Conversion of Black Liquor

in a Fluidized Bed Steam Reformer

Kevin Whitty
Institute for Combustion & Energy Studies (ICES)
The University of Utah

7th International Colloquium on Black Liquor Combustion and Gasification

July 31 August 2, 2006
Jyvskyl, Finland
 Outline

Intro BL steam reforming

Fluidized bed steam reforming
Commercial installations
Steam reforming research
This study Experimental system
Liquor conversion in a steam reformer
Fate of organic carbon
Factors impacting carbon conversion
Development-scale versus full-scale
Conclusions

2
 Outline

Intro BL steam reforming

Fluidized bed steam reforming
Commercial installations
Steam reforming research
This study Experimental system
Liquor conversion in a steam reformer
Fate of organic carbon
Factors impacting carbon conversion
Development-scale versus full-scale
Conclusions

3
 Black Liquor Steam Reforming
Alternative to combustion in
recovery boiler
Product gas
Improved energy efficiency
Better environmental performance
Can improve pulp yield and quality
Safer technology
Fluidized bed reforming
Steam for fluidizing and reactant Flue
Product
Operating temp. ~1120F (605C) gas+air gas
Endothermic process indirect
heating
Bed solids made of "ash" product Pulsed
from reforming Black liquor heaters

Developers Bed solids Steam

MTCI Process development
TRI Commercial installations
4
 Norampac Steam Reformer

Trenton, ON, Canada

Startup June 2003
1x100 tds/day
reformer
Carbonate liquor
No product gas
conditioning
Sent directly to boiler
Bed heaters fired on
natural gas

5 Photos courtesy of Norampac

 G-P Big Island Steam Reformer

Big Island, Virginia

Startup Spring 2004
2x100 tds/day reformer
Carbonate liquor
Product gas handling
Superheater
Venturi scrubber
Gas cooler
H2S scrubber
Bed heaters fired with
clean product gas

6 Photos courtesy of Georgia-Pacific Corp.

 Steam Gasification Research

Atmospheric studies
1980s 1990s
Van Heiningen
Pressurized studies
1990s
Whitty, Frederick, Hupa (bo Akademi)
VTT Finland
In-house development at MTCI
1980s 1990s
Proprietary

7
 Outline

Intro BL steam reforming

Fluidized bed steam reforming
Commercial installations
Steam reforming research
This study Experimental system
Liquor conversion in a steam reformer
Fate of organic carbon
Factors impacting carbon conversion
Development-scale versus full-scale
Conclusions

8
 U.Utah Steam Reforming System
Pressure Gas to slipstream reactors
control valve

Dry gas to analyzers

Internal
cyclone
Black Liquor
Tank (heated) H2O
Freeboard H2O out

H2O in

Natural
Gas Air

Circ.
pump Exhaust
After-
Feed Bed burner
pump heaters

Air
CW in CW out
Steam
Distributor

N2 Cooler/
Water Steam condenser
Soften R.O.
Pressure
release
Super Lock
Natural gas Boiler
heater hopper

Condensate
Air Nitrogen Bed solids

9
 Gasification Research Facility

Entrained-flow
gasifier
Slipstream
reactors

Product
Fuel tank
gas cooler

Afterburner
Boiler Fluidized bed
steam reformer
Superheater
(under grating)

10
 Steam Reformer Bed Section

Sample
Thermocouple
Port
Thermocouple
Leads

Heater
Bundles
Power
Leads

Sample
Port

Liquor
Injector
11
 Steam Reformer Bed Section

12
 Outline

Intro BL steam reforming

Fluidized bed steam reforming
Commercial installations
Steam reforming research
This study Experimental system
Liquor conversion in a steam reformer
Fate of organic carbon
Factors impacting carbon conversion
Development-scale versus full-scale
Conclusions

13
 Black Liquor Conversion

Volatiles, H2O H2, CO, CO2

Moisture tars

Char
Drying Pyrolysis gasification

Droplet Solids Char Smelt

H2O(g) + C(s) H2(g) + CO(g)

H2O(g) + CO(g) H2(g) + CO2(g)

14
 Fate of Organic Carbon

Gas
(CO, CH4, CO2)

Organic
Tars
carbon

Bed
Solids

15
 Carbon Conversion
Approximate fate of organic carbon

Gases: 65-85%
Utah Tars: 10-30%
Bed Solids: 2-8%

Gases: 58-80%
Big Island Tars: 4-20%
Bed Solids: 10-25%

Gases: 95-99%
PDU Tars: 0%
Bed Solids: 0.5-2%

16
 Tars Variation in Results
Residence time
Utah: 2 + 8 seconds in bed + freeboard
Big Island: 10 + 7 seconds in bed + freeboard
Temperature
Utah freeboard exit temperature: 420C (790F)
Big Island freeboard exit temp: 590C (1095F)
Measurement technique
Utah: Cold trap to 20C with dichloromethane
Big Island: Difference from system balance plus
cold trap measurements
MTCI PDU: No specific effort to trap tars

17
 Char Conversion Studies
Determine factors that impact char carbon
conversion (residual bed carbon)
Temperature
Presence of product species (H2 and CO)
Consider difference between small scale
PDU studies and full-scale systems
Small-scale systems achieve >95% conversion
to gases (+ tars)
Full scale system achieving only 70-85% carbon
conversion

18
 Bed Carbon versus Time
Pure steam. No liquor feed.

14%

Organic Carbon Content (wt%) 12%

Reaction order = 0.0
10%

8%
0.5
6%

4%
1.0
2%

0%
0 2 4 6 8 10 12 14 16 18 20 22 24

Time (hours)
19
 Lab-Scale Char Conversion Studies
Influence of hydrogen on gasification rate

20
2% H2
Max. rate (x104), s1 4% H2
16

12

0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
H2 partial pressure, bar
20
 Lab-Scale Char Conversion Studies
Influence of carbon monoxide on gasification rate

14
2% CO
Max. rate (x104), s1 12 4% CO
10

0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
CO partial pressure, bar
21
 Bed Carbon versus Time
Pure steam. No liquor feed.

14%

Carbon Content [wt%] 12%

10%

8%

6%

4%

2%

0%
0 2 4 6 8 10 12 14 16 18 20 22 24
Hours
22
 Bed Carbon versus Time
Addition of 25% H2

14%
25% H2 Present
Carbon Content (wt%) 12%

10% Ave. 0.16%C/hr

8%

6% Ave. 0.75%C/hr

4%

Pure Steam
2%
Steam with 25% H2

0%
0 2 4 6 8 10 12 14 16
Time (hours)
23
 Bed Carbon versus Time
Addition of CO

14%
6.4% CO 2.6% CO Pure Steam
Carbon Content (wt%) 12% With CO addition
Ave.
10% 0.48 %C/hr

8%
Ave. Ave.
0.75 %C/hr 0.52 %C/hr
6%

4%
Ave.
0.56 %C/hr
2%

0%
0 2 4 6 8 10 12 14 16 18 20 22 24
Time (hours)
24
 Reactor Comparison
Parameter PDU Utah Full-scale

Bed height, ft 4 5 33
Bed area, ft2 2.3 0.54 104
Bed mass, lb 725 200 233,000
Steam feed, lb/hr 223 42 12,250
BLS feed, lb/hr 14 12 6,400
Steam/fuel ratio 16 3 2
Feed/bed area 6 22 61

17 psia 44 psia
25
 Full versus PDU Scale
Gas partial pressures through reactor

Steam and H2 H2 and CO

3.0 0.45
H2O - Full Scale H2 - Full Scale
0.40
2.5 H2O - PDU H2 - PDU
H2 - Full Scale 0.35 CO - Full Scale
Partial Pressure, atm

Partial Pressure, atm

H2 - PDU CO - PDU
2.0 0.30

0.25
1.5
0.20

1.0 0.15

0.10
0.5
0.05

0.0 0.00
0% 20% 40% 60% 80% 100% 0% 20% 40% 60% 80% 100%
Percent through Bed (bottom to top) Percent through Bed (bottom to top)

Steam only with no liquor injection

Assumes 0.5 wt% of bed (as C) converted per hour
Uses bed mass, steam flows from real systems
Assumes water-gas shift always at equilibrium
Assumes bed solids are well-mixed
26
 Full versus PDU Scale
Rates and associated conversions

Full/PDU ratios at top of bed: Van Heiningen

3 10 9 [C ][H 2O ]e 25,200 / T
Rate =
PH2: 7.8 [H 2O ] + 1.42 [H 2 ]
PCO: 53.0
Rate (van Heiningen): 0.706
Whitty 1
Rate (Whitty 1): 0.600
1 1
28,000 9.01
Rate = 10 4 e 923 T
Rate (Whitty 2): 0.021 pH 2
1 + 0.449 p + 7.09 pCO
H 2O

Whitty 2
Decrease from 97% to 75%
carbon conversion requires ( )
Rate 10 4 = 3.312 + 1.157 pH 2O + 0.07119 pCO
2
2

0.6595
that the rate becomes 20% as 2.943 pH 2 3.869 pCO +
pCO
fast (for reaction order = 0.5)

27
 BL Char vs. Bed Solids

50 m 50 m

Black liquor char Reformer bed solids

BET Surface area: BET Surface area:
5-100 m2/g < 0.5 m2/g

28
 Outline

Intro BL steam reforming

Fluidized bed steam reforming
Commercial installations
Steam reforming research
This study Experimental system
Liquor conversion in a steam reformer
Fate of organic carbon
Factors impacting carbon conversion
Development-scale versus full-scale
Conclusions

29
 Conclusions
Higher concentrations of product gases in
large fluidized bed reformer contributes to
decreased conversion relative to small
system
Higher concentrations of H2 and CO
Higher pressure of large system
Surface area of particles in large reformer
may also contribute to lower conversion
Pressure at black liquor injection point roughly 3
times higher
May impact coating of black liquor
Fundamental rate information for bed solids
would be useful
30
 Acknowledgements

U.S. Department of Energy

Georgia-Pacific Corporation
Thermochem Recovery International
Norampac Corporation
bo Akademi University
Mauricio Naranjo
Carolina Rubiano
Mike Siddoway
Adriaan van Heiningen

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