BIomass pyroysis

1. Different Aspects of Biomass Pyrolysis:
A General Review
Ersan Pütün
Anadolu University, Department of Materials Science and
Engineering, Eskisehir, Turkey
eputun@anadolu.edu.t

2.  Energy needs and demands
 Biomass
 Biomass potential of the World and Turkey
 Thermochemical Conversions
 Pyrolysis
 Carbonaceous products obtained from pyrolysis
and their characterization methods
 Bio-oil
 Bio-char
 A research example
 Environmental, Economical and Future Aspects of Biomass
Pyrolysis
Outline

3. 3E
Energy Economy Ecology
Meeting the global energy challenge….
Sufficient
Available
Secure
Reliable
Sustainable
Fossil Fuels ↔ Biomass
Energy?

4. • The term biomass is ascribed to biological materials derived from
living, or recently living organisms.
• The chemical composition of biomass is complex and very different
from that of fossil fuels.
Biomass
Agricultural
crops& residues
Industrial
residues
Forestry crops&
residues
Animal
residues
Municipal solid
waste
Energy crops

5.  Currently biomass provides approximately 13% of world primary energy
supply and more than 75% of global renewable energy.
 Indeed it is estimated that bio-energy could contribute 25–33% of global
energy supply by 2050.
 World production of biomass is estimated at 146 billion metric tons a
year, mostly wild plant growth.
.
5
http://www.eia.doe.gov/
Biomass Potential of the World
http://www.eia.doe.gov/

6. Agricultural Biomass Potential of Turkey
Total available waste amount= 16 MT
(303,2 PJ total heating value)
Foresty Biomass Potential of Turkey…
Total forestry waste= 48 MT (1,5 MTEP)
Biomass Potential of Turkey
http://www.eia.doe.gov/

7.  Biomass can be considered as a natural composite material which is mainly consisted of cellulose, hemicellulose, and
lignin.
 Minor amounts of minerals and lower molecular weight organic materials (solvent extractives) are also included in the
biomass structure
Lignocellulosic
Material
Cellulose
(40-50 %)
Glucose monomer
Hemicellulose
(25-35 %)
Xylose monomer
Lignin
(16-33 %)
Phenyl propanoid
monomer units
Water
(3-10 %)
Organic extractives
Inorganics
(K, Na, Ca, Mg, P…etc.)

8. Different thermal degradation reactions:
• T> 200° C water is lost
• T> 250° C several competing pyrolytic reactions
grouped into three basic classifications:
o At lower temperatures → water, CO, CO2 and a
carbonaceous char
o At higher temperatures → depolymerization of the
cellulose chain → anhydroglucose derivatives, volatile
organic materials and tars.
o At still higher temperatures →bond cleavage of
cellulose → low molecular weight compounds.
Thermal Degradation of Cellulose

9. • Hemicellulose decomposes → 200-260 °C
→ more volatiles, less tars, and less chars
than cellulose.
• Hemicellulose is lost in slow pyrolysis of
wood → 130-194 °C, with most of this loss
occurring above 180 °C.
Thermal Degradation of Hemicellulose

10. Thermal Degradation of Lignin
• Lignin decomposes → 280-500 °C.
• Lignin pyrolysis → more residual char
• DTA studies → a broad exotherm
plateau → from 290 °C to 389 °C →
followed by a second exotherm, peaking
at 420 °C →tailing out to beyond 500 °C.
• Lignin decomposition in wood → begins
at 280 °C → continues to 450-500 °C →
with a maximum rate at 350-450 °C.

11. Thermochemical Conversions
Biomass
Combustion
Hot gases
Gasification Pyrolysis Liquifaction/ Hydro
thermal upgrading
Low-energy
gas
Medium-energy
gas
Char Hydrocarbons
Fuel-oil
and
distillates
Fuel gases
Methane
Syn Liquids
Methanol
Gasoline
Internal
Combustion
Engines
Steam
Process
Heat
Electricity
Thermochemical
Process
Intermediate
Process
Final
Product
Main processes, intermediate energy carriers and final energy products from the thermo-chemical conversion of biomass

12. Pyrolysis
• …….the thermo-chemical decomposition of organic materials by heating in the absence of
oxygen.
• It commonly refers to lower temperature thermal processes producing liquids as the
primary product.
C containing feedstock
Pyrolysis
C rich char
Volatiles
Liquid products
Gaseous products

13. Operating conditions
 Temperature
 Heating rate
 Pressure
 Catalyst presence
 Sweeping gas
 Vapor residence time
 Reactor type (Retorts, Kilns, Screw Reactors,
Rotary drum reactors, Moving bed reactors,
Microwave reactors, Fluidised bed reactors…
Feedstock characteristics
 Particle size
 Biological constituent content (cellulose,
hemicelloluse, lignin & extractives)
 Moisture content
 Ash content
 Mineral content
 Morphology
Factors Effecting Biomass Pyrolysis….

14. Bio-char
• can be used as solid fuel in boilers
• can be used futher for the gasification process to obtain
hydrogen rich gas by thermal cracking,
• could be used directly as activated carbons or for the
production of activated carbon via applying different
methods,
• useful as a sorbent for air pollution control as well as
for wastewater treatment.
• serve as catalysts and catalyst supports

15. • used as combustion fuel,
• used for power generation,
• can be used for production of chemicals and resins,
• can be used as a transportation fuel and could be a good
substitute for fossil fuels,
• suitable blend with diesel oil may be used as diesel engine
fuels,
• easily stored and transported, and hence need not to be used
at the production site.
Bio-oil

16. • Complete chemical characterization of bio-oil is difficult and many
instrumental and analytical techniques are used for characterization:
o GC, GC-MS→volatile compounds
o HPLC, HPLC-electrospray MS→nonvolatile compounds
o NMR→nuclear magnetic resonance → types of hydrogens or carbons in
specific structural groups, bonds, area integrations
o FT-IR→ Fourier transform infrared spectroscopy → functional groups
o GPS→Gel Permentation Spectroscopy → molecular weight distributions
Chemical characterization of bio-oil

17. Chemical characterization of char
o Solid state NMR→nuclear magnetic resonance → types of carbons in
specific structural groups
o FT-IR→ Fourier transform infrared spectroscopy → functional groups
o SEM → Scanning Electronic Microscopy → surface morphology
o EDX → Energy-dispersive X-ray Spectroscopy → surface chemicals
o XRD → X-Ray Diffraction → crystallographic structure
o Gas adsorption → Surface area determination

18. Pyrolysis
Oil shale & Coal Plastics Biomass
Liquid
Solid
Heavy
Metals
Toxic
Dyes
Phenolic
Compounds
Adsorption
Activated
Carbon
Gas
Chemical
Activation
Physical
Activation
Pesticides
Petroleum
Hydrocarbons
GC
TG-FTIR
TG-MS
Carbon Materials
Carbonaseous Material
Decomposition
Activated Carbon
Carbon Foam
C-Fiber
Pathway of our studies

19. A research example carried on pyrolysis….
Project Title; Investigation of pyrolysis kinetics of coal,biomass and plastic blends by thermogravimetry and characterization
of the products
(Supported by Anadolu University Scientific Research Council, Project No: 1001F68)
Purpose; Identification of pyrolytic and co-pyrolytic behaviours of different biomass samples with coal and plastics

20. Waste PET bottles Lignite
Corn stalk and cotton stalk were agricultural wastes.
Hazelnut shells were industrial wastes of food
processing.
Enormous production of hazelnut, cotton and corn in
Turkey leads to availibility of bio-wastes….
Hazelnut production 1st country
Cotton production 8th country
Corn production 21st country
throughout the world
Raw materials and their selection
Polyethylene terephthalate (PET) is one of the
most commonly used polymers.
In 2011 7.5 million tons and 1.6 million tons of
PET were collected in worldwide and Europe,
respectively.
Biomass Samples
Turkey has approximately 2% of the world's
lignite reserves.
However, Turkish lignites have low calorific
value and contain relatively higher amounts
of ash and sulphur.

21. Experimental Procedure
RAW MATERIALS
Air dried, ground, screen analysis, proximate, ultimate and compositional analysis
Preperation of blends (with a ratio of 1/1 wt./wt.)
Bio-oil Bio-Char
CHARACTERIZATION
Elemental Analysis
FT-IR
BET surface area
SEM-EDX
PYROLYSIS
Elemental Analysis
FT-IR
1H-NMR
GC-MS
In fixed bed reactor
In combined TGA/FT-IR/MS
system
Kinetic Studies
Evolved Gas Analysis (EGA)

22. Results (Product Yields)
Heating rate= 10 oC/min
Pyrolysis temperature= 550 oC
Nitrogen flow rate= 100 cm3/min
Higher tar yield Highest char yield

23. Results (Product Yields, cont’d)
 PET caused synergetic effect on co-pyrolysis of biomass by increasing liquid product yields.
 Lignite addition of biomass decreased liquid product yield and increased char yield due to high ash content.
Heating rate= 10 oC/min
Pyrolysis temperature= 550 oC
Nitrogen flow rate= 100 cm3/min

24. Results (Elementel Analysis & Heating Values)
wt. % Cotton stalk Corn stalk Hazelnut shells PET Lignite
C 40,28 35,95 48,36 61,34 56,25
H 5,95 5,42 6,22 4,28 4,96
N 1,46 1,49 0,50 0,00 1,58
S 0,29 0,12 0,00 0,00 0,37
O 52,02 57,02 44,92 34,38 36,84
H/C 1,760 1,796 1,533 0,831 1,051
O/C 0,967 1,191 0,697 0,421 0,492
High heating value
(HHV) (MJ/kg)
12,856 9,709 17,233 20,726 19,576
Raw materials
Highest C content
Highest HHV

25. Cotton
stalk
Corn
stalk
Hazelnu
t shells
Lignite Cotton s.
+PET
Corn s.
+PET
Hazelnuts.
+PET
Cotton s. +
Lignite
Corn s.
+Lignite
Hazelnut s.
+ Lignite
PET
+Lignite
C 67,47 66,44 68,04 75,33 59,33 65,84 84,12 68,98 65,57 70,56 60,22
H 7,80 7,39 7,15 7,92 5,29 5,70 7,49 7,59 7,41 6,98 4,53
N 1,32 0,78 0,90 0,46 0,02 0,44 0,26 0,65 0,84 1,01 0,38
S - - - - - - - - - - -
O** 23,41 25,39 23,91 16,29 35,36 28,02 8,13 22,78 26,18 21,45 34,87
H/C 1,38 1,33 1,25 1,25 1,06 1,03 1,06 1,31 1,35 1,18 0,90
O/C 0,26 0,29 0,26 0,16 0,45 0,32 0,07 0,25 0,30 0,23 0,44
HHV
(MJ/kg)
29,86 28,56 29,02 33,97 21,33 25,45 37,80 30,18 28,15 30,07 20,62
Liquid products
Results (Elementel Analysis & Heating Values)
Highest C content
Highest HHV

26. Cotton
stalk
Corn
stalk
Hazelnut
shells
Lignite
Cotton s.
+PET
Corn s.
+PET
Hazelnuts.
+PET
C 63,74 57,55 85,43 67,92 67,20 71,20 86,54
H 1,22 1,21 1,61 1,53 1,38 1,48 1,59
N 0,46 0,91 0,014 1,40 0,36 0,81 0,05
S 0,31 0,00 0,00 0,39 0,28 0,00 0,00
O 34,27 40,33 12,946 28,76 30,78 26,51 11,82
H/C 0,228 0,251 0,225 0,268 0,245 0,248 0,219
O/C 0,404 0,526 0,114 0,318 0,344 0,280 0,103
HHV(MJ/kg) 17,171 13,941 28,889 20,034 19,20 21,441 29,439
Chars
Results (Elementel Analysis & Heating Values)
Highest C content
Highest HHV

27. Sample BET Surface Area(m2/g)
Hazelnut shell 10,37
Corn stalk 102,60
Cotton stalk 0,97
Lignite 10,57
Hazelnut Shell +PET 143,28
Hazelnut shell+Lignite 117,37
Corn stalk +PET 294,91
Corn stalk + Lignite 78,36
Cotton stalk +PET 20,29
Cotton stalk + Lignite 43,14
PET-Lignite 61,34
Results (BET Surface Areas of Chars)
In co-pyrolysis, cotton stalk and
lignin presence decreased BET
surface area values.
On the other hand, co-pyrolysis wit
PET increased BET surface areas.

28. Results (FT-IR and SEM-EDX Analysis of Chars)
 Pyrolysis caused evolvemet of oxygen from the structure of raw materials and cracking of the aromatic structures
which leads to carbonaceous solid products.
 Morphologies of bio-chars were observed different when PET and lignite were blended with biomass samples.
 BET surface area of corn stalk+PET char were foung highest and SEM micrographs showed formation of porous
structure due to pyrolysis
SEM micrograph and EDX analysis of Corn stalk + PET sample

29. Results
As a general conclusion of the project , valuable solid and liquid products can be achieved from co-pyrolysis of biomass
with lignite or PET under proper conditions. By this way, disposal of plastics and evaluation of low-ranked coals by co-
pyrolysis may be a sustainable and an enironmentally-friendly choice.

30. • Biomass pyrolysis technology offers a great deal of potential
for human and environmental gain
• No net CO2 or SOx addition to the atmosphere
• Unfortunately, combustion of bio-oil also has its drawbacks.
oHigh particulate content
Environmental, Economical and Future Aspects of Biomass Pyrolysis

31. • In the short term, carbonaceous products from biomass cannot hope to compete
with the vast fossil fuel.
• Studies have emerged, however, of smaller niche markets available for biomass
pyrolysis technology.
• In the long term, larger scale “biorefineries” which would integrate every step of
processing and refinement will take place and these bio-refineries will be more
economical than today’s smaller markets.
• To reinforce the utilization of biomass conversion technologies the states should
reduce the taxes and support manufacturers for production.
Environmental, Economical and Future Aspects of Biomass Pyrolysis (cont’d)

32. • Biomass provides a promising answer to world energy needs and a potentially viable
alternative to fossil fuels.
• The utilization of a significant amount of these biomass resources would also require a
concerted R&D effort for developing technologies to overcome the cost barriers.
Demonstration projects and incentives (e.g., tax credits, price supports, and subsidies)
would be required.
• Additional efforts would be required to discern the potential impact that large-scale
forest and crop residue collection and production of perennial crops could have on
traditional markets for agricultural and forest products.
Environmental, Economical and Future Aspects of Biomass Pyrolysis (cont’d)

33. • Unique among biomass-generated fuels in its variability and limitless feedstock
possibilities, bio-oil is the most versatile alternative fuel on the market.
• In order for bio-oil to gain a larger share of this market, a few important issues need to be
addressed.
o Scale-up from smaller models used now
o Reduce overhead costs
o Set industry-wide product quality standards
o Encourage developers and investors
o Disseminate information to the public
o Address environmental and safety issues in handling and storage
Environmental, Economical and Future Aspects of Biomass Pyrolysis (cont’d)