Black Liquor and

Recovery boilers

Mika Järvinen, Associate Professor

Academy Research Fellow 2012-17

Department of Energy Technology

Laboratory of Thermodynamics
and Combustion
 Learning objectives
• To know what is black liquor and how it relates
to papermaking
• To understand the main functions of a recovery
boiler - to recover chemicals and heat
• To understand the nature of black liquor droplet
combustion - drying, pyrolysis, char reactions and
smelt reduction and oxidation
• Very aggressive fuel - reactivity and swelling
• To introduce some new combustion characteristics
that has been learned from our research work
 Contents
1. What is black liquor? (April 14th)
2. Main recovery boiler processes (April 14th)
3. Trends for the future (April 14th)
4. Principles of droplet combustion
5. Updated perspectives through research work
6. Summary, what should you remember from this
lesson?
 What is black liquor?
• Black liquor is
a valuable
intermediate
product of
papermaking
• Only the fibers
of the wood
are used in
paper
 What is black liquor ?

3 800 000 000 tons oil in the world/year

1 000 000 000 tons gasoline
200 000 000 tons black liquor is produced and burned

1 350 000 000 tons grain

410 000 000 tons milk
120 000 000 tons sugar (Poltto ja Palaminen)

In Finland, 11 % of total heat and power is produced from black

liquor, ~ 46 % of bio-energy (Helynen et al. 2002)
Significance to Finland

Electricity production 2000-11

 Modern paper mill
White liquor
NaOH + Na2S
Lime kiln CaO
Wood
CaCO3 chips
Causticizing Cooking
Green liquor
Na2CO3+Na2S Washing Pulp

Weak black
Dissolving tank liquor, ds ~15 %
Smelt
Evaporation
Black liquor
Steam
Combustion in Black liquor
Recovery Boiler ds 75-85 %
 Composition
Wood Black liquor Main organic
water 20-40 20-25 species lignin,
C 50 39.8
H 6 4.2 aliphatic acids and
O 43 36.0 extractives
N 1 0.1
S - 4.0
Na - 15.5 Inorganic species
K - 0.1 Na2S, NaOH,
Cl - 0.3
Na2SO4, Na2CO3,
etc….
Numbers given as weight-%
 Dry solids
In older boilers dry solids content of liquor was 55-
65 %
In modern Finnish boilers, dry solids of black liquor
is 78-85 %
By burning dryer liquor, capacity of the boiler can
be increased (less flue gas H2O), combustion
temperature increases, less SO2 emissions
 Heating value
Effective heating value of black liquor is low 12-13
MJ/kg.
For comparison, coal 28 MJ/kg, peat 22 MJ/kg and
wood 17 MJ/kg.
This means that less heat can be produced in
black liquor combustion, resulting in lower
combustion temperature
 Volatile matter
Organic matter in black liquor is very easily
volatilizable, more than 80 % of organic matter can
release as gases in pyrolysis  Most of organic
combustion takes place in gas phase.
Other fuels:
Coal 30 % volatile, Brown coal 60 % and Peat 70
%.
 Swelling and reactivity
• significant
swelling during
pyrolysis
• char reactivity
very high due
to swollen
structure and
catalysing
inorganics
 Fouling behavior of salts
”Ash” content of black liquor is very high 35 %.
Due to chemical composition ash will melt at
very low temperature ~ 750 °C  boiler gets
easily fouled or even plugged. Difficult fuel!
Other fuels:
Coal 12 % ash, melts at 1200 °C, Brown coal
22 %, 1100 °C and wood 2 %, 1300 °C.
 Black liquor as a fuel
Good (+)
Large amount of volatile matter (gases burn faster than solids)
Black liquor is a biofuel!!
High swelling and reactivity
Bad (-)
Low heating value (lower combustion temperature)
High water content (evaporation, large amout of flue gas)
High ash content (large droplet size is required)
Low melting temperature of ash (fouling)
Main recovery boiler
processes
Objectives of Recovery Boiler
1. To burn the organic matter in black liquor for heat
and steam production: Organics + O2 = H2O/CO2

2. To convert chemicals back into valuable form:

Na2SO4 + 4C = Na2S + 4CO

3. Minimize emissions of SO2, NO and CO2

 Heat to Heat
furnace walls
recovery
Modern
Tertiary air
70-100 m

recovery
Black liquor spraying

boiler
Combustion in flight
Organics + O2 → CO2/H2O +
Secondary air
Heat

Primary air
Char bed, Na2SO4 + C → Na2S + CO Smelt to dissolution,
sulfur mainly as
Na2S

Chemical
12-15 m recovery
Recovery boiler
schematic c

a) Liquor is sprayed
to the furnace
c
b) particles burn in
b
furnace
c) combustion heat a

is recovered by
heat exchangers
Recovery boiler
schematic
d) Large particles fall
into char bed,
e
Na2SO4 is reduced
into Na2S, smelt to
dissolving tank
e) Small particles are d
entrained by flue
gases
Recovery boiler
schematic
d) Flue gas salts are
captured at ESP and
returned to mixing
tank e
Future trends
Adding the value from black liquor

• Recovery boiler utilizes the organic combustion

heat for heat and power production and recycles
Na2S and Na2CO3 back to process.
• Very robust technology and the dry solids content
still increases, already above 80-85%
• Capacity of the boilers are increasing, latest
designs are huge!
Adding the value from black liquor
Adding the value from black liquor

• Capacity of the
boiler can also be
increased by
reducing organic
fraction prior to
combustion, such as
Lignoboost®
(removing lignin),
less flue gas to
boiler, more liquor
can be fired.
Adding the value from black liquor

• Gasification technology of black liquor is still under

development. Nobody wants to take the risk of
investing to large scale gasifier vs. robust boiler.
• If successfull, overall efficiency can be improved by
burning the gas in gas turbine and coupling this
with Rankine steam cycle.
• Gases can also be used in chemicals production,
e.g. automotive fuels.