Biomass Fast Pyrolysis for Bio-oil

Xifeng ZHU
University of Science & Technology of China (USTC)

Outline
1. Introduction 2. Biomass Fast Pyrolysis 3. Bio-oil and its application 4. Up-grading of Bio-oil

Biomass Resource in China

Biomass resource in China is characterized by agriculture. Agriculture residues & wastes are more than 700 million tons per year. Other biomass is also abundant.

Energy Consumption in China

China is the second largest country of energy consumption in the world. Oil consumption in China will be continue to fast increase in 10 to 20 years. The total consumption of oil in 2007 is more 360 million tons, and nearly 50% of them need to be imported. 40~50 million tons of oils per year are used as fuel oils for boil and kiln. So we should try to develop the new technology for replaceable liquid fuel based on renewable resource.

Liquid fuels from Biomass

Gasification Lignocellulose
- agricultural wastes

Syn-liquids Fuel ethanol Bio-oil

Hydrolysis Fast Pyrolysis

Our research is focused on fast pyrolysis.

Outline
1. Introduction 2. Biomass Fast Pyrolysis 3. Bio-oil and its application 4. Up-grading of Bio-oil

What is Biomass Fast Pyrolysis

The pyrolysis temperature of 450~500 is relatively mild. Energy density of bio-oil is much higher than that of biomass. 1.9~2.1GJ/m3 of biomass ~10 times 19~20GJ/m3 of bio-oil so bio-oil is much convenient in transport & storage. The value of bio-oil is two times more than that of biomass. 2.0 tons of biomass 1.0 tons of bio-oil
2350 RMB/ton 1500RMB/ton

Biomass fast pyrolysis can be dispersedly built in rural area.

Heat Gas Tar Biomass Char Bio-oil Gas

Process of Biomass Fast Pyrolysis

Comminution Drying Feeding Fast pyrolysis Char separation Flowchart of biomass fast pyrolysis at USTC Liquid recovery

Drying of Biomass
The drying temperature is between 120~130. The moisture in the dried biomass is less than 10.0wt.%.
Fluid-bed dryer
(0.25m6.0m)

Dried biomass

Gas velocity =3.0~4.0 m/s

Biomass inlet

drying in system

Hot flue gas

Biomass Fast Pyrolysis Reactor

Pyrolysis conditions: High heating rate (103~104 k/s) moderate temperature (450~550) short gas residence time (2s)
Biomass inlet Charcoal combustor Charcoal Flue gas Pyrolysis products Pyrolysis reactor

Heat exchanger

pyrolysis in system
Air

Fluidized gas

Charcoal Separation with Cyclone

The gas velocity inside cyclone is 20~25m/s. The separation efficient is more than 95% for more than 20m particles.
Pyrolysis steam Pyrolysis products

Charcoal

charcoal separation in system

Liquid Recovery for Bio-oil

The hot pyrolysis steam be quickly cooled with spraying of bio-oil. The heat is carried out by cooling water.
Spraying Pyrolysis steam
(300~320) 55~60

Uncondensable

gas
Cooling water

Bio-oil Heat exchanger

30~35

Bio-oil outlet

Cooling tower

condenser in system

Fast Pyrolysis Results

Results Bio-oil yields (wt%) Caloric value (MJ/kg) Moisture (wt%) Density (kg/m3) Viscosity (mm2/s) pH C (wt%) H (wt%) O (wt%) N (wt%) S (wt%) Rice husk 51 16.4 27.2 1120 128 2.8 41.7 7.7 50.3 0.3 0.2 Corn Stalk 57 16.8 26.9 1140 140 2.3 43.6 6.9 47.4 0.2 0.1 Cotton Stalk 56 17.2 26.7 1155 156 2.6 46.5 7.3 49.8 0.2 0.1 Sawdust 60 17.4 24.0 1180 240 2.1 53.5 6.4 40.2 0.2 0.1

The yields of bio-oil is more than 50~60% !

Demo Plant of Fast Pyrolysis

A demo-plant with capacity of 3000 tons of bio-oil per year, located at Shushan Industry Park, Hefei, has been built on March, 2007. The process of pyrolysis is auto-thermal. The feedstock mainly is rice husk. The cost of bio-oil is less than 1000 per ton. Now the bio-oil is mainly used as fuel oils. Now we are developing new technology for biomass fast pyrolysis. The bulk and cost of new equipment with same capacity can be forecast to cut down 30%.

Outline
1. Introduction 2. Biomass Fast Pyrolysis 3. Bio-oil and its application 4. Up-grading of Bio-oil

Functional Groups of Organic Compositions in Bio-oil

Frequency range /cm-1 3050-3600 3000-2800 2350-2000 1750-1640 1650-1580 1450-1350 950-1300 900-650 Group O-H stretching C-H stretching C=C stretching C=O stretching C=C stretching C-H bending C-O stretching C-H bending Class of compounds Polymeric O-H, water impurities Alkanes Alkynes Ketones, aldehydes, carboxylic acids Alkenes, Aromatic compounds Alkanes
Primary,secondary and tertiary alcohol,Phenol,ester,ethers

Aromatic compounds

Chromatogram of Bio-oil from Rice Husk

100 80 60 4 sample 1 5 9 10 3.5 3.73.9 4.1 4.3 4.7 5.1 5.5 8 100 111213 14 15 80 4 60 40 15 4 5 1617 6 7 8 9 20 18 10 11 0 100 80 5 60 40 219 2 6 2.5 3 3.5 4 4.5 11 5 5.5 6 5 22 11 3.5 4 4.5 5 2 5
sample 3

1219

20

Relative abundance/%

40 3 20 1 27 6 0 100 80 60 40 20 0 2 4 3

1.6 1.9 2.2 2.5

67 3 4 5 6 7 8 9 10 11

sample 2

4 sample 4

20 1 19 2 6 21 0 2 2.5 3

Time/min

Time/min

Major Chemical Compounds in Bio-oil from Rice Husk

Chemical compound identification Acetic acid methyl acetate ethyl isobutyrate furan-2-carbaldehyde 2-oxopropyl acetate phenol o-cresol p-cresol 1,2-benzenediol m-cresol anthracene pyrene Quantification (Area% of GC-MS) 17.72 5.32 0.36 4.83 1.04 2.14 1.12 1.30 5.55 4.67 0.80 0.52 Chemical compound identification 2,5-diethoxy-tetrahydrofuran
2-hydroxy-3-methylcyclopent-2-enone

Quantification (Area% of GC-MS) 2.66 2.14 0.65 0.44 6.84 2.40 1.67 1.95 0.45 1.91 2.86

1-(3,5-dimethoxyphenyl)ethanone 4-allyl-2,6-dimethoxyphenol 4-hydroxy-2-methoxybenzaldehyde 2,5-dimethoxybenzaldehyde 2-methoxy-4-methylphenol 2-methoxyphenyl acetate 4-ethyl-2-methoxyphenol 4-allyl-2-methoxyphenol 3-methylbenzaldehyde

Potential Applications of Bio-oil

Bio-oil Seperate Boiler Turbine Engine Heat Electricity Vehicle fuels etc. H2 Chemicals Upgrade Gasify Reform Synthesis

Bio-oil Combustion and its Application

Bio-oil can be directly and steadily burned in boilers and kilns and its combustion temperature is more than 1300. Bio-oil has been used as fuel oils in Yixing, Jiangsu Province and Hefei, Anhui Province.

Emulsification of Bio-oil and its Application

Diesel Bio-oil
Emulsified liquid

1. Bio-oil can be used in engine with emulsification method to partly substitute diesel. 2. Emulsification of bio-oil with diesel has potential in the future.

Outline
1. Introduction 2. Biomass Fast Pyrolysis 3. Bio-oil and its application 4. Up-grading of Bio-oil

Bio-oil Refinery: Catalytic Steam Reforming

H2CO, CO2 etc.

Bio-oil Steam

CH3OH C2H5OH

CatalystC12A7-M

Microporous Crystal Structure of 12CaO7Al2O3 (C12A7)

Crystal Structure: 12 cages/unit cell (cage size : 0.4nm) [Ca24Al28O64]4+2O2Anionic Cage Contents: O2-,O-,O2-, S2-,OH-,F-,Cl-

XRD Patterns of C12A7-O-Samples

# C 12A7 (a ) # # # # # # # # # #

C 12A7 M gO

*
C 1 2 A 7 -O /1 8 % M g (b ) # # # #
-

* * # * #
# # # # #

* * *
75 90

a fte r r e a c tio n
# # # 15 #

*
# # 45 # # 60
o

(c )
0

30

2/ ( )

(a) C12A7O sample. (b) C12A7O18%Mg sample before the reforming of the bio-oil. (c) C12A7O18%Mg sample after running the reforming of the bio-oil for 4 hours.

Producing Hydrogen from Bio-oil

C12A7-Mg Catalyst

Bio-oil

Syngas

H2 CnHmOk+ (n - k)H2O nCO + (n + m/2-k)H2 nCO + nH2O nCO2 + nH2

Hydrogen Generation Catalyzed by C12A7-Magnesium

80 70

120
( a)
HZSM 5 C12A7 C12A7- 12% Ce

g C 7-18M 12A
100
Carbon Conversi on(% )

(b)

Hydr ogen Yi el d ( s t . %

60 50 40 30 20 10 0

80 60 40 20 0 0

H -5 ZSM C 7-12% 12A C e C 7 12A g A 2O 12M l 3+ g A 2O 18M l 3+ g A 2O 24M l 3+

x

C12A7- 18% g M g Al 2O3+12 M g Al 2O3+18 M

x

g Al 2O3+24 M

200

300

400

500 T(
o

600

700

800

C)

100

200

300

T( C )

400

500

600

700

800

Producing Hydrogen from bio-oil with electrochemical catalytic

100 90
Car bon Conver si on%

80 70 60 50 40 30 20 10 0 400 450 500 550 600

T e mp e r a t u r e ( )

0A 1A 2A 3A 4A

100 90
Hydr ogen Yi el d( s t . % )

80 70 60 50 40 30 20 10 400 450 500 550 600

T e mp e r a t u r e ( ) 0 1 2 3 4 A A A A A

Clean Bio-fuels from Bio-oil

Bio-oil

Gasoline

Fischer-Tropsch synthesis using the bio-oil-syngas CO2 + H2 CO + H2O (Reverse Water-Gas Shift) nCO + 3nH2 nCH4 + nH2O ( Methanation ) nCO + (2n+1)H2 CnH2n+2 + nH2O (Paraffins) nCO + 2nH2 CnH2n + nH2O (Olefins)

Synthesis of Gasoline from Syngas

C5

80
C6

Fe/Cu/Al/K

Syngas

Gasoline
40

C4

1.5 MPa, 300

C7 C8

C9

C10

C11

C12

C13 C14 C15 C16 C17 C18 C19

C20 C21

0 0 40 80

Carbon numbers in the synthesized products analyzed by GC

Gasoline from Bio-oil (II)

hydrocarbon products selectivity (%)

80 70 conversion (%) 60 50 40 30 CO2 20 0 .5 1 .0 1 .5 p r e ssu r e (M P a ) 2 .0 2 .5 C O +C O 2

100 90 80 70 60 50 40 30 20 10 0 0 .5 1 .0 1 .5 p r e s s u r e (M P a ) 2 .0 2 .5 o le f in in C 2 C 5+ C 2 -C 4 CH4

(a )

CO

(b )

Effect of pressure on (a) carbon oxide conversion; (b) hydrocarbon products selectivity; Model syngas: H2/CO/CO2/N2 (62/8/25/5, vol.%) Reaction conduction: T=300oC, W/F(H2+CO+CO2) = 12.5 gh/mol

for Your Attention!

Thank You