CHEMICAL PULPING
Nordic Pulp & Paper Research Journal Vol 32 no 2, 2017 --- DOI 10.3183/NPPRJ-2017-32-02-p299-308
The Effect of Bulk Crystals on Sodium Salt Scaling in
Black Liquor Evaporators
Erik Karlsson, Mathias Gourdon and Lennart Vamling
KEYWORDS: Crystallization fouling, Scaling, Falling
film evaporation, Sodium carbonate, Black liquor
ABSTRACT: Black liquor evaporation is an essential unit
operation in the chemical recovery cycle of a pulp mill.
The high concentrations of sodium carbonate and sodium
sulphate in black liquor cause crystallization fouling, or
scaling, in the concentrator effect, which affects the
operation negatively.
The focus of this work was to evaluate the effect the
content and size of the bulk crystals had on the scaling rate
of the sodium salts. This was done experimentally by
evaporating both pure sodium carbonate solution (to
crystallize anhydrous sodium carbonate) and black liquor.
It was found that bulk crystals were required to suppress
rapid scaling during primary nucleation (when passing the
metastable limit), which was tenfold higher than scaling
during continuous crystallization under steady-state
operation. The amount of bulk crystals did not, however,
affect the scaling rate during continuous crystallization. It
was also found that the scaling rate increased when the
largest crystals were removed, in this case by a
hydrocyclone. The results were similar for both sodium
carbonate solutions and black liquor, although the latter
had a finer crystal size and scale structure.
ADDRESSES OF THE AUTHORS:
Erik Karlsson (erik.karlsson@chalmers.se),
Mathias Gourdon (mathias.gourdon@chalmers.se),
Lennart Vamling (lennart.vamling@chalmers.se):
Chalmers University of Technology, Dept. of Chemistry
and Chemical Engineering, Division of Chemical
Engineering, SE-412 96 Gothenburg, Sweden.
Corresponding author: Erik Karlsson
Introduction
Black liquor is an essential stream in the pulp mill because
it contains not only the spent cooking chemicals but also
dissolved wood components, that, when combusted, can
provide process steam and electricity. Evaporation is
required to allow for its combustion in the recovery boiler:
its concentration is increased from 15-20% to 75% or
higher in the evaporation plant. This is an energy-intense
unit operation, making the evaporation plant the part of the
pulp mill that consumes the most steam (Gullichsen and
Fogelholm 1999).
A significant issue associated with the evaporation of
black liquor is fouling: more than 40% of Swedish mills
have reported that this is a problem (Haag and Stigson
2003). The crystallization of water-soluble sodium salts
(mainly crystals containing sodium, carbonate and
sulphate) is one of the most common causes of fouling, and
regular cleaning is normally necessary to avoid process
stops (Schmidl and Frederick 1998). This type of fouling,
involving crystallization or precipitation, is often called
scaling, and is the term used throughout here.
299
Sodium salt scaling is not only common, it also has the
potential of fouling an evaporator effect completely:
within hours under the worst possible conditions (Karlsson
et al. 2013a). The potential high rate of scaling is a
consequence of the high concentration of the sodium salts:
black liquor solids typically consist (by weight) of 10 %
sodium carbonate and 5 % sodium sulphate (Schmidl and
Frederick 1998).
The solubility limit of the sodium carbonate and sodium
sulphate system in black liquor is typically exceeded at a
dry solid content (DS) of about 50%. This means that the
concentrator actually operates as a crystallizer, making
scaling more or less unavoidable (Adams 2001). On the
other hand, sodium salts dissolve rapidly in water and are
therefore relatively easy to remove. Cleaning (or boil-out)
is normally performed by feeding condensate, or black
liquor at low concentration, into the evaporator effect for
a time sufficiently long to dissolve the scales (Karlsson et
al. 2015; Verrill and DeMartini 2006).
Crystallization of sodium salts and scaling
The solubility of the sodium carbonate and sodium
sulphate system will be exceeded as the liquor is
concentrated in the evaporator plant. Crystallization will,
however, only occur on crystal surfaces of the same
species: if none are available, then crystallization will not
occur despite reaching supersaturation (Frederick et al.
2004; Mersmann 2001). Nuclei or seeds need to be formed
before crystallization can begin. It is first when
supersaturation reaches a critical limit, called the
metastable limit, that nucleation will start spontaneously
(Mullin 2001). The term primary nucleation is used for this
event to distinguish it from secondary nucleation, in which
new nuclei are formed by fragments breaking loose from
existing crystals. In pilot experiments the degree of
supersaturation at the metastable limit has been measured
as being 14-25% in black liquor (Gourdon et al. 2010a).
The composition of the crystals formed depends on the
molar ratio of sodium carbonate and sodium sulphate in
the solution, which is defined as x = Na2CO3 / (Na2CO3 +
Na2SO4), and temperature (Shi et al. 2003). The two most
important crystals in terms of the formation of scale in
black liquor evaporators are burkeite, with an composition
of 1.6-2.6Na2SO4·Na2CO3, and sodium sulphate
dicarbonate (referred to as dicarbonate hereafter), with an
composition of Na2SO4·1.6-3.0Na2CO3, where the latter is
reported as having a significantly higher tendency to form
scales at the heat transfer surface (DeMartini and Frederick
Jr. 2008; Gourdon et al. 2010b). When crystallizing from
black liquor, burkeite will typically form in the region 0.2
< x < 0.68 and dicarbonate in 0.82 < x < 0.9. There are
indications that a third double salt, sodium carbonate
sulphate ≈1.5Na2SO4·Na2CO3, forms in the region 0.68 <
x < 0.82 and shows potential to cause rapid scaling
(DeMartini and Frederick Jr. 2008).These salts, which are
formed above about 30°C, have inverse solubility: their
 CHEMICAL PULPING
Nordic Pulp & Paper Research Journal Vol 32 no 2, 2017 --- DOI 10.3183/NPPRJ-2017-32-02-p299-308

solubility decreases as the temperature increases Wash liquid

(DeMartini and Verrill 2007). Evaporator TI RI FI DI
z(m)
achieved by direct crystallization and not just by
agglomeration. Another factor influencing the scaling rate 0 Condenser
is the concentration profile along the heat transfer surface
0.15
(Gourdon 2011): e.g. a higher temperature difference (or Cooling
heat flux) and/or a lower flow rate gives a higher scaling TI Water
rate. Gourdon et al. (2010c) showed that scales start to
grow at the bottom part of the evaporators heat transfer PI
surface. They also showed that the internal residence time Condensate
 
did not affect the scaling rate (for the range investigated of 1.9
Outflow
approx. 1-4 min.). FI
The formation of scales can be divided in two steps (Bott
1997):
 Initiation: the first crystals are formed on the heat Scale  DI
transfer surface, often after a certain time known as 3.9 thickness  CLD
the induction or initiation period. measure‐ VI
ment
 Growth: scales grow on the crystal surfaces 4.5
available. Buffer 
The first step is probably the most crucial as, once tank LI
Feed
FI TI TI
formed, scales will grow also at lower levels of Hydro‐
supersaturation. There are two possible mechanisms for PI cyclone Sampling
the formation of scales (Mullin 2001): (fine)
 Crystallization of the dissolved salts.
Steam  Steam Wash  Sampling Sampling
 Deposition of existing crystals. condensate liquid Incl. filtration (coarse)
In the case of initiation, the first mechanism gives
nucleation on the surface, which is dependent on the Fig 1 - Simplified flowsheet of the pilot falling film evaporator
surface properties: cavities in the material can, for plant. The valves are set to indicate normal operation with the
example, catalyse nucleation (Mullin 2001). Experiments coarse fraction from the hydrocyclone to the evaporator (white
have shown that the rate of surface nucleation can be valve = closed). Abbreviations for sensors: CLD = chord length
reduced considerably by making the surface very smooth distribution, D = density, F = flow rate, L = level, P = pressure, R
and having a low affinity for the crystallizing salts = refractive index, T = temperature and V = viscosity.
(Mersmann 2001). The deposition of existing (bulk)
crystals can potentially give very high rates of scale influences the scaling rate. The experiments were
formation, as it is not limited by the crystallization rate, but performed on a pilot scale under industrial-like conditions.
is more likely for small crystals (<50 µm) as they have a Both sodium carbonate solution and black liquor were
stronger tendency to agglomerate (Mullin 2001). studied in order to obtain a deeper understanding of the
As shown by both Gourdon et al. (2010c) and Karlsson phenomena involved.
et al. (2013a), the scaling rate is significantly higher at
nucleation (i.e. when passing the metastable limit)
Experimental
The strategy of the experiments was to run the pilot
compared to continuous crystallization during steady-state
evaporator under steady-state conditions long enough to
operation. A general guideline is therefore to avoid
form a significant amount of scales, and thereby acquire
operation at DS close to solubility (or the metastable limit).
high quality data for the scaling rate. The bulk crystal
Apart from crystallization at the heat transfer surface,
population was varied between the experiments by using a
crystals will also form and grow in the bulk phase. The
hydrocyclone in some cases.
competition between surface and bulk crystallization
determines just how much of the potential scaling will Equipment
actually occur. Moreover, these phenomena are The flowsheet in Fig 1 shows the most important
complicated to model and predict because they involve the equipment and sensors in the pilot evaporator used in this
chemistry of the solution and surface as well as molecular study. The evaporator itself was of the vertical falling film
mass transport phenomena (Zhao and Chen 2011). To our type, with the liquor on the outside of a vertical tube. It
knowledge, no publications are available that study how was designed to be large enough to produce results
bulk crystal population influences scaling (at least not for relevant to industrial conditions and simultaneously be
continuous crystallization during steady-state operation), sufficiently flexible to be able to simulate a high variety of
although the question is commonly discussed, e.g. by operational conditions. The evaporator tube was 4.5 m
Frederick and Euhus (2015). long with an outer diameter of 60 mm, which gave it an
The aim of this work was to provide new insight into the active outer heat transfer area of 0.85 m2. The tube was
link between bulk and surface crystallization by heated on the inside with condensing saturated steam.
experimentally studying how the bulk crystal population Further details of the pilot evaporator can be found in
Gourdon (2009).

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Nordic Pulp & Paper Research Journal Vol 32 no 2, 2017 --- DOI 10.3183/NPPRJ-2017-32-02-p299-308
73 221
(mm)
25
ID 12.6
ID 41.9
ID 16.1
Fig 2 - Drawing of the hydrocyclone installed in the pilot
evaporator plant, where ID denotes the inner diameter. The inlet
is from below, the fine fraction leaves to the left and the coarse
fraction leaves to the right in the figure.
The salt solution or black liquor was fed to the top of the
evaporator using a circulation pump: an overflow
distributor integrated into the top of the tube ensured that
a circumferentially-uniform liquid distribution of a variety
of flow rates was obtained. The vapour and the
concentrated liquid flowed from the evaporator tube into a
tank serving both as a buffer volume (about 50 l) and
vapour-liquid separator. The bottom of the tank was then
connected to the circulation pump as shown in Fig 1; the
vapour flowed into a condenser controlling the pressure in
the system.
A hydrocyclone was used in order to change the crystal
composition of the bulk. It was designed to separate
particles larger than 50 µm at a viscosity of 50 mPa·s and
an inflow of 900 l/h. The dimensions of the hydrocyclone
are shown in Fig 2. It was installed together with a number
of valves that enabled two operational modes, where either
the fine (top) or coarse (bottom) fraction was fed into the
evaporator (Fig 1). The other fraction was recirculated
back to the buffer tank. The valves also enabled
measurements to be made of the chord length distribution
(CLD) of the bulk crystals in both the fine and coarse
fractions, but only one at a time. The sensor used was
focused beam reflectance measurement (Mettler Toledo
Lasentec FBRM D600L): it is described further in
Gourdon et al. (2008) and the performance of the
hydrocyclone is described further in Karlsson et al. (2016).
The pilot evaporator was equipped with sensors to
monitor the operation and acquire data: the most important
sensors are shown in Fig 1. The flow rate and density were
measured using Endress and Hauser Promass Coriolis
meters with a stated accuracy of 0.15% for flow rate and
0.5 kg/m3 for density. PT100 meters were used to measure
temperature with a stated accuracy of 0.1 K. Yokogawa
EJA meters were used to measure pressure with a stated
accuracy of 0.20%. The refractive index was measured at
589 nm using K-Patent PR-23-SD with a stated accuracy
of 0.0002.
Monitoring bulk crystals
Two different methods were used to determine the amount
of bulk crystals contained in the stream entering the
evaporator. In the experiments with salt solutions, density
measurements were used and the crystal fraction (cf) was
calculated as follows. From the conservation of mass (m)
and volume (V), two balance equations can be defined:
CHEMICAL PULPING
, [1]
. [2]
As density (ρ) is the property being measured, the
following definitions are also needed:
ID 16.1 , [3]
, [4]
. [5]
The crystal fraction, cf = mcrystals/mtotal, as a function of
the densities can be derived from Eq 1-5, giving the
following expression:
1 1
. [6]
1 1
Value from the literature was used for the density of the
crystals, which should be close to burkeite, i.e. 2570 kg/m3
(Giuseppetti et al. 1988), and the total density was
measured during the experiments. The density of the
saturated solution was obtained from measurements of
refractive index, which is unaffected by the presence of
crystals. The relationship between refractive index and
solution density was measured by evaporation a salt
solution in which no crystals were present under equal
operational conditions, i.e. by increasing the concentration
gradually from below solubility to metastable. This
procedure is also reported by Gourdon et al. (2010b).
During steady-state operation, with a well-developed
population of bulk crystals, the solution was saturated in
the streams where the density was measured (i.e. the
retention time in the buffer tank was sufficiently long to
allow equilibrium to be reached between the bulk crystals
and the solution).
A different method was used to calculate the crystal
fraction in the black liquor: being a complex mixture, its
density is not only dependent on salt and crystal content.
Instead, samples were taken and the dry solids content
analysed. The crystal fraction could then be calculated by
taking samples of liquor both with crystals and without
(i.e. removed by filtering). The following expression was
derived from a mass balance over the filter:
, [7]
1
where DS refer to the dry solids mass fraction in the
filtered and unfiltered samples.
The online sample filtration method developed by
Gourdon (2009) was used. A filtration unit was connected
to a stream that was recirculated over the recirculation
pump shown in Fig 1; a sintered filter element with 7 µm
pore size was used. Based on the distribution in Fig 5, it
was found that the crystals small enough to pass through
the filter constituted only a negligible part of the total mass
301
 CHEMICAL PULPING
Nordic Pulp & Paper Research Journal Vol 32 no 2, 2017 --- DOI 10.3183/NPPRJ-2017-32-02-p299-308
of crystals. The methods used to determine the crystal
fraction are also described in Karlsson et al. (2016).
Sampling failed in some of the experiments with black
liquor, so density measurements were used instead to
estimate the crystal fraction. The accuracy of the crystal
fractions determined was estimated to 0.5 percentage
points for both the salt solution and the black liquor.
The chord length distribution of the bulk crystals was
also monitored. However, the instrument was used mainly
for experiments with salt solution: when the Lasentec
FBRM (Focused Beam Reflectance Measurement) sensor
was used for black liquor, the light from the laser was
absorbed by the (black) liquor and the visibility of the
particles (crystals) changed with the dry solids content.
The chords represent random cross-cuts through the
particles studied, and are therefore related to the particle
sizes. The chord length distribution of spherical particles
will be close to the particle size distribution because the
most probable chord lengths are close to the diameter (Li
and Wilkinson 2005). The total chord count in the system
studied here was found to be correlated to the crystal
fraction.
Monitoring scaling
The rate of scaling was monitored using both total and
local heat transfer. The total heat transfer coefficient (i.e.
the average of the entire heat transfer surface) was
calculated from the flow rate of the heating steam
condensate, as described in Karlsson et al. (2013b). Local
heat transfer coefficients were also calculated at different
vertical and circumferential positions along the evaporator
tube using the temperature difference measured by pairs of
thermocouples installed in the tube wall: see Johansson et
al. (2006) for details. Six local positions were studied in
this work, with distances from the top of the tube of 0.4 m,
2.4 m, 2.9 m, 3.4 m and two at 3.9 m (i.e. on opposite
sides).
A decreasing trend in the calculated heat transfer
coefficient means scaling when all other operational
parameters are kept constant. The scaling observed was
quantified by converting the heat transfer trends into
fouling resistance acording to the following expression
(Bott 1995):
1 1
. [8]
The next step was to convert the fouling resistance trend
into a measure of the rate of scaling. This was done by
linearising the trend and dividing it by time (i.e. the
duration of experiment), which gave the expression ΔR/Δt
((m2K/W)/min). The rates of scaling were unfortunately
not always constant, tending to be higher at the beginning
of experiments. An uncertainty range was calculated for
each experiment to evaluate the errors due to linearization
and measurement uncertainties.
Experimental conditions
The experiments are categorized, and the operational
conditions summarized, in Table 1. The conditions were
chosen to correspond to the situation in industry, i.e. the
concentrator effect where crystallization is taking place.
The two most important parameters to test were crystal
302
Table 1 - General operational conditions of the experiments.
Exp. Dry solids Temp. Wetting rate Hydrocyclone
series content diff. operation
Salt N1 ≈33% 10°C 1 kg/(m·s) Total/Coarse
Salt C1 30-35% 10°C 1 kg/(m·s) Total/Fine/Coarse
Salt C2 30-35% 25°C 1 kg/(m·s) Total
Salt C3 30-35% 25°C 2 kg/(m·s) Total
Liq. N1 ≈52% 10°C 1 kg/(m·s) Coarse
Liq. N2 ≈52% 15°C 1 kg/(m·s) Coarse
Liq. C1 55-56% 10°C 1 kg/(m·s) Fine/Coarse
Liq. C2 55-56% 15°C 1 kg/(m·s) Fine/Coarse
Liq. C3 55-56% 15°C 0.4 kg/(m·s) Fine/Coarse
fraction, in the range 0-6%, and hydrocyclone
fractionation. The driving force for heat transfer, i.e. the
temperature difference, was tested both at a normal value
(10°C) and a higher value to promote higher scaling rates
(15°C or 25°C depending on experimental limitations). A
wetting rate (Γ) of 1 kg/(m·s) was mainly used, although
significantly higher and lower rates were also tested to see
how that affected the scaling. Wetting rate is defined here
as the mass flow rate to the evaporator tube divided by the
circumference of the tube (Schnabel 2010).
The majority of the experiments were performed in
steady-state mode with continuous crystallization, denoted
Salt C# and Liq. C# in Table 1, with the purpose of
measuring the rate of scaling at different crystal fractions.
Three experimental series, with different experimental
conditions, were performed for both the salt solution and
black liquor; nucleation scaling was studied (Salt N# and
Liq. N#) as a reference.
The evaporation temperature was controlled by the
condenser and conducted at 120°C for all of the
experiments. The temperature difference was altered by
adjusting the temperature of the steam. For the salt
experiments, the dry solids content was directly
proportional to the mass fraction of crystals and, therefore,
varied slightly between the experiments. In the case of
black liquor, on the other hand, the dry solids content was
relatively constant (with the exception of a lower value at
nucleation) in spite of the fact that the crystal fraction
varied. This is possible because black liquor is comprised
of several other components that can decrease in amount
as crystals are being enriched in the system.
The experiments were prepared by first filling the system
with the salt solution or black liquor, and then heating and
evaporating it to the desired conditions. Depending on the
type of scaling experiment, i.e. nucleation or continuous
crystallization, slightly different procedures were
employed.
Nucleation (N) experiments: The salt solution or liquor
was concentrated from below solubility to supersaturation;
at a certain point the concentration became high enough
(the metastable limit) to trigger primary nucleation and
initiate scaling. Measurements continued until the scaling
rate decreased significantly or the evaporation process
stalled due to severe scaling; the time-scale was between
0.5 and 1 hour.
Continuous crystallization (C) experiments: In the
steady-state mode, vapour was removed as in the
 CHEMICAL PULPING
Nordic Pulp & Paper Research Journal Vol 32 no 2, 2017 --- DOI 10.3183/NPPRJ-2017-32-02-p299-308
nucleation experiments, but with fresh salt solution (below
solubility) or liquor (at 31% dry solids content) being fed
so that the density of the stream into the evaporator tube
was kept constant. Concentrated solution or liquor was
ejected to maintain a constant level in the buffer tank. This
procedure gave conditions close to an industrial evaporator
under steady-state operation.
A substantial amount of scales was often formed during
the initial preparation to reach the desired conditions: the
tube was therefore cleaned to ensure that the
measurements of fouling resistance began with no scales
being present. This was done by closing the valves into and
out from the evaporator, recirculating the salt solution or
liquor to the buffer tank to sustain mixing, and then
pumping in wash liquid, see Fig 1. This method enabled
cleaning with a minimum of disturbances; the system was
back in operation after a break, on average, of 5-10 min
(see Karlsson et al. (2013a) for details). In the salt solution
experiments, the crystal fraction could be controlled
directly by the set-point for the density in the stream into
the evaporator. The feed rate was then controlled
automatically to maintain a constant density: with the
exception of some fluctuations at the beginning, the crystal
fraction was therefore constant in the experiments. The
throughflow meant that both the crystal population and the
liquid solution were renewed continuously. In the black
liquor experiments, a density corresponding to 55% dry
solids content was set. The hydrocyclone was then used to
change the crystal fraction in the liquor and simultaneously
keep other properties as constant as possible.
Most of the steady-state salt experiments lasted for 5-22
hours: those with black liquor were more difficult and
ranged between 2-6 hours.
Hydrocyclone operation: The crystal population
entering the evaporator unit was changed for some of the
experiments, as shown in Table 1. This was achieved by
operating the hydrocyclone in three different modes:
 Total: the whole flow from the buffer tank was fed
into the evaporator, i.e. the hydrocyclone was not in
operation.
 Coarse: the coarse fraction (bottom fraction) was
fed into the evaporator unit. The fine fraction was
recirculated back to the buffer tank.
 Fine: the fine fraction (top fraction) was fed into the
evaporator unit. The coarse fraction was recirculated
back to the buffer tank.
Chemical characterization of the fluids
In the salt solution experiments sodium carbonate, with a
purity of 99.9%, was used to crystallize anhydrous sodium
carbonate; black liquor, originating from a Swedish Kraft
pulp mill processing softwood, was used in the other
experiments. The contents of the most important inorganic
compounds that compose the black liquor were analysed
by MoRe Research in Örnsköldsvik, Sweden, and are
reported in Table 2. Analysis of the dry solids content was
performed in-house, using the TAPPI 650 om-09 method.
Based on the molar ratio Na2CO3/( Na2CO3+ Na2SO4), the
crystal species most likely to form during the experiments
was burkeite (Shi and Rousseau 2003).
Pure sodium carbonate was evaporated instead of a
mixture of sodium carbonate and sodium sulphate because
303
Table 2 - Content of important inorganic compounds in the black
liquor.
Method Value Unit
Calcium SCAN-N 38 200 mg/kgdry
Potassium SCAN-N 38 20.6 g/kgdry
Sodium SCAN-N 38 199 g/kgdry
Carbonate SCAN-N 32 55.7 g/kgdry
Sulphate SCAN-N 6 43.6 g/kgdry
Dry solids content (DS) SCAN-N 22 31.4% by mass
Na2CO3/( Na2CO3+ Na2SO4) 0.67 mol/mol
Content Na2CO3 9.8% by dry mass
Content Na2SO4 6.5% by dry mass
it simplified the experiments substantially. When a salt
solution is being evaporated, a large part of the salt
crystallizes and, due to sedimentation, becomes inactive in
the experiment. Using a mixture of salts makes it difficult
to control the composition of the solution and thereby the
crystal species that is crystallizing. The scaling rate of pure
sodium carbonate is in the same range as burkeite and
dicarbonate, so the results here should be relevant to the
evaporation of black liquor (Gourdon et al. 2010b).
Results and discussion
Scaling rate of salt solution during nucleation
The scaling rates measured in the nucleation (N)
experiments using sodium carbonate solution are plotted
in Fig 3: here, two distinctly different behaviours can be
observed. In three of the experiments, a substantial amount
of bulk crystals was formed during nucleation: the crystal
fraction reached 2-3% at the end of the experiments. In the
four remaining experiments, very few bulk crystals were
detected by FBRM and density measurements: as little as
0-0.5%. The rate of scaling was high in both cases: after
15-30 minutes the evaporation capacity was halved.
Nevertheless, the figure also shows that there is no clear
correlation between the scaling rate and bulk crystal
fraction.
One important difference between the two behaviours
was that, when bulk crystals were available, the rate of
scaling decreased after an initial period of being high but,
when bulk crystals were absent, the system was fixed in a
situation where all crystallization occurred on the heat
transfer surface. In former case, evaporation could
therefore continue (with reduced capacity) following the
period of nucleation scaling. In the latter case, the absence
of crystals meant that the system eventually shut down due
to insufficient heat transfer. In all seven experiments the
degree of supersaturation was 3-5% at nucleation,
although it decreased more rapidly when bulk crystals
were available.
To the authors’ knowledge, the behaviour of nucleation
scaling with essentially no bulk crystals present has not
been reported to date in work related to the evaporation of
black liquor. The common explanation offered for the rate
of scaling being high during nucleation is that fine crystals
agglomerate and form scales (reported for burkeite and
dicarbonate by Frederick et al. (2004)). The new behaviour
seen here indicates that a fast scaling rate also can be
achieved by direct crystallization and not just by
agglomeration.

Nordic Pulp & Paper Research Journal Vol 32 no 2, 2017 --- DOI 10.3183/NPPRJ-2017-32-02-p299-308
ΔT=10°C, Γ=1 kg/(m∙s)
40
35
ΔR/Δt [(m2K/W)/min] ∙ 106
30
25
20
15
10
5
0 0
0,0% 0,5% 1,0% 1,5% 2,0%
Crystal fraction (by mass)
Fig 3 - Rate of scaling in the nucleation (N) experiments using
sodium carbonate solution. The crystal fraction was not constant
during the experiment: the value here refers to the maximum
value, reached in the later part of the experiments. Error bars
indicate errors due to linearization and measurement
uncertainties
Finally, it is of interest to mention that, in one of the
nucleation experiments with few bulk crystals present, a
majority of the scales fell off after a time lapse of 9
minutes. However, new scales were formed within
minutes and, taking the whole experiment into
consideration, the scaling rate was relatively unaffected by
this event.
Scaling rate of salt solution during continuous
crystallization
Fig 4 shows the scaling rates obtained in the continuous
crystallization experiments using sodium carbonate
solution. These rates were about one-tenth of those in the
nucleation experiments measured under the same
operational conditions, which agrees with previous
reports. The rate of scaling in the two, steady-state,
crystallization experiments with a temperature difference
of 25°C (series: Salt C2 and C3) was of the same order of
magnitude as for the nucleation experiments with a
temperature difference of 10°C. A wetting rate of 1
kg/(m·s) gave a significantly higher scaling rate than 2
kg/(m·s).
It was found that the scaling rate was higher when the
operation was unstable. The two points labelled “unstable”
in Fig 4 suffered from crystals plugging the pipe entering
the evaporator unit. This resulted in poor wetting of the
heat transfer surface for one of the experiments and the
initiation of a short period of rapid scaling in the other.
An important result was that the rate of scaling was
unaffected by the crystal fraction during steady-state
operation with continuous crystallization: this can be seen
in Fig 4 when the points with unstable operation and
operation in fine mode are excluded. In the beginning of
all these experiments, the formation of scales was initiated
on the lowest parts of the tube up to a certain height (about
0.8 m from the bottom). The scales just grew thicker there
from then on, independent of the crystal fraction, while the
remainder of the tube remained clean. In the fine and
CHEMICAL PULPING
ΔT=10°C, Γ=1 kg/(m∙s) ΔT=25°C, Γ=1 kg/(m∙s)
ΔT=25°C, Γ 2=kg/(m∙s)
20
18
ΔR/Δt [(m2K/W)/min] ∙ 106
16
14
12
10
8
Fine
6 Unstable
4
2   Unstable
  Coarse
       
2,5% 3,0% 0,0% 1,0% 2,0% 3,0% 4,0% 5,0% 6,0%
Crystal fraction (by mass)
Fig 4 - Rate of scaling in the continuous crystallization (C)
experients using sodium carbonate solution. Coarse and fine
refer to the hydrocyclone operational modes used. Experiments
without comment were conducted without hydrocyclone
fractionation. Error bars indicate errors due to linearization and
measurement uncertainties.
unstable experiments, however, the formation of scales
was also initiated higher up at the tube.
Although it may seem like there is some disagreement
regarding the importance of bulk crystals when the
nucleation and continuous crystallization experiments are
compared, there are some important differences between
the experiments that should be emphasized. The rate of
crystallization was significantly higher in the nucleation
experiments, which started with a supersaturated solution
and, unlike the continuous crystallization experiments, had
no inflow that diluted the solution. The necessity of having
bulk crystals to neutralize the supersaturation is hence
greater in nucleation experiments. In the continuous
crystallization experiments, sufficient crystal surfaces
(bulk crystals and scales) were available to avoid the build-
up of supersaturation even at the lowest crystal fractions
measured.
The crystal population was altered by the hydrocyclone
operation. No significant difference in the rate of scaling
was observed when the coarse mode (i.e. the small crystals
were removed) was compared to the total mode (when the
hydrocyclone was not used). In the fine mode (i.e. the
coarse crystals were removed), on the other hand, the rate
of scaling was significantly higher than for the other
modes. Unfortunately, only one experiment was conducted
in the fine mode due to operational difficulties: the outflow
was plugged due to the high content of crystals in the
recirculation flow to the buffer tank.
Measurements of chord length distributions were used to
evaluate the hydrocyclone operation and how it affected
the crystal population (Fig 5). Long chords always mean
that particles of that size are present, whereas shorter
chords can come from both small and large particles: the
latter is especially true for particles that are acute or oblong
in shape. Many of the larger bulk crystals here were
probably agglomerates, which can produce many short
chord counts. Chord counts relate mainly to the number of
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0.9% Tot 0.9% Fine ΔT=10°C, Γ=1 kg/(m∙s) ΔT=15°C, Γ=1 kg/(m∙s)

ΔT=15°C, Γ=0.4 kg/(m∙s)
1.9% Tot 2.6% Tot 3,0
2.9% Coarse 5.2% Tot
2,5

ΔR/Δt [(m2K/W)/min] ∙ 106
300
2,0 Fine
250
Chord count [#/s]

1,5
200 Fine
1,0 Fine Coarse
150
Fine Coarse
100 0,5 Coarse

50 0,0
Coarse
0 ‐0,5
1 10 100 1000 0,0% 1,0% 2,0% 3,0% 4,0% 5,0% 6,0%
Chord length [µm] Crystal fraction (by mass)

Fig 5 - Cord length distributions measured using FBRM for some
of the experiments using sodium carbonate solution. Each series
is labelled with the crystal fraction (mass percentage) and the
hydrocyclone operational mode used.
particles while the crystal fraction relates to the total mass,
of which the large particles often constitute the majority.
The experiment in fine mode (0.9% crystal fraction) had
significantly fewer chord counts from large crystals
compared to experiments in coarse and total modes
(Fig 5). The chord counts were significantly lower at 40
µm, and no particles were detected above 100 µm. The
experiment in fine mode also had significantly higher
chord counts of fines compared to experiments in total
mode at the same crystal fraction (0.9%). There are
therefore two possible explanations for the high scaling
rate in fine mode: the lack of larger crystals or the high
content of smaller crystals. However, in comparison with
the experiments at higher crystal fractions, there is no clear
evidence from FBRM (Fig 5) that the experiment in fine
mode had a significantly higher number of fine crystals.
Therefore, the lack of larger crystals is the most reasonable
explanation for the high scaling rate.
When the chord length distributions between coarse and
total modes were compared, no significant difference
could be detected. Both these observations agree with the
results obtained for the rate of scaling, i.e. that only the
experiment in fine mode showed significant differences,
thus providing further evidence that large crystals are
necessary if rapid scaling is to be avoided.
Fig 5 illustrates that a higher fraction of crystals resulted
in a higher chord count for all chord lengths below a
maximum length of about 300 µm. There were, however,
some variations between the experiments: for example, the
experiment with a crystal fraction of 1.9% had a higher
ratio between the large and short counts than the other
experiments in total and coarse modes.
Scaling rate of black liquor
The results from continuous crystallization experiments
using black liquor are presented in Fig 6, while those from
the nucleation experiments are reported in Table 3. In
conformity with salt solution, the rate of scaling in black
liquor was found to be tenfold higher during nucleation
than in steady-state operation with continuous
crystallization. The influences of temperature difference
Fig 6 - Ratio of scaling in the continuous crystallization (C)
experiments with black liquor. Coarse and fine refer to the
hydrocyclone operational modes used. Error bars indicate errors
due to linearization and measurement uncertainties.
and the rate of wetting also agreed with the results obtained
from the salt solution experiments: the rate of scaling was
higher when the temperature difference was high and when
the flow rate was low (during both nucleation and
continuous crystallization). These results agree with the
observations by Gourdon (2011), i.e. that there is a positive
correlation between concentration increase along the heat
transfer surface and scaling rate.
In the case of the two continuous crystallization
experiments at a temperature difference of 10°C (series
Liq. C1), the scaling rate was significantly higher when
operating in fine mode (Fig 6). As they both had the same
fraction of crystals, this clearly shows that the crystal size
itself affects scaling. A small amount of scales can actually
improve heat transfer due to increased turbulence, and is
believed to be the cause of the scaling rate being negative
in the experiment in coarse mode: this is a common
behaviour when scales are being initiated.
The results from the continuous crystallization
experiments at a temperature difference of 15°C (series
Liq. C2 and C3) are less clear: the experiments in fine
mode had lower fractions of crystals than in coarse mode.
Fine mode resulted nevertheless in a higher rate of scaling
at wetting rates of both 0.4 kg/(m·s) and 1 kg/(m·s),
although it could not be determined whether this is because
the crystals are smaller in size or the crystal fraction is
smaller. Comparing the three experiments in coarse mode
(15°C), there is no indication of a decrease in the rate of
scaling at higher fractions of crystals: it may be noted that
the point at 0.4 kg/(m·s) was more likely to have a higher
rate of scaling (due to the low flow rate) than the two
points at 1 kg/(m·s).
Table 3 - Rate of scaling in the nucleation (N) experiments with
black liquor.
Temp. Wetting Hydrocyclone Scaling rate·106
difference rate operational mode
10°C 1 kg/(m·s) Coarse 9.5 (m2K/W)/min
10°C 1 kg/(m·s) Coarse 8.3 (m2K/W)/min
15°C 1 kg/(m·s) Coarse 13 (m2K/W)/min

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a b
c d
e f
Fig 7 - Photographs from experiments with sodium carbonate
solution (a-e) and black liquor (f).
The experiments with salt solution and black liquor
showed similar behaviour for all the parameters discussed.
Consequently, conclusions drawn from the salt
experiments are likely to be valid for black liquor.
Growth behaviour of scales
Visual observations revealed that the growth behaviour
and appearance of the scales varied: some typical
examples are shown in Fig 7. The experiments with salt
solution (Fig 7a-e) showed greater variations, and the
scales where normally thicker at the end of the experiment.
Scales from salt solution could also be comprised of large
formations (knobs and ridges in centimetre size). The
scales were polycrystalline in appearance: white scales
that were grainy in structure. This can be compared to the
scales formed from sodium carbonate monohydrate
(evaporation at 80°C during preparation of the
experiments), which had a monocrystalline appearance:
glass-like scales that were more transparent in nature, with
306
10 mm
Fig 8 - Typical structure of scales resulting from black liquor. The
scales, which were washed gently prior to being photographed,
had a thickness of about 1.5 mm.
a much smaller tendency to crystallize on the heat transfer
surface.
Smooth and evenly-distributed scales (Fig 7b) were more
common during nucleation or at high evaporation rates
(experiments at 25°C temperature difference). The scales
grew evenly on the heat transfer surface, propagating as a
front moving upward from the lowest part (Fig 7a) and,
finally, covered most of the tube (Gourdon et al. (2010c)
also observed that the growth started from the lowest part).
During continuous crystallization at 10°C temperature
difference, the scales were only initiated in patches (Fig
7c) up to a certain height, after which they grew into larger
structures (clumps). These structures eventually grew
together to cover the whole heat transfer surface but, due
to the low initiation rate of scaling, some areas remained
clean throughout the duration of the experiments (Fig 7d).
The two growth behaviours are probably related to the
degree of supersaturation, as the initiation of the growth of
scales at the heat transfer surface requires a higher degree
of supersaturation compared to crystallization on existing
scales and bulk crystals. When the scales grew evenly
(Fig 7a-b), initiation was substantial and rapid, leading to
the formation of a smooth surface: the degree of super-
saturation was also higher here than for the patchy
behaviour.
The growth behaviour is connected directly to the rate of
scaling acquired from the heat transfer measurements
(Fig 3 and Fig 4): a thick layer of scales on a small part of
the tube resulted in significantly lower levels of heat
transfer resistance compared to a thin layer of scales on a
large part of the tube.
In the longest (>10 h) salt experiments, it was common
that soft scales were also formed in the lower part of the
evaporator (Fig 7e). These soft scales consisted of bulk
crystals that had settled: they had a snow-like appearance
and were loosely attached to the inner part of hard scales.
The soft scales in the top right area of Fig 7e could be
removed by a gentle touch.
Scales formed during the evaporation of black liquor
showed smaller variations; they were more evenly
distributed and did not form large clumps (Fig 7f). Their
surface had a structure similar to that of coarse sandpaper.
Fig 8 shows how they grew as small grains and were
evenly distributed. As the scales became thicker, the grains
grew together to form a coherent layer of scale which,
however, was not perfectly smooth.
The difference in the growth behaviour between the salt
solution and the black liquor can be explained by transport
phenomena, in which viscosity is an important parameter:
it was about ten times higher in the experiments using
black liquor. Assuming that the Stokes-Einstein relation,
which gives a relation between viscosity and diffusivity, is
valid here (Welty et al. 2009), the diffusivity was then
about ten times lower. The growth of crystals is either
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limited by diffusion (the transportation of ions to the
crystal’s surface) or integration (the integration of ions in
the crystal’s lattice). The difference in both the viscosity
of and diffusivity in black liquor decreases the convection-
diffusion transport of salt ions to the crystal surfaces, and
thereby limits the rate of crystallization. This can lead to
higher degrees of supersaturation in black liquor, which
might explain why scales are initiated more evenly.
Small crystals are often limited by integration, while
large crystals are limited by diffusion (Mersmann 2001).
One hypothesis is that the lower diffusivity of black liquor
causes its bulk crystals to be smaller in size: this also
agrees with the visual observations made. Bulk crystals
grow not only by crystallization but also agglomeration,
although high viscosity and low diffusivity decrease the
latter (Mersmann 2001), which also strengthens the
hypothesis.
Discussion on scaling mechanisms
One of the most important questions in understanding
sodium scaling is that of how scales are formed: i.e.
initiation and subsequent growth. There are two possible
answers: either by direct crystallization or the
agglomeration of (fine) bulk crystals on the heat transfer
surface. Once crystal surfaces have been formed, it
becomes easier for scales to grow. Frederick et al. (2004)
identified the rapid growth that occurs during nucleation
as being caused by the agglomeration of fine bulk crystals
on the heat transfer surface, whereas the growth of crystals
resulting from direct crystallization from supersaturated
solution causes scaling during continuous crystallization.
The same mechanisms were observed for both burkeite
and dicarbonate. It is then interesting to note that, in the
nucleation scaling experiments performed in this study
using sodium carbonate, fast scaling also occurred with
few bulk crystals, thus contradicting the finding that a high
rate of scaling is caused by the agglomeration of fine
particles. It seems that more research is necessary on how
scales are initiated and grow: knowledge that can be
valuable in discovering new mitigation strategies.
It should be beneficial to remove fine crystals if their
agglomeration produces scales. The results found here,
however, show the importance of keeping large crystals in
the system: they likely serve as an alternative (competing)
place for fine crystals to agglomerate, because they are less
stagnant in the flow, and are therefore more effective in
reducing supersaturation even though they have a smaller
surface area than fines.
Conclusions
Evaporation during primary nucleation (when exceeding
the metastable limit) gives the most severe scaling, with a
rate of scaling tenfold higher than for continuous
crystallization during steady-state operation. A certain
quantity of bulk crystals is required to address this high
scaling rate: all crystallization will otherwise continue to
occur at the heat transfer surface. This will lead to losses
in the evaporation capacity and immediate cleaning will be
necessary.
The fraction of the bulk crystal has no significant effect
on the rate of scaling during continuous crystallization in
steady-state mode under the conditions investigated.
307
However, there are indications that the presence of large
crystals (>40 µm in the case of salt solutions) is necessary
in the system to avoid rapid scaling from occurring.
Scales normally grow on the majority of the heat transfer
surface during primary nucleation; during continuous
crystallization scales, they only grow up to a certain height
of the tube and the rest of the heat transfer surface remains
clean (for the tube length investigated). Growth behaviour
during continuous crystallization is, however, similar to
that of primary nucleation during operation with a high
temperature difference (25°C for salt solutions). A
temporary loss of wetting has also the potential of
initiating similar scaling behaviour.
The results are similar for both sodium carbonate solution
and black liquor, although both the bulk crystals and the
structure of the scales are finer for black liquor. This is in
accordance with the theory that it is black liquor with a
significantly higher viscosity, and the lower diffusivity of
salts in it, that promotes the formation of smaller crystals.
Acknowledgements
This work was co-funded by the Swedish Energy Agency, Valmet
AB, Tröedsson forskningsfond, Bo Rydins stiftelse and Chalmers
Energy Initiative.
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