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

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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)

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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

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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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