Pre-feasibility Study Of The

Implementation Of Gasification And

Fuel Cell Technologies In The Pulp
And Paper Industry
Ibrahim Karidio and Vic Uloth
Paprican Boiler Optimization & Emissions Control

Franois Girard , Terrance Wong

National Research Council Canada

7th Black Liquor Colloquium, Jyvskyl, Finland, July 31 August 2, 2006

Overview of Canadian Pulp and Paper
Industry
Capital intensive and Energy intensive industry comprised of:
~50% Kraft pulps
~46% Mechanical pulps
~4% Sulphite / Semi-chemical pulps

Kraft pulp sector self generates more energy than the industry
average. Kraft mills are 60-80% energy self-sufficient.

Energy cost can be 10-25% of pulp production cost

Therefore, there are significant economic incentives to reduce

both energy use and costs. This may be achievable through
the use of innovative energy generation technologies such as
gasification integrated with combined cycle or fuel cell
technologies.
7th Black Liquor Colloquium, Jyvaskyla, Finland, July 31 August 2, 2006
Canadian Pulp & Paper Industrys Energy
Consumption

In 1990 By 2010

Total energy in Petajoules 755 1067

/ year
Wood wastes 13% 17%
Spent liquors 27% 42%

Fossil fuel 28% 19%

In 1995: 881 Petajoule (55.7% from hog and spent liquors).

1 Petajoule = 1015 joules = one million Giga Joules.

7th Black Liquor Colloquium, Jyvaskyla, Finland, July 31 August 2, 2006
 Objectives

To examine the feasibility of integrating gasification and

fuel cell technologies in Canadian kraft pulp mills.
2 options: (1) Black liquor gasification and/or (2) wood wastes
gasification.

To examine the impact of this integration on:

Greenhouse gas emissions
Energy profile of typical Canadian kraft mills
Mill economy

7th Black Liquor Colloquium, Jyvaskyla, Finland, July 31 August 2, 2006

The Kraft Cycle: Opportunity

White liquor
(NaOH, Na2S)

pulping
causticizer
Recovery boiler,
Black liquor smelter Green liquor
(NaOH, Na2SO4, organics)
(Na2CO3, Na2S)

CO2
Electricity
NOx
Steam
SOx

7th Black Liquor Colloquium, Jyvaskyla, Finland, July 31 August 2, 2006

The Kraft Cycle: Opportunity
White liquor
(NaOH,
pulping Na2S)
causticizer
Black liquor Green liquor
(NaOH, Na2SO4, (Na2CO3)
organics)

H2, CO, CH4

Gasifier Fuel cell air
H2 S
CO2 steam
electricity

7th Black Liquor Colloquium, Jyvaskyla, Finland, July 31 August 2, 2006

 Gasification
Several technologies being developed.
Comprehensive reviews of black liquor gasification
technologies were conducted by Grace et al as well as
Whitty et al.

We chose for this evaluation the ChemRec (Kvaerner)

gasifier
Closest to commercialisation
Air blown and oxygen blown versions
Temperature of operation: 900-1000 C
Pressure: 25 bar

7th Black Liquor Colloquium, Jyvaskyla, Finland, July 31 August 2, 2006

Fuel cell options
5 major types of fuel cells classified according to the
nature of their electrolyte:
Proton Exchange Membrane Fuel Cell Protons H+ are
(PEMFC) generated
Phosphoric Acid Fuel Cell (PAFC)

Alkaline Fuel Cell (AFC) Negatively

Molten Carbonate Fuel Cell (MCFC) charged ions are
generated
Solid oxide fuel cell (SOFC)

For this study we chose the SOFC technology:

Anode: H2 + O2- H2O + 2e- Cathode: O2 + 2e- O2-

7th Black Liquor Colloquium, Jyvaskyla, Finland, July 31 August 2, 2006

Operating Environment of Fuel cells

Proton Exchange Membrane Fuel Cell (PEMFC) -

1960s: 80-100 C; up to 120 psi; Pt based catalysts at
electrodes; Electrolyte: Nafion (proton conducting
polymeric membrane). Disadvantages: Extreme
sensitivity to CO and low quality heat.

Phosphoric Acid Fuel Cell (PAFC) - 1960-1967:

150-210 C; Platinum based catalysts; Electrolyte:
liquid concentrated phosphoric acid (H4P2O7);
Disadvantages: Sensitive to CO and Sulfur.

7th Black Liquor Colloquium, Jyvaskyla, Finland, July 31 August 2, 2006

Operating Environment of Fuel cells (Ctd)
Alkaline Fuel Cell (AFC) - 1932-1952: 60-250 C; from
atmospheric to 750 psi; Ni or Ag based catalysts at electrodes;
Electrolyte: Aqueous or molten KOH suspended in a matrix
(asbestos). Disadvantages: Corrosive and liquid electrolyte. Low
quality heat generated; Extreme sensitivity to CO2.

Molten Carbonate Fuel Cell (MCFC) - 1940s: 600-800 C; up

to 150 psi operating pressures; Nickel based electrodes; Molten
Li or K-Na Carbonate electrolyte. Fuel: CO and H2.
Disadvantage: low S tolerance.

Solid oxide fuel cell (SOFC) - 1937-1965: 650-1000 C;

Ambient pressure; Ceramic electrodes; Ceramic electrolyte.
Fuel: CO and H2. Disadvantages: Low conductivity of electrolyte
and varying thermal expansion properties of ceramic materials.

Efficiency for electricity generation: 40 - 60%;

Overall efficiency can reach 80% if heat is also recovered.
7th Black Liquor Colloquium, Jyvaskyla, Finland, July 31 August 2, 2006
Oxygen-Blown Black Liquor Gasifier
Gas Composition
Production of gas (t/tds) - 1.34
Species Vol % Volume (m3) per tds
Ar 0.87 13.01
CH4 2.15 32.15
CO 23.06 344.81
CO2 18.57 277.67
COS 0.05 0.75
H2 22.37 334.49
H2O 31.52 471.31
H2S 1.08 16.15
NH3 0.00 0.00
N2 0.32 4.78
Total useful fuel for a fuel cell 45.43 679.31

Data derived from literature.

7th Black Liquor Colloquium, Jyvaskyla, Finland, July 31 August 2, 2006
Syngas cleanup and conditioning
Product gases from black liquor gasification contains
S gases, particulates and alkali metal compounds in
the aerosol form as well as in the gas phase.
Important to use gas cleanup technologies that
operate at high temperatures
Ceramic candle filters (for particulate removal)
Calcium based chemical absorption for H2S removal
(dEntremont & Van Heiningen, 2001)
Use of sulfide specific fuel cells (to remove S) prior to SOFC
Scrubbing with green liquor (Disadvantage: CO2 absorption
and temperature sensitivity)

7th Black Liquor Colloquium, Jyvaskyla, Finland, July 31 August 2, 2006

Assumption for Calculations
Fuel utilization: 80%
Efficiency of conversion to electricity: 50%
No loss from intermediate operations (e.g. gas cleanup)

Energy produced per m3 of fuel gas: 1.08 kWh/m3

For oxygen-blown black liquor gasifier integrated with fuel cell,
power generation estimated at 734 kWh/t dry black liquor solids

For air-blown black liquor gasifier Fuel cell system: 606 kWh/m3
Power production at a given kraft mill: 770 1130 MWh/day.

7th Black Liquor Colloquium, Jyvaskyla, Finland, July 31 August 2, 2006

Energy Profile of Typical Kraft Mills in
Various Regions of Canada
Region Typical Black Power Power Purchased Source of
pulp liquor demand demand power purchased
production solids (kWh/t) (MWh/d) (MWh/d) power
per mill production
(t/d) (tds/d)
BC 1009 1756 857 865 510 Hydro

Prairies 1072 1865 853 914 239 Natural gas

Ontario 1011 1759 826 835 668 Natural gas

Quebec 730 1270 853 623 623 Hydro

Atlantic 768 1336 853 655 292 Oil

Data from Levelton Engineering, 1999

7th Black Liquor Colloquium, Jyvaskyla, Finland, July 31 August 2, 2006
Added Pulp Production following
Gasification Fuel Cell Implementation
1200

BC
1000 Prairies
Ontario
Quebec
Added production (t/d)

Atlantic
800

600

400

200

0
0 10 20 30 40 50 60 70 80 90 100

Incremental addition (%)

7th Black Liquor Colloquium, Jyvaskyla, Finland, July 31 August 2, 2006
Potential Revenues Generated by
Incremental Pulp
200

BC
Annual profits from additional Prairies
150 Ontario
pulp production (M$)

Quebec
Atlantic

100

50

0
0 10 20 30 40 50 60 70 80 90 100

Incremental addition (%)

7th Black Liquor Colloquium, Jyvaskyla, Finland, July 31 August 2, 2006

Extra Electricity Generated with
Incremental Pulp Production
100

BC
Prairies
80 Ontario
Quebec
Atlantic
% of purchased energy

60

40

20

0
0 20 40 60 80 100

Added capacity (%)

7th Black Liquor Colloquium, Jyvaskyla, Finland, July 31 August 2, 2006

 Annual p rofit (p ulp ) a n d sa vin g s (e le ctricity) (M $ )
C ap ita l co st (F C @ $ 1 50 0 /kW )
C ap ita l co st (F C @ $ 3 00 0 /kW ) Gasifier: 0.06M$/t
C ap ita l co st (F C @ $ 5 00 0 /kW )
100
Annual revenues/capital cost (M$)

80

60

40

20

0
BC P ra irie s O n ta rio Quebec A tla n tic

R e g ion
Gasifier costing estimate by Stigsson, 1994.
Costs for fuel cell technology are target costs estimate.
7th Black Liquor Colloquium, Jyvaskyla, Finland, July 31 August 2, 2006
 FC @ $1500/kW
FC @ $3000/kW Gasifier: 0.06M$/t
FC @ $5000/kW
5
Scenario $/kWh $/t pulp
4.5

4
1 0.03 250
Payback period (years)

3.5

3 2 0.03 200
2.5
3 0.03 300
2

1.5
4 0.04 250
1

0.5 5 0.05 250

0
1 2 3 4 5

Scenario

7th Black Liquor Colloquium, Jyvaskyla, Finland, July 31 August 2, 2006

 Scenario $/kWh $/t pulp 1 500$/kW 3 000$/kW 5 000$/kW

1 0.03 250 1.64 2.50 3.65

2 0.03 200 2.04 3.11 4.53

3 0.03 300 1.37 2.09 3.05

4 0.04 250 1.63 2.48 3.62

5 0.05 250 1.62 2.46 3.60

7th Black Liquor Colloquium, Jyvaskyla, Finland, July 31 August 2, 2006

30% incremental production of pulp
Autosufficient incremental production (electricity-wise)
Between $15-$25 M profit (pulp) yearly
Up to 25% electricity savings for the total process
(purchased)
Payback within 5 years even at fuel cell cost of
$5000/kW
$0.03/kWh
300 days operation/year
cost of gasifier: $0.06 M/ t pulp
profit: $250/incremental ton of pulp

7th Black Liquor Colloquium, Jyvaskyla, Finland, July 31 August 2, 2006

Conclusions

Incremental addition also promising

Additional revenues from pulp production
Flexibility towards fuel cell capital cost
Challenges
Gas cleanup technologies (particulates, H2S,
chemicals, etc.)
Precise economic assessment
Thermal energy recovery (electricity/steam ratio)

7th Black Liquor Colloquium, Jyvaskyla, Finland, July 31 August 2, 2006

Acknowledgements

NRC Fuel Cell Program

PAPRICAN

Thank you for your attention

7th Black Liquor Colloquium, Jyvaskyla, Finland, July 31 August 2, 2006