Evaporation Principles &
Black Liquor Properties
David T. Clay
Senior Process Consultant
Jacobs Engineering
Outline
Slide 2
Evaporator basics
Multiple effect evaporation
Black liquor properties
Kraft Black Liquor Production
Slide 3
~ 3000 lb of black liquor solids
per ton
of air-dried unbleached pulp
Slide 4
Evaporation Required to Burn Liquor
Weak BL from washers
15-20% solids
80-85% water
BL to recovery boiler
65-85% solids
15-25% water
Principle of Evaporation
Slide 5
vapor
liquor
liquor
steam
condensate
liquor
Types of Black Liquor Evaporators
Slide 6
Rising Film
Falling Film
Direct Contact
Forced Circulation
Slide 7
Evaporator Material and Energy Balance
If the heat content of the steam was used
only once, 100,000 lbs of steam would
evaporate only 100,000 lbs of water from
the liquor
Venting, radiation and other losses
prevent attaining theoretical efficiency
Slide 8
Single Effect Operation
116k lb/hr steam
45k lb/hr SBL
50% TS
105k lb/hr vapor
116k lb/hr condensate
150k lb/hr WBL 15% TS
Steam Economy =
water evaporated
steam supplied
105
= 116
= 0.9
Slide 9
Multiple Effect Evaporation
If the heat content of the steam was used only
once, 100,000 lbs of steam would evaporate
only 100,000 lbs of water from the liquor
Venting, radiation and other losses prevent
attaining theoretical efficiency
Economic operation dictates the multiple
effective use of the heat content of the steam
Two-Effect Operation
57k lb/hr
steam
54k lb/hr
vapor
Slide 10
51k lb/hr vapor
111k lb/hr
condensate
45k lb/hr
50% BL
99k lb/hr
23% BL
150k lb/hr
15% BL
Steam Economy = 105/57 = 1.8
Simple Six-Effect Evaporator Set
Slide 11
Condenser
Steam
Product
liquor
Weak
black
liquor
Steam Economy ~ 5
Heat Transfer in Evaporators
Slide 12
Evaporation rate = Q = U*A*T
U is the overall heat transfer coefficient
A is the total heat transfer surface area
Overall T is the temp difference
Steam temperature in first effect minus...
Condensing vapor temperature in last effect
Slide 13
Black Liquor Properties
Basis of evaporation equipment design
Changes in liquor cycle chemistry can
impact evaporator performance if
properties depart from design values
Viscosity
Boiling point rise
Concentration of scaling species
Black Liquor Composition
Slide 14
Wet basis
Organics
Water
Inorganics
Dry solids basis
Alkali lignin, wt-%
Wood acids &
Polysaccharides
Inorganics, salts
Resins, fatty acids
Methanol
30 - 45
30 - 45
30 - 45
3-5
~1
Black Liquor Specific Gravity
Slide 15
Important for performance calculations
Baum (hydrometer up to 50% solids),
must be corrected for temperature
SG of BL @ 60F / water @ 60F = 145/(145 - B)
Solid content inferred from Baum, but
correlation changes with wood species!
Black Liquor Density Correlations
Slide 16
Correlation for 50% BLS, T 100C
, g/cm3 = 1.007 + 0.006*(%S) - 0.000495* (TC)
Ex: 15% BLS, 82oC (180oF) > 1.06 g/cm3
Ex: 49% BLS, 93oC (200oF) > 1.26 g/cm3
Non-linear behavior at high solids
Extrapolation to firing conditions 10%
Black Liquor Thermal Properties
Slide 17
Properties needed for detailed calculations
noted in paper.
Thermal conductivity
Specific heat (Cp)
Heat of vaporization
Typical Black Liquor Viscosities
Slide 18
Viscosity of room temp water ~ 1 cp (mPa-s)
Viscosity of SAE 30 oil at 80F ~ 200 cp (mPa-s)
BL Dry Solids Temp., F Temp., C Viscosity, cP
66
1.0
150
18%
82
0.9
180
21%
93
1.0
200
26%
110
1.3
230
34%
116
2.3
240
42%
121
4.9
250
51%
127
88
260
70%
Viscosity, cP or mPa-s
Black Liquor Viscosity vs. Solids
500
100C
(212F)
400
300
125C
(257F)
Slide 19
150
150C
(302
(302F)
Concentrated BL
200
100
0
50%
60%
70%
80%
Black Liquor Dry Solids, wt-%
Slide 20
What Determines Black Liquor Viscosity?
Total solids content & Temperature
Wood species & cooking conditions
Residual alkali / pH
Correlations exist, but actual black liquor
viscosity differs 400%!!
Viscosity must be measured for evap design
10
Slide 21
Impacts of Viscosity
Evap design affected greatly by viscosity
Heat transfer coefficient (U value)
Power usage in units with recirculation pumps
Evaporator capacity can be affected by
changes in viscosity, e.g. wood species
Viscosity up 5 fold, U value down 50%
Black Liquor Boiling Point Rise
Slide 22
BL boils at temps above water boiling point
Boiling point rise (BPR) increases with solids
BPR depends on inorganic content of liquor
Black
Liquor
225F
107C
50% liquor
Vapor &
Condensate
212F
100C
11
45
40
BPR = BPR50*
20
35
30
15
25
20
10
15
10
5
BPR50 = 7.5C
5
(13.5F)
0
0
0% 20% 40% 60% 80% 100%
25
9.1*S
8.1 7.1*S
Boiling Point Rise, F
Boiling Point Rise, C
Boiling Point Rise vs. Solids
Slide 23
Black Liquor Dry Solids, wt-%
Slide 24
BPR at Each Effect
Effect #
6
5
4
3
2
1
Total
BL Dry Solids
18%
21%
26%
34%
42%
51%
BPR, C
1.8
2.2
2.8
4.1
5.6
7.8
24.3
BPR, F
3.2
3.9
5.1
7.3
10.1
14.0
43.7
Total T = Tsteam - Tcondenser - BPR (total)
12
Slide 25
Impacts of BPR
Evap design affected greatly by BPR
Cumulative impact in multiple effect units
Evaporator capacity can be affected by
changes in BPR, e.g. alkali/wood charge
Higher alkali charge can result in higher
inorganic content and higher BPR
Typical Black Liquor Composition
Major
Element
Carbon
Hydrogen
Oxygen
Sodium
Potassium
Sulfur
C
H
O
Na
K
S
wt-% BLS
35.0%
3.3%
35.7%
19.7%
1.6%
4.0%
Slide 26
Minor
Element
Calcium
Aluminum
Silicon
Iron
Carbonate
Sulfate
Ca
Al
Si
Fe
CO3
SO4
wt-% BLS
600 ppm
50 ppm
700 ppm
150 ppm
8%
3%
13
Black Liquor Evaporator Scaling
Slide 27
Na, SO4=, CO3= cause soluble Na scale
Dissolved Ca causes insoluble calcium scale
Al and Si cause aluminosilicate scale
Organics increase scaling and fouling rate
Scaling reduces U values and can rob available
heat-transfer area by plugging tubes
Summary
Slide 28
Weak BL is ~ 15% dry solids
As-fired BL must be 65% to 85% solids
Variation in BL properties relative to design
values affects evaporator performance
Higher viscosity reduces U values at high solids
Higher boiling point rise reduces available T
Changes in liquor components can foul heater
surfaces
14
Acknowledgement
Slide 29
Christopher L. Verrill
International Paper Corporation
Author and presenter of 2007 slides, which
formed the basis of this presentation.
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