Hydrogen and Synthesis Gas from Black Liquor, Colloquium on Black Liquor Combustion and Gasification May 13-16, 2003, Park City Marriott, Park City, Utah http://www.eng.utah.edu/~whitty/blackliquor/colloquium2003/

1. 1
Hydrogen and Synthesis
Gas from Black Liquor
Cosmas Bayuadri, Delphine Boisseau,
José Canga Rodríguez, Sergio Blanco
Rosete and Jim Frederick
Chalmers University of Technology
Sustainable Development
"Meeting the needs of the
present without compromising
the ability of future generations
to meet their own needs."
Bruntland Commission, 1987

2. 2
Green Chemistry and
Green Chemical Engineering
The invention, design, and application of
chemical products and processes that
consume only renewable raw materials and
energy Biomass
make highly efficient use of raw materials
and energy Gasification
reduce or eliminate the use and generation
of hazardous substances
reduce or eliminate the release of
substances harmful to humans and the
environment Gasification
Forest-Based Biomass Refinery
(Ohlstrom et al., 2001)

3. 3
Expected Conversion
Efficiencies
Fuel Product Efficiencya Source
Black liquor Elec(Stm) 10 Larson, 2001
Elec(IGCC) 20
Biomass H2 55 Utrecht, 2002
MeOH 60
Biomass H2 59 VTT, 2001
MeOH 56
Black liquor H2 46-60 Frederick &
Way, 1995
a Net efficiency, adjusted for differences in cogeneration
where applicable.
Low Level Energy Utilization is
Critical for a Biomass Refinery
Pulp and
Paper Mill
Gasification
Hydrogen,
Methanol, or
DME Plant
Power
Plant
Biomass Biomass
Black
Liquor
Product Gas
Fuels PowerPaper

4. 4
Key Components in Biomass-to-
Hydrogen/Methanol Production
MeOH
Prod’n
H2
Prod’n
Pretreat Gasify Gas
Cleaning
Reform
HC’s
Shift
CO/H2
Biomass
Gas
Turbine
Steam
Turbine
Elec
H2
MeOH
Lignin Separation from Black Liquor
An Option for Pulp Mills With Excess Fuel
Lignin
PrecipitationCO2
H2SO4
Washing
H2S
Recycle
Drying
Black liquor
Lignin
Water
Heat
Effluent
Recycle
Source: Uloth et al., 1991
Lignin separation process currently under
development by Theliander et al., Chalmers

5. 5
Challenges
Gasification
Rapid and high carbon conversion at low
temperature
Minimal tar production
Gas Cleaning and Conditioning
Remove tar, acid gases, particulates, CO2
Do it cheaply
Minimal impact on energy conversion
efficiency
Energy and Mass Integration
Within plant
Within society
Tertiary Tar Species
in Gasifier Product Gas
Indene
(CAS 95-13-6)
Naphthalene
(CAS 91-20-3)
Acenaphthene
(CAS 83-32-9)
Biphenylene
(CAS 259-79-0)
Anthracene
(CAS 120-12-7)
Phenanthrene
(CAS 85-01-8)
Phenalene
(CAS 203-80-5 )
Fluoranthene
(CAS 207-08-9)
Perylene
(CAS 198-55-0)
Pyrene
(CAS 129-00-0)

6. 6
Challenges: Gasification
Rapid and high carbon
conversion at low
temperature
Kinetics?
Reactor type, design?
Minimal tar production
In-process options?
Tar quantity versus
toxicity?
Impact of gasification
conditions?
Particle residence time, sParticle residence time, s%Cinputconvertedto%Cinputconvertedto
nonvolatilenonvolatiletarstars
0.00.0
0.20.2
0.40.4
0.60.6
0.80.8
1.01.0
0.00.0 0.40.4 0.80.8 1.21.2
700700°°CC
800800°°CC
900900°°CC
10001000°°CC
CC1010--CC2020
PyrolysisPyrolysis in Nin N22
Challenges: Gas Cleaning
and Conditioning
Remove tar, acid gases, particulates,
CO2
Need robust processes that can handle
multiple contaminants
Absorption (DEA, MDEA, etc.)
Need solvents that are more stable and
require lower regeneration energy
Other separation options
Membranes?
?
Reuse of recovered CO2, etc.?

7. 7
Challenges: Energy and Mass
Integration
Energy integration within plant
Energy integration within society
Local power generation and district
heating
Eco-industrial complexes
Mass integration within society
Eco-industrial complexes
Kalundborg
Community
Heat
Novozymes
Novonordisk
BPB Gyproc
Kemira
Sulfuric
Acid Plant
Greenhouses
Agricultural Sludge
Fish Farming
Lake
Fjord
Delivery Network
for NovoSlam
Air Emissions
Material Transfer
Extraction and/or
Discharge of Water
Fly Ash, Clinker
Gypsum
Waste Heat
Waste Water
Cooling Water
Gas
Steam
Liquid
Sulfur
Gas
Refinery
Power
Plant
Steam

8. 8
Assessment of Sustainability: LCA
Impact Evaluation (ET short Sweden)
Ash to landfill: 6%
H2S emissions: 0.2%
CO2 emissions: 4%
CO emissions
37%
CH4 emissions: 0.4%
N2O emiss.
16%
HC emissions
2%
Tar emissions
35%
Assessment of Sustainability: LCA
Impact Categories (ET short Sweden)
Ozone Layer
Depletion <0.1%
Disposal of
Ash & Tar
Acidification
14%
Photo-
oxidation
45%
Global Warming
5%
36%

9. 9
References
Hamelinck, C.N.; Faaij, A.P.C. (2002).
Future prospects for production of
methanol and hydrogen from biomass. J.
Power Sources, V. 111, No. 1, pp. 1-22.
Stiegel, G.J.; Maxwell, R.C. Gasification
technologies: the path to clean, affordable
energy in the 21st century. Fuel Processing
Technology 71, 2001, 79–97.