The Kraft Recovery Process

Honghi Tran
Pulp & Paper Centre
University of Toronto
Toronto, Canada

Tappi Kraft Recovery Short Course

St. Petersburg, Florida, January 7-10, 2008

Kraft Pulping Process

Most important chemical pulping process
Global kraft pulp production: 130 million
metric tons/year (67% of total)
Advantages
High pulp strength
Versatility - ability to handle a wide range of wood
species
Favorable economics - High chemical recovery
efficiency (96 - 98%)

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 Kraft Pulping Process
Fibre

Lignin
Fibre

White
+ Liquor
(NaOH + Na2S)
Wood 155oC
900 kPa
Black Liquor

A 1000 t/d Kraft Pulp Mill

produces 1500 t/d BL d.s.
8000 ~ 10,000 t/d weak black liquor
3000

2500
Chemicals Chemicals
2000
t/d

Black
Dissolved Liquor
1500
Organics
1000 Wood

500 Fibre Pulp

2
 Kraft Recovery Process
A Closed Cycle Process with 3 Main Functions:

Eliminate the waste

material (black liquor) Pulping

Recover pulping
NaOH, Na, S, Organics
chemicals (NaOH and Na2S
Na2S)
Recovery
Generate steam and
power
Steam &
Power

Kraft Recovery Process

Wood
Pulping
Digester
Pulp
Washing
Washing

Weak
Black Liquor
15 18% ds

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 Kraft Recovery Process

Wood
Pulping
Digester
Pulp
Washing
Washing

Weak
Black Liquor

Evaporators
Ash
Heavy
Black Liquor
Recovery 65 85% d.s.
Boiler Makeup
Na2SO4

As-Fired Black Liquor Composition

(750 liquor samples; All Wood Species)
Typical Range
Solids content, % 72 65 85
HHV, MJ/kg 13.9 12.5 15.5
C, wt% d.s. 33.9 30 40
H 3.4 3.2 4.0
Composition

O 35.8 34 38
Na 19.6 17 22
S 4.6 3.6 5.6
K 2.0 13
Cl 0.5 0.1 4

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 Smelt Formation
0.4 kg smelt /kg BL d.s.
C
H Na2CO3
O 2/3

Na 1/3
Na2S (Reducing Conditions)
S
K Others:
Cl Na2SO4, NaCl
K2CO3, K2S, K2SO4, KCl

Smelt Spout

Smelt

Na2CO3 + Na2S

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 Kraft Recovery Process

Wood
Pulping
Digester
Pulp
Washing
Washing
NaOH
Weak
Black Liquor

Evaporators
Na2CO3 Green Water
Liquor Heavy
Na2S Recovery
Black Liquor

Smelt Boiler

Kraft Recovery Process

Wood
Lime Kiln Pulping
Digester

White Pulp
Lime Liquor Washing
Washing
Lime
Mud
Weak
Black Liquor
Causticizing
Causticizing
Plant
Plant Evaporators

Green Water
Liquor Heavy
Black Liquor
Recovery
Smelt Boiler

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 Na and Ca Cycles
Makeup
Wood
Lime Kiln Pulping
Digester

NaOH Pulp
CaO Na2S Washing
Washing
CaCO3 Calcium
Na, S
Causticizing
Causticizing
Sodium
Plant Evaporators
Na2CO3 Water
Na2S Na, S

Recovery
Makeup Boiler

Sulfur Cycles

SO2 Fuel Wood

Lime Kiln Pulping
Digester
S
Pulp
CaSO4 Na2S NCG/
SOG Washing
Washing
Na2SO4

S Loss/ Scrubbing/ S
Recovery Incineration
Causticizing
Causticizing
Plant NCG/SOG
Evaporators
Na2S
Water
SO2
Na2SO4 S
Recovery
S Makeup Boiler

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Makeup Chemicals (Na, S and Ca)
Sodium
8 to 16 kg/ADt as Na2O
NaOH, Na2CO3, Na2SO4 (salt cake)
Organic Na compounds (acetate, etc.)
Sulfur
1.4 to 4 kg/ADt as S
Na2SO4, NaSH, H2SO4, Na3H(SO4)2, Elemental S
S in lime kiln fuels
Calcium
4 to 8 kg/ADt as CaO
Purchased lime
Lime rock

Main Sources of NPEs

(Non Process Elements)
Wood: Si, Al, Cl, K, Mg, Mn, P, Fe, Ni, Cr, etc.
Makeup caustic: Cl
Additive: Si, Mg
Makeup lime: Si, Al, Mg, P, Fe
Refractory bricks: Si, Al
Corrosion products: Fe, Ni, Cr

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 Types of NPEs

Form soluble compounds: Cl, K

Be with the liquor
Accumulate
Form partially soluble compounds: Si, Al
Precipitate under appropriate conditions
Form insoluble compounds: Most other
elements
Do not accumulate
Be removed from the recovery system with grits,
dregs and lime mud/dust

Energy Recovery
1.9 GJ/ADt
Wood
Loss Lime Kiln Pulping
Digester
Pulp
White Washing
Washing
Lime Liquor
Lime
Mud
Power LP Steam
Weak
Causticizing
Causticizing Black Liquor
Plant
Plant Pulping
Turbine
Evaporators

Green HP Steam
Liquor Heavy
Recovery 22 GJ/ADt
Black Liquor

Smelt Boiler Loss

1 GJ/t = 0.860 MM Btu/ton

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 Recovery Boiler Energy
Production
Steam
Typically 3.5 kg/kg BLds
May vary from 2.5 to 3.8 kg/kg BLds
Power
A 1000 t/d kraft pulp mill may generate 25 to
35 MW of electricity from black liquor
combustion

Technological Advancements
Evaporators/concentrators
Falling film, plate-type
High solids (75 to 85%)
Recovery boilers
High solids firing
High steam temperature/pressure
High efficiency
Recaust and lime kilns
Pressurized filters
Lime mud dryer

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 Recovery Boiler Firing Capacity
6000
11 million lbs/d
5000
Capacity (t ds/d)

Maximum
4000

3000

2000

1000

0
1930 1940 1950 1960 1970 1980 1990 2000 2010
Year
Vakkilainen (2006)

Maximum Recovery Boiler Steam

Temperature and Pressure
600 180
Temperature 960 F
Steam temperature (C)

Steam Pressure (bar)

500 150
1813 psi
Pressure
400 120

300 90

200 60

100 30

0 0
1930 1940 1950 1960 1970 1980 1990 2000 2010
Year
Vakkilainen (2006)

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Benefits of High Solids Firing
Significantly increases steam generation
Improves combustion stability
Lower TRS and SO2 emissions
Less boiler fouling and plugging
Increase capacity in existing units.

Operating Problems
Many problems can occur
They can be:
Equipment related
Process related
Liquor chemistry related

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 Common Operating Problems
Evaporators
 Scaling
 Corrosion
 High steam consumption
 Low solids in product liquor
Recovery Boilers
 Fouling and plugging
 Tube corrosion and cracking
 Spout corrosion and cracking
 Low steam production
 Poor sootblowing efficiency
 Poor water circulation
 Smelt-water emergencies
 Gaseous/particulate emissions
 Tube damage by falling deposits
 Unstable combustion/blackouts
 Jelly roll smelt/smelt run-off 
 Low reduction efficiency
 High dregs in smelt
Problems Can Be Costly
Recovery Boiler Plugging
0.8 - 1.5 million USD
Recovery Boiler Tube Corrosion/Cracking
5 - 20 million USD
Lime kiln ringing
10,000 - 500,000 USD
Environmental impacts
??? USD
Lime kiln and Recausticizing
 High kiln fuel consumption
 Ring formation
 Refractory damage
 Chain damage
 NCG/SOG burning
 Gaseous/particulate emissions
 Poor lime quality/availability
 Overliming/underliming
 Poor causticizing efficiency
 Poor mud settling and low solids
 Clarifier corrosion
 Process control
Liquor Cycle
 NPE Accumulation (Cl and K)
 High deadload
Chemical makeup
 Na and S imbalance
 High sulphidity operation
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 This Course is Designed to
Help You To:
Understand process principles
Understand possible causes of problems
and find solutions to them
Recognize potential problems that may
occur and devise means to prevent them
from occurring

Challenges
Increased economy
Increase production capacity
Lower operating costs
Increased environmental protection
Increase recovery efficiency
Reduce emissions and discharge
New technologies, sensors and control
strategies
Process simplification

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