Design challenges of Black Liquor Evaporation

By
Dr. Surendra Pratap Singh

Contents

Multi-talent bio-refinery inside modern pulp mill

High dry solids evaporator
Fouling & crystallization technology
Material selection
High quality secondary condensate

Multi-talent bio-refinery inside modern pulp mill

INLET FLOWS
FLOWS
Weak black liquor

OUTLET
Firing liquor at high DS and optimum
temperature for RB

Bio sludge
ClO2 plant waste

CNCG&DNCG to incineration
Warm water

CTMP filtrates
Methanol fuel
Foul condensates
Bleaching effluents
Effluent/wash waters

Cl & K purge
(ARC/ALE)
High quality secondary condensates at right
temperatures

Whats Black Liquor?

Complex

Spent

mixture

pulping chemicals (Inorganic salts, caustic, etc.)

Organic

matter (Lignin) dissolved from the wood

Non-Process-Elements
Brought
No

(NPE) such as K, Cl, etc.

in with wood, water and fresh chemicals

purge points: Constantly recycled

Black Liquor Properties

Chemical

composition
Major role on the performance of the evaporators
Na2SO4, Na2CO3 co-precipitate at high solids
Risk of scale formation

Critical

physical properties
Boiling Point Rise (BPR)
Viscosity which impacts heat transfer

Viscosity

Viscosity is an important rheological property of black liquor. Viscosity, which changes with the
composition and temperature of black liquor as well as with pulp mill operating practices, is of
interest because of its effect on evaporation rate, heat transfer rate, and liquor spray size. In heat
exchangers and evaporators, the heat transfer coefficient decreases as viscosity increases,
according to the approximate relationship below,

Heat transfer ~

1
( vis cos ity , cp ) 0.4

This relationship shows how the capacity (evaporation rate) of an evaporator changes with liquor
viscosity with all other factors held constant. A decrease in viscosity by a factor of 10 can
increase evaporator capacity by 1.5 to 2 times. Conversely, an increase in viscosity by a factor of
10 halves the capacity. The effect of viscosity on capacity is greater at higher viscosities (more
concentrated liquors).
Most common fluids such as water have viscosities, which are not affected by the flow conditions
such as shear rate; these fluids are referred to as Newtonian fluids. Under all circumstances the
shear force for these fluids is directly proportional to the shear rate. The viscosity of black liquor
is reasonably Newtonian, or independent of shear rate at solids levels below about 50%, but
becomes non-Newtonian (thixotropic or shear-thinning) at higher solids content.

Reduced viscosity as a function of reduced solids for several black liquors

A simple curve fit of this data is shown in figure , the equation used,

bl
[ST * /T]/{67.9 - 0.656[ST * /T]}
w

log
bl

= viscosity of black liquor, Pa-s

S = black liquor dry solids content, %
T = temperature, oK
T* = arbitrary reference temperature = 373o K
The viscosity of water can be calculated from equation,

For, 333oK<T<73oK

Most common fluids such as water have viscosities, which are not affected by the flow
conditions such as shear rate. These fluids are referred to as Newtonian fluids. For these
fluids under all circumstances, the shear force is directly proportional to the shear rate
resulting in the commonly used expression for shear stress,

dv

dy
Where,
= Sear stress. Pa
= Viscosity, Pa-s
v = velocity, m/s
y= distance from surface, m
Black liquor, like many other polymer melts and solutions, is non-Newtonian under
certain conditions. At low shear rates, the viscosity is a constant and black liquor can be
treated as a Newtonian fluid. At higher shear, raise the apparent viscosity decreases. This
is referred to as shear thinning. For nearly all liquors at conditions typical of practical
mill operation, this effect is very small.

Exposure to high temperature appears to irreversibly reduce viscosity, although

the effect varies from liquor to liquor, figure .shows the impact of heat
treatment on viscosity of a high solids birch black liquor.

Effect of liquor heat treatment on black liquor viscosity

Effect of increase in the percentage of total solid of the BPR

Boiling Point Rise

Boiling point rise (BPR) is the difference between the boiling temperature of black liquor and
that of pure water at the same pressure. This property is important to the design and performance
of evaporators.

BPR

K (S )
(100 S )

Where,
S = Black liquor dry solids content, %
K = Boiling point rise at 50% dry solids

Key requirements for modern evaporation plant

Uninterrupted liquor flow to recovery boiler

High dry solids at optimum spraying temperature
Maximized steam economy to minimize operating costs
Secondary condensate fractionating and handling to get clean process water
for the mill
High methanol recovery
Handling & treatment of mill by-product streams

High dry solids (> 80 %) concentration

Sustainabletechnology

Liquor heat treatment (LHT)

Crystallization technology
Twin tank -concept
Proper material selection
Condensate treatment
Benefits in recovery boiler

Challenges

14

Viscosity
Fouling
Corrosion and material selection
Sulphur release
MeOH generation

Increased efficiency
Lower SO2 emissions
Increased power production
Increased capacity

Rising Film Evaporator (LTV)

Vapor
outlet

Vapor (steam)
inlet

Liquor product

NCG
vent

Liquor feed

Condensate outlet

Rising Film Evaporator (LTV)

Liquor film formed by generated

vapors from boiling liquor at the
bottom of the tubes
Poor turndown, cant handle
high viscosities, minimum T
requirement
Was the workhorse of the
Industry, now found only in
older mills

Rising Film Evaporator (LTV)

Low

operating cost

Low

propensity for foaming

Low

liquor viscosity and high

flow-rate are ideal conditions

Only

used today in WBL pre-

evaporation where foaming is an

issue:
Blow Heat Recovery

Falling Film Evaporator

Recirculating liquor

Vapor (steam) inlet

NCG vent

Vapor outlet

Condensate outlet

Liquor feed
Liquor product
10

Falling Film Evaporator

Film formed by mechanical means

(Distribution plate)

High turndown, can handle higher viscosity

(Gravity helps)

Primary technology worldwide for

concentrations up to 50%TS

Plate-type FF Evaporator
Vapour outlet

Distributor

Vapor inlet
Plate heating element

Liquor feed
NCG vent

Liquor product

Condensate

Falling Film Evaporator

Can operate at low T

Flexible (High turndown)
Good resistance to scaling
Moderate HP consumption
Easily automated
Foams easily at low %TS

Falling Film Concentrators

FF

heat transfer
Evaporation takes place at the heat transfer surface

High supersaturation developed within the liquor

Potential for excessive crystal nucleation
Risk of uncontrolled scale formation

High dry solids evaporator

Due to the high viscosity:

MP-steam as heating medium
Liquor temperature 175 C in final concentrator
Evaporator acts also as a LHT-reactor
Extended shell long residence time
High temperature
Long polysaccharides cracked & viscosity reduced
Proper wetting on heat transfer surfaces
Duplex construction material
High alkali may cause Stress Corrosion Cracking (SCC)

Falling Film Concentrators

1st approach: FF Crystallizer

Keep

supersaturation low

Minimize evaporation/tube
Low Heat Flux (BTU/Sq.ft.)
Large surface area
High recirculation rate

High

cost and HP usage

Falling Film Concentrators

High

turndown capability

Moderate
Easily

HP consumption

automated

On-line

washing (switching type designs)

Falling Film Concentrators

Highly sensitive performance

Liquor chemistry changes
Soap and fiber
Poor operation at high viscosity
Distribution and heat transfer
Operation at high temperatures (Calcium
scaling)
Liquor Heat Treatment (Expensive)
Product %TS swings (Switching type designs)
High risk of plugging (Non-switching designs)

Forced Circulation Crystallizer

Reynolds Enhanced Crystallizer (REX)

Spiral

tube inserts disrupts the

boundary layer at the tube wall,

highest resistance to heat transfer
Apparent

Reynolds number in

the turbulent region even at high

liquor viscosities
High

U coefficient

Lower

tube velocities

Lower

HP

Forced Circulation Crystallizer

Boiling suppression
No

evaporation during heat transfer very low

supersaturation levels developed

Crystallization point is never exceeded within the

heaterEliminates uncontrolled scale formation

Liquor viscosity
Not

as much an issue: No film, no distribution device

Can

be operated at lower temperatures Lower risk for

liquor decomposition and hard scale formation

Forced Circulation Crystallizer

Excellent

resistance to scaling

Very

infrequent washing needed, if any

High

tolerance to liquor chemistry swings

High

turndown capability

Moderate
Easily

HP consumption

automated

Simple

and robust

Falling Film (FF) Multiple Effect Evaporation

Film

created by mechanical means

Liquor recirculation and distribution device
No minimum T issues
Higher efficiencies achievable

Falling Film (FF) Multiple Effect Evaporation

Several

7 and 8 effect FF trains

High

turndown
~ 20% of design rate

Modern

mills can rely on a single

line of FF evaporators
Easily matches evaporation
demand from production

Typical Evaporation plant, evaporation 330 t/h

Falling film lamella surface for high dry solids

Steam
flowing in
INSIDE
lamellas

Liquor film
flowing
Downwards
OUTSIDE
lamellas

Heat surface
Wide turn down ratio, 30-100 % from capacity.
Enabled by internal liquor circulation
High turbulence liquor film
Non plugging design & good self cleaning
properties compared to tubular design

High Solids Technology

Enhanced
FC
Crystallize
r
F
F
Crystallizer
S
w
i
t
c
h
i
n
g
F
F
Evaporator

wt-% BLS

Soluble Na2SO4 + Na2CO3,

Crystallization technology & twin tank -concept

Total solids content, %

DS << 1st critical

point
DS >> 1st critical
point
DS >> 1st critical
point

Crystallization technology & twin tank -concept

All concentrator bodies operated over 1st critical point all the time. No crystallization on
heat transfer surfaces
Constant feed to concentrators from HBL storage tank and no flow order switching
Constant temp & DS-%
Smooth & steady operation slows up corrosion and fouling
No bypassing of 1st critical point in effect 1
Constant & smooth feed to RB from FL storage tank. Also liquor from HBL storage tank
can be used as RB feed
Low washing frequency, only 3 concentrator bodies needed
All concentrator bodies produce firing liquor

Chemicals in black liquor

In a closed circulation mill, salts & NPEs

accumulate into liquor cycle
Evaporation plant is located at the intersection of
different process stream
Challenge to manage scaling & corrosion issues in
evaporation plant, caused by various chemical
compounds

Fouling areas in evaporation plant

Material selection for high dry solids evaporator

General corrosion & Stress Corrosion Cranking (SCC) caused by high temperature, alkali
& tensions in steel
Liquor alkali concentration & temperature increases with dry solids
Avoid dry spots on heat surfaces, proper wetting!!
No SCC on duplex or LDX, SCC occurs 316 > 304 > duplex
General corrosion in AISI 316 5-10 times faster than in duplex & AISI 304

General corrosion steady &

predictable process

SCC, rapid &

unpredicted process

Handling of secondary condensates

Sustainable technology

Duct Stripper technology

Traditional stripper technology
Segregative lamellas
Dedicated condensing of dirty
secondary vapor fractions
Benefits for the mill

Challenges

Too much MeOH & COD in

condensates
High fresh water
consumption in mill
Need for warm water
High water treatment costs
Too much mill discharges
How to meet customers demands on
condensate qualities, with low
equipment & operating costs

Energy savings
More MeOH & TRS to
combustion
Replacement of fossil fuels
Energy efficient condensate heating
Lower water treatment costs
Closing mills water circulation

Condensate segregation inside lamellas

Evaporated secondary vapor out

Lamellas are acting as a

stripping column
Vent
Flow
1% M
eOH 1
0%
Foul C
o
Flow 1 ndensate
0% Me
OH 8 0
%

Secondar
y
Liquor out
Liquor in

Clean Condensate
Flow 89& MeOH 10%

vapor in

Counter current stripping of

condensate inside lamellas

Duct Stripper condensate cleaning system

Secondary condensate is sprayed into vapor
duct
Condensate is cleaned and heated
vapor flow

up by

MeOH-, sulfur- and other VOCs are routed

inside lamellas into foul condensate and vent
gases
Simple, flexible & easy to operate system

Integrated stripping and MeOH liquefaction in evaporation plant

Evaporation Technologies

Task of the evaporator

Take

a waste stream (WBL) and turn it into fuel (SBL)

for the recovery boiler

Condense

steam (or vapors) on one side of a heating

surface while boiling liquor on the other side

Process

governed by the heat transfer law

Q = U x A x T

 Q:

Heat exchange amount which can be accomplished

A:

Heat transfer surface

T:

Temperature differential
T = Sat. Vapor T In Liquor T Out

U:

Heat transfer coefficient, a measure of the resistance to

heat transfer
Depends

on heating surface material & cleanliness

Depends

on liquor properties & turbulence

Process Considerations at high solids

Precipitation of supersaturated components

14

Process Considerations at high solids

Precipitation

of supersaturated components
Units > ~ 50%TS must be designed as crystallizers
Control the precipitation process
Crystals form and grow within the liquor
Not as scale on the heat transfer surfaces

VS

Process Considerations at high solids

High liquor viscosity

Impacts heat transfer due to low turbulence
Impediment
Pressurized

to crystal growth
storage or heat treatment needed?

Temperature

becomes a critical design parameter

High temperatures enhance hard scaling risk

Process Considerations at high solids

Increased

corrosion tendencies
Stress Corrosion Cracking in 300 series SS due
to
High temperatures to control viscosity
High alkalinity at high %TS
Duplex

alloys required >75%TS

17

Photographs of evaporating black liquor falling film for three different circulation flows:
2.87 105 m3/s (Re 300), 1.11 104 m3/s (Re 2400) and 3.61 104 m3/s (Re 3800) for
the left, middle, and right images, respectively. The temperature was 110 oC and the
temperature difference between the heating steam and the evaporating black liquor film
was 8 oC

Detailed schematic of the bubble formation process in an evaporating,

falling black liquor film.

Operation conditions and fundamental results.

S.No.

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16

Dry solids
(kg/kg)

0.436
0.44
0.44
0.559
0.559
0.615
0.615
0.615
0.667
0.671
0.671
0.726
0.724
0.724
0.786
0.849

Liquor
Density (kg/m3) temperature
(C)
1220
1228
1228
1280
1280
1300
1300
1320
1340
1350
1350
1370
1390
1380
1420
1460

110
100
100
110
110
130
130
110
140
130
130
160
140
140
160
175

Heat flux
(W/m2)

11100
10200
10400
9300
9500
8400
8700
8900
8300
8400
8200
7400
6700
7800
4800
3500

Mass flow
rate (kg/m s)

0.89
0.9
2
0.52
2.04
0.91
2
2.02
2
0.91
2
2
0.91
2
2.1
1.5

Dynamic
viscosity (Pa s)

0.0017
0.0022
0.0022
0.0073
0.0073
0.016
0.012
0.012
0.017
0.028
0.028
0.028
0.067
0.067
0.16
0.57

Heat transfer
coefficient
(W/m2 K)
2190
1880
1970
1450
1600
1300
1550
1500
1400
1300
1350
1100
900
1150
600
140