Catalytic Destruction of Tars Formed During

Black Liquor and Biomass Gasification

Scott Sinquefield,
Taishan Fan, and Kristiina Iisa

Black Liquor Colloquium

August, 2006

1
 Tars from Black Liquor Gasification

Formation of Tars
0.5 30% of organic carbon in black liquor forms tar.
Tars foul process equipment and gas turbines.
Tars represent lost energy.

Black Liquor Tar Species

Mostly monoaromatic and polyaromatic ring compounds
from incomplete breakdown of lignin

Tar Removal Methods

Physical: scrubbers, filters, sorbents
Chemical: thermal decomposition, catalytic decomposition

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 Catalyst for Black Liquor Tar
Destruction Must Be Sulfur and Alkali
Metal Tolerant
Commercial catalysts (dozens) were tested using
benzene as model tar, along with added H2S and alkali.
Virtually all were deactivated within hours or minutes.
Sulfided CoMoOx/-Al2O3 showed promise but lost
50% activity in 300 hours. A cyclic
regeneration/resulfiding process was developed.
Sulfided CoO tested and found to give superior
performance.

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Experiments with Benzene as
Model Tar Compound

4
The Catalyst Test Reactor

5
 Experimental Conditions
Sulfided CoO/ -Al2O3 (40%)
Feed: 2300 ppm benzene, 1.2 % steam, 300-500
ppm H2S, He/balance
Temperature: 600-800oC
Space velocity: 12 l/(g catalyst h)
Catalyst particle size: 180-250 m

6
Sulfided CoO/-Al2O3 Demonstrated Stability over 23
Days at 800 0C

120

100
conversion (%)

80

60 CO+CO2

40

20

0
0 200 400 600
Reaction time (hours)

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Sulfided CoO/-Al2O3 Resists Alkali Deactivation

100

80
Conversion (%)

60

40

20

0
0 100 200 300 400 500
Time (h)
800C

0.1 g Na2S, 0.1g NaCl, 0.1g Na2SO4 and 0.1g Na2CO / 1g catalyst
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Experiments with Tar from Bench-
Scale Black Liquor Gasifier

9
 Experimental Conditions
Tar in raw gases from a bench-scale
gasifier/pyrolyzer.
~6800 ppm benzene equivalent
Temperature: 700-800 0C
Space velocity: 60 l/(g catalyst h)
Catalyst particle size: 180-250 m

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The BL Tar Generator and Catalyst Reactor

11
 Tar concentration in Raw Gas
12000
Concentration (ppm)

10000

8000

6000

4000

2000

0
0 1 2 3 4 5 6 7
Reaction Time (h)

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Test of Catalyst in Syngas from Bench-
Scale Gasifier
Temperature affect on tar conversion

CO2 Before catalyst

1.5

Catalyst: 700C
Absorbance(%)

1
H2O CO
Tars
Catalyst: 800C
0.5

H2O
0
0 1000 2000 3000 4000 5000

-0.5
Wave number

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 Stability Using Real BLG tars (8000C)

100%

80%
Conversion

60%

40%

20%

0%
0 50 100 150 200 250
Time, h

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 Stability at 700 0C
100%

80%
Conversion

60%

40%

20%

0%
0 50 100 150
Time, h

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 Arrhenius Plot Shows Differences between
Benzene and Syngas Tars
5
4.5
4 Bench-Scale Gasifier
ln(k/(m3/(kg h))

3.5
3
2.5
2 Benzene
1.5
1
0.5
0
0.9 0.95 1 1.05 1.1 1.15 1.2
1000/T, 1/K

Ea = 68 kJ/mol for benzene Assumption: 1st order kinetics

Ea = 29 kJ/mol for gasifier tar
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 Catalyst Requirements for Full Scale System

Catalyst Requirement, kg/(Nm3/h)

Desired X: 90% 99% 99.9%

800C 0.03 0.06 0.09

700C 0.04 0.08 0.12

600C1 0.06 0.12 0.18

Preliminary estimate of catalyst requirement for tar destruction

based on BLG syngas tars assuming 1st order kinetics. 100,000
Nm3/h would require 6000 kg catalyst at 600C

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Impact of Catalyst loading on Catalyst Activity

200

150
k, m3/(kg h)

100

50

0
0% 10% 20% 30% 40% 50%
CoO Loading

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 Conclusions

Sulfided CoO/-Al2O3 (at 40% CoO) is a viable

catalyst for tar destruction in commercial black
liquor gasification systems
The catalyst is resistant to deactivation by sulfur
and alkali salts. It has remained stable for up to
1000 h with no loss of activity

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 On-Going/Future Work

Catalyst being tested at NREL on biomass-derived

syngas in their bench and pilot scale gasifiers.
100% conversion for destruction of ethylene
with no measured loss in activity in 8 hours
Additional and more challenging tests are under
way.
Kinetic measurements, effect of Cl, NH3
Test the catalyst with a slip stream of raw syngas
from an industrial gasifier (preferably using BL but
could be biomass). Contingent on funding.

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