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Biomass Fast Pyrolysis

for Bio-oil

Xifeng ZHU

University of Science & Technology of China (USTC)

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1. Introduction2. Biomass Fast Pyrolysis

3. Bio-oil and its application4. Up-grading of Bio-oil

Outline

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Biomass Resource in ChinaBiomass resource in China is

characterized by agriculture.Agriculture residues & wastes

are more than 700 million tonsper year.

Other biomass is also abundant.

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Energy Consumption in ChinaChina 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 beimported.

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.

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Liquid fuels from Biomass

Fast Pyrolysis

Hydrolysis

Gasification

Bio-oil

Syn-liquids

Lignocellulose- agricultural w astes Fuel ethanol

Our research is focused on fast pyrolysis.

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1. Introduction2. Biomass Fast Pyrolysis

3. Bio-oil and its application4. Up-grading of Bio-oil

Outline

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What is Biomass Fast Pyrolysis The pyrolysis temperature of450~500 is relatively mild. Energy density of bio-oil is much higher than that of biomass.

1.9~2.1GJ/m3

of biomass 19~20GJ/m3

of bio-oilso 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.

~10 times

Gas

Biomass Bio-oil

Char

HeatTar

Gas

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Process of Biomass Fast Pyrolysis

Drying

Char separation

Comminution

Fast pyrolysis

Liquid recoveryFlowchart of biomass fast pyrolysis at USTC

Feeding

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Drying of Biomass The drying temperature is between

120~130. The moisture in the dried biomass is

less than 10.0wt.%.

drying in system Hot flue gas

Biomass inlet

Dried biomass

Fluid-bed dryer(0.25m6.0m) Gas velocity

=3.0~4.0 m/s

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Biomass Fast Pyrolysis Reactor

pyrolysis in system

Pyrolysis conditions:

High heating rate (10

3

~10

4

k/s) moderate temperature (450~550) short gas residence time (2s)

Biomass inlet Heatexchanger

Fluidized gas

Charcoal

Air

Pyrolysisproducts

Charcoal

combustor

Pyrolysisreactor

Flue gas

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charcoal separation in system

Pyrolysisproducts

Pyrolysissteam

Charcoal

The gas velocity inside cyclone is20~25m/s.

The separation efficient is morethan 95% for more than 20mparticles.

Charcoal Separation w ith Cyclone

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Liquid Recovery for Bio-oil

condenser in system

The hot pyrolysis steambe quickly cooled with

spraying of bio-oil.

The heat is carried out bycooling water.

Pyrolysissteam

Bio-oiloutlet

Bio-oil

Coolingwater

Heatexchanger

Coolingtower

Uncondensablegas

Spraying

(300~320) 55~60

30~35

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A demo-plant with capacity of 3000 tons

of bio-oil per year, located at Shushan

Industry Park, Hefei, has been built onMarch, 2007.

The process of pyrolysis is auto-thermal.

The feedstock mainly is rice husk.

The cost of bio-oil is less than1000 perton.

Now the bio-oil is mainly used as fuel oils.

Demo Plant of Fast Pyrolysis

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%.

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1. Introduction2. Biomass Fast Pyrolysis

3. Bio-oil and its application4. Up-grading of Bio-oil

Outline

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Functional Groups of Organic

Compositions in Bio-oil

Frequency range /cm-1 Group Class of compounds

3050-3600 O-H stretching Polymeric O-H, water impurities

3000-2800 C-H stretching Alkanes

2350-2000 C=C stretching Alkynes

1750-1640 C=O stretching Ketones, aldehydes, carboxylic acids

1650-1580 C=C stretching Alkenes, Aromatic compounds

1450-1350 C-H bending Alkanes

950-1300 C-O stretching Primary,secondary and tertiaryalcohol,Phenol,ester,ethers

900-650 C-H bending Aromatic compounds

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2 2.5 3 3.5 4 4.5 5 5.50

192

4

5

6 11

20

40

60

80

100

18

17

16

1587

6

5

4

3 21

5.5

2 3 4 5 6 7 8 9 10 11

3.53.73.9 4.1

109

11

4.3

15141312

4.7 5.1

0

20

40

60

80

100

Re

lativeabunda

nce/%

sample 1

sample 2

2 3 4 5 6 7 8 9 10 11

76

5

4

1.6 1.9 2.2 2.5

1219 6 20

0

20

40

60

80

100sample 3

6

Time/min

11216

22

5

4

192

1

2 2.5 3 3.5 4 4.5 50

20

40

60

80

100sample 4

Time/min

Chromatogram of Bio-oilfrom Rice Husk

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Major Chemical Compoundsin Bio-oil from Rice Husk

Chemical compound

identification

Quantification

(Area% of GC-MS) Chemical compound identification

Quantification

(Area% of GC-MS)

Acetic acid 17.72 2,5-diethoxy-tetrahydrofuran 2.66

methyl acetate 5.32 2-hydroxy-3-methylcyclopent-2-enone 2.14

ethyl isobutyrate 0.36 1-(3,5-dimethoxyphenyl)ethanone 0.65

furan-2-carbaldehyde 4.83 4-allyl-2,6-dimethoxyphenol 0.44

2-oxopropyl acetate 1.04 4-hydroxy-2-methoxybenzaldehyde 6.84

phenol 2.14 2,5-dimethoxybenzaldehyde 2.40

o-cresol 1.12 2-methoxy-4-methylphenol 1.67

p-cresol 1.30 2-methoxyphenyl acetate 1.95

1,2-benzenediol 5.55 4-ethyl-2-methoxyphenol 0.45

m-cresol 4.67 4-allyl-2-methoxyphenol 1.91

anthracene 0.80 3-methylbenzaldehyde 2.86

pyrene 0.52

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Potential Applications of Bio-oilBio-oil

ReformGasifyUpgradeBoiler

Turbine

Engine

Synthesis

Seperate

H2Vehicle fuels etc.ElectricityHeat Chemicals

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Bio-oil Combustion and itsApplication

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.

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Emulsification of Bio-oil and

its Application

Diesel

Emulsifiedliquid

Bio-oil

1.Bio-oil can be used in engine with

emulsification method to partlysubstitute diesel.

2.Emulsification of bio-oil with diesel

has potential in the future.

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1. Introduction2. Biomass Fast Pyrolysis

3. Bio-oil and its application4. Up-grading of Bio-oil

Outline

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CatalystC12A7-M

Bio-oil

Steam

H2CO,CO2etc.

CH3OHC2H5OH

Bio-oil Refinery: Catalytic Steam

Reforming

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Crystal Structure:12 cages/unit cell

(cage size : 0.4nm)

[Ca24Al28O64]4+2O2-

Anionic Cage Contents:

O2-,O-,O2-, S2-,OH-,F-,Cl-

Microporous Crystal Structure of12CaO7Al2O3 (C12A7)

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0 1 5 3 0 4 5 6 0 7 5 9 0

# #

*## # # #

# # #

#

# #

##

# # # ##

#

#

#

## # #

#

#

# *

*

*

*

**

*

*

C 1 2 A 7

M g O*#

a f t e r r e a c t io n

C 1 2 A 7

C 1 2 A 7 - O-/ 1 8 % M g

( c )

( a )

( b )

2 / ( o )

(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.

XRD Patterns of C12A7-O-Samples

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Bio-oil Syngas

H2

C12A7-Mg Catalyst

Cn

Hm

Ok+ (n -k)H2OnCO + (n +m/2-k)H2

nCO +nH2OnCO2 +nH2

Producing Hydrogen from Bio-oil

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Hydrogen Generation Catalyzedby C12A7-Magnesium

( a)

0

10

20

30

40

50

60

70

80

200 300 400 500 600 700 800

T(oC)

Hydrogen

Yield

(st. HZSM- 5

C12A7

C12A7- 12%Ce

C12A7- 18%Mg

Al 2O3+12 MgAl 2O3+18 MgAl 2O3+24 Mg

x

x

(b)

0

20

40

60

80

100

120

0 100 200 300 400 500 600 700 800T(

oC)

CarbonConversio

n%

C12A7-18MgHZSM-5

C12A7-12%Ce

C12A7

Al 2O3+12MgAl 2O3+18MgAl 2O3+24Mg

x

x

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Producing Hydrogen from bio-oil

w ith electrochemical catalytic

4 0 0 4 5 0 5 0 0 5 5 0 6 0 00

1 0

2 0

3 0

4 0

5 0

6 0

7 0

8 0

9 0

1 0 0

Carbon

Conversion%

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

0 A

1 A

2 A

3 A

4 A

4 0 0 4 5 0 5 0 0 5 5 0 6 0 0

1 0

2 0

3 0

4 0

5 0

6 0

7 0

8 0

9 0

1 0 0

Hydrogen

Yield(s

t.

%)

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

0 A

1 A

2 A

3 A

4 A

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Clean Bio-fuels from Bio-oil

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)

Bio-oil Gasoline

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Synthesis of Gasoline from Syngas

0 40 80

0

40

80

C8

C21C20C19C18

C17C16C15

C14C13C12C11C10

C9

C7

C6

C5

C4

Carbon numbers in the synthesized products analyzed by GCCarbon numbers in the synthesized products analyzed by GC

Syngas Gasoline

Fe/Cu/Al/K

1.5 MPa, 300

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0 .5 1 .0 1 .5 2 .0 2 .5

2 0

3 0

4 0

5 0

6 0

7 0

8 0

C O

C O2

C O + C O2

p r e ss u r e (M P a )

conversion(%)

(a )

0 .5 1 .0 1 .5 2 .0 2 .50

1 0

2 0

3 0

4 0

5 0

6 0

7 0

8 0

9 0

1 0 0

C H4

C2-C

4

olef in in C 2

C5 +

p r e s s u r e (M Pa)

hyd

rocarbonproductsselectivity(%)

(b )

Effect of pressure on (a) carbon ox ide 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

Gasoline from Bio-oil (II)

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Thank Youfor Your Attention!