Research Note

pubs.acs.org/IECR

Scale Inhibition and Removal in Continuous Pulp Digesters

Sujit Banerjee* and Tuan Le
Institute of Paper Science and Technology, School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, 500
Tenth St. NW, Atlanta, Georgia 30332-0620, United States

Peter W. Hart
MeadWestvaco Corporation, 1735 Peachtree St., Atlanta, Georgia 30309, United States

ABSTRACT: Calcium carbonate scaling occurs in the chip feed system and the cooking vessel of continuous digesters in pulp
mills, and it arises from the reaction of calcium from wood chips with carbonate in the cooking liquor. Commercial antiscalants
are typically expensive and rarely keep the system scale-free. Lignin derivatives have been proposed as antiscalants, because of
their ability to chelate calcium, but they have not been adopted commercially. We demonstrate that addition of ∼1% black liquor
to white liquor reduces or prevents calcium scaling, as shown by a simple new test that measures the degree to which scale resists
abrasive removal from a metal surface. These findings were validated in a full-scale mill trial, where the black liquor not only
inhibited calcium scale formation, but also removed existing scale.

■ INTRODUCTION
Calcium scaling is an expensive problem in pulp and paper
mills, as well as in other water-intensive industries. The type of
scale deposited depends on the unit operation involved. For
example, calcium carbonate is most commonly found under
alkaline conditions. Calcium oxalate is present in oxidative
bleaching stages,1 and pirssonite (CaCO3·Na2CO3) often
occurs during green liquor (GL) clarification.2 Barium sulfate
is formed in systems that employ alum or sulfuric acid.1
Burkeite (2Na2SO4·Na2CO3) is frequently found in black liquor
evaporators.3 Calcium scaling is more prevalent in continuous
digesters than in batch operations.4
Commercial antiscalants work by threshold inhibition of
nucleation or by blocking active sites for crystal growth and/or
by altering the morphology of the growing crystals.5
Phosphonates are frequently used in the Kraft process.6−8
Lignin derivatives are an attractive alternative to synthetic
antiscalants, because they contain carboxylates and other
components capable of complexing with and solubilizing
Deposition measurements were made by immersing a 20-g
stainless steel coupon in GL supplemented with up to 1% black
liquor by volume. GL was used in laboratory work because it
contains carbonate and also because this study was done in the
context of ongoing work on GL-modified Kraft pulping.13,14
CaCl2 was added to the liquor at 20−60 ppm Ca. The coupon
was heated in the liquid for 2 h at 120 °C in a Teflon bomb.
The coupon was removed and air-dried overnight, and the
weight gain was measured. For measurements with added
lignin, the coupon was heated as above, dried at 150 °C and
then ignited at 525 °C to burn off organics.
The procedure used for measuring scale removal was adapted
from a test developed for measuring the tack of adhesives.15 A
piece of aluminum oxide sandpaper (336U, frit grain 100 from
3M) of the same area as the coupon was placed on the coupon
and weighted with a 100-g load also of the same area as the
coupon. The sandpaper was dragged slowly (over 10 s) twice
across each face of the coupon. Loose material was allowed to
fall off the coupon by turning it over, and the weight loss
determined.

calcium.9−11 A combination of synthetic antiscalants and
surfactants has also been proposed.12 Chemical treatment
delays scale formation but does not usually prevent it. The
deposits must be removed through steam shocks, hydroblasts,
or acid cleaning.5
In this report, we demonstrate, through laboratory work and
a full-scale trial, that the addition of ∼1% black liquor (BL),
which is the major lignin stream in a pulp mill, to white liquor
can be an effective and inexpensive alternative to chemicals in
current commercial use. In addition, the BL provides an
unexpected benefit of removing existing scale.
■
RESULTS AND DISCUSSION
Laboratory Studies. We started by studying the effect of
lignin (Indulin) on scaling in GL supplemented with CaCl2 (30
ppm as Ca). The results, provided in Figure 1, show that
deposition is reduced somewhat at lower levels of lignin, but
that it returns at higher levels. Regardless, the degree of scale
inhibition in the best case is ∼30%. Next, measurements were
made with 1% BL (instead of lignin) in GL and with the Ca
supplement increased to 60 ppm. The results in Figure 2 show
that 1% BL increased deposition slightly. Nevertheless, a crucial

■ MATERIALS AND METHODS

Softwood and hardwood BL was obtained at 18% solids from
Received:
Revised:
May 23, 2012
July 5, 2012
the MeadWestvaco Evadale, TX, mill. Acid-precipitated lignin Accepted: July 15, 2012
(Indulin AT) was also obtained from MeadWestvaco. Published: July 15, 2012

© 2012 American Chemical Society 10283 dx.doi.org/10.1021/ie301352j | Ind. Eng. Chem. Res. 2012, 51, 10283−10286
Industrial & Engineering Chemistry Research
Figure 1. Effect of lignin on deposition on a coupon heated in green
liquor (GL) containing 30 ppm Ca for 2 h at 120 °C. The coupon was
ignited at 525 °C. Uncertainties are average deviations obtained from
two determinations.
Figure 2. Effect of 1% black liquor (BL) on deposition on a coupon
heated in GL containing 60 ppm Ca for 2 h at 120 °C. Uncertainties
are average deviations obtained from three determinations.
finding was that the BL-treated coupon could be wiped
completely clean with a tissue, whereas acid cleaning was
necessary for the untreated coupon. A deposit test conducted
with a 60 ppm Ca supplement as above and with a commercial
antiscalant used by the Evadale mill reduced coupon scale in
the calcium-supplemented GL used above by ∼30%. However,
the scale was not removable by wiping, and the antiscalant was
not considered further. The ability of BL to remove existing
scale was demonstrated by heating a coupon immersed in GL
supplemented by 20 ppm Ca at 120 °C for 2 h. As expected,
scale deposited on the coupon. BL was then added to the GL at
a final concentration of 1%. The system was reheated as done
previously and the coupon retrieved and air-dried. The scale
was easily removed with a tissue.
It seemed that a conventional static deposit test was
inadequate in a dynamic system with turbulent flow where
particulate material could scour the scale. We modified the
deposit test through a procedure developed earlier for
evaluating the strength of adhesive binding to coupons. After
exposure to liquor in the bomb, the scaled coupon was air-
dried. A weighted piece of sandpaper was dragged over each
face of the coupon and the weight loss was measured. For the
example illustrated in Figure 3, the coupons were heated in GL
supplemented with 20 ppm Ca at 120 °C for 2 h. The lower
panel in Figure 3 shows the scale deposit after air-drying; only a
small benefit accrues from the addition of 1% BL. Sanding the
BL-treated samples removes a significant fraction of the
deposits as is evident from the results in the upper panel.
The effect of softwood and hardwood BL concentration on
deposits both before and after sanding is shown in Figure 4,
where the GL was supplemented with 20 ppm Ca. Despite the
10284
Research Note
Figure 3. Effect of sanding on scale reduction on coupons heated in
GL containing 20 ppm Ca for 2 h at 120 °C. Uncertainties are average
deviations obtained from three determinations.
Figure 4. Effect of BL on scaling on coupons heated in GL containing
20 ppm Ca for 2 h at 120 °C. Uncertainties are average deviations
obtained from three determinations.
relatively high uncertainty, some of which was probably caused
by variability in the surface roughness of the coupon, it is clear
that the BL is effective in the range of 0.5%−1%. A higher dose
of BL was not considered because a 1% BL dose was sufficient
to eliminate white liquor scaling in the full-scale trial discussed
below. Softwood BL is marginally more effective than
hardwood BL. Although the components in BL responsible
for antiscalant activity were not identified, it is likely that
polycarboxylates from degraded lignin play a role. The
antiscalant properties of polyacids are well-known.9 However,
other components in BL must also be important because, while
lignin products are known to suppress scaling,9 they are not
known to remove existing scale.
Mill Trial. MeadWestvaco’s Evadale, TX, pulp mill modified
the piping arrangement feeding cooking liquor (white liquor)
into its hardwood digester (1200 air-dry tonnes/day) to be able
to control a volumetric flow of softwood BL into the feed end
of the digester. The BL line was equipped with a magnetic flow
meter and flow control valves. The purpose of the white liquor
strainers is to remove small wood particles from the liquor
recirculation loop to prevent them from plugging the slotted
screens elsewhere in the digester. The white liquor strainer
system is equipped with an in-line spare, which is cleaned and
transferred into service on a weekly basis. Some calcium
carbonate scale is noted upon the weekly cleaning of this
strainer. In addition to their designed function, the in-line
strainers have been successfully used by the Evadale mill as a
first-line “canary” to evaluate and determine operational or
upset conditions that may lead to increased scale formation
within the digester. Figure 5 shows the layout of the digester.
Because the digester is prone to calcium carbonate scale
formation under typical operating conditions, it has employed
dx.doi.org/10.1021/ie301352j | Ind. Eng. Chem. Res. 2012, 51, 10283−10286
Industrial & Engineering Chemistry Research
Figure 5. Diagram of the Evadale two vessel hydraulic digester with modified continuous cooking showing the in-line strainers as well as where BL is
taken from the pine digester and where the BL is reinjected into the chip circulation loop. (Figure courtesy of Metso.)
various commercial antiscalant products for several years.
Softwood BL was applied in place of the commercial antiscalant
for several months at a savings of well over half a million dollars
per year per digester. Since the start of this trial, there has been
no significant scale formation on the in-line strainers.
Another method of determining the extent of scale formation
inside the digester is to evaluate the flow of liquor recirculated
through the chip circulation loop of the digester feed system. As
the slots in the separator begin to scale, the available surface
area for extracting liquor decreases and restricts the liquor flow.
During the initial commercial trial, the chip circulation loop
liquor flow was already significantly restricted, with a nominal
flow rate of 5750 L/min. After three days of applying 55−60 L/
min of BL directly into the flow loop, the chip circulation flow
increased to 7875 L/min, suggesting that the treatment not
only prevented the formation of additional scale but actually
removed some of the scale that was already formed. Once the
liquor circulation flow stabilized at the higher level, liquor
circulation within this loop did not change significantly during
the two months of this trial. Therefore, the BL is uniquely
effective in both preventing and removing scale. It is likely that
the chelants present in BL inhibit scaling and the surfactants
remove existing deposits. Since the start of this trial, no adverse
effects have been identified in other unit operations, such as the
multieffect black liquor evaporators or black liquor crystallizers
within the mill.
■
CONCLUSIONS
A full-scale demonstration showed that calcium carbonate
scaling in the impregnation vessel of a continuous pulp digester
can be completely removed by the addition of ∼1% black liquor
(BL) to the pulping liquor, with softwood BL being slightly
more effective than hardwood BL. Further scaling is also
inhibited. A new test was developed to determine the amount
of recalcitrant scale as opposed to material that can be easily
removed.
10285
Research Note
■ AUTHOR INFORMATION
Corresponding Author
*Tel.: 404 894 9709. Fax: 404 894 4778. E-mail: sb@gatech.
edu.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was supported by the Department of Energy
(Contract DE-FC36-04GO14308) and by MeadWestvaco
Corporation.
■ REFERENCES
(1) Rudie, A. W.; Hart, P. W. Formation and prevention of calcium
oxalate scale in the bleach plant. Solutions People, Processes Pap. 2005,
88 (6), 45−46.
(2) Frederick, W. J.; Krishnan, R.; Ayers, R. J. Pirssonite deposits in
green liquor processing. Tappi J. 1990, 73 (2), 135−140.
(3) Verrill, C. L.; Frederick, W. J. Evaporator foulingSodium salt
crystallization and soluble-scale fouling. Presented at the TAPPI
Conference, Philadelphia, PA, August 2005.
(4) Hartler, N.; Libert, J.; Persson, B. The problem of scale
formation: A literature survey. Svensk Papperstid. 1970, 73 (22), 731−
736.
(5) Severtson, S. J.; Duggirala, P.; Carter, P. W.; Reed, P. E.
Mechanism and chemical control of CaCO3 scaling in the kraft
process. Tappi J. 1999, 82 (6), 167−174.
(6) Area, M. C.; Felissia, F. E.; Graca, M.; Carvalso, V. S.; Ferrira, P.
J.; Barboza, O. M.; Bengoechea, D. I. Characterization of Eucalyptus
garndis kraft pulps treated with phosponates in different stages of TCF
bleaching. BioResources 2011, 6, 2077−2090.
(7) Guo, J.; Severtson, S. J. Inhibition of calcium carbonate
nucleation with amino-phosphonates at high temperature, pH and
ionic strength. Ind. Eng. Chem. Res. 2004, 43, 5411−5417.
(8) Felissia, F. E.; Area, M. C.; Barboza, O. M.; Bengoechea, D. I.
Anti-scaling agents in kraft pulping. BioRes. 2007, 2, 252−264.
(9) Severtson, S. J.; Guo, J. Influence of ozonized kraft lignin on the
crystallization of CaCO3. J. Colloid Interface Sci. 2002, 249, 423−431.
(10) Alén, R.; Käkölä, J.; Pakkanen, H. Monitoring of kraft pulping by
a fast analysis of aliphatic carboxylic acids. Appita J. 2008, 61 (3), 216−
219.
dx.doi.org/10.1021/ie301352j | Ind. Eng. Chem. Res. 2012, 51, 10283−10286
Industrial & Engineering Chemistry Research Research Note

(11) Loy, J. E.; Guo, J.; Severtson, S. J. Role of adsorption

fractionation in determining the CaCO3 scale inhibition performance
of polydisperse sodium polyacrylate. Ind. Eng. Chem. Res. 2004, 43,
1882−1887.
(12) Crump, D. K.; Cooper, L. A.; Hopkins, T. M. Scale inhibition
formulations for kraft digesters. U.S. Patent 4,799,995, 1989.
(13) Ban, W.; Lucia, L. A. Kinetic profiling of green liquor-modified
kraft pulping. Ind. Eng. Chem. Res. 2005, 44, 2948−2954.
(14) Ban, W.; Singh, J.; Lucia, L. A. Kraft green liquor pretreatment
of softwood chips. Part III: Lignin chemical modifications.
Holzforschung 2003, 57, 275−281.
(15) Banerjee, S.; Le, T.; Haynes, R. D.; Bradbury, J. E. Solubilizing
and detackifying stickies with ß-cyclodextrin. BioResources 2012, 7,
1533−1539.

10286 dx.doi.org/10.1021/ie301352j | Ind. Eng. Chem. Res. 2012, 51, 10283−10286