Pulping and Bleaching

PSE 476/Chem E 471

Lecture #15
The Kraft Recovery Process

1
 Agenda

Overview of process
Black Liquor
Evaporation
Recovery Furnace
Smelt
Causticizing
Lime Kiln

2
 Basics of the Kraft Recovery
System
Cooking
This diagram (taken Pulp
&
Chips
Washing
from Kraft Pulping:
A Compilation of
Notes shows what BLACK LIQUOR
WHITE LIQUOR
Alkali Lignin
will be covered in Hydrolysis Salts NaOH
Na2S
Sulfonation Products
this lecture. The
object of this system
is to regenerate the Evaporation
&
GREEN LIQUOR
Na2CO3 Causticizing

cooking chemicals Burning Na2S

and to generate heat Heat Water

CaCO3
= steam & power. Makeup Chemicals CaO

3
Black liquor separation

4
Basics of the Kraft Recovery
System II

5
 Black Liquor

Chips

NaOH Inorganics
Na2S
Digester Pulp NaOH (7%)
Na2S (19%)
Black Liquor Na2CO3 (36%)
Na2SO3 (9%)
14-18% Solids Na2SO4 (13%)
pH 12+ Na2S2O3 (16%)
65% Organics
35% Inorganics
Notes
6
 Evaporation I

In order to burn the black liquor, the solids content needs to

be raised to over 60%.
This means that over 80% of the water needs to be removed.
This is accomplished through the use of multiple effect
evaporators.

7
 Evaporation II

Evaporation is accomplished through:

Direst contact with flue gasses (old)
Indirect contact with steam
- Falling film (new)
- Raising film (old)
With indirect contact, steam is applied
countercurrent to the liquor (high temperature/pressure
steam is applied to thickest liquor). The steam produced
from the liquor is used to heat the next effect
(evaporator) at a lower temperature and pressure.
This continues to the first effect (most dilute liquor)
which is run under vacuum. (Please read the reading)

8
Evaporation III

9
 Recovery Furnace

Concentrated black liquor is burned in a

recovery furnace. The functions of the recovery
furnace are:
Remove remaining water from black liquor.
Burn the black liquor organic compounds
- Solves disposal issues.
- Produces steam (for heating and energy).
Reduce sulfur species to sulfide.
Generate Na2CO3 which will later be converted to
NaOH
10
 Recovery Furnace III

System for recovery

of heat to generate power

(A)
Combustion
Zone
Air (C)
Liquor Air
(B) Gasses from Pyrolysis Air Reduction
Zone (D)
Smelt (molten Na2CO3, Na2S, etc)
Notes
11
 Recovery Furnace IV

Liquor is sprayed
to char bed (droplet
size 2-3mm)
Particles should be
dry before landing
the char bed
Char is required in
bed for effective
reduction of
sulfates

12
 Reduction of Inorganics

Formation of sodium carbonate (Na2CO3)

Combustion of organics results in the formation of
CO2 and CO. Sodium compounds are converted into
Na2O.
Na2O + CO2 Na2CO3
Na2S + H2O + CO2 Na2CO3 + H2S
Reductive reactions in the char results in the
formation of sodium sulfide (Na2S)
Na2SO4 + 2C Na2S + 2CO2
Na2SO4 + 4C Na2S + 4CO
13
 Smelt

The molten inorganics at the bottom of the

recovery furnace are known as the smelt. This
material at 1500F leaves the furnace and is added
to water in the smelt tank.
This results in the formation of green liquor
This is also a dangerous operation. The extremely hot
smelt causes the water to instantly vaporize in a violent
reaction.
Green liquor composition: NaOH (8%), Na2S (20%),
Na2CO3 (60%), Na2SO3 ( 3%), Na2SO4 (6%), Na2S2O3 (3%).
14
 Caustizing

Caustizing is the process in which sodium

carbonate is converted into sodium
hydroxide.
In the first step, green liquor is clarified to
remove insoluble materials.
Calcium compounds
Unburned carbon
Metals
Clarified green liquor is sent to a slaker
where lime (CaO/Ca(OH)2) is added .
15
 Slaker (Causticizing)
Chemistry
Calcium carbonate (CaCO3) has extremely low
solubility in water while sodium carbonate (Na2CO3)
has fairly high solubility. When lime (CaO) is added to
a Na2CO3 solution, the following reaction occurs:
(important to note that CaO + H2O Ca(OH)2 this is the slaking
reaction).
Ca(OH)2 + Na2CO3 CaCO3 + 2 NaOH
The calcium carbonate precipitates out of solution driving the
reaction to the right side of the above equation thus forming
sodium hydroxide.
Calcium carbonate is removed through clarification forming
white liquor. This step completes the circle as the white liquor is
returned to the digester for pulping.

16
 Lime Kiln

The wet calcium carbonate slurry is treated in

a lime kiln.
This is a very long, refractory brick lined, slightly
tilted, rotating tube which is extremely hot (1500 to
2100F).
The calcium carbonate slurry is dried in the first
section of the kiln and then the calcium carbonate is
converted to CaO: CaCO3 + heat CaO + CO2

17
Black versus green liquor

18