A REVIEW OF DERESINATORS AS DIGESTER ADDITIVES FOR KRAFT PULPING

John Adiwinata
Bastech, LLC
Jacksonville, FL USA

Brian N. Brogdon
Future Bridge Consulting & Training, LLC
Marietta, GA USA

ABSTRACT

The goal of this paper is to review the scientific literature and analyze the application of deresinator digester additives for
augmenting kraft pulping of softwoods and hardwoods. Deresinators are generally used to control pitch deposition on
process equipment and to minimize bleached pulp extractive levels, particularly with dissolving pulp grades.
Applications of this technology are observed to improve kraft and kraft-AQ cooking by reducing pulp reject and active
alkali levels, in addition to lowering pulp extractive levels. Improved cooking liquor penetration with these nonionic or
anionic surfactants can positively affect the global cooking rate (i.e., H-factor).

INTRODUCTION

Kraft pulping is an inherently heterogeneous process [1-10], whereby alkaline solutions breakdown and dissolves lignin
under high temperatures and pressures in order to facilitate the liberation of cellulosic-based fibers from a solid wood
matrix. This process involves chemical transport and reaction kinetics. The first steps involves the transport of
chemicals from the bulk liquor solution to the exterior surface of the wood chip, the transport of chemicals from
chemicals from exterior to the interior through the porous infrastructure, and the transport of chemicals from the interior
to chemical reaction sites by diffusion. The next steps involve the chemical reactions of the reactants with lignin,
carbohydrates and extractives. Afterwards, the degradation products formed from these reactions are transported from
the wood interior to the bulk liquor solution in a process reversed to that described earlier for chemical reactants. The
overall reaction rate of kraft pulping is often governed by chemical kinetics and transport phenomena, of which either
aspect can be the rate-limiting factor.

Ideally, it would be highly desirable to distribute uniformly the chemical reactants from the bulk liquor solution to every
reaction site within the wood matrix before the chemical reactions occur. In this theoretical case, the reaction system
would behave like a homogenous system. Unfortunately, commercial kraft digesters are far from this idealized system.
A number of factors introduce additional heterogeneity to the process besides the solid-liquid reaction system described
earlier. Some factors involve the wood itself. These include variability of the wood species comprising the wood chips,
moisture content, extractive levels, chip size and thickness, chip age, ect. [1,7-12]. Other factors that affect pulping
heterogeneity are the seasonal and weather effects [13-15]. The pulping process itself also introduces some variability
such as how well the cooking chemicals are impregnated into the wood chips prior to the start of pulping chemical
reactions [5-18].

Adequate chemical penetration of cooking liquor into the wood chips in some commercial digesters can be problematic,
especially considering most digesters are operating above their original design capacity. This increased throughput often
requires shorter chemical impregnation times, quicker rises to cooking temperature, and/or slightly higher cooking
temperatures in order to overcome equipment limitations. These changes to the process can potentially result in reduced
pulp yields, viscosity, physical strength and quality.

A significant amount of work has been published [1-11,16-27] that has examined both chemical and physico-chemical
factors involved in kraft pulping, and how these process can be manipulated to improve pulp uniformity, yield and
selectivity. Much of this research focused on the chemistry and kinetics of pulping, as well as digester design, chemical
feeds and chemical profiling. Another area of published research, which has received some attention, is the use of
chemical aids, such as anthraquinone (AQ) [22-25] and deresinators [12,26-39]. The goal of this paper is to review some

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of the literature regarding deresinators/surfactants in pulping, with and without AQ, and to show how these additives
affect pulping operations.

HISTORY OF DERESINATORS

The use of deresinator in chemical pulping has a long history. One of the main applications of deresinators was with
acid sulfite pulps [33,38-40]. Pulps produced by acid sulfite, which are often used in specialty and dissolving pulp
grades, often contain trace levels of wood resins. These wood resins, if not removed, can cause processing problems
such as pitch deposits on pulp mill equipment or papermachines, or filtration problems with viscose production. In these
operations, a deresination surfactant, such as polyethoxylated nonyl phenol, was added in hot caustic extraction (HCE) of
sulfite pulps in order to lower the level of wood resins not removed during acid sulfite pulping. The alkaline conditions
of HCE saponify some of the resin acids and fatty acids esters of wood resin and the surfactant assist with the dispersion
of these fatty acids, along with the unsaponifiable resins, into the liquor solution. Deresinator surfactants have been used
for dissolving-grade hardwood kraft pulps. Prehydrolyzed softwood kraft pulps generally do not require surfactant
addition to assist with resin removal; softwood resins tend to be easily dispersed since they contain more free fatty and
resin acids than hardwoods [38,39,41], which aid in the dispersion of unsaponifiable resins into the black liquor (Fig. 1).
Hardwood tends to contain more fats and nonpolar unsaponifiable resins that compose its extractives; these components
of hardwood extractives are not easily removed during kraft pulping without the aid of deresinators or mechanical
treatment [12,29,30,33-35,42].

Figur e 1. Differences in extractives composition of a

hardwood (Aspen) and a softwood (Jack Pine). Data from
Ekman and Holmbom [41].

SO3Na
O
O OH
0 to 6 n-1 O

Linear Alcohol Ethoxylate NaO3S

(n = 6-15) SO3Na
O Diphenyloxide Disulfonate
O O R
OH H O OH
O
n O
n-1 q O Y
m n-1
R
0 to 6
R= alkyl group
Nonylphenol Ethoxylate Ethylene Oxide/Propylene Oxide Y= -SO3Na, -OSO3Na, Alkylnapthalene
(n = 6-15) Block Co-Polymer -COONa, -PO3Na2, ect. Sulfonate
(m+n = 8-260; q = 25-50)
Derivitized Anionic
R' Alcohol Ethoxylate (n = 6-15)
O
N
C R"
2 to 12
R', R"= -CH3, CH2CH2OH, COONa
H-[OCH2CH2]n-OH, ect. 2 to 12
SO3Na
Fatty amide or alkanolamide Saponified Fatty Acid
Alkyl Benzene Sulfonate
Figur e 2. A few examples of non-ionic and anionic surfactants used as deresinator and alkaline pulping aids. The
subscripts m, n and q refer to the moles of ethylene oxide (EO) or propylene oxide (PO) contain in the surfactant
molecule [28-35,43-50].

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Figure 2 illustrates just a few of the surfactants which have either been tested or have been used as deresinators. The
most common surfactant used is nonyl phenol ethoxylates (NPEs). This nonionic surfactant behaves as a wetting agent
with little to no foaming tendencies; it is also relatively stable to strong alkaline environments. The use of NPE as
deresination aids have been declining due to increasing governmental regulations. Breakdown products from NPEs in
aquatic environments have been implicated as estrogen disruptors [34]. Many mills have limited the use of the broad
surfactant class of alkylphenol ethoxylates (APEs) due to similar concerns associated with the NPEs subclass.
Alternatives to APEs deresinators for sulfite pulps and prehydrolyzed kraft pulps are the nonionic alcohol ethoxylates
(AEs), and in particular the linear alcohol ethoxylates (LAEs). In some cases, the LAEs are as effective or more
effective at pulp deresination as NPEs, as been demonstrated by Borchardt et al. [33,34] with a hemlock sulfite pulp
treated in HCE. Most of the non-ionic surfactants used as pulping aids have moderate level of ethoxylation (~6 to 20
moles of (EO)).

Other deresinator surfactants that have been used or examined in pulping include anionic surfactants, such as alkyl
benzene sulfonates, diphenyloxide disulfonates, alkylnapthalene sulfonates, as well as derivatized alcohol ethoxylates,
and non-ionic alkyl amides and ethylene oxide/propylene oxide block co-polymers ((EO)/(PO)). Most commercial
deresination aids are proprietary formulations, which may or may not be blends of various surfactants. It is desirable that
any surfactants that are used in the digester have both thermal and alkaline stability, and is able to function in a highly
ionic environment; it is also desirable that they have low-foaming characteristics and are in a form that is easily pumped,
particularly in the colder winter months.

One of the oldest pulping deresinator/pulping aids is tall oil soap [39]. Many of the Scandinavian mills add 1 to 3% of
softwood tall oil soap to the kraft digester when pulping birch. The saponified tall oil fatty acids assist in dispersing
some of the sterols, triterpenyl esters and unsaponifiable extractives contained in the birch wood.

HOW DERESINATORS ASSIST THE KRAFT PULPING PROCESS

The mechanism of how deresinator surfactants assist kraft pulping is different from other pulping adjuncts, such as
anthraquinone (AQ) or polysulfide (PS). Polysulfide behaves somewhat similar to how sodium hydrosulfide and sodium
hydroxide of white liquor, in which it is consumed during the pulping reactions [1]; PS oxidizes the reducing ends of the
carbohydrates [1], which inhibits wood yield losses caused from alkali peeling reactions. Anthraquinone acts as a
pulping catalyst [22-25], in which AQ oxidizes the reducing ends of the carbohydrates (yield increased/stabilized) and
AQ intermediates (i.e., anthrahydroquinone (AHQ)) fragments the lignin (delignification rate increased) (Fig. 3). The
reactions of AQ with the carbohydrates generate the AHQ intermediates, and the reactions of AHQ with lignin result in
the regeneration of AQ, which establishes the redox cycle. Deresinator surfactants do not behave as chemical reactants,
like sodium hydrosulfide and sodium hydroxide of white liquor, nor do they behave as pulping redox catalysts, such as
AQ. Pulping surfactants affect the physico-chemical aspects of kraft pulping [32], which involve phase-boundary
interactions of the exterior surfaces and interior lumen openings of wood chips with the cooking liquor.

AQ
O
2 x Carbohydrate-CHO 2x
(Carbohydrate End Group)
+ 2x O-Lignin
Figur e 3. Catalytic redox reactions involving AQ OCH3
(New Lignin
End Group)
and its intermediate, anthrahydroquinone anion O OH

(AHQ2-), in carbohydrate stabilization and lignin End group stabilization End group fragmentation
Carbohydrate yield gain Delignification Rate Gain
(Oxidation) (Reduction)
fragmentation reactions during alkaline pulping
O
[22-25].
2 x Carbohydrate-COOH O-Lignin
(Stabilized End Group) 2x
O
2- OCH3
AHQ
OH
(Lignin End Group)

Pulping surfactants, such as those used as deresinators, generally facilitate the wetting of the cooking liquor with the
hydrophobic components on the solid surfaces. These surface-active agents also increase the capillary penetration of the
cooking liquor into the chip’s interior surfaces through the lumen openings [26-32,43-50]. In addition to improved
wetting by reduced liquor surface tension, deresinators act like detergents to detach hydrophobic extractives at the solid
surfaces [32], and dispersing them into the bulk liquor and exposing new surfaces to the cooking liquor. All of these
actions help in the chemical mass transport of pulping reactants to the reaction sites in porous wood matrix. It must be

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 stressed that deresinator surfactants only affect the penetration of the cooking liquor and not the diffusion of chemical
reactants. Diffusion is a component of mass transport phenomenon whereby the dissolved reactants move to the reaction
sites by a concentration gradient at the molecular scale level. Penetration, on the other hand, occurs at macro-scale level
whereby the cooking liquor flows into the porous matrix of the wood chip.

(A) (B)

Figur e 4. Influence of softwood chip thickness on the overall cooking rate (H-factor) for various chip thickness.
Delignification rate curve for a “typical commercial chip mixture” is calculated based on a chip distribution shown in
(B). Rate curves for specific chip thicknesses (i.e., (A)) are from Mortha and Jain [3,4]; simulated cooking conditions
are given in Figure 6. Chip distribution (B) is from Luu and Shariff [11].

(A) (B)

Figur e 5. Influence of softwood chip thickness on delignification uniformity on the fiber-to-fiber level. Pulping for (A)
2 mm and (B) 10 mm softwood chips at 548, 1274 and 1892 H-factors. Graphs calculated from data of Boyer and Rudie
[19,20]. Cooks with thin chips results in a narrower standard deviation around the average kappa number, whereas thick
chips result in a broader standard deviation characteristic of a multi-modal Gaussian distribution.

Figur e 6. Influence of softwood chip thickness on

residual alkali concentration inside the wood toward the
end of the cook. Calculation are based on fifteen equal
slices. The profile from outside slice (position 1) to the
center (Position 8) are shown. Simulated cooking
conditions: 19.4% EA, 20% sulfidity, L:W of 4.6:1,
170°C and H-factor of 1450. Calculated from Mortha
and Jain [3,4].

Liquor penetration can influence the overall delignification rate, as is seen with seen in laboratory studies conducted with
chips that are uniform in size and thickness [3-11,16-21]. Thinner chips (2-5 mm) cook more rapidly (Fig. 4) and
produce a delignified pulp that is more uniform (e.g., narrow distribution) than oversized thick chips (>8 mm) (Fig. 5).
This reflects that the cooking liquor has more difficulty penetrating the thicker chip which results in the outer portion of
the chip are overcooked and the inner portion is overcooked (Fig.6); the resulting pulp may have the desired targeted
kappa number but is non-uniform in lignin distribution at the fiber-to-fiber level [20,21].

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(A) (B)

Figur e 7. Influence of a non-ionic surfactant deresinator on the overall cooking rate (H-factor) and rejects a for southern
US mixed pine. Data from Duggirala [31]. Chip distribution: 5% of pins & fines, 80% of 3 to 8 mm thick, 10% of >8
mm thick, and 5% of oversized (>45 mm in length).

Laboratory studies performed by Duggirala [31] examined how the addition of a non-ionic surfactant impacted the
cooking rate of southern US pine chips (Fig. 7). Cooks were performed with a distribution of chip sizes that might be
typical for commercial kraft cooks. The overall cooking rate shown in Figure 7A with and without surfactant has some
similarities to how chip thickness impacts the delignification rate (Fig. 4A). An analysis of Duggirala’s pulping study
[31] indicates a reduction of 130 to 200 H-factor units is possible when a surfactant is used when cooking to kappa
number of 25 to 35 versus the control. This reduction in H-factor can be used to lower the cooking temperature by 1 to
2°C (2 to 5°F), reduce cooking time by 7 to 14% or increase wood processing throughput by 7 to 14%. Further analysis
indicates that screen yields increase by 1.5 to 3% units when compared to a targeted kappa number. A portion of this
screen yield improvement is a reduction in the rejects (Fig. 7B), which indicates the surfactant is assisting cooking liquor
penetration into the chips, particularly the ones that are oversized and/or >8 mm thick.

It should be noted, however, that there is a distinction in how oversized and/or over thick wood chips cook when
compared to knots. Knots result from the chipping of wood where a branch emanated. These wood structures generally
result in oversized “chips” that are denser and are enriched with lignin and extractives when compared to normal wood.
Knots are ordinarily resistant to liquor penetration whether or not a deresinator surfactant is used; such structures
contribute to screen rejects at the end of the kraft cook [51].

EFFECTIVENESS OF VARIOUS DERESINATOR SURFACTANTS AS PULPING AIDS

The scientific literature of the past fifteen years contains a few systematic studies [12,26-37], which have evaluated
various types/classes of surfactants for their effectiveness as deresinators and digester aids. Duggirala [28-31] has
conducted some laboratory screening studies for various anionic and non-ionic surfactants for softwood (Table 1 and
Fig. 8 & 9) and hardwood (Table 2 and Fig. 8 & 9) kraft pulping. The results from the author’s various studies indicate
alkylated diphenyloxide disulfonate (DODS), nonylphenol ethoxylate (NPE) and alcohol etholxylate (AE) surfactants
work well as deresinators and as pulping aids for softwoods and hardwoods. The additions of these surfactants tend to
reduce the amount of rejects and increase the residual active alkali (RAA) when compared to the control (without
surfactant). Analysis of Duggirala’s data suggests that surfactants that are very effective deresinators, such as alcohol
ethoxylates, are very effective digester aids over a range of targeted kappa numbers. In some cases, some yield
improvement is seen, especially in terms of screen yield.

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Table 1. The effect of various anionic and non-ionic deresinator surfactants on extractives level, kappa number, rejects
and residual active alkali (AA) for kraft pulping of southern US mixed pines. Surfactants added at 0.10% on wood.
Kraft cooks conducted at: 1800 H-factor, 30% sulfidity, 18% AA, 3.5:1 liquor/wood ratio and 170°C cooking
temperature. Chip distribution similar to that of Figure 7. Data from Duggirala [28].
Deresinator Surfactant Extractives (%) Kappa Number Rejects (%) Residual AA (g/L)
Control 0.132 30.0 2.8 4.5
Anionic
Alkylbenzene Sulfonate 0.129 27.1 3.3 4.9
Alkylated Diphenyloxide Disulfonate 0.121 27.2 2.1 5.2
Alkylated Naphathalene Sulfonate 0.128 30.2 3.2 4.7
Non-ionic
Alkanol amide 0.131 32.5 2.9 5.1
Nonylphenol Ethoxylate (NPE) 0.113 27.5 2.1 5.1
Alcohol Ethoxylate (AE) 0.099 26.1 1.5 6.1

Table 2. The effect of various anionic and non-ionic deresinator surfactants on extractives level, kappa number, rejects
and residual active alkali (AA) for kraft pulping of southern US mixed hardwood chips. Surfactants added at 0.10% on
wood. Kraft cooks conducted at: 1000 H-factor, 25% sulfidity, 18% AA, 3.5:1 liquor/wood ratio and 170°C cooking
temperature. Chip distribution: 5% of pins & fines, 74% of 3 to 8 mm thick, 15% of >8 mm thick, and 6% of oversized
(>45 mm in length).. Data from Duggirala [29].
Deresinator Surfactant Extractives (%) Kappa Number Rejects (%) Residual AA (g/L)
Control 0.490 20.0 3.0 4.9
Anionic
Alkylated Diphenyloxide Disulfonate 0.450 18.9 2.0 5.3
Non-ionic
EO/PO Block Co-polymer 0.460 20.3 2.8 5.1
Nonylphenol Ethoxylate (NPE) 0.450 19.0 2.0 5.3
Alcohol Ethoxylate (AE) 0.391 17.9 1.6 5.8

(A) (B)

Figur e 8. Influence of various deresinator surfactants on extractives versus brownstock kappa number for southern US
mixed pine (A) and mixed hardwood (B) chips. Cooking conditions given in Tables 1 and 2 for mixed pines and mixed
hardwoods, respectively; H-factor held constant with %AA charge varied from 15 to 18%. Surfactants added at 0.10%
on wood. Surfactants: AE – alcohol ethoxylate, NPE – nonylphenol ethoxylate, and DODS diphenyloxide disulfonate.
Data from Duggirala [28-30].

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(A) (B)

Figur e 9. Influence of various deresinator surfactants on brownstock kappa number versus total or screened yield for
southern US mixed pine (A) and mixed hardwood (B) chips. Cooking conditions given in Tables 1 and 2 for pine and
hardwoods, respectively; H-factor held constant with %AA charge varied from 15 to 18%. Surfactants (alcohol
ethoxylate) added at 0.10% on wood. Data from Duggirala [28-30].

(B)
Figur e 10. Impact of a deresinator surfactant on kraft
and kraft-AQ pulping of a southern US pine mix: (A)
effect on overall cooking rate (H-factor), (B) total yield
and (C) rejects. Cooking conditions given in Tables 1
with variable H-factor and a fixed %AA charge of 18%.
Surfactant (alcohol ethoxylate) added at 0.05% on wood
and AQ added at 0.05% on wood. Data from Duggirala.
[30].

(A) (C)

In a later study, Duggirala [30] examined the impact of a non-ionic surfactant with kraft and kraft-AQ pulping with US
southern pine mix. The use of a non-ionic surfactant yielded similar delignification rate as kraft-AQ (Fig. 10A),
although the mechanism of how each impacts the overall rate is different. The combination of surfactant with kraft-AQ
resulted in additional improvements in overall delignification rate. The use of both AQ and non-ionic surfactant could
result in a reduction of 375 to 450 H-factor units compared to a regular kraft cooking to kappa number of 25 to 35. This
reduction in H-factor roughly translates to a 2 to 5°C decrease in cooking temperature, or a 10 to 30% decrease in
cooking time. Employing a surfactant with kraft-AQ pulping results in an incremental total yield increase of ~0.5 to 1
units (Fig. 10B). This increase in yield is likely the result of fewer rejects being generated by the improve penetration of
cooking liquor and AQ into the wood chip. Duggirala [30] did not report what the rejects levels were with surfactant
kraft-AQ pulping, but he did report the rejects levels for kraft, kraft-AQ and kraft-surfactant pulping (Fig. 10C). The
amount of rejects as a function of brownstock kappa number for kraft and kraft-AQ pulps tend to be linearly related
whether or not AQ is used. These results suggest that AQ does not affect rejects, whereas the surfactant, on the other
hand, does significantly.

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MILL APPLICATIONS OF DERESINATOR SURFACTANTS IN PULPING

Basso [12,35] reported the results of various trials with an anionic deresinator surfactant for a northern US kraft pulp mill
that utilizes aspen wood chips. Several short-term trials in the late winter showed a reduction of pulp extractives of
~30% and of bleached dirt counts of ~20% when ~0.1% (on wood) of the surfactant was added to the batch digester.

Figur e 11. Seasonal effect on extractives levels in aspen

wood chips in the northern US [12,35].

A month long trial of the deresinator was done later in the year (late fall) [12,35]. The trial showed a reduction in pulp
extractives of ~9% and in rejects by 50% for the ~16 kappa number brownstock. The change in extractives reduction
reflects the seasonal changes in the amount of extractives in the aspen chips in the fall versus winter (Fig. 11), as well as
the fall chips were seasoned versus the green chips of the winter months. The mill observed a reduction of 0.2% units of
AA in the white liquor need for cooking. The black liquor soap content increased by 113% and the amount of steam
generated per kilogram of black liquor solids fired increased by 3%. The mill observed an increase in bleached pulp
yield of ~0.3 to 0.8% units (from ~55.2% pulp yield prior to the trial); this increase was probably due to the reduction of
rejects, which tend to run ~0.5% for 16 kappa aspen brownstocks. Bleaching costs were reduced by ~15% during the
trial versus the pre-trial period.

Short-term mill trials of a similar anionic deresinator surfactant have been conducted at a southern US kraft pulp mill
utilizing mixed pine and mixed hardwood species [35]. The mill uses ~0.03% AQ on wood for both fiber lines. The
addition of AQ/deresinator combination yielded ~1% unit increase in pulp yield for both fiber lines compared to kraft-
AQ alone (i.e., 43.5% versus 42.5% for pines at 26.5 kappa, and 47.6% versus 48.6% for hardwoods at 14.5 kappa). The
amount of effective alkali needed for the pine cooks decreased from 15.1% to 14.5%, and for the hardwoods cooks
decreased from 14.6% to 13.7%.

The above mill results for not atypical of kraft-AQ. Manji [36] reported short-term mill trial results of AQ and AQ-
surfactant pulping of costal softwoods from British Columbia with a kraft continuous digester (Table 3). The author
noted that the addition of an anionic surfactant to kraft-AQ pulping to ~32 kappa number resulted in a yield increase of
~0.4% units, as well as a reduction in digester steam and a reduction of black liquor solids per ton of pulp.

Table 3. Short-term trials of AQ and AQ/Surfactant (anionic) for the kraft pulping of costal British Columbia softwood
mix. Surfactant added at 0.0.05% on wood and AQ added at 0.05% on wood; bleaching with (C50D50)(EOP)D1E2D2.
Data from Manji [36]. Continuous digester operated at ~28% sulfidity.
Measured Quantity Control AQ AQ/Surfactant
Kappa No. 31.8 31.4 31.8
% EA (as Na2O) 14.3 14.7 14.3
Residual EA (g/l) 12.3 11.4 11.9
Weak black liq. Solids Kg/ton pulp 1794 1764 1727
Total Digester Steam (Kg/ton pulp) 1687 1629 1565
Brownstock Yield (% on wood) 47.7 48.8 49.2
Bleached Brightness (% ISO) 90.2 89.9 90.2
Bleached Dirt Count (number/sq. ft.) 1 to 5 1 to 4 1 to 2

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 (B)
Figur e 12. Impact of a non-ionic surfactant on soda-AQ
pulping of a southern US hardwood mix over a year long
trial: (A) effect on brownstock kappa number (B) % AA
on wood (as Na2O) and (C) bleached brightness. Non-
ionic surfactant added at 0.025% on wood and AQ added
at ~0.064 to 0.069% on wood. Data from Parthasarathy
et al. [37].

(A) (C)

Results from longer mill trials of deresinator surfactants in kraft or kraft-AQ pulping are not as extensively reported in
the scientific literature. However, a notable study by Parthasarthy and co-workers [37] disclosed the results of long-term
mill trials of a non-ionic deresinator to soda-AQ pulping of mixed hardwoods (Fig. 12). The authors observed a
reduction of cooking liquor AA from ~15.79% to 14.69% (as Na2O) and a reduction of H-factor of ~34 units (from 1100
to 1065) when cooking to a target kappa number of ~17.5 (Table 4). The addition of the deresinator also improved the
bleached pulp yields of soda-AQ process, from 44.7 to 44.4%. The authors did notice that the surfactant/soda-AQ pulps
could be bleached to the same targets or better than soda-AQ pulps, and under some cases, there were some significant
bleach savings with the elimination of post-bleaching with hydrogen peroxide in high density storage. Parthasarthy et al.
did not report any data regarding reject levels in the mill. The effect of the surfactant on soda-AQ pulping is seen over
the course of a year. It is important that comparisons be done relative to the season, since there is a periodical seasonal
effect on pulping operations [13-15].

Table 4. Yearly summary of the effect of a non-ionic surfactant on soda-AQ pulping of a southern US hardwood mix
for a long-term trial. Non-ionic surfactant added at 0.025% on wood and AQ added at ~0.064 to 0.069% on wood;
bleaching with (C50D50)(EOP)D1. Data from Parthasarathy et al. [37].
Measured Quantity Year 1 (Control) Year 2 (w/ Surf.)
Kappa No. 17.5 17.1
% AA (as Na2O) 15.79 14.96
Residual AA (g/L as Na2O) 6.10 7.51
H-factor 1100 1065
Wood Processing Rate (normalized to Year 1) 1.000 ~1.036
Bleached Yield (% on wood) 44.65 46.38
Bleached Brightness (% ISO) 85.70 87.64

FINAL COMMENTS

The use of deresinators, either as a stand-alone pulping aid or as an adjunct to AQ pulping, can provide benefits to
augment kraft pulping, in addition to reducing pulp extractives. The application of such products should be carefully
considered for each individual case. In some instances, a deresinator surfactant can improve pulping operations, either

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by increasing wood yield, increasing wood production rate, lowering rejects, lowering H-factor, lowering cooking alkali
requirements, ect. In other cases, the benefits of this additive addition are not economically justified depending on pulp
mill operations. It is often difficult to evaluate the effectiveness or economic impact of a deresinator on a commercial
scale. Part of this dilemma deals with the lack of well-define control of pulping conditions in a mill digester when
compared to a laboratory study [28-31]. A factor that contributes to this variability is the seasonal factors impacting chip
properties. Hart [14], and Hart and Ransdell [13] have noted that chip moisture can increase or decrease by 5% units,
and the amount of pins & fines, as well as bark content, in the chip feed to the digester can increase or decrease by
~1.5% units depending on the time of the year. These chip quality issues tend to swing in the spring (March – May) and
fall months (October – November). Likewise, the amount of extractives in the wood chips can experience wide swings
during these periods (Fig. 11) [12]. These changes in chip quality are due to temperature swings from winter to summer
and vice versa. Short-term mill trials of any digester additive should be carefully timed to avoid these time periods for
evaluation. Longer term trials of a digester additive should be compared to similar time periods in previous years to
eliminate seasonal variability bias [13,14,37].

The results presented in this literature review suggest that some deresinator aids can complement kraft and kraft-AQ
pulping. These aids can potentially improve screen pulp yields for bleachable softwood brownstocks in the 25 to 30
kappa number range and bleachable hardwood brownstocks of 18 to 25 kappa number range. Most of this yield gain is
related to lower rejects generated, as well as to milder cooking conditions (e.g., lower alkali and/or cooking time). Yield
gains with deresinators are not as evident for extended delignification for softwood brownstocks <25 kappa or for
hardwood brownstocks <16 kappa; however, under these circumstances, a deresinator can still assist with lowering the
alkali requirements for cooking or reduce the cooking time (i.e., H-factor). A reduction in H-factor can assist a mill who
is looking to incrementally increase their production rate without additional capital expenditures by increasing the
amount of wood being processed in the digester that is operating beyond its original design capacity. We will be
reporting in a future publication regarding how deresinator aids can assist mills facing production bottlenecks due to
equipment limitations.

CONCLUSIONS

This paper reviewed and analyzed the scientific literature on the application of deresinator digester additives for
augmenting kraft pulping of softwoods and hardwoods. Many nonionic and anionic deresinator surfactants improve
kraft and kraft-AQ pulping by increasing cooking liquor penetration into the wood chips. Improved liquor penetration
assists in accelerating the global cooking rate (i.e., H-factor) and lowering extractive levels and pulp rejects. The use of
deresinator aids can improve pulp screen yields and/or assist in lowering the alkali requirements of the cooking liquor.
The effectiveness of deresinator digester additives has to be carefully evaluated with short- and long-term trials, taking
into consideration the periodic variations in chip quality caused by seasonal changes.

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PEERS 2011 Page 946

 A REVIEW OF DERESINATORS AS
DIGESTER ADDITIVES FOR
KRAFT PULPING

John Adiwinata Brian N. Brogdon

Bastech, LLC FutureBridge Consulting
& Training, LLC

PEERS 2011 Page 947

 Introduction
 Kraft pulping is an inherently
heterogeneous process
 Reactants in solution (NaOH & NaSH)
 Porous solid chip matrix

 Delignification reactions
 Reactants transported by liquor penetration
in porous wood structure (large scale)
 Next, reactants diffuse into matrix (small
scale)
 Chemical reactions occur
 Reaction products diffuse out
 Overall reaction rate influenced by mass
transport and intrinsic chemical reactions

PEERS 2011 Page 948

 Introduction
 Improving pulp uniformity
 Insure complete cooking liquor impregnation in
chips prior to start of chemical reactions
 Uniform chip size in 3 to 7 mm in thickness

 Unfortunately, many factors cause

additional pulp non-uniformity
 Shorter impregnation time to increase digester
throughput beyond design capacity
 Variation of liquor circulation
 Variation of cooking temperature
 Variation of chip moisture
 Variation in wood species mixture
 Bark contamination
 Seasonal factors

PEERS 2011 Page 949

 Liquor Penetration – Chip Thickness
75
Chip Center

Residual NaOH (g/L as Na2O)

12 mm
18
9 mm
Brownstock Kappa No.

65
7 mm
5 mm
55 16
3 mm
Chip
45 Thichness
14 3 mm
35 5 mm
9 mm
12 12 mm
25 Commercial Chip
Mixture (circles)
15 10
800 1200 1600 2000 2400 0 1 2 3 4 5 6 7 8 9
H-Factor Slice Position within Chip

 Thin chips (3 - 5 mm) cook at similar rates (H-Factor); even

alkali profile across chip
 Thick chips (9 - 12 mm) cook slower; significant alkali gradient
 Thicker chips limited by alkali transport from bulk solution

PEERS 2011 Page 950 Calculated from Morthra & Jain (2008)
 Liquor Penetration – Chip Thickness
0.20 0.20
15. 9 Kappa 2 mm Chips 10 mm Chips
Brownstock
0.16 0.16
Relative Frequency

Relative Frequency
0.12 32.0 Kappa 0.12
Brownstock
23.4 Kappa
0.08 0.08 Brownstock
54.6 Kappa
Brownstock 33.4 Kappa 63.7 Kappa
0.04 0.04 Brownstock Brownstock

0.00 0.00
0 10 20 30 40 50 60 70 80 90 0 10 20 30 40 50 60 70 80 90
Kappa Number at Fiber Scale Kappa Number at Fiber Scale

 Thin chips (2 mm): smaller kappa no. st. dev. around average
– more uniform distribution
 Thick chips (10 mm): larger kappa no. st. dev. around average
–non-uniform distribution; exhibit multi-modal “tails”

PEERS 2011 Page 951 Calculated from Boyer & Rudie (2007)
 Deresinator and Liquor Penetration
 Use of deresinators has long history
 Originally used to reduce resin & extractives
with acid sulfite pulps
 Also used with prehydrolyzed kraft pulps (HW)
 Nonylphenol ethoxylates (NPEs) & pine tall oil
commonly used in above applications
 Deresinators have received increased attention
in 1990s for kraft pulping

 Current kraft pulp deresinator surfactant &

blends
 Anionics – alkylated diphenyloxide disulfonate
 Non-ionics – EO/PO block polymers,
alcohol ethoxylates (AEs), NPEs
 Derivatized non-ionics w/ polar ionic groups

PEERS 2011 Page 952

 Deresinator and Liquor Penetration
 Deresinators effect physico-chemical:
 Not consumed as reactants (NaOH & NaSH)
 Do not act as delignification catalysts (AQ)
 Disperses & removes hydrophobic extractives
 Reduces cooking liquor surface tension;
improves wetting & capillary action
 Can assist with initial dispersion of
hydrophobic AQ into cooking liquor

 Deresinator do not participate in intrinsic

chemical reactions
 However, deresinators can influence
overall reaction rate (H-Factor)
 Can decrease pulp rejects & cooking
liquor alkali requirements (%EA or %AA)
PEERS 2011 Page 953
 Deresinator – Impact on H-Factor
US Southern Pine Mix
50 50
Control Control
0.05% AQ

Brownstock Kappa No.

Brownstock Kappa No.

45 45 0.05% Surf.
0.05% Surf.
0.05% Surf./0.05% AQ
40 Series3 40 Series3

Series4
35 35

30 30

25 25

20 20
1000 1400 1800 2200 1000 1400 1800 2200
H-Factor H-Factor

 Duggirala demonstrated that alcohol ethoxylate (AE) alone

has similar impact on H-Factor reduction as AQ
 Additional H-Factor reduction with AE/kraft-AQ combination
 AQ accelerates delig. reactions; AE improves alkali transport

PEERS 2011 Page 954 Data from Duggirala (2000)

 Deresinator – Impact on Yield & Rejects
US Southern Pine Mix [Varying H-factor; Fixed % AA]
52 4.5
AQ (0.05%) Surf.

Pulp Rejects (% on wood)

Total Yield (% on wood)

51 AQ/Surf. (0.05%) 4.0

Control
(0.05%/0.05%)
Control 3.5 (Solid Circles)
50
3.0
49
2.5 AQ , 0.05%
48 (Open Circles)
2.0
47
1.5 Surf.
46 (0.05%)
1.0
45 0.5
24 28 32 36 40 44 24 28 32 36 40 44
Brownstock Kappa Number
Brownstock Kappa Number

 Duggirala demonstrated that alcohol ethoxylate (AE) can

improve pulp yield with kraft and kraft-AQ
 Yield increase w/ AQ from carbohydrate end stabilization
 Yield increase w/ AE from reduction of pulp rejects; AQ does
not reduce rejects at a given kappa no.
PEERS 2011 Page 955 Data from Duggirala (1999)
 Deresinator – Impact on Yield & Rejects
Varying %AA; Fixed H-factor
46
Southern HWs Mix Southern Pines Mix
% Total or Screened Yield

% Total or Screened Yield

Surf. (Total) 47
44 Control Surf. (Total) Control (Total)
(Total)
45
42

Surf. (Screened) Surf. (Screened)

43
40

38 41 Control (Screened)
Control
(Screened)
36 39
14 18 22 26 30 34 38 42 24 28 32 36 40 44
Brownstock Kappa Number Brownstock Kappa Number

 Duggirala demonstrated that alcohol ethoxylate (AE) can

improve pulp yield, particularly screened yield for various
%AA levels (15 – 18%) for both hardwoods & softwoods

PEERS 2011 Page 956 Data from Duggirala (1999)

 Various Deresinator Surfactants
Varying %AA; Fixed H-factor
30
Brownstock Kappa Number

Brownstock Kappa Number

Southern HWs Mix NPE Southern Pines Mix
44 Control (circle)

26 40

36
22

AE NPE (diamond)
32
DODS (triangle)
18 Control (circle) AE (square)
28

DODS (triangle)
14 24
0.35 0.4 0.45 0.5 0.55 0.6 0.65 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45
Extractives (% on pulp) Extractives (% on pulp)

 %AA ranged from 15% (high kappa) to 18% (low kappa)

 HW deresination: alcohol ethoxylate (AE) > nonylphenol eth-
oxylate (NPE) ≈ alkylated diphenyloxide disulfonate (DODS)
 SW deresination: AE ≈ NPE ≈ DODS
 Deresinator reduce ~0.5 to 1.0% AA units at given kappa
PEERS 2011 Page 957 Data from Duggirala (1999)
 Mill Trials – Seasonal Trends
16.8 18.5
Control w/AQ AQ/Surf. Control w/AQ
% AA on Wood (as Na2O)

Brownstock Kappa No.

16.4
18.0 AQ/Surf.
16.0

15.6 17.5

15.2
17.0
14.8
16.5
14.4

14.0 16.0
1 2 3 4 5 6 7 8 9 10 11 12 1 2 3 4 5 6 7 8 9 10 11 12
Month Month
 Mill trials with deresinator/surfactant should be aware of
seasonal variations that influence operations (chip moisture,
extractive levels, bark contamination, ect.)
 Soda-AQ pulping of US mixed hardwoods with anionic
deresinator reduce %AA by ~1% unit & H-factor by from 1100
to 1065; increased bleached yield ~1.7% units
PEERS 2011 Page 958 Data from Parthasarthy et al. (1996)
 Deresinator Mill Trials with Kraft-AQ
 Month-long mill trials conducted on SW
and HW lines with an anionic deresinator

 Softwoods (SW)
 Yield: 42.5%  43.5% at ~27 kappa no.
 %EA: 15.1%  14.6%
 Hardwoods(SW)
 Yield: 47.6%  48.6% at ~14.5 kappa no.
 %EA: 14.6%  13.7%

 Above results are similar with published

laboratory studies & Parthasarathy et al.
soda-AQ mill study

 Plans to present future mill trial results

PEERS 2011 Page 959 Unpublished data from Friel (2010)

 Conclusions
 Cooking liquor penetration can influence pulp uniformity &
overall cooking rate
 Deresinator surfactants can assist with liquor penetration by
dispersing extractives and improving liquor wetting of chips
 Deresinator surfactants increase reaction rate (lower H-
factor); not related to intrinsic chemical reaction as with AQ
catalyst or consumable reactants (e.g., NaOH & NaSH)
 Deresinator surfactants can increase pulp yield by reducing
reject levels
 Deresinator surfactants can lower cooking liquor alkali
requirements by 0.5 to 1.0% units
 Mill trials with deresinator surfactant should be aware of
seasonal variations that influence operations
PEERS 2011 Page 960
Questions?

PEERS 2011 Page 961