions of gasoline, kerosene, and diesel.

30. Comparison of production
Oil Crop
Gallons of Oil per
Acre
Soybeans
48
Rapeseed
127
Jatropha
435-2000
Algae
5000-15,000

31. Bio-fuel from algae
• Algal strains with high oil content can be used as feed
stock for biodiesel production.
• Several species of algae with high starch content are
now being tested to produce ethanol.
• Algae produces a lot more oil per acre than all the other
oil crops put together. And this is why algae biodiesel is
gaining more and more interest.
• Ex: Botryococcus braunii, Chlorella, Dunalielle
tertiolecta, Gracilaria, Pleurochrysis carterae,
sargassum(10 times more out put volume of Gracilaria)
Contd…

32. Advantages of Bio-fuel
from algae
• Compared to other feedstock's, algae can provide a highyield source of bio-diesel, ethanol and aviation fuels .
• It does not effect food supplies, rainforests or arable land.
• Algae are the fastest growing plants in the world.
• They use photosynthesis to harness sunlight and carbon
di oxide.

33. Pilot units

India have 20+ years of application of gasification
technology for thermal, motive power and electrification.
Over 1600 gasifier systems, having 16 MW total
capacity, have generated 42 million Kilo Watt hour
(KWh) of electricity, replacing 8.8million liters of oil
annually (CMIE, 1996)
Contd…

34. Contd…

Four gasifier Action Research Centers (ARCs) located
within different national institutions and supported by the
MNES have developed twelve gasifier models, ranging
from 3.5 to 100 KW. Two co-generation projects (3 MW
surplus power capacity) in sugar mills and one rice
paddy straw based power project (10 MW) were
commissioned.
Contd…

35. Contd…




BTL process for the production of bio-fuels are
under development, and several pilot units are
under construction or already running.
The most advanced unit is the pilot plant from
Choren Industries in Freiberg (Germany) in
cooperation with shell.
Petroalgae a USA based company want to
launch its fuel from algae by next year.
IOC R&D centre in association with NTPC to
scale up algal growth by utilizing CO2 rich flue
gas from thermal stacks.
Contd…

36. Contd…


Praj a pune based company, has established a
pilot plant of 2 ton/day capacity for converting
ligno-cellulosic materials to ethanol and are
planing to put up a much larger capacity plant
next year.
The
lignocellulosic
biomass
fractionation
technology developed by NCL, Pune, has been
scaled up by Godavari Biorefineries.
• ExxonMobil invested $300 million in Synthetic
Genomics to develop algae biofuel.

37. Major Obstacles

High investment costs

Low volumetric energy density of bio mass

Lack of infrastructure

Limitations to the productivity of photosynthesis

Available of cultivable land areas for the
production of bio energy plants, which are in
competition with food production

38. Present challenge



Understanding the mechanism of the catalytic
conversion of lignocellulosic biomass into bio-oil,
including structure-property relationships and
product distribution.
Catalyst development, regarding porosity,
acidity, basicity, metal support interactions,
controlled formation of catalyst particles,
improved hydrothermal stability, resistance to
catalyst deactivation
Process condition and large scale production

39. Recent Bioenergy news updates from India
 March 22, 2011: “The country is aiming to generate about 10,000MW of energy from
biomass over the next decade” said Deepak Gupta, Secretary of the Ministry of New
and Renewable Energy (MNRE), in Bangalore.
K. Verma, MD, Karnataka State Forest Industries Corporation Limited, highlighted the
importance of plantation, especially bamboo, to provide sustainable supply of
feedstock for power generation
 Jan 25, 2011: International Finance Corporation (IFC), a member of the World Bank,
has guaranteed $300 million, for renewable energy projects in India.
Jan 24, 2011: Reliance Venture Asset Management has completed the Series A
funding for AllGreen Energy Ltd for its biomass project in Perundurai. Tamil Nadu.
AllGreen is one of the leading players in the Indian renewable energy marketplace,
through the usage of its biomass gasification power plants that use agricultural waste
to generate power
 Nov. 18, 2010: Clenergen Corporation is to join forces with Yuken India Limited to
install a 4 MW/h Gasification Biomass Power Plant operating on gas engines at their
manufacturing facility in Bangalore, India.
 August 27, 2010: Orient Green Power Company, Chennai set a target of 200MW of
biomass power generation and at present is generating 40MW from biomass plants.

40. List of Companies working on
Biomass to Energy
• Reliance Venture Asset Management
• Abellon Clean Energy Ltd, India - Gujarat , India
• BioEnergy Consult - Uttar Pradesh, India
• Deep Industries - Gujarat, India
• Saltmarch Media - Karnataka, India
• Yuken India
• Orient Green Power Company…… etc

41. Conclusive Remarks
 In 20th and early 21st century the development of countries were designed
around crude oil, due to high availability and low prices. But today,
scenario based on crude oil is unsustainable at long term.
 The conversion of wood based biomass to energy and chemicals is an
attractive area since the raw material is available in plenty and at
cheaper rate.
 Wood based biomass contains cellulose, hemicellulose and lignin. All
these can be converted into energy with suitable treatment.
 Heterogeneous solid catalysts play a major role in gasification, acid
hydrolysis, cracking steps in biomass conversion.
 So far the drawbacks of reported catalysts are their low hydrothermal
stability, lower activity and poor recyclability.
 Hydrothermally stable zeolites or carbon based catalysts may be a
future for hydrolysis and cracking of biomass.
Contd…

42. Continued…
 A race to develop a better catalyst is still on.
 R&D is necessary in this field for the complete utilization of biomass
into fuel and specialty chemicals.
 Next century development will be limited by the supply of crude oil.
 As the biomass composition varies from species to species catalyst
development is challenging.
 Global energy may not be fulfilled by biomass only, hybrid with other
renewable energy source may be utilized.

43. References:
1) Biofuels and Biomass-To-Liquid Fuels in the Biorefinery: Catalytic Conversion of
Lignocellulosic Biomass using Porous Materials -Michael Stöcker, Angew.Chem. Int. Ed.
2008, 47, 9200 – 9211 DOI: 10.1002/anie.200801476
2) A solid-acid-based process for the conversion of hemicellulose -Paresh Laxmikant Dhepe
and Ramakanta Sahu Green, Chem., 2010, 12, 2153–2156 | 2153, DOI: 10.1039/c004128a
3) Design of solid catalysts for the conversion of biomass -Roberto Rinaldi and Ferdi
Schuth, Energy Environ. Sci., 2009, 2, 610–626, DOI: 10.1039/b902668a
4) Selective hydrolysis of cellulose into glucose over solid acid catalysts -Ayumu Onda,
Takafumi Ochi and Kazumichi Yanagisawa, DOI: 10.1039/b808471h
5) Sustainable biomass power for rural India : Case study of biomass gasifier for
village electrification -N. H. Ravindranath, H. I. Somashekar, S. Dasappa and C. N.
Jayasheela Reddy, CURRENT SCIENCE, VOL. 87, NO. 7, 10 OCTOBER 2004
6) BIOMASS ENERGY IN INDIA : TRANSITION FROM TRADITIONAL TO MODERN - P.R.
Shukla, http://www.e2analytics.com, The Social Engineer, Vol. 6, No. 2
7) Fixed Bed Catalytic Cracking Of Non-Edible Oils Using Zeolites For The Production Of
the Bio-Fuel. –G. Ramya & T. Sivakumar, Bulletin Of the Catalysis Society Of India, Vol.9,
Issue 3 & 4 (2010) 83-90.

44. Thank you