Pulping and Bleaching

PSE 476/Chem E 471

Lecture
Lecture #15
#15
The
The Kraft
Kraft Recovery
Recovery Process
Process

1
 Agenda

•• Overview
Overview ofof process
process
•• Black
Black Liquor
Liquor
•• Evaporation
Evaporation
•• Recovery
Recovery Furnace
Furnace
•• Smelt
Smelt
•• Causticizing
Causticizing
•• Lime
Lime Kiln
Kiln

2
 Basics of the Kraft Recovery
System
Cooking
This
Thisdiagram
diagram(taken
(taken
Pulp
&
Chips
Washing
from
from “Kraft
“KraftPulping:
Pulping:AA
Compilation
CompilationofofNotes”
Notes”
shows
showswhat
whatwill
willbebe BLACK LIQUOR
Alkali Lignin WHITE LIQUOR
covered
covered ininthis
this Hydrolysis Salts NaOH
Sulfonation Products Na2S
lecture.
lecture. The
Theobject
objectofof
this
thissystem
systemisisto
to
regenerate
regeneratethe
thecooking
cooking Evaporation GREEN LIQUOR
Na2CO3 Causticizing
&
chemicals
chemicalsand
andto to Burning Na2S

generate
generateheat
heat==steam
steam Heat Water
&&power.
power. Makeup Chemicals
CaCO3
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
Inorder
orderto
toburn
burnthe
theblack
blackliquor,
liquor,the
thesolids
solidscontent
contentneeds
needsto
to
be
beraised
raisedto
toover
over60%.
60%.
»» This
Thismeans
meansthat
thatover
over80%
80%of
ofthe
thewater
waterneeds
needsto
tobe
beremoved.
removed.
•• This
Thisisisaccomplished
accomplishedthrough
throughthe
theuse
useof
ofmultiple
multipleeffect
effect
evaporators.
evaporators.

7
 Evaporation II

•• Evaporation
Evaporationisisaccomplished
accomplishedthrough:
through:
»» Direst
Direst contact
contact with
with flue
flue gasses
gasses (old)
(old)
»» Indirect
Indirect contact
contact with
with steam
steam
-- Falling film (new)
Falling film (new)
-- Raising film (old)
Raising film (old)
•• With
Withindirect
indirectcontact,
contact,steam
steamisisapplied
applied
countercurrent
countercurrentto tothe
theliquor
liquor((high
hightemperature/pressure
temperature/pressure
steam
steamisisapplied
appliedto
tothickest liquor). The
thickestliquor). Thesteam
steamproduced
produced
from
fromthetheliquor
liquorisisused
usedto toheat
heatthethenext
next effect
effect
(evaporator)
(evaporator)at ataalower
lowertemperature
temperatureand andpressure.
pressure.
This
Thiscontinues
continuesto tothe
thefirst
firsteffect
effect(most
(mostdilute
diluteliquor)
liquor)
which
whichisisrunrununder
undervacuum.
vacuum. (Please
(Pleaseread
readthe
thereading)
reading)

8
Evaporation III

9
 Recovery Furnace

•• Concentrated
Concentratedblack
blackliquor
liquorisis burned
burnedinin aa
recovery
recoveryfurnace.
furnace. The
Thefunctions
functions ofofthe
therecovery
recovery
furnace
furnaceare:
are:
»» Remove
Removeremaining
remainingwater
waterfrom
fromblack
blackliquor.
liquor.
»» Burn
Burnthe
theblack
blackliquor
liquororganic
organiccompounds
compounds
-- Solves
Solvesdisposal
disposalissues.
issues.
-- Produces
Producessteam
steam(for
(forheating
heatingand
andenergy).
energy).
»» Reduce
Reducesulfur
sulfurspecies
speciesto
tosulfide.
sulfide.
»» Generate
GenerateNa
Na22CO
CO33which
whichwill
willlater
laterbe
beconverted
convertedto
to
NaOH
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
Formationof
ofsodium
sodiumcarbonate
carbonate(Na
(Na22CO
CO33))
»» Combustion
Combustionof oforganics
organicsresults
resultsin
inthe
theformation
formationofofCO
CO22
and
and CO.
CO. Sodium
Sodiumcompounds
compoundsare areconverted
convertedinto
intoNa
Na22O.
O.
»» Na
Na22O CO22
O++CO Na
Na22CO
CO33
»» Na
Na22SS++H
H22O CO22
O++CO Na
Na22CO
CO33++HH22SS
•• Reductive
Reductivereactions
reactionsin
inthe
thechar
charresults
resultsin
inthe
the
formation
formationof
of sodium
sodiumsulfide
sulfide (Na
(Na22S)
S)
»» Na
Na22SO 2C
SO44++2C Na
Na22SS++2CO
2CO22
»» Na
Na22SO 4C
SO44++4C Na
Na22SS++4CO
4CO

13
 Smelt

•• The
Themolten
molten inorganics
inorganics at atthe
thebottom
bottomof ofthe
therecovery
recovery
furnace
furnaceare areknown
known as as the
thesmelt.
smelt. This
This material
materialat
at
1500°F
1500°F leaves
leaves the
thefurnace
furnaceand andisis added
addedto towater
waterinin
the
thesmelt
smelttank.
tank.
»» This results in the formation of green liquor
This results in the formation of green liquor
»» This
Thisisisalso
alsoaadangerous
dangerousoperation.
operation. The
Theextremely
extremelyhot hotsmelt
smelt
causes
causesthethewater
waterto
toinstantly
instantlyvaporize
vaporizein inaaviolent
violentreaction.
reaction.
»» Green
Greenliquor
liquorcomposition:
composition: NaOH
NaOH(8%),
(8%),Na Na22SS(20%),
(20%),
Na
Na22CO
CO33(60%),
(60%),Na
Na22SO
SO33((3%),
3%),Na
Na22SO
SO44(6%),
(6%),Na
Na22SS22O
O33(3%).
(3%).

14
 Caustizing

•• Caustizing
Caustizing isisthe
theprocess
process in
in which
which sodium
sodium
carbonate
carbonateisisconverted
convertedinto
intosodium
sodiumhydroxide.
hydroxide.
•• In
Inthe
thefirst
firststep,
step, green
greenliquor
liquorisis clarified
clarifiedto
to
remove
removeinsoluble
insolublematerials.
materials.
»» Calcium
Calciumcompounds
compounds
»» Unburned
Unburnedcarbon
carbon
»» Metals
Metals
•• Clarified
Clarifiedgreen
green liquor
liquorisis sent
sentto
toaa“slaker”
“slaker”
where
wherelime
lime(CaO/Ca(OH)
(CaO/Ca(OH)22))isisadded
added..
15
 Slaker (Causticizing)
Chemistry
•• Calcium
Calciumcarbonate
carbonate(CaCO
(CaCO33))has
hasextremely
extremelylow
low
solubility
solubilityin
inwater
waterwhile
whilesodium
sodiumcarbonate
carbonate(Na
(Na22CO
CO33))
has
hasfairly
fairlyhigh
highsolubility.
solubility. When
Whenlime
lime(CaO)
(CaO)isisadded
addedto to
aaNa
Na22CO
CO33solution,
solution,the
thefollowing
followingreaction
reactionoccurs:
occurs:
(important
(importanttotonote
notethat
thatCaO
CaO++HH2O  Ca(OH)2 this is the slaking
2O  Ca(OH)2 this is the slaking
reaction).
reaction).
3  CaCO3 + 2 NaOH
»» Ca(OH)
Ca(OH)22++Na Na2CO
2CO3  CaCO3 + 2 NaOH
»» The
Thecalcium
calciumcarbonate
carbonateprecipitates
precipitatesout
outof
ofsolution
solutiondriving
drivingthe
the
reaction to the right side of the above equation thus forming
reaction to the right side of the above equation thus forming
sodium
sodiumhydroxide.
hydroxide.
»» Calcium
Calciumcarbonate
carbonateisisremoved
removedthrough
throughclarification
clarificationforming
forming
white
whiteliquor.
liquor. This
Thisstep
stepcompletes
completesthe
thecircle
circleas
asthe
thewhite
whiteliquor
liquorisis
returned
returnedto tothe
thedigester
digesterfor
forpulping.
pulping.

16
 Lime Kiln

•• The
The wet
wetcalcium
calcium carbonate
carbonate slurry
slurry isis treated
treatedin
in
aa lime
lime kiln.
kiln.
»» This
Thisisisaavery
verylong,
long,refractory
refractorybrick
bricklined,
lined,slightly
slightly
tilted,
tilted,rotating
rotatingtube
tubewhich
whichisisextremely
extremelyhot hot(1500
(1500toto
2100°F).
2100°F).
»» The
Thecalcium
calciumcarbonate
carbonateslurry
slurryisisdried
driedininthe
thefirst
first
section
sectionofofthe
thekiln
kilnand
andthen
thenthe
thecalcium
calciumcarbonate
carbonateisis
converted
convertedto toCaO:
CaO:CaCO heat
CaCO33++heat CaO
CaO++CO CO22

17
Black versus green liquor

18