Universiti Teknologi MARA

Cost-Effective Technologies for Thermochemical

Conversion of Biomass to Produce Fuels,
Chemicals, Materials and Power

Mohammad Asadullah
Professor (Dr)

Faculty of Chemical Engineering

Universiti Teknologi MARA
Content
 Introduction to R & D Projects Based on Biomass
 Background
 Problem Statement
 Objectives
 Malaysian Government Policy of Utilizing Biomass
 Biomass Potentiality in Malaysia
 Technologies for Thermochemical Conversion of
Biomass
 Gasification of Biomass and Model of Commercial Plant
 Pyrolysis of Biomass and Model of Commercial Plant
 Summary and Conclusion
 R&D/Commercialization Projects

Power
First R&D
Project: Liquid
Biomass Fuels
Gasification
Heat
Second R&D
Project: Biomass Chemicals
Pyrolysis &
Biorefinery
Materials

Power
 Background

What is Biomass

• Biomasses are organic materials derived from

living organisms, i.e. from plants or animals.
• Depending on the source of biomass, it can be
classified as primary and secondary biomasses.
 Formation of Biomass

C6H12O6+ 6 O2
6H2O + 6CO2

Cellulose +
Hemicellulose +
Lignin
Primary
Biomass
Secondary
Biomass
 Biomass is the Source of Fuels,
Chemicals, Materials & Power
Every single
carbon used
from fossil
resources would
be excess into
the atmosphere.
Millions
of years

Fuels Chemicals Materials Power

Global Carbon Cycle
Burning of
fossil fuel 103
4.5
101
1.5
50
53 48
Burning of 1
53
biomass

5 2

100

95
Mass Balance of the Global
Carbon Cycle

CO2 Release
Plant and soil respiration = 100.0 Bt/y
Land use = 1.0 Bt/y
Fossil fuels burning = 4.5 Bt/y
Biomass burning = 1.5 Bt/y
CO2 Consumption
Ocean uptake (Sedimentation)
= 2.0 Bt/y
Photosynthesis = 100.0 Bt/y
Mass Balance
NET EMISSION = OUTPUT - INPUT
= (100 + 4.5 + 1.5 + 1.0) - (100.0 +2.0)
= 5.0 Bt/y
 Global Mean Temperature Profile

These are the

overall problems
related to the fossil
resources.

The global temperature is supposed to

increase by 5oC within 2050.
Overall Objective of this Technology

Millions Overall objective

of years is to reduce
0 year
millions of years
to zero year.
Modern
technology

Fuels Materials Fuels Materials

Chemicals Power Chemicals Power
Why Biomass is a Carbon
Neutral Fuel

6H2O + 6CO2 6CO2 + 6H2O

Energy

Artificial Cycle Natural

C6H12O6
Cycle

X
Gas or Pyrolysis Heat or
Liquid Bacterial
Gasification Biomass action
 Malaysian Governmental Policy of
Utilizing Renewable Resources, 2011
 On June 10, 2010, the government announced the National
Renewable Energy Policy and Action Plan with a goal of
increasing renewable energy from 1% to 5.5% of electricity
supply by 2015.
 The program is going to be launched by the second
quarter of 2011.
 The current proposal limits the program to 219 MW in
2011, increasing to nearly 1,000 MW in 2015. The bulk of
the new generating capacity to be installed under the
program is set aside for biomass and minihydro.

Source: Renewable energy world.com, August 16, 2010

Quota of Biomass Energy out of Total
Renewable Energy Generation
Comparison of Tariffs for PV and
Biomass Energy
Technology for Thermochemical
Conversion of Biomass
Biomass Conversion Technology

Combustion Gasification Pyrolysis

Presence of Presence of Absence of O2
excess O2 limited O2

Fast pyrolysis Slow pyrolysis

• Tar xx • Tar 5% • Liquid 75 % • Liquid 40 %

• Gas CO2 • H2+CO 85 % • Gas 12 % • Gas 10 %
• Ash -- • Char 10 % • Char 13 % • Char 50 %
Problems with Existing Gasification
Technology

 High temperature method > 1000oC

 Tar yield > 5%

 Tar deposits in the down stream application

of syngas and makes problems
 Tar separation by physical filtration is
not technically viable
Fundamental Concept of Gasification in
a Down Draft Gasifier
Biomass

Zone I
Pyrolysis

Char (Liquid vapour + CO, H2,

Volatiles H2O, CO2, CH4, C2H2)
Air
O2 Zone II C + ½O2  CO
H 2O Oxidation C + O2  CO2
CO2 H2+ ½O2  H2O
(CO, H2, H2O, CO2,
Char + Ash Volatiles CH4, C2H2, N2)

Zone III
C + CO2  2CO
Reduction C + H2O  CO + H2
CO + H2O  CO2 + H2

Char + Ash CO, H2, H2O, CO2, CH4, C2H2, N2, tar
 Catalytic Gasification of Cellulose

Asadullah et al., Catalysis Communication, 2, 2001, 63-68.

Asadullah et al., Industrial and Engineering Chemistry Research, 40, 2001, 5894.
Result of Catalyst Screaming
Catalytic Gasification of Cellulose

Feeder Vibrator

Product
gas

Catalyst particles

Furnace

Thermocouple Distributor
Air

Asadullah et al., Industrial and Engineering Chemistry Research,

41, 2002, 4567-4575
Asadullah et al., Applied Catalysis A: General, Volume 255,
Issue 2, 8 December 2003, Pages 169-180
TEM Images of Rh/CeO2 Catalyst

Rh/CeO2
sintered and
deactivated

30 nm 30 nm

Asadullah et al., Industrial and Engineering Chemistry Research,

41, 2002, 4567-4575
TEM Images of Rh/CeO2/SiO2 Catalyst

Rh/CeO2/SiO2
No sintering
at all after
reaction

TEM images of Rh/CeO2/SiO2; (a) fresh catalyst, (b) after reaction

Asadullah et al., Journal of Catalysis, 208, 2002, 255-259

 Rh/CeO2/SiO2 Catalyst for Real
Biomass Gasification

Ash
problems
No problems
at all even at
650oC

Asadullah et al., Applied Catalysis A: General 255 (2003) 169–180.

 Effect of Temperature on the Gasification of
Various Biomass on Rh/CeO2/SiO2 Catalyst
Formation rate C- Char Coke Tar
T (oC) (mmol/min) H2/CO conv yield yield yield
CO H2 CO2 CH4 (%-C) (%-C) (%-C) (%-C)
Cedar 550 2152 2686 1841 517 1.3 78 20.8 1.2 0
600 2599 3232 1752 269 1.2 80 19.1 0.8 0
650 2902 3541 1605 148 1.2 81 18.5 0.5 0
Jute stick 550 2032 2634 1729 323 1.3 71 24.0 3.0 2.0
600 2362 3036 1818 306 1.3 78 17.0 1.0 0.0
650 3057 3255 1577 218 1.1 84 14.5 0.5 0.0
Bagasse 550 1850 2057 1645 416 1.1 68 21.0 4.0 7.0
600 2050 2357 1739 516 1.2 75 21.0 2.0 2.0
650 2965 3264 1587 205 1.1 82 17.0 1.0 0.0
Rice
straw 550 1797 2057 1569 366 1.2 65 21.0 4.0 10.0
600 2102 2162 1677 452 1 74 19.0 4.0 3.0
650 2878 3167 1524 172 1.1 80 16.0 2.0 2.0
Conditions: Catalyst 3 g, ER = 0.24, feeding rate 150 mg/min (moisture: 5 – 10%), N2
flow 100 ml/min, O2 flow 35 ml/min through the catalyst bed.
Properties of Various Biomasses

100

80
Weight ratio /%

60
Rice straw
Cedar
40
Jute stick
20 Bagasse

0
450 550 650 750 850 950 1050

Temperature/K
Mechanism of Rh/CeO2/SiO2
Catalytic Reaction

Tar CO + H2 CH4 CO2 + H2O Char

O
H2O H2O Rh 2
CeO2
SiO2 O2
Mobility
Oxidized
catalyst
CeO2 high
Reduced SiO2
catalyst

High
Very surface
active area
Problem Statement and Objectives
for Further Development of Catalysts

Problem:

 Rh catalyst is expensive

Objectives:

 To develop cheap catalysts with high activity

 To produce highly dispersed catalyst on high

surface area cheap materials
Cheap Catalyst for Tar Reforming

Char
supported
catalyst

Asadullah et al., Fuel (In Press, 2011)

Asadullah, et al., Fuel, doi:10.1016/j.fuel.2010.12.039.
 Performance of Char Supported
Catalyst

35 35
Pyrolysis
Tar yield (wt% of biomass,db)

Tar yield (wt% of biomass,db)

Reforming no catalyst Pyrolysis
30 30
Reforming with H-char Reforming no catalyst
25 Reforming with Fe-char 25
Reforming with ilmenite
Reforming with Ni-char
20 20

15 15

10 10

5 5

0 0
400 500 600 700 800 900 400 500 600 700 800 900
o
Temperature ( C) Temperature (oC)

Char supported
Ilmenite Catalyst
catalyst
Performance of Char Supported
Catalyst
Intensity (a.u., per g of biomass (db))

Intensity (a.u., per g of biomass (db))

2500 2500
Pyrolysis Pyrolysis
Reforming no catalyst Reforming no catalyst
2000 Reforming with H-char 2000 Reforming with H-char
Reforming with Fe-char Reforming with Fe-char
1500 Reforming with Ni-char 1500 Reforming with Ni-char

1000 1000

Intensity (a.u., per g of biomass (db))

500 2500 500
Pyrolysis
Reforming no catalyst
0 2000 0
Reforming with H-char
Reforming with Fe-char
260 300 340 380 420 460 500
260 300 340 380 420 460
1500
500 Reforming with Ni-char
Wavelength (nm)
Wavelength (nm)
(b)
(a) 1000
Intensity (a.u., per g of biomass (db))

2500 500

Intensity (a.u., per g of biomass (db))

Pyrolysis 2500
Pyrolysis
Reforming no catalyst Reforming no catalyst
2000 0
Reforming with H-char 2000 Reforming with H-char
Reforming with Fe-char
260 300 340 380 420 460 500 Reforming with Fe-char
Reforming with Ni-char Reforming with Ni-char
1500 Wavelength (nm) 1500
(e)

1000 1000

500
500
0
0 260 300 340 380 420 460 500
260 300 340 380 420 460 500 Wavelength (nm)
Wavelength (nm) (d)
(c)

Constant energy (Δν = -2800 cm-1) synchronous spectra of mallee wood tar solution (4
ppm) after the steam reforming of its volatiles with/without the char-supported
catalysts at the temperatures of (a), 500°C; (b), 600°C; (c), 700°C; (d), 800°C and
(e), 850°C.
 Char Characteristics Studies

Asadullah et al., Bioresource

Technology,
doi:10.1016/j.biortech.2010.05.048
Asadullah et al., Industrial and
Engineering Chemistry Research,
48, 2009, 9858-9863.

Asadullah et al., Fuel Processing

Technology In Press, Corrected
Proof, Available online 3
September 2009.

A schematic diagram of the fluidised-bed

reactor used for the fast heating pyrolysis.
Lab Scale Demonstration Plant for
Biomass Gasification

Water
Air inlet

Product gas
outlet

Thermocouple
Thermocouple Steam
 Lab Scale Demonstration Plant for
Biomass Gasification
1-100 rpm

Solid
sampling Looking
Thermoco
port uple 340 glass
Gas sampling mm Looking
port 399 glass
Solid sampling
mm port
Gas sampling
port
Looking
glass
Solid sampling
1500
mm port
Gas sampling 400
Rotating port mm Looking
glass
shaft Solid sampling
Gas sampling port Solid
port
Thermoco sampling
uple
port
150
mm
 Inner Design

Cone

Hot gas 150 mm

out

Moving 20o
340 mm
Fixed 350 mm
399
mm
35o
Moving 20o
1350 mm
Fixed
Rotating 350 mm
110 35o
shaft mm
Moving 20o

Fixed 350 mm

35o

25o 120 mm 80 mm
Moving
160 80 mm
mm
 Inner Design

Water out

300 mm
Rotating Water in
Arms
Hot gas 150 mm
out
Moving
20o
350 mm
360
mm
Moving
1350 mm
20o
350 mm
120
mm
Moving
20o
350 mm

80 mm
Moving
 Out View of the Gasifier Main Body
Biomass Catalyst
Hopper Wa Ai
Hopper
ter r

Gas outlet

1500
mm

150
mm 120
mm
 Inner Design

Water
Air

Volatiles inlet
1500
into the mm
catalyst
chamber

150
mm 120
mm
Picture of Complete Gasifier
Picture of Complete Gasifier
Picture of Complete Gasifier
Picture of Complete Gasifier
Picture of Complete Gasifier
 Product Gas Quality from Non-
Catalytic Experiment
Gasification temperature, oC 850±50 850±50 850±50 850±50 850±50
Biomass feeding rate, kg/h 4 4 4 4 4

Air fuel ratio 0.09 0.18 0.27 0.36 0.53

Steam flow rate, kg/h 0.6 0.6 0.6 0.6 0.6
Gas composition

H2 26.62 17.54 19.77 15.11 16.11

CO 30.42 33.59 27.27 31.34 24.76

CH4 11.55 12.50 10.55 10.55 9.73
C2H6 0.32 0.43 0.38 0.39 0.39
C2H4 1.74 2.42 2.17 2.59 2.45
CO2 12.87 11.12 12.94 13.55 13.36
N2 10.38 14.73 21.73 24.94 30.67
O2 0.24 0.85 1.29 0.08 1.00
LHV, MJ/kg 13.43 12.60 10.75 10.14 9.21
LHV, MJ/Nm3 11.76 12.10 10.36 10.35 9.34
Tar yield, mg/Nm3 5100 9900 8600 8400 10900
Tar yield, mg/MJ 929 725 866 1027 589
 Product Gas Quality from
Catalytic Experiment
Gasification temperature, oC 850±50 850±50 850±50
Biomass feeding rate, kg/h 4 4 4
Air fuel ratio 0.09 0.27 0.53
Steam flow rate, kg/h 0.6 0.6 0.6
Gas composition
H2 50.50 35.98 31.37
CO 32.15 35.89 33.30
CH4 4.14 6.14 7.22
C2H6 0.08 0.07 0.05
C2H4 0.24 0.36 0.37
CO2 5.05 6.72 9.54
N2 6.58 10.01 13.97
O2 0.02 0.03 0.01
LHV, MJ/kg 13.74 12.03 9.18
LHV, MJ/Nm3 10.44 9.95 8.31
Tar yield, mg/Nm3 2400 4900 2200
Tar yield, mg/MJ 929 866 589
Biomass Potentiality in Malaysia

Empty Fruit Bunches 19.00 million tones/y

Mesocarp Fiber 13.00 million tones/y
Shell 5.20 million tones/y
Palm Kernel Expeller 2.11 million tones/y
Total 47.61 million tones/y
Approximate energy 8.09 x 1011 MJ
content 2.24 x 105 GWh
Total price 6.27 x 104 BRM
 Input and Output of a 20 MW
Power Plant

Raw Materials Wood chips 176 t/day 64,689 t/y

Power Gasification New type

Generation Efficiency >50%
Electricity to 636 x 106 kWh 231 x 109 kWh
be sold
Total sell 177 MRM/day 64 BRM/y
price- RM
Environmental CO2 reduction 91,000 t/y
Effects
Energy saving 60,944 t heavy
oil/y
 Model of Commercial Power Generation
from Biomass (Wood Log)
To Stack

Gas Cooler Steam

power
Gas Filter generation
Conveyer

Gas Scrubbing
Catalytic
Reformer
Gas Buffer
Tank
Fly Ash

Gasifier

Water
Ash
Steam + collector Gas
Air
Engine
 Model of Commercial Power Generation
from Biomass (Agricultural Residues)
To Stack

Conveyer Gas Cooler Gas Filter Town

Heating
Gas
Scrubbing
Catalytic
Reformer
Gas Buffer
Condenser Tank
Fly
Ash
Pyrolyser

Char
Collector
Bio-oil
Water
Transportation
Steam
Gas Engine
 Novelty of the Process

 Moisture content 0-50% in biomass can be used

 Biomass particle size 3-5 cm3, real size from the large scale
chipper, can be used

 Almost all kinds of cellulosic biomass can be used

 Pyrolyser is a compact and high throughput design

 Catalyst is char supported and thus very cheap

 Biorefinery Concept to Produce Fuels,
Chemicals, Materials and Power
Light Olefine, CO2
Wet Biomass

Wet Biomass
Water
H2 Option 2b HO
HO
HO O
ZSM-5 H2 O OH
Route 1c HO
OH
400-500oC OH OH HO
Light Alkane HO HO
(to Steam Reformer OH OH CH3
Option 2a or Furnace)
High Temperature

Option 3
Hydrogenation OH
HO OH
OH
Dryer O OH
HO O OH
O O O HO OH
Route 1b OH HO H2 HO HO
O OH
HO
O CH3
OH O
O Low Temperature
Hydrogenation

Option 1
Pyrolyzer Option 2 O
O

Distillery
Route 1a O
O
O O
Route 1

O O
H H

Oxidizer Esterifier
Bi-oil H2O2 Ethanol
Route 2

Char O HO
Polymerizer
OH HO Resin
O O
OH

Steam
Gas (H2) Gas
Reformer
H2O Engines Electricity
or Fuel
Gasifier Gas (H2) Cells

Steam Activated Carbon Adsorbent

Activator

Fertilizer Slow Release

absorber Fertilizer
Rotating Cone Reactor for
Fast Pyrolysis
Flue gas
Combustor
Bin

Cooling
Water
Screw feeder

Product
Control Condenser gas
Reactor
panel

Liquid
collector
Compressor

Pump
120
mm
120
mm
Product Distribution from Jute
Stick Pyrolysis
Pyrolysis conditions
Jute stick feeding rate, kg/h 0.50
Temperature, oC 500
Nitrogen gas flow rate, ml/min 300
Pyrolysis products
Bio-oil
First condenser, kg/h (wt%) 0.14 (28)
Second condenser, kg/h (wt%) 0.16 (32)
Total, kg/h (wt%) 0.30 (60)
Char, kg/h (wt%) 0.12 (24)
Gas, kg/h (wt%) 0.08 (16)
Effect of Temperature on Product
Distribution
100 20
Gas
Yield of bio-oil and char, wt%

80 16

Yield of gas, wt%

Char
60 12

Bio-oil
40 8

20 4

0 0
0 200 400 600 800
Temperature, oC
 What is Bio-oil?

Bio-oil
Bio-oil is a dark brown liquid. It contains about 200 types of
chemicals mainly phenols, aromatic hydrocarbons, carboxylic
acids and other highly oxygenated materials.
 Physical Properties of
Bio-oil
Properties
Density, g/cc 1.07 - 1.09

pH 3.20 - 3.35

Water content, wt% 15 - 20

Char/Solid content, wt% 0.07 - 0.10

Pyrolytic lignin 3.83 - 4.91

Acid Value 122.5 - 134.2
Ash content, wt% 0.03
Viscosity, Centipoise 2.59
 Next Step – Pilot Plant

Light

Biomass
Wet
Biomass
Wet
Olefine, CO2
Water
H Optio HO HO

HO
2 ZSM-5 n 2b H OH O
O
OH
Route HO
OH OH HO

1c 400- Light Alkane 2 OH

HO
OH
HO
CH3
o
500 C Option (to Steam
High

n3
Optio
Reformer
2a or Temperature
HO
OH
OH
OH
Dryer Furnace) O
O OH
Hydrogenati OH
HO OH
O O HO
Route
O
on
Conveyer H OH HO HO HO
O OH
HO
O CH3
O
1b 2
O
OH
Low

n1
Optio
Pyrolyze Optio Temperature
O
O

y
Distiller
O
r Route n2 Hydrogenati
O O
O

e1
Rout Rout
1a on H
O
H
O

Oxidize Esterifi
H2O2 Ethanol
Bi-oil r er

e2
O

O HO
Char OH HO Polymerize
O O Resin
OH
r

Steam
Gas Gas
Reformer
H2 (H2) Engine
Electricity
O s or
Gasifier Gas
Fuel
(H2) Cells
Steam
Activato Activated Adsorbent
r Carbon
Fertilize
Slow Release
r
Fertilizer
absorb
er

Condenser
Pyrolyser
Bio-oil for
10 kg/h Refining

Bio-oil Tank
Char Collector
 Novelty of this Process

 Compact and high throughput pyrolyser has been designed.

 Big particles of biomass can be pyrolysed as a fast heating

pyrolysis.
 A novel catalyst has been developed for bio-oil reforming.
 Bio-oil has been separated in high volatile fraction and high
molecular organic fraction.
 Novolac resin has been synthesized from organic fraction.
 High surface area activated carbon has been produced from
char.
 Summary and Conclusion

 Gasification technology is almost ready for large scale

pilot plant testing.

 For pilot plant, approximate costing may be RM 1,000,000 to

5,000,000 depending on the plant size from 50 kg to 1 ton/h.

 Pyrolysis technology is ready for lab scale pilot plant with

the capacity of 20 kg/h – 50 kg/h. Approximate costing may
be RM 2,000,000 for pyrolysis and refining setup.

 From bio-oil, liquid fuels, chemicals, materials including

bioplastic and resin and power can be produced.