Strategies for controlling sodium salt scaling in black liquor

evaporator– The influence ofthe bulk crystalpopulation

Authors:Erik K arlsson*,LennartVam ling,M athiasG ourdon
Chalm ersU niversity ofTechnology,SE 412 96,G othenburg,Sweden
*Corresponding author:erik.karlsson@ chalm ers.se

Abstract:Black liquorevaporation is an essentialunitoperation in the chem icalrecovery cycle ata pulp m ill.Since
black liquor contains high concentrations of sodium carbonate and sodium sulphate, these salts will start to
crystallize when dry solids content typically exceeds 50% . The concentrator effect will therefore work as a
crystallizerand itsoperation ischallenging since crystallization isunavoidable,which,in turn,often causesscaling.In
this paper,the relationship between scaling and bulk crystals is investigated experim entally on a pilotscale,by using
hydrocyclone separation to change the bulk crystalpopulation.Recom m endations for scale controlare given based
on the observed results. It was found that the larger crystals contributed to a lower degree of scaling and are
therefore m ore im portantin the system than the sm allercrystals.Provided thata m inim um am ountofbulk crystals
is available during norm aloperation (continuous crystallization),it was also found that a further increase in the
am ountofbulk crystalswillnotdecrease the scaling rate.

Keyw ords:scaling,black liquor,sodium carbonate,sodium sulphate,falling film evaporation.

IN TR O D U CTIO N
D uring operation of black liquor evaporators,fouling decreases the perform ance and regular cleaning is needed to
m aintain capacity and stability.D ifferentcom ponentsin the black liquorm ay cause the fouling,eitherinorganic salts
precipitate ororganic com poundsdepositon the surfaces[1].G enerally,the inorganic fouling caused by precipitates
of sodium or calcium salts is believed to be m ost problem atic [2].Because of the abundant am ounts of sodium
reaching up to 20% of the dry solids,the sodium salts are known to be the cause of rapid precipitation fouling
(scaling),m ainly togetherwith carbonate and sulphate as anions.The solubility ofthese salts is typically exceeded at
around 50% D S (dry solids content)in the black liquor;m eaning thatscaling ofsodium salts willonly occur in the
evaporator effects with this high D S,i.e.the concentrator (effect 1) and possibly effect 2.In a norm alcleaning
schedule,the concentratoristypically cleaned on weekly basis depending on the operators’previousexperience with
scaling.H owever,the problem with scaling variesa lotfrom m illto m ill:som e needsdaily cleaning while othersonly
clean once a year.

The m ain focus of m any research studies has been to apply existing fundam entalknowledge of crystallization and
provide directadvice of how to operate the evaporator to controlit[3-7].The generalrules are (i)avoid operation
close to solubility lim itofthe sodium salts,as this willrisk prim ary nucleation and cause rapid scaling,and (ii)avoid
a high carbonate-sulphate ratio,because a high ratio willresultin the crystallization ofdicarbonate which isreported
to cause m ore scaling than burkeite.These m itigation strategies have been proven to work on fullscale in a num ber
ofcase studies[8,9].

Concentrations clearly above the solubility lim it im ply the presence of a significant am ount of bulk crystals.The
supersaturation of the sodium salts caused by the evaporation process would, to a larger extent, lead to
crystallization on these bulk crystals instead of on the scales or evaporator surface.The population of bulk crystals
can also be increased by recirculating black liquor of higher concentration and thereby introduce additional(seed)
crystals.This is used in som e m ills today,and has been discussed in a num berofstudies [5,10,11].H owever,there
is no experim entaldata thatinvestigates the influence of bulk crystalrecirculation.A disadvantage of recirculating
highly concentrated black liquor is that organic com pounds and dissolved salts would be also recirculated,which
would increase viscosity and boiling pointelevation,and hence decrease the evaporatorcapacity.A workaround for
this is suggested in a patent[12]whereby a hydrocyclone is used to separate a crystal-rich fraction from the highly-
concentrated liquor before it is recirculated.This was further investigated in another publication by the authors,
where hydrocyclone separation of bulk crystals from black liquor was dem onstrated and suggestions for how bulk
crystalrecirculation could be im plem ented in industry were given [13].

The focus of this study was to investigate the relation between scaling and bulk crystals, which was done
experim entally on a pilot scale. The aim was to clarify the role of bulk crystals in order to further develop
recom m endations for controlling scaling in black liquor evaporators.The data in this study is also used in another
work by the authors[14],buthere itisreanalysed,com pared with othersand the focusism ore towardsim plications
forscale control.
Crystallization and scaling ofthe sodium carbonate-sodium sulphate salts
The com position of the crystals form ed during black liquor evaporation depends on the m olar ratio of sodium
carbonate and sodium sulphate in the solution.The two m ost im portant crystal species in term s of scaling are
burkeite, with an approxim ate com position of 2N a2SO 4 · N a2CO 3, and sodium sulphate dicarbonate (norm ally
referred to as dicarbonate),with an approxim ate com position ofN a2SO 4 · 2N a2CO 3,where the latteris reported as
having a significantly higher tendency to form scales at the heat transfer surface [4,15].They have both inversed
solubility,i.e.the solubility decreases with tem perature,m eaning that supersaturation can actually be generated by
two m echanism s:(i)increased localconcentration caused by evaporation of the solvent,which takes place on the
fluid-vapour interfaces for the low heating rates used during black liquor evaporation, and (ii) increased local
tem perature caused by heating of the solution,generated close to heat-transfer surfaces due to heat transfer from
the tube wall.

For the system studied here,supersaturation is created m ainly due to evaporation from the falling film of black
liquor.Crystallization occurson the heattransfersurface (asscaling)oron free bulk crystals,shown schem atically in
Fig. 1. There will be com petition between these two locations, which is controlled by both the crystal surface
available and m ass transfer phenom ena: if, for exam ple, the bulk crystals constitute the m ajority of the crystal
surfaces available and the hydrodynam ic conditions (e.g.turbulence) favour a low m ass transfer resistance in the
bulk,scaling willnotbe prom oted.

Crystallization will, however, only occur on surfaces of the sam e crystal species: if none are available, then
crystallization willnotoccurdespite reaching supersaturation.H owever,as the supersaturation exceeds the so called
m etastable lim it,nuclei,or seeds,are form ed spontaneously and crystallization begins rapidly.This nucleation can
take place both in the bulk and at(m etal)surfaces.The term prim ary nucleation is used forthe eventto distinguish
it from secondary nucleation,in which new nucleiare form ed by fragm ents breaking loose from existing crystals.
W hen studying the relationship between scaling and crystallization in the bulk,itis im portantto consider both the
effectofprim ary nucleation and subsequentcrystallization on the available crystalsurfaces[16].

Vapour
Heat transfer surface

Falling film of black liquor

• Dissolved Na2C03, Na2SO4
• Dissolved organic + inorganic
• Water

Heating
Vapour

Free (bulk) crystals

Scaling

Fig.1 -Schem atic diagram ofcrystallization in an evaporating falling film ofblack liquor.

The form ation ofscalescan be divided into two steps[17].Firstoccursthe initiation:the firstcrystalsare form ed on
the heattransfer surface,often after a certain tim e known as the induction or initiation period.This is followed by
growth due to continues crystallization on the crystalsurfaces available.The firststep is probably the m ostcrucial
as,once form ed,scaleswillgrow also atlowerlevelsofsupersaturation.

There are two possible m echanism s for the form ation ofscales;crystallization ofthe dissolved salts and deposition
ofexisting crystals (agglom eration).In the case ofinitiation,the firstm echanism favours nucleation on the surface,
which is dependent on the supersaturation leveland surface properties.For exam ple,cavities in the m aterialcan,
catalyse nucleation [16].Experim ents have shown thatthe rate ofsurface nucleation can be reduced considerably by
m aking the surface very sm ooth giving a low affinity forthe crystallizing salts [18].The deposition ofexisting (bulk)
crystals can also give very high rates ofscale form ation,as itis notlim ited by the crystallization rate,butdeposition
ism ore likely forsm allcrystals(<50 µm )asthey have a strongertendency to agglom erate [16].
E XPE R IM E N TAL
The evaporation of black liquor has been studied in a num ber of experim ents in this work.Black liquor is a very
com plex m ixture [1].Therefore,m odelsolutions can be used to sim plify the system to provide better controlover
the experim ents.The experience of our group is that water solutions of sodium carbonate exhibit sim ilar scaling
behaviours to dicarbonate and,as it consists of only one salt,solutions of sodium carbonate were therefore also
studied.

The pilotplant
The flowsheetin Fig.2 shows the m ostim portantequipm entand sensors in the pilotevaporator.The evaporator
itself was of the falling film type,with the liquor on the outside of a verticaltube.The evaporator tube was 4.5 m
long,with an outer diam eter of60 m m ,giving itan active outer heattransfer area of0.85 m 2.The tube was heated
on the inside with condensing saturated steam . The salt solution or black liquor was fed into the top of the
evaporator using a circulation pum p (displacem ent pum p):an overflow distributor integrated into the top of the
tube ensured thatthe distribution ofthe liquid was circum ferentially uniform fora variety offlow rates.The vapour
and the concentrated liquid flowed from the evaporator tube into a tank serving both as a buffervolum e (about50
l)and vapour-liquid separator(buffertank in Fig.2).The bottom ofthe tank was then connected to the circulation
pum p;the vapourflowed into a condensercontrolling the pressure in the system .

Evaporator TI RI FI DI
z(m)

0 Condenser
0.15
Cooling
TI Water

PI
Condensate
1.9
Outflow
FI
Scale
thickness
measure-
ments
DI
3.9 CLD
VI
4.5

Buffer
tank Feed
TI LI TI
FI TI
Hydro-
PI cyclone Sampling
(fine)

Steam Steam Wash Sampling Sampling Wash liquid

condensate liquid incl. filtration (coarse)
Fig.2 -Sim plified flow sheetofthe pilotfalling film evaporatorplant.The valves are setto indicate norm al
operation w ith the coarse fraction from the hydrocyclone being sent to the evaporator (w hite valve =
closed). CLD = chord length distribution, D = density, F = flow rate, L = level, P = pressure, R =
refractive index,T = tem perature and V = viscosity.

A hydrocyclone was used to change the crystalcom position of the bulk,which was designed to separate particles
larger than 50 µm ata viscosity of 50 m Pa·s and an inflow of 900 l/h.Itwas installed together with a num ber of
valves thatenabled two operationalm odes,where either the fine (top)or coarse (bottom )fraction was fed into the
evaporator (Fig. 2). The rem aining fraction was recirculated back to the buffer tank. The valves also enabled
m easurem ents to be m ade of the chord length distribution (CLD )of the bulk crystals in both the fine and coarse
fractions,but only one at a tim e.The sensor used for this was focused beam reflectance m easurem ent (M ettler
Toledo Lasentec FBRM D 600L)and is described further in [19];the design and installation of the hydrocyclone is
described in m ore detailin [13].

E xperim entalprocedure
The experim ents were prepared by first filling the system with either the salt solution or black liquor,and then
heating and evaporating itto the desired conditions.D epending on the type ofscaling experim ent,i.e.nucleation or
continuouscrystallization,slightly differentprocedureswere em ployed.
N ucleation (N ) experim ents: The salt solution or liquor was concentrated from below solubility to
supersaturation;at a certain point the concentration becam e high enough (the m etastable lim it) to trigger prim ary
nucleation and initiate scaling. M easurem ents continued until the scaling rate decreased significantly or the
evaporation processstalled due to severe scaling;the running tim e wasbetween 0.5 and 1 hour.

Continuous crystallization (C) experim ents:In the steady-state m ode,vapour was rem oved as in the nucleation
experim ents,butwith either fresh saltsolution or liquor,both atconcentrations below solubility,being fed so that
the density of the stream into the evaporator tube was kept constant. Concentrated solution or liquor was
sim ultaneously ejected to m aintain a constantlevelin the buffer tank.This procedure gave conditions close to an
industrial evaporator under steady-state operation. A substantial am ount of scales was often form ed during the
initialpreparation to reach the desired conditions:the tube was therefore cleaned to ensure thatthe m easurem ents
of fouling resistance began with no scales being present.M ost of the steady-state salt experim ents lasted for 5-22
hours:those with black liquorwere m ore difficultand ranged between 2-6 hours.

H ydrocyclone operation:The crystalpopulation entering into the evaporator unit was changed for som e of the
experim ents.Thiswasachieved by operating the hydrocyclone in the following three differentm odes:
• 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 buffertank.
• Fine:the fine fraction (top fraction) was fed into the evaporator unit.The coarse fraction was recirculated
back to the buffertank.

M onitoring bulk crystals

Two different m ethods were used to determ ine the am ount of bulk crystals present in the stream entering the
evaporator.In the experim ents with saltsolutions,density m easurem ents were used and the m ass fraction (cf)ofthe
crystalswascalculated from :
1 1
−
= . (1)
1 1
−

This expression was derived using the conservation of m ass and volum e.Values from the literature were used for
the density ofthe crystals,ρcry,which should be close to thatofburkeite,i.e.2570 kg/m 3 [20].The totaldensity,ρtot,
was m easured during the experim ents and the density ofthe saturated solution,ρsat,was obtained from a correlation
developed from data where a salt solution in which no bulk crystals were present was evaporated at the sam e
operationalconditions.

A different m ethod was used to calculate the crystalfraction in the black liquor.As it is a com plex m ixture,its
density is notonly dependenton its contents of saltand crystals,butalso on other organic and inorganic m aterial
present. Instead, sam ples were taken and the dry solids content analysed. The crystal fraction could then be
calculated by sam ples of liquor both with,D Sunfilt,and withoutcrystals,D Sfilt,(rem oved by filtering).The following
expression wasderived from a m assbalance overthe filter:
−
= . (2)
1−
The online sam ple filtration m ethod developed by G ourdon [21]wasused.

M onitoring scaling
The rate ofscaling wasm onitored using both the totaland localheattransfer.The totalheattransfercoefficient,i.e.
the average ofthe entire heattransfersurface,isbased on the m easurem entofthe steam condensate flow,which isa
directm easurem entofthe rate ofheating.

A decreasing trend in the heattransfercoefficientwhen allotheroperationalparam eters are keptconstant,indicates

the occurrence of scaling.The scaling observed was quantified by converting the heat transfer trends into fouling
resistance,R,according to the following expression:
1 1
= − . (3)
ℎ ℎ
H ere,hfouled is the heattransfercoefficienton the outside ofthe tube,including the heattransfer resistance from the
growing scales, and hclean is the heat transfer coefficient at clean conditions. The fouling resistance trend was
converted into a m easure of the rate of scaling.This was done by linearising the trend and dividing itby tim e (i.e.
the duration of the experim ent),which gave the expression ∆R/∆t ((m 2K /W )/m in).U nfortunately,the rates of
scaling were notalways constant,tending to be higher atthe beginning of the experim ents.An uncertainty range
wascalculated foreach experim entto evaluate the errorsdue to linearization and m easurem entuncertainties.

Chem icalproperties ofthe fluids

In the saltsolution experim ents sodium carbonate,with a purity of99.9% ,wasused to crystallize anhydroussodium
carbonate.Black liquor,originating from a Swedish K raft pulp m illprocessing softwood,was used in the other
experim ents.Analysis ofthe dry solids contentwas perform ed in-house,using the TAPPI 650 om -09 m ethod.The
m olar ratio of sodium carbonate was analysed,N a2CO 3 / (N a2CO 3+ N a2SO 4)= 0.67,and the crystalspecies m ost
likely to form during the experim entswasburkeite according to [22].

E xperim entalconditions
A num ber of experim ents were perform ed for salt solution (sodium carbonate) and black liquor,both nucleation
(N )and continuouscrystallization (C)experim ents.D ifferenthydrocyclone operationalm odeswere tested to change
the bulk crystal population.The operational tem perature was 120°C.The rate of heating was controlled by the
differentialtem perature (∆T)between the saltsolution or black liquor and the condensing steam .The wetting rate,
i.e.the m ass flow rate per unit with (Γ,in kg/(m ·s)) was controlled by the feed rate to the evaporator.Further
detailscan be found in [14]and [23].

R E SU LTS AN D D ISCU SSIO N

Behaviourduring prim ary nucleation
The results from the nucleation experim ents with sodium carbonate solution are shown in Fig.3,together with
sim ilarm easurem entsby G ourdon [21].Both ofthese worksm easured sim ilarscaling rates,although the operational
conditions were slightly different.The scaling rate was a little lowerin G ourdon’sexperim entwith a 6°C differential
tem perature (∆T),which can be expected as this would give lower crystallization rate.The wetting rates were also
slightly higher in G ourdon’s experim ent (1 and 1.3 kg/(m ·s), respectively), leading to a slightly lower expected
scaling rate as well.As shown in Fig.3,there was no significant deviation between the two works.The crystal
fraction was also m easured in the experim ents,and in four of the experim ents in this study very few bulk crystals
were form ed.The crystalfraction showed a parabolic correlation with the scaling rate,butitis notsignificantand
m ore m easurem ents are needed to prove it.A possible explanation for the behaviouris thatbulk crystals serve as a
com peting crystallization site and supresses the scaling, but as the crystal fraction increase above about 1.5% ,
deposition becom es a significant effect which increases scaling again.It should be noted that this num ber is not
valid in the case ofcontinuous crystallization as the conditions are differentthen.The crystalfraction is,ofcourse,
zero atthe startso the value reported here isaftera stable bulk crystalpopulation has been form ed.The scaling rate
during prim ary nucleation in black liquor showed sim ilar values as for the salt solution: the rates in the two
experim ents conducted at∆T = 10°C and Γ = 1 kg/(m ·s)were 9.5·10-6 and 8.3·10-6 (m 2K /W )/m in,respektively.
Furtherdetailscan be found in [14].
ΔT=10°C, Γ=1 kg/(m·s) Gourdon ΔT=10°C, Γ=1.3 kg/(m·s)
Gourdon ΔT=6°C, Γ=1.3 kg/(m·s)

40
35
ΔR/Δt [(m2K/W)/min] · 106

30
25
20
15
10
5
0
0,0% 0,5% 1,0% 1,5% 2,0% 2,5% 3,0%
Crystal fraction (by mass)

Fig.3 -Rates ofscaling in the nucleation experim ents using sodium carbonate solution as a function of
the crystalfraction,w here data from G ourdon [21]is included as w ell.
The relationship between bulk crystalsand scaling wasfound to be com plex:on one hand,no significantcorrelation
between the scaling rate and the crystalfraction is apparentfor saltsolution in Fig.3 but,on the other hand,bulk
crystals were still found to be im portant to slow down the high scaling rate that occurs during the prim ary
nucleation.This is analysed furtherin Fig.4,where the heattransfercoefficient(h)and chord counts are plotted for
two of the nucleation experim ents shown in Fig.3:one where bulk crystals were form ed after nucleation and one
where no (orfew)crystals were form ed.The chord countis a m easure ofthe num berofparticles in the system and
showsclearly how bulk crystalsare form ed in one ofthe experim ents.The decrease in the heattransfercoefficientis
sim ilarin the firstpartforboth the experim ents,which im plies sim ilarscaling rates:in the laterpart(afteraround 25
m in), however, the experim ent with crystals stabilises at a higher value. After 37 m in, the evaporation stalled
com pletely in the experim ents without crystals (the operation of the condenser had to be halted to m aintain the
tem perature of the salt solution),while operation could be continued (at a low rate) when crystals were available.
The trend for the chord counts in allthe nucleation experim ents with crystals available was sim ilar:a rapid increase
initially and then a shiftto a m uch lower increase rate.A generaltrend was also thatthe crystalsize was sm aller at
the onsetofprim ary nucleation and then increased during the experim ent.H owever,due to the rapid scaling during
prim ary nucleation and the chaotic behaviour of the crystallization process,fluctuations in the system were created
and the trendsofthe heattransfercoefficientand chord countsvaried slightly between the experim ents.

h h Chord counts Chord counts

4 500 14000
Heat transfer coeffcient [W/(m2K)]

4 000 12000
3 500 Chord counts [#/s]
10000
3 000
2 500 8000
2 000 6000
1 500
4000
1 000
500 2000

0 0
0 10 20 30 40 50
Time [min]

Fig.4 -Rates ofscaling in tw o nucleation experim ents presented in Fig.3 using sodium carbonate
solution,one w hen bulk crystals w ere form ed and one w hen not.

Behaviourduring continuous crystallization

The results from the continuous crystallization experim ents using sodium carbonate solution are shown in Fig.5;
the rate of scaling was approxim ately one-tenth of the value during prim ary nucleation in Fig.3.In two of the
experim ents in Fig.5,the operation was disturbed (labelled “U nstable” in the figure) due to crystals plugging the
flow to the evaporator,which resulted in significantly higherscaling rates.In one ofthem ,the scaling rate was high
justfora shortpartofthe experim ent,which isshown by the high width ofthe errorbar.

In two experim ents,the hydrocyclone was used to change the crystal population.The coarse m ode experim ent
showed no difference in scaling rate,while the fine m ode gave higherscaling rate.This indicates thatthe large-sized
crystals are im portantto keep in the system to reduce the scaling rate.Itm ightbe expected thatm ore bulk crystals
would com pete with the crystallization on the heat transfer surface and thereby reduce the scaling rate,but the
resultshere show no correlation between scaling rate and crystalfraction.
 ΔT=10°C, Γ=1 kg/(m·s)

10
9
ΔR/Δt [(m2K/W)/min] · 106

8
7 [CELLRANGE]
6 [CELLRANGE]
5
4
3
2
[CELLRANGE] [CELLRANGE]
1
0 [CELLRANGE] [CELLRANGE] [CELLRANGE]
[CELLRANGE]
[CELLRANGE] [CELLRANGE]
[CELLRANGE]
0,0% 1,0% 2,0% 3,0% 4,0% 5,0% 6,0%
Crystal fraction (by mass)

Fig.5 -Rate ofscaling in the continuous crystallization (C)experim ents using sodium carbonate solution.
Coarse and fine refer to the hydrocyclone operational m odes used.U nstable refer to unstable operation.
E xperim ents w ithoutcom m entw ere conducted w ithouthydrocyclone fractionation.

Continuouscrystallization experim entswere also perform ed using black liquor,butthe experim entswere perform ed
under different wetting rates (Γ) and differentialtem peratures (∆T).In addition,both the crystalfraction and the
operationalm ode of the hydrocyclone differed in the experim ents;the influence of these two param eters becom e
clearer when the data was plotted as follows.G ourdon [24]found thatthe m ajority of the variation in the rate of
scaling caused by the wetting rate and the differentialtem perature could be described by the concentration profile
along the heattransfer surface.This was calculated as the initialincrease of dry solids contentfrom the top to the
bottom (∆x0), with initial referring to the reference state when m easurem ents began: the increase in dry solids
contentdecreasesasscalesare form ed and decreasesthe heattransfer.Thisparam eterwasused in Fig.6,asitallows
a com parison of experim ents at different wetting rates and differential tem peratures to be m ade. A positive
relationship between the scaling rate and ∆x0 can be observed,aswasalso concluded from experim entsby G ourdon
[24].
Coarse Fine
3,0

2,5
ΔR/Δt [(m2K/W)/min] · 106

2,0 [CELLRANGE]

1,5
[CELLRANGE]
1,0 [CELLRANGE][CELLRANGE]
[CELLRANGE]
[CELLRANGE]
0,5 [CELLRANGE]
0,0
[CELLRANGE]
-0,5
0,0% 1,0% 2,0% 3,0% 4,0% 5,0% 6,0% 7,0%
Δx0 [kg/kg]

Fig.6 -Rates ofscaling in continuous crystallization (C)experim ents using black liquor.Coarse and fine
referto the operationalm ode ofthe hydrocyclone.The size ofthe circle w ith corresponding values referto
the crystalfraction.

The crystal fraction is shown in Fig. 6 by the size of the circle, in com bination with a label of the value. N o
correlation between rate ofscaling and fraction ofcrystals can be observed:the two highestpoints (5.4% and 6.0% )
do notshow a lowerrate ofscaling.The figure also showshow the operationalm ode ofthe hydrocyclone influences
the scaling rate: all points in the fine m ode had a higher rate of scaling then those in the coarse m ode when
com paring at the sam e value of ∆x0,albeit the differences are som etim es sm all.Like what was found for sodium
carbonate solutions,large crystals seem to be im portantin reducing the rate ofscaling.Possible explanation forthis
is that the large crystals do note adhere to the scale surface and/or have m ore favourable conditions for
crystallization.Thisisfurtherdiscussed in [14].
Finaldiscussion
N o correlation between the rate of scaling and the fraction of crystals was found in the continuous crystallization
experim ents,butthe rate of scaling increased when the larger-sized crystals were rem oved.A m inim um am ountof
large crystals is probably needed to suppress scaling (i.e.high degree of localsupersaturation),whilstthe system is
insensitive above this lim it.This can explain why no correlation with the crystalfraction was observed:the am ount
present in the experim ents with low fractions of crystals was sufficiently high to supress scaling. N o other
explanations could be found,for exam ple supersaturation (none was detected in the inflow to the evaporator tube
when operating in fine m ode,as it was m easured from refractive index for the salt solution),although there was
slightly m ore fluctuation in the system ,caused by experim entallim itations when operating in fine m ode.It is not
possible to quantify this lim itfrom the data and itis likely dependenton the localdegree ofsupersaturation (which
depends on the operation). For the prim ary nucleation experim ents the situation was different as the global
supersaturation was high atstartand a largeram ountofcrystals are probably needed to supress the scaling then,i.e.
caution isneeded when com paring resultsfrom the two typesofexperim ents.

The m ostrelevantstudies by other researchers thatwere found have partly contradictory results.The relationship
between the chord counts ofbulk crystalfrom FBRM m easurem ents and the scaling rate was investigated forthree
experim ents in connection with studies of internalresidence tim e by G ourdon [21]:no correlation was found.In
three adjacent experim ents,G ourdon also studied the relationship between the dry solids content and the scaling
rate:the highestrate of scaling was observed closestto the solubility lim it(or m etastable lim it).This was explained
by the low contentofbulk crystals when operating close to solubility,and thus a dependency ofthe crystalfraction
observed in thiscase.

Frederick and Euhus [5]discuss the im portance ofbulk crystals to provide sufficientgrowth area forcrystallization,
and have exam plesofcalculationsforestim ating the retention tim e needed to avoid supersaturation and the prim ary
nucleation ofdicarbonate.Theirestim ationsim ply thatretention tim es significantly longerthan those currently used
in industry are necessary to allow for crystallization on bulk crystals and to handle the supersaturation caused by
evaporation.This,however,doesnotagree with the observationsm ade in thiswork,where supersaturation afterthe
buffertank was only observed in the firstpartofthe nucleation experim ents.A possible explanation forthis can be
the unusually low estim ation of the crystalfraction:they assum e that0.0021 m 3 crystals/m 3 black liquor is form ed
when concentrating to 65% dry solidscontent.Increasing the crystalfraction by a factorof10 would bring the value
close to thatexpected in black liquor(and m easured in thisstudy),and the calculated retention tim esrequired would
be closerto thatbeing used in industry today.

Recom m endations forscale control

The knowledge gained from the research conducted in this study can be used to provide recom m endations forhow
to m itigate scaling:

• K eep operation assteady aspossible

• Reduce the increase in dry solidscontentalong the heattransfersurface by:

o H igh wetting

o Low differentialtem perature

o Shortand wide heattransfersurface (iftubes:shortbutm ore ofthem )

• Avoid passing m etastable lim itsand triggerprim ary nucleation which leadsto rapid scaling

• K eep a stable population ofbulk crystalsin the system

• The growth oflarge-sized crystalsshould be favoured,ifthisispossible.

These are,to a large extent,in line with the generalrecom m endations of others [4,6,7,10,22].As itis com m only
recom m ended to favoura high contentofbulk crystals in the concentrator,a new conceptforscaling m itigation by
recirculating the bulk crystalwas presented in [13](sim ilar to the patentof O lausson etal.[12]).The application of
this concept needs, however, to be reconsidered as no decrease in the degree of scaling was found when the
concentration ofbulk crystalwasincreased in continuouscrystallization (i.e.norm aloperation).
The solubility lim itis often passed during start-up,aftercleaning orduring m ajorchangesin the process(e.g.altered
liquor com positions or dry solids contentin Effects 1 or 2). Then itshould be im portant to add seed crystals to
avoid high levels of supersaturation, leading to the passing of the m etastable lim it and prim ary nucleation.
O therwise,when the evaporator is back in norm aloperation,its capacity is already affected negatively by the scales
thatare form ed during the start-up phase.The im portance ofa correctstart-up procedure aftercleaning isdiscussed
by Verrilland D eM artini[11],who also conclude thatthe addition ofseed crystalsisim portant.Correctstart-up can
be considered atleastas im portantas correctcleaning,and should notbe forgotten when troubleshooting scaling
problem s.Furtherinform ation can also be found in [23].

In addition,introducing new m easurem ent technology also has the potentialto assist im proved operation of the
evaporators. If, for exam ple, the crystal fraction and/or supersaturation level could be m easured online the
operators would have m ore inform ation about the status of the process: this would, in turn, im prove the
understanding of the crystallization phenom ena and sim plify the operation.M oreover,online m easurem ents of dry
solids content in each of the concentrator units (or effects operation above 50% D S) would also im prove
m onitoring of the process. D evelopm ent of new, inexpensive and robust m easurem ent technology is therefore
desirable to im prove the operation offuture evaporation plants.

CO N CLU SIO N S
• The rate ofscaling istenfold greaterduring prim ary nucleation than continuouscrystallization:bulk
crystalsare required to stop thishigh scaling rate,allcrystallization willotherwise occuron the heat
transfersurface,leading to severe operationaldisturbancesand the need forcleaning within hoursorless.

• Providing thata m inim um am ountofbulk crystalsisavailable during norm aloperation (continuous

crystallization),a furtherincrease in the am ountofbulk crystalswillnotdecrease the rate ofscaling.

• The largercrystalscontribute to a lowerdegree ofscaling and are therefore m ore im portantin the system
than the sm allercrystals.

• Itisim portantto feed the evaporatorwith crystalsduring start-up aftercleaning and otheroperational
changesleading to a risk ofpassing the m etastable lim it:prim ary nucleation can otherwise be initiated,with
a high risk ofsubstantialscaling occurring before the evaporatorisback in norm aloperation.

ACKN O W LE D G E M E N TS
This work was co-funded by the Swedish Energy Agency,Valm etPower AB,Troëdssons research foundation,Bo
Rydinsresearch foundation and Chalm ersEnergy Initiative.

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